CN109721070A - The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method - Google Patents
The production method of Titanium Sieve Molecular Sieve and the Titanium Sieve Molecular Sieve and Ammoximation reaction method produced by this method Download PDFInfo
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Abstract
The invention discloses a kind of Titanium Sieve Molecular Sieve and its production methods, it include: that organic silicon source, titanium source, template and water are successively subjected to the first hydrolysis-condensation reaction and the second hydrolysis-condensation reaction, obtain hydrolytic condensation mixture, during hydrolysis-condensation reaction, the steam of generation is drawn and condensed；Hydrothermal crystallizing is carried out after hydrolytic condensation mixture is mixed at least partly condensate liquid；After the contents on dry basis for optionally improving hydrothermal crystallizing mixture, spray shaping is carried out.The invention also discloses the Ammoximation reaction methods using the Titanium Sieve Molecular Sieve as catalyst.Titanium Sieve Molecular Sieve is produced using method of the invention, the decomposition of template in hydrothermal crystallization process can be effectively inhibited, and the process that the mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation can be omitted, reduces the wastewater flow rate that production process generates.When being used for the catalyst of Ammoximation reaction using the Titanium Sieve Molecular Sieve that method of the invention produces, the catalytic activity improved can be obtained.
Description
Technical field
The present invention relates to technical field of molecular sieve preparation, in particular it relates to a kind of producer of Titanium Sieve Molecular Sieve
Method and the Titanium Sieve Molecular Sieve produced by this method, the invention further relates to the amidoximes using the Titanium Sieve Molecular Sieve as catalyst
Change reaction method.
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, as the organic base of template and/or the reaction mixture of basic anhydride, by this reaction mixture in autoclave
In in 130-200 DEG C hydrothermal crystallizing 6-30 days, then separate, wash, dry, roast and obtain product.
Although researcher conducts in-depth research the preparation process of Titanium Sieve Molecular Sieve, the system of Titanium Sieve Molecular Sieve
Standby process still has some problems, needs that existing Titanium Sieve Molecular Sieve production method is improved and optimized.
Summary of the invention
The present inventor has found that existing Titanium Sieve Molecular Sieve production technology is primarily present following ask in practice process
Topic:
(1) in hydrothermal crystallization process, template is decomposed, and not only influences the quality of Titanium Sieve Molecular Sieve, but also template is
Higher raw material is worth in Titanium Sieve Molecular Sieve production process, template decomposition is difficult to recycle, to guarantee molecular sieve
Quality need to increase the inventory of template, it is clear that can improve the production cost of Titanium Sieve Molecular Sieve；In addition, the template decomposed is formed
Oily phase not only influences the crystallization of molecular sieve, and the upper layer of hydrothermal crystallizing slurries can be swum in after standing, and part oil phase substance can be attached
In hydrothermal crystallizing kettle inner surface, hydrothermal crystallizing kettle is polluted, the cleaning difficulty of hydrothermal crystallizing kettle is increased；
(2) existing method titanium sieve molecular sieve product as obtained from separating, washing, drying, roast is used, separates and washes
A large amount of ammonia nitrogen waste waters can also be generated by washing process, and the COD value of these ammonia nitrogen waste waters is high, need to carry out to expire after purified treatment
The requirement that foot is discharged and/or recycled, the purified treatment of a large amount of ammonia nitrogen waste waters have aggravated the life of Titanium Sieve Molecular Sieve manufacturer
Produce burden.
In view of the above-mentioned problems, the present inventor has made intensive studies, discovery will produce during hydrolysis-condensation reaction
Raw steam is condensed, and it is brilliant that hydro-thermal is carried out after the mixture that hydro-thermal condensation reaction obtains is mixed at least partly condensate
Change, can effectively inhibit the decomposition of template in hydrothermal crystallization process, at the same the obtained mixture of hydrothermal crystallizing can directly into
Row spray shaping, avoids the generation of ammonia nitrogen waste water, while also reducing production energy consumption.The present invention is completed on this basis.
According to the first aspect of the invention, the present invention provides a kind of production method of Titanium Sieve Molecular Sieve, this method packets
It includes:
(1) organic silicon source, titanium source, template and water are subjected to the first hydrolysis-condensation reaction, it is mixed obtains the first hydrolytic condensation
Object is closed, the first hydrolytic condensation mixture is subjected to the second hydrolysis-condensation reaction, the second hydrolytic condensation mixture is obtained, in institute
During stating the first hydrolysis-condensation reaction and second hydrolysis-condensation reaction, the steam of generation is drawn and condensed, is obtained
To condensate liquid；
(2) after mixing the hydrolytic condensation mixture at least partly described condensate liquid, hydrothermal crystallizing is carried out, water is obtained
Thermal crystallisation mixture；
(3) optionally, the contents on dry basis for improving hydrothermal crystallizing mixture, obtains slurries；
(4) the hydrothermal crystallizing mixture or the slurries are subjected to spray shaping.
According to the second aspect of the invention, the present invention provides the preparations of the method as described in first aspect of the present invention
Titanium Sieve Molecular Sieve.
According to the third aspect of the present invention, the present invention provides a kind of Ammoximation reaction method, this method is included in ammonia
Under the conditions of oximation reaction, cyclohexanone, ammonia and hydrogen peroxide are contacted with Titanium Sieve Molecular Sieve, wherein the Titanium Sieve Molecular Sieve is this
Titanium Sieve Molecular Sieve described in invention the second aspect.
Titanium Sieve Molecular Sieve is produced using method of the invention, template in hydrothermal crystallization process can not only be effectively inhibited
It decomposes, and the process that the mixture for obtaining hydrothermal crystallizing is separated by solid-liquid separation and is washed can be omitted, considerably reduce life
The wastewater flow rate that production process generates.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
According to the first aspect of the invention, the present invention provides a kind of production method of Titanium Sieve Molecular Sieve, this method packets
It includes:
(1) organic silicon source, titanium source, template and water are subjected to the first hydrolysis-condensation reaction, it is mixed obtains the first hydrolytic condensation
Object is closed, the first hydrolytic condensation mixture is subjected to the second hydrolysis-condensation reaction, the second hydrolytic condensation mixture is obtained, in institute
During stating the first hydrolysis-condensation reaction and second hydrolysis-condensation reaction, the steam of generation is drawn and condensed, is obtained
To condensate liquid；
(2) after mixing the hydrolytic condensation mixture at least partly described condensate liquid, hydrothermal crystallizing is carried out, water is obtained
Thermal crystallisation mixture；
(3) optionally, the contents on dry basis for improving hydrothermal crystallizing mixture, obtains slurries；
(4) the hydrothermal crystallizing mixture or the slurries are subjected to spray shaping.
The organic silicon source can be the various substances that silica is capable of forming under the conditions of hydrolytic condensation, such as can be with
For one or more of silicon-containing compound shown in the Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl.The C1-C4Alkyl include C1-C4Straight chained alkyl and
C3-C4Branched alkyl, specific example can include but is not limited to: methyl, ethyl, n-propyl, isopropyl, normal-butyl, Zhong Ding
Base, isobutyl group and tert-butyl.
Preferably, the silicon source is selected from methyl orthosilicate, ethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate
One or more of with positive silicic acid N-butyl.
The titanium source can be the usually used titanium source of technical field of molecular sieve preparation.Specifically, the titanium source can be
Organic titanium source (such as organic titanate) and/or inorganic ti sources (such as inorganic titanium salt).The inorganic ti sources can be TiCl4、
Ti(SO4)2、TiOCl2, titanium hydroxide, titanium oxide, one or more of nitric acid titanium salt and phosphoric acid titanium salt.It is described organic
Titanium source can be one or more of fatty alcohol titanium and organic titanate.The titanium source is preferably organic titanium source, into one
Step is preferably organic titanate, is still more preferably formula M4TiO4Shown in organic titanate, wherein 4 M can be identical,
It can also be different, respectively preferably C1-C4Alkyl.The titanium source be particularly preferably tetraisopropyl titanate, four n-propyl of metatitanic acid,
One or more of butyl titanate and tetraethyl titanate.
The template can be the usually used template of technical field of molecular sieve preparation, be specifically as follows urea, amine,
One or more of hydramine and quaternary ammonium base.
The quaternary ammonium base can be various organic level Four ammonium alkali, and the amine can be to contain at least one ammonia in molecular structure
The organic compound of base, the hydramine can be organising containing at least one amino and at least one hydroxyl in molecular structure
Close object.
Specifically, the quaternary ammonium base can be quaternary ammonium base shown in Formula II,
In Formula II, R5、R6、R7And R8It is identical or different, respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-
C4Branched alkyl, such as: R5、R6、R7And R8Respectively can for methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl,
Isobutyl group or tert-butyl.
The aliphatic amine that the amine can indicate for formula III,
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-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, 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.
The aliphatic hydramine that the hydramine can indicate for formula IV,
(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.Preferably, the hydramine is single
One or more of ethanol amine, diethanol amine and triethanolamine.
The specific example of the template can include but is not limited to urea, tetramethylammonium hydroxide, tetraethyl hydroxide
Ammonium, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, four pentyl ammonium hydroxide, ethamine, n-butylamine, butanediamine, hexamethylene diamine, list
One or more of ethanol amine, diethanol amine and triethanolamine.
Preferably, the template is quaternary ammonium base, more preferably tetraethyl ammonium hydroxide and/or tetrapropylammonium hydroxide.
According to the method for the present invention, in step (1), organic silicon source, titanium source, the dosage of template and water can be conventional
Selection.Generally, the molar ratio of organic silicon source, titanium source, template and water can be 100:(0.005-10): (0.005-40):
(200-10000), preferably 100:(0.05-8): (0.5-30): (500-5000), more preferably 100:(0.2-8): (5-
25): (800-4000), further preferably 100:(1-6): (10-20): (1200-3000), the organic silicon source is with SiO2
Meter, the titanium source is with TiO2Meter, the template is with NH3Meter.
In step (1), organic silicon source, titanium source, template and water can be added in reaction kettle simultaneously and carry out the first water
Condensation reaction is solved, template and water the aqueous solution containing template can also be configured to, titanium source and organic silicon source is configured to
Mixture containing titanium source and organic silicon source, by the aqueous solution containing template and the mixture containing titanium source and organic silicon source
It is added in reaction kettle simultaneously and carries out the first hydrolysis-condensation reaction.
The mixture containing titanium source and organic silicon source can be by the way that titanium source and organic silicon source to be obtained by mixing.It is preferred that
Ground, the mixture containing titanium source and organic silicon source can be obtained using method comprising the following steps: with stirring, by titanium
Source and organic silicon source 0-60 DEG C, preferably 15-40 DEG C, it is 20-30 DEG C of mixing 1-2 hours more preferable.
The aqueous solution containing template can be obtained by the way that template to be dispersed in water, and the mixing can be
20-60 DEG C, preferably 15-40 DEG C, it is 20-30 DEG C more preferable at a temperature of carry out, the mixed duration can for 1-2 it is small
When, the template can be provided in the form of pure material, can also be provided in the form of concentrated solution.
First hydrolysis-condensation reaction can 35-80 DEG C, preferably 40-60 DEG C at a temperature of carry out.Generally, described
The duration of first hydrolysis-condensation reaction can be 1-20 hours, preferably 5-18 hours, more preferably 10-15 hours.
In step (1), first hydrolysis-condensation reaction can be at normal pressure (that is, 1 normal atmosphere pressure carry out), can also be with
It carries out under pressure.Generally, first hydrolysis-condensation reaction can under the pressure of -0.2MPa to 0MPa into
Row, the pressure are gauge pressure.
Second hydrolysis-condensation reaction can 70-98 DEG C, preferably 80-96 DEG C, it is more preferable 90-95 DEG C at a temperature of into
Row.The duration of second hydrolysis-condensation reaction can be 1-15 hours, and preferably 3-12 hours, more preferably 6-10 was small
When.
In step (1), second hydrolysis-condensation reaction can be at normal pressure (that is, 1 normal atmosphere pressure carry out), can also be with
It is carried out under conditions of reducing pressure.Generally, second hydrolysis-condensation reaction can be under the pressure of -0.2MPa to 0MPa
It carries out, the pressure is gauge pressure.
In step (1), hydrolysis-condensation reaction occurs for titanium source and organic silicon source, while discharging small molecule compound, usually
Alcohol.These small molecule compounds, which are volatilized, to be formed steam and escapes from reaction system.According to the method for the present invention, the steam that will escape out
It is condensed, and collects condensate liquid.
The condensate liquid contains water and alcohol.Generally, on the basis of the total amount of condensate liquid, the content of alcohol can be 80-96
Weight %, preferably 83-95 weight %, more preferably 88-92 weight %, the content of water can be 4-20 weight %, preferably
5-17 weight %, more preferably 8-12 weight %.In addition to water and alcohol, the condensate liquid also contains nitrogen, and the nitrogen is logical
Often derive from template.In the condensate liquid, the concentration of nitrogen can be 0.01-50mmol/L, preferably 0.02-
20mmol/L, more preferably 0.04-5mmol/L, further preferably 0.05-3mmol/L.It is particularly preferred that the condensate liquid
In, the concentration of nitrogen is 0.5-1.5mmol/L, can preferably inhibit the decomposition of template in hydrothermal crystallization process in this way.
According to the method for the present invention, in step (2), whole condensate liquids can be mixed with hydrolytic condensation mixture, it can also
Partial condensation liquid to be mixed with hydrolytic condensation mixture.Preferably, described relative to 100 parts by weight hydrolytic condensation mixtures
The dosage of condensate liquid can be 1-50 parts by weight, preferably 2-40 parts by weight.It contracts it is highly preferred that being hydrolyzed relative to 100 parts by weight
Mixture is closed, the dosage of the condensate liquid is 5-30 parts by weight.It is further preferred that mixed relative to 100 parts by weight hydrolytic condensations
Close object, the dosage of the condensate liquid is 10-25 parts by weight, can inhibit in this way template in hydrothermal crystallization process decomposition and
It can be further improved the quality of the molecular sieve of hydrothermal crystallizing acquisition.
It, can be by the hydrolytic condensation mixture and the part condensate liquid at 20-80 DEG C, preferably 40-60 in step (2)
It is mixed 1-6 hours, preferably 1-3 hours at a temperature of DEG C.The mixing can be carried out by way of stirring.
In step (2), the hydrothermal crystallizing can carry out under normal conditions.According to the method for the present invention, with existing water
Thermal crystallisation condition is compared, in the identical situation of remaining condition, even if the hydro-thermal for carrying out shorter time at lower temperatures is brilliant
Change, can also obtain the Titanium Sieve Molecular Sieve with expected crystalline form.According to the method for the present invention, in step (2), the hydrothermal crystallizing is excellent
Be selected in 120-190 DEG C, it is 140-185 DEG C more preferable, 160-180 DEG C further preferred at a temperature of carry out.The hydrothermal crystallizing
Duration is preferably 6-30 hours, more preferably 9-25 hours.The hydrothermal crystallizing usually carries out at autogenous pressures, can also
Additionally to apply pressure in hydrothermal crystallization process.Preferably, the hydrothermal crystallizing carries out at autogenous pressures.
Method according to the invention it is possible to step (3) are carried out, it can also be without step (3).
According to the method for the present invention, in one embodiment, without step (3), hydrothermal crystallizing mixture is direct
It is sent into step (4) and carries out spray shaping, technique can be further simplified in this way, and further decrease operation material consumption and energy consumption.
According to the method for the present invention, in another embodiment, including step (3), hydrothermal crystallizing mixture is improved
Contents on dry basis obtains slurries, and the slurries are sent into step (4) and carry out spray shaping.From further increasing by spray shaping
The angle of the quality of obtained Titanium Sieve Molecular Sieve particle is set out, and the contents on dry basis of hydrothermal crystallizing mixture is preferably risen to 25-
The contents on dry basis of hydrothermal crystallizing mixture is more preferably risen to 28-40 weight % by 45 weight %.In the present invention, contents on dry basis
Refer to that the quality after hydrothermal crystallizing mixture is 8 hours dry at 120 DEG C accounts for the percentage of the quality of hydrothermal crystallizing mixture.
According to the embodiment, in an example, into hydrothermal crystallizing mixture addition supplement Titanium Sieve Molecular Sieve to
Improve the contents on dry basis of hydrothermal crystallizing mixture.The supplement Titanium Sieve Molecular Sieve of addition can be to make with by step (1) and step (2)
The consistent Titanium Sieve Molecular Sieve of the topological structure of standby Titanium Sieve Molecular Sieve, or with the titanium by step (1) and step (2) preparation
The different Titanium Sieve Molecular Sieve of the topological structure of si molecular sieves.Preferably, the Titanium Sieve Molecular Sieve prepared by step (1) and step (2)
Topological structure with supplement the topological structure of Titanium Sieve Molecular Sieve it is consistent, it is highly preferred that by step (1) and step (2) preparation titanium
The topological structure of si molecular sieves and the topological structure of supplement Titanium Sieve Molecular Sieve are the Titanium Sieve Molecular Sieve of MFI structure, such as titanium silicon
Molecular sieve TS-1.
In this embodiment, hydrothermal crystallizing mixture and supplement Titanium Sieve Molecular Sieve can be mixed using conventional method equal
It is even.For example, hydrothermal crystallizing mixture and supplement Titanium Sieve Molecular Sieve can be uniformly mixed by way of stirring.
In this embodiment, the condition that hydrothermal crystallizing mixture and supplement Titanium Sieve Molecular Sieve mix is not limited especially
It is fixed, it can carry out under normal conditions.For example, can 20-100 DEG C, preferably 30-60 DEG C, it is more preferable 30-40 DEG C at a temperature of
Hydro-thermal hydrothermal crystallizing mixture is uniformly mixed with supplement Titanium Sieve Molecular Sieve.The mixed duration is with can be by hydrothermal crystallizing
Subject to mixture and supplement Titanium Sieve Molecular Sieve are uniformly mixed., generally, the mixed duration can be small for 0.1-12
When, preferably 0.5-6 hours, more preferably 1-3 hours.
According to the embodiment, in another example, hydrothermal crystallizing mixture can be distilled, to remove part
Liquid phase substance, so that the contents on dry basis of obtained slurries is adjusted to the model in 25-45 weight %, preferably 28-40 weight %
Within enclosing.The distillation can be air-distillation, or vacuum distillation, preferably air-distillation.
In step (4), the condition of spray shaping can be conventional selection, this is not particularly limited in the present invention.Generally,
The inlet temperature of spray shaping can be 200-450 DEG C, preferably 250-400 DEG C.
According to the method for the present invention, the sieve particle that spray shaping obtains can be used directly, such as directly as urging
Agent uses；It uses after can also being roasted, such as is used after roasting as catalyst.The present invention is for the roasting
Condition be not particularly limited, can carry out under normal conditions.Specifically, the roasting can be in 300-800 DEG C of temperature
Lower progress, preferably 450-650 DEG C at a temperature of carry out, more preferably 500-600 DEG C at a temperature of carry out.The roasting is held
The continuous time can be 2-12 hours, preferably 2-6 hours.The roasting can carry out in air atmosphere, can also be non-live
It is carried out in property atmosphere.
According to the second aspect of the invention, the present invention provides the titanium of the preparation of the method as described in first aspect of the present invention
Si molecular sieves.
The Titanium Sieve Molecular Sieve prepared by first aspect the method for the present invention, with the titanium silicon point using conventional method preparation
Son sieve is compared, and external surface area increases.Specifically, it is generally using the external surface area of the Titanium Sieve Molecular Sieve of conventional method preparation
20-30m2/ g, the external surface area using the Titanium Sieve Molecular Sieve of first aspect the method for the present invention preparation is usually 35-
80m2/ g, preferably 40-75m2/g。
The bulk density of the Titanium Sieve Molecular Sieve prepared using first aspect the method for the present invention is 0.2-0.4g/mL's
In range.The bulk density of the Titanium Sieve Molecular Sieve prepared using conventional method is usually in the range of 0.6-0.8g/mL.
According to the third aspect of the present invention, the present invention provides a kind of Ammoximation reaction method, this method is included in ammonia
Under the conditions of oximation reaction, cyclohexanone, ammonia and hydrogen peroxide are contacted with Titanium Sieve Molecular Sieve, wherein the Titanium Sieve Molecular Sieve is this
Titanium Sieve Molecular Sieve described in invention the second aspect.
Ammoximation reaction method according to the present invention, is not particularly limited Ammoximation reaction condition, can be in routine
Under the conditions of carry out.
Generally, the molar ratio of cyclohexanone, ammonia and hydrogen peroxide can be 1:0.2-5:0.5-2, preferably 1:1-3:
0.8-1.5。
The contact can carry out in a solvent, can also carry out in the absence of solvent.The solvent can be with
For one or more of alcohol, nitrile, ether, ester and water.The specific example of the solvent can include but is not limited to methanol, second
One or both of alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, methyl tertiary butyl ether(MTBE), acetonitrile and water with
On.Preferably, the solvent is the tert-butyl alcohol.The dosage of solvent is not particularly limited in the present invention, can be conventional selection.One
As, relative to 100 parts by weight cyclohexanone, the dosage of the solvent can be 10-5000 parts by weight, preferably 100-4000 weight
Measure part, more preferably 1000-3000 parts by weight.
Cyclohexanone oxamidinating reaction method according to the present invention, the contact of cyclohexanone, ammonia with hydrogen peroxide can be in 40-
100 DEG C, preferably 60-95 DEG C, it is 70-90 DEG C more preferable at a temperature of carry out.The contact can carry out in fixed bed reactors,
It can also be carried out in paste state bed reactor.When being contacted in fixed bed reactors, volume space velocity can when the liquid of cyclohexanone
Think 0.1-50h-1, preferably 0.2-25h-1, more preferably 1-20h-1, further preferably 2-15h-1.In paste state bed reactor
In when being contacted, the weight ratio of cyclohexanone and Titanium Sieve Molecular Sieve can be 100:1-50, preferably 100:2-20.
The present invention will be described in detail with reference to embodiments, but the range being not intended to limit the present invention.
It is prepared in embodiment and preparation comparative example below, X-ray diffraction analysis (XRD) is in Siemens D5005 type X-ray
It is carried out on diffractometer；Infrared spectrum analysis carries out on 8210 type Fourier infrared spectrograph of Nicolet.
It is prepared in embodiment and preparation comparative example below, mole composition of molecular sieve is in Rigaku Electric Co., Ltd
It is measured on 3271E type Xray fluorescence spectrometer；External surface area and Kong Rong are measured using BET method；Bulk density uses GB/T
The measurement of method specified in 6286-1986.
It is prepared in embodiment and preparation comparative example below, point of template in hydrothermal crystallization process is calculated using following methods
Solution rate:
The resolution ratio (%) of the template=(template being added before the weight/crystallization for the oily phase isolated after 1- hydrothermal crystallizing
The total weight of agent) × 100%, wherein the template being added before the weight and crystallization of the oily phase isolated after hydrothermal crystallizing
Total weight is in terms of N element.
It is prepared in embodiment and preparation comparative example below, contents on dry basis refers to hydrothermal crystallizing mixture at 120 DEG C in normal
Solid obtained from drying 8 hours accounts for the mass percent of hydrothermal crystallizing mixture under pressure (that is, 1 standard atmospheric pressure).
In following experimental example and Experimental comparison's example, each ingredient contains in the reaction solution that is obtained using gas chromatography analysis
Following formula is respectively adopted on this basis to calculate yclohexanone conversion ratio and caprolactam selectivity in amount:
Yclohexanone conversion ratio (%)=[(mole of the unreacted cyclohexanone of the mole-of the cyclohexanone of addition)/add
The mole of the cyclohexanone entered] × 100%；
Caprolactam selectivity (%)=[mole/(mole of the cyclohexanone of addition for the caprolactam that reaction generates
Amount-unreacted cyclohexanone mole)] × 100%.
Preparation embodiment 1-10 is for illustrating Titanium Sieve Molecular Sieve and its production method of the invention.
Reference example 1
Method described in this reference 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 synthesizing titanium-silicon molecular sieve TS-1.
(20 DEG C) at room temperature, by 22.5 grams of ethyl orthosilicates, (estersil 28 founds Kate's Chemical trade purchased from Zhangjagang City west
Co., Ltd) it is mixed with 7.0 grams of tetrapropylammonium hydroxide, and 59.8 grams of distilled water are added, in normal pressure and 60 DEG C after being stirred
Lower hydrolysis 1.0 hours, obtains the hydrating solution of ethyl orthosilicate, is slowly added into vigorous stirring by 1.1 grams of four fourths of metatitanic acid
Gained mixture is stirred 3 hours at 75 DEG C, obtains clear glue by solution composed by ester and 5.0 grams of anhydrous isopropyl alcohols
Body.This colloid is put into stainless steel sealing reaction kettle, is placed 3 days in 170 DEG C of at a temperature of constant temperature, obtains the mixing of crystallization product
Object；It by the filtering of this mixture, is washed with water, and 60 minutes dry in 110 DEG C, obtains molecular screen primary powder.By this molecular screen primary powder
It is roasted in air atmosphere 3 hours in 550 DEG C of temperature, obtains molecular sieve.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.The nature parameters of the molecular sieve are listed in table 4.
Prepare embodiment 1
(1) in 20 DEG C and the pressure of 1 normal atmosphere, with stirring, by 50 weight % tetrapropylammonium hydroxide concentrated solutions, (this is dense
The solvent of solution is water) it is added in deionized water, it mixes 1 hour, obtains the aqueous solution containing template.
In 20 DEG C and the pressure of 1 normal atmosphere, adjoint stirring will be as the butyl titanate of titanium source and as organic silicon source
Ethyl orthosilicate (estersil 28, with reference example 1) mixes 1 hour, obtains the mixture containing titanium source and organic silicon source.
Aqueous solution containing template and the mixture containing titanium source and organic silicon source are fed according to the ratio that table 1 is listed
Into reaction kettle, according to the reaction condition that table 1 is listed, the first hydrolysis-condensation reaction and the second hydrolysis contracting are successively carried out with stirring
Reaction is closed, hydrolytic condensation mixture is obtained.
During hydrolysis-condensation reaction, auxiliary is purged with nitrogen, and the steam in reaction kettle is taken out of, and using cold
Condensate condenses the steam taken out of, and condensate liquid enters in condensate tank, and the composition of condensate liquid is listed in table 2.
(2) the hydrolytic condensation mixture for obtaining step (1) is sent into hydrothermal crystallizing kettle, is then added into hydrothermal crystallizing kettle
Enter step (1) collection condensate liquid, 40 DEG C at a temperature of stir 3 hours.Wherein, condensate liquid is hydrolyzed relative to 100 parts by weight
The dosage of condensation mixture (in terms of butt) is listed in table 3.
Then, hydrothermal crystallizing kettle is sealed, the temperature in hydrothermal crystallizing kettle is increased to hydrothermal crystallizing temperature, in self-generated pressure
Lower carry out hydrothermal crystallizing, the resolution ratio of template is listed in table 3 in the condition and hydrothermal crystallization process of hydrothermal crystallizing.
After the completion of hydrothermal crystallizing, after the temperature in hydrothermal crystallizing kettle is down to 30 DEG C naturally, hydrothermal crystallizing kettle, Xiang Shui are opened
Titanium-silicon molecular sieve TS-1 (preparing using method identical with reference example 1) is added in thermal crystallisation kettle will obtain after stirring 2 hours
Slurries (contents on dry basis be 28 weight %) output.
(3) obtained slurries are subjected to spray shaping, obtain sieve particle, the condition of spray shaping is listed in table 4.
Sieve particle is roasted 2 hours in 580 DEG C of temperature in air atmosphere, obtains molecular sieve.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.The nature parameters of obtained sieve particle are listed in table 4.
Prepare comparative example 1
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (2), not to hydro-thermal
Condensate liquid step (1) collected is added in crystallizing kettle, but the hydrolytic condensation mixture that step (1) is obtained is sent into hydrothermal crystallizing
In kettle, 40 DEG C at a temperature of stirring 3 hours after sealing hydrothermal crystallizing kettle carry out hydrothermal crystallizing.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare comparative example 2
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (2), step (1)
The condensate liquid of collection with etc. the deionized waters of weight replace.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare comparative example 3
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (2), step (1)
The condensate liquid of collection with etc. the ethyl alcohol of weight replace.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare comparative example 4
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (2), step (1)
The condensate liquid of collection with etc. the water of weight and the mixed liquor (composition in table 2 list) of ethyl alcohol replace.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare comparative example 5
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (2), step (1)
The condensate liquid of collection with etc. the mixed liquor (composition is listed in table 2) of the water of weight, ethyl alcohol and tetrapropylammonium hydroxide replace.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare embodiment 2
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (3), not to hydro-thermal
Titanium-silicon molecular sieve TS-1 is added in crystallizing kettle, but the mixture for directly obtaining hydrothermal crystallizing carries out spray shaping.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare embodiment 3
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (1), according to table 1
Condensation reaction is hydrolyzed in the reaction condition listed.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare embodiment 4
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (1), according to table 1
Condensation reaction is hydrolyzed in the reaction condition listed.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare embodiment 5
(1) at 25 DEG C and 1 normal atmosphere is depressed, with stirring, it is small that tetrapropylammonium hydroxide with deionized water is mixed 1.5
When, obtain the aqueous solution containing template.
In 25 DEG C and the pressure of 1 normal atmosphere, adjoint stirring will be small as the mixing 1.5 of organic silicon source as the sum of titanium source
When, obtain the mixture containing titanium source and organic silicon source.
By the tetrapropylammonium hydroxide as template, the tetraisopropyl titanate as titanium source, as organic silicon source just
The ratio that silester (estersil 40 founds Kate's Chemical trade Co., Ltd purchased from Zhangjagang City west) and water are listed according to table 1
It is fed in reaction kettle, according to the reaction condition that table 1 is listed, the first hydrolysis and the second hydrolysis is successively carried out with stirring, is obtained
Hydrolytic condensation mixture.
During hydrolysis-condensation reaction, auxiliary is purged with nitrogen, and the steam in reaction kettle is taken out of, and using cold
Condensate condenses the steam taken out of, and condensate liquid enters in condensate tank, and the composition of condensate liquid is listed in table 2.
(2) the hydrolytic condensation mixture for obtaining step (1) is sent into hydrothermal crystallizing kettle, is then added into hydrothermal crystallizing kettle
Enter step (1) collection condensate liquid, 50 DEG C at a temperature of stir 2 hours.Wherein, condensate liquid is hydrolyzed relative to 100 parts by weight
Condensation mixture (in terms of butt) dosage is listed in table 3.
Then, hydrothermal crystallizing kettle is sealed, the temperature in hydrothermal crystallizing kettle is increased to hydrothermal crystallizing temperature, in self-generated pressure
Lower carry out hydrothermal crystallizing, the resolution ratio of template is listed in table 3 in the condition and hydrothermal crystallization process of hydrothermal crystallizing.
After the completion of hydrothermal crystallizing, after the temperature in hydrothermal crystallizing kettle is down to 40 DEG C naturally, hydrothermal crystallizing kettle, Xiang Shui are opened
Titanium-silicon molecular sieve TS-1 (preparing using method identical with reference example 1) is added in thermal crystallisation kettle will obtain after stirring 1 hour
Slurries (contents on dry basis be 38 weight %) output.
(3) obtained slurries are subjected to spray shaping, obtain sieve particle, the condition of spray shaping is listed in table 4.
Sieve particle is roasted 5 hours in 520 DEG C of temperature in air atmosphere, obtains molecular sieve.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.The nature parameters of obtained sieve particle are listed in table 4.
Prepare comparative example 6
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 5, unlike, in step (2), not to hydro-thermal
Condensate liquid step (1) collected is added in crystallizing kettle, but the hydrolytic condensation mixture that step (1) is obtained is sent into hydrothermal crystallizing
In kettle, 50 DEG C at a temperature of stirring 2 hours after sealing hydrothermal crystallizing kettle carry out hydrothermal crystallizing.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare comparative example 7
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 5, unlike, in step (2), step (1)
The condensate liquid of collection with etc. the mixed liquor (composition is listed in table 2) of the water of weight, ethyl alcohol and tetrapropylammonium hydroxide replace.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare embodiment 6
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 5, unlike, condensate liquid is relative to 100 weights
Amount part hydrolytic condensation mixture (in terms of butt) dosage is listed in table 3.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare embodiment 7
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 5, unlike, in step (3), not to hydro-thermal
Titanium-silicon molecular sieve TS-1 is added in crystallizing kettle, but the mixture for directly obtaining hydrothermal crystallizing carries out spray shaping.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Prepare embodiment 8
(1) at 30 DEG C and 1 normal atmosphere is depressed, with stirring, it is small that tetrapropylammonium hydroxide with deionized water is mixed 1
When, obtain the aqueous solution containing template.
In 30 DEG C and the pressure of 1 normal atmosphere, adjoint stirring will be as the butyl titanate of titanium source and as organic silicon source
Ethyl orthosilicate (estersil 40 founds Kate's Chemical trade Co., Ltd purchased from Zhangjagang City west) mixing 1 hour, obtains containing titanium source
With the mixture of organic silicon source.
Aqueous solution containing template and the mixture containing titanium source and organic silicon source are fed according to the ratio that table 1 is listed
Into reaction kettle, according to the reaction condition that table 1 is listed, the first hydrolysis-condensation reaction and the second hydrolysis contracting are successively carried out with stirring
Reaction is closed, hydrolytic condensation mixture is obtained.
During hydrolysis-condensation reaction, auxiliary is purged with nitrogen, and the steam in reaction kettle is taken out of, and using cold
Condensate condenses the steam taken out of, and condensate liquid enters in condensate tank, and the composition of condensate liquid is listed in table 2.
(2) the hydrolytic condensation mixture for obtaining step (1) is sent into hydrothermal crystallizing kettle, is then added into hydrothermal crystallizing kettle
Enter step (1) collection condensate liquid, 60 DEG C at a temperature of stir 1 hour.Wherein, condensate liquid is hydrolyzed relative to 100 parts by weight
Condensation mixture (in terms of butt) dosage is listed in table 3.
Then, hydrothermal crystallizing kettle is sealed, the temperature in hydrothermal crystallizing kettle is increased to hydrothermal crystallizing temperature, in self-generated pressure
Lower carry out hydrothermal crystallizing, the resolution ratio of template is listed in table 3 in the condition and hydrothermal crystallization process of hydrothermal crystallizing.
After the completion of hydrothermal crystallizing, after the temperature in hydrothermal crystallizing kettle is down to 40 DEG C naturally, hydrothermal crystallizing kettle is opened, by water
Thermal crystallisation mixture carries out air-distillation, obtains the slurries that contents on dry basis is 30 weight %.
(3) obtained slurries are subjected to spray shaping, obtain sieve particle, the condition of spray shaping is listed in table 4.
Sieve particle is roasted 6 hours in 500 DEG C of temperature in air atmosphere, obtains molecular sieve.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.The nature parameters of obtained sieve particle are listed in table 4.
Prepare comparative example 8
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 8, unlike, in step (2), not to hydro-thermal
Condensate liquid step (1) collected is added in crystallizing kettle, but the hydrolytic condensation mixture that step (1) is obtained is sent into hydrothermal crystallizing
In kettle, 60 DEG C at a temperature of stirring 1 hour after sealing hydrothermal crystallizing kettle carry out hydrothermal crystallizing.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare comparative example 9
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 8, unlike, in step (2), step (1)
The condensate liquid of collection with etc. the mixed liquor (composition is listed in table 2) of the water of weight, ethyl alcohol and tetrapropylammonium hydroxide replace.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare comparative example 10
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 8, unlike, in step (1), hydrolytic condensation
It in reaction process, is purged without nitrogen, the steam for reacting generation, which is condensed back to, to be flowed back in reaction kettle.In step (2), not to water
Condensate liquid is added in thermal crystallisation kettle, but the hydrolytic condensation mixture that step (1) is obtained is sent into hydrothermal crystallizing kettle, at 60 DEG C
At a temperature of stir 1 hour after sealing hydrothermal crystallizing kettle carry out hydrothermal crystallizing.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare embodiment 9
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 8, unlike, condensate liquid is relative to 100 weights
Amount part hydrolytic condensation mixture (in terms of butt) dosage is listed in table 3.
It is that there are specific to MFI structure between 22.5 ° -25.0 ° in 2 θ in the XRD spectra of gained molecular sieve through detecting
The five fingers diffractive features peak shows that the molecular sieve 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.Above-mentioned characterization result shows preparation
Molecular sieve be titanium-silicon molecular sieve TS-1.
Prepare embodiment 10
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 8, unlike, in step (3), not to hydro-thermal
Titanium-silicon molecular sieve TS-1 is added in crystallizing kettle, but the mixture for directly obtaining hydrothermal crystallizing carries out spray shaping.
Through detecting, the XRD crystal phase of gained molecular sieve is that there are specific to MFI structure five between 22.5 ° -25.0 ° in 2 θ
Refer to diffractive features peak, shows that the molecular sieve has the MFI structure of similar TS-1.In 960cm in fourier infrared spectrogram-1Vicinity
There is the unexistent characteristic absorption peak of silica zeolite, shows that titanium has entered sample skeleton.Above-mentioned characterization result shows preparation
Molecular sieve is titanium-silicon molecular sieve TS-1.
Table 1
Table 2
| Number | Alcohol content (weight %) | Nitrogen element content (mmol/L) |
| Prepare embodiment 1 | 90 | 1.23 |
| Prepare comparative example 4 | 90 | 0 |
| Prepare comparative example 5 | 90 | 1.23 |
| Prepare embodiment 3 | 82 | 2.39 |
| Prepare embodiment 4 | 95 | 0.09 |
| Prepare embodiment 5 | 89 | 0.89 |
| Prepare comparative example 7 | 89 | 0.89 |
| Prepare embodiment 8 | 93 | 0.57 |
| Prepare comparative example 9 | 92 | 0.53 |
Table 3
Table 4
Prepare embodiment 2,7 and 10 as a result, it was confirmed that using method of the invention, the hydrothermal crystallizing that hydrothermal crystallizing obtains is mixed
Object is closed without additional addition Titanium Sieve Molecular Sieve and bonding agent or its precursor, spray shaping can be directly carried out, simplify operation
Process reduces operation material consumption and energy consumption.
It prepares embodiment 1,5 and 8 and prepares comparative example 1-10's as a result, it was confirmed that producing titanium silicon using method of the invention
Molecular sieve, it is brilliant that at least partly condensate liquid that hydrolysis-condensation reaction process is generated carries out hydro-thermal after mixing with hydrolytic condensation mixture
Change, the decomposition of template in hydrothermal crystallization process can be effectively inhibited, improve the amount of the template of recycling, reduces mould
The consumption of plate agent, and then reduce the production cost of Titanium Sieve Molecular Sieve.
Experimental example 1-10 is for illustrating cyclohexanone oxamidinating reaction method of the invention.
Experimental example 1-10
Experimental example 1-10 uses following methods, and the Titanium Sieve Molecular Sieve of preparation embodiment 1-10 preparation is respectively adopted as hexamethylene
The catalyst of ketone oxamidinating reaction, carries out cyclohexanone oxamidinating reaction.
The Titanium Sieve Molecular Sieve for preparing embodiment 1-10 preparation is seated in fixed bed reactors respectively, forms catalyst bed
Layer (ratio of height to diameter of catalyst bed be 5), by cyclohexanone, ammonia, hydrogen peroxide (concentration of hydrogen peroxide is 30 weight %) and molten
Agent is sent into fixed bed reactors according to the ratio of table 5, is reacted under the reaction condition that table 5 is listed.It is small to be carried out continuously 80
When reaction.The reaction product exported from fixed bed reactors is collected, its composition is measured, calculates yclohexanone conversion ratio and acyl in oneself
Amine selectivity.
Each preparation embodiment repeats 3 batch Titanium Sieve Molecular Sieve of preparation, and every batch of Titanium Sieve Molecular Sieve carries out 3 groups in parallel in fact
It tests, each preparation embodiment is total to carry out 9 groups of experiments, and 9 groups of yclohexanone conversion ratios tested and caprolactam selectively take
The catalytic performance test for the Titanium Sieve Molecular Sieve that average value is prepared as the preparation embodiment is as a result, concrete outcome is listed in table 5.
Experimental comparison's example 1-10
It is reacted using method cyclohexanone oxamidinating identical with experimental example 1-10, unlike, preparation comparison is respectively adopted
The Titanium Sieve Molecular Sieve of example 1-10 preparation is as catalyst.Experimental result is listed in table 5.
Reference experiment example 1
It is reacted using method cyclohexanone oxamidinating identical with experimental example 1-10, unlike, it is prepared using reference example 1
Titanium Sieve Molecular Sieve is as catalyst.Experimental result is listed in table 5.
Table 5
Experimental example 1-10's as a result, it was confirmed that the Titanium Sieve Molecular Sieve prepared using method of the invention as cyclohexanone oxamidinating
The catalyst of reaction can obtain more excellent catalytic performance.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (15)
1. a kind of production method of Titanium Sieve Molecular Sieve, this method comprises:
(1) organic silicon source, titanium source, template and water are subjected to the first hydrolysis-condensation reaction, obtain the first hydrolytic condensation mixture,
The first hydrolytic condensation mixture is subjected to the second hydrolysis-condensation reaction, obtains the second hydrolytic condensation mixture, described the
During one hydrolysis-condensation reaction and second hydrolysis-condensation reaction, the steam of generation is drawn and condensed, is obtained cold
Lime set；
(2) after mixing the hydrolytic condensation mixture at least partly described condensate liquid, hydrothermal crystallizing is carried out, obtains hydro-thermal crystalline substance
Change mixture；
(3) optionally, the contents on dry basis for improving hydrothermal crystallizing mixture, obtains slurries；
(4) the hydrothermal crystallizing mixture or the slurries are subjected to spray shaping.
2. according to the method described in claim 1, wherein, in step (1), organic silicon source, titanium source, the molar ratio of template and water
For 100:(0.005-10): (0.005-40): (200-10000), preferably 100:(0.05-8): (0.5-30): (500-
5000), more preferably 100:(0.2-8): (5-25): (800-4000), further preferably 100:(1-6): (10-20):
(1200-3000), the organic silicon source is with SiO2Meter, the titanium source is with TiO2Meter, the template is with NH3Meter.
3. method according to claim 1 or 2, wherein the organic silicon source is selected from silicon-containing compound shown in Formulas I,
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl；
Preferably, the organic silicon source is selected from methyl orthosilicate, ethyl orthosilicate, positive n-propyl silicate, positive isopropyl silicate
One or more of with positive silicic acid N-butyl.
4. method described in any one of -3 according to claim 1, wherein the titanium source is TiCl4、Ti(SO4)2、TiOCl2、
Titanium hydroxide, titanium oxide, nitric acid titanium salt, phosphoric acid titanium salt, tetraisopropyl titanate, four n-propyl of metatitanic acid, butyl titanate and metatitanic acid
One or more of tetra-ethyl ester.
5. method described in any one of -4 according to claim 1, wherein the template is urea, amine, hydramine and quaternary ammonium
One or more of alkali；
Preferably, the template is quaternary ammonium base shown in Formula II,
In Formula II, R5、R6、R7And R8It is identical or different, respectively C1-C4Alkyl；
It is highly preferred that the template is tetraethyl ammonium hydroxide and/or tetrapropylammonium hydroxide.
6. according to the method described in claim 1, wherein, first hydrolysis-condensation reaction is at 35-80 DEG C, preferably 40-60 DEG C
At a temperature of carry out, the duration of first hydrolysis-condensation reaction is preferably 1-20 hours, preferably 5-18 hours, more excellent
It is selected as 10-15 hours.
7. method according to claim 1 or 6, wherein second hydrolysis-condensation reaction is at 70-98 DEG C, preferably 80-96
DEG C, it is 90-95 DEG C more preferable at a temperature of carry out；
It is highly preferred that the duration of second hydrolysis-condensation reaction be 1-15 hours, preferably 3-12 hours, more preferably
6-10 hours.
8. method according to any one of claims 1-7, wherein the condensate liquid contains water and alcohol, with described cold
On the basis of the total amount of lime set, the content of alcohol is 80-96 weight %, preferably 83-95 weight %, more preferably 88-92 weight %,
The content of water is 4-20 weight %, preferably 5-17 weight %, more preferably 8-12 weight %.
9. method described in any one of -8 according to claim 1, wherein the condensate liquid contains nitrogen；
Preferably, in the condensate liquid, the concentration of nitrogen is 0.01-50mmol/L, preferably 0.02-20mmol/L, more excellent
It is selected as 0.04-5mmol/L, further preferably 0.05-3mmol/L, is still more preferably 0.5-1.5mmol/L.
10. method described in any one of -9 according to claim 1, wherein in step (2), hydrolyzed relative to 100 parts by weight
Condensation mixture, the dosage of the condensate liquid are 1-50 parts by weight, preferably 2-40 parts by weight, more preferably 5-30 parts by weight,
Further preferably 10-25 parts by weight.
11. method described in any one of -10 according to claim 1, wherein in step (2), with stirring, by the water
Solution condensation mixture and the part condensate liquid 20-80 DEG C, preferably 40-60 DEG C at a temperature of mix 1-6 hours, preferably 1-3
Hour.
12. according to claim 1 or method described in 11, wherein in step (2), the hydrothermal crystallizing 120-190 DEG C, more
It is preferred that 140-185 DEG C, it is 160-180 DEG C further preferred at a temperature of carry out；
Preferably, in step (2), the duration of the hydrothermal crystallizing is 6-30 hours, more preferably 9-25 hours.
13. according to the method described in claim 1, wherein, in step (3), the contents on dry basis of hydrothermal crystallizing mixture is improved
For 25-45 weight %, the contents on dry basis of hydrothermal crystallizing mixture is preferably risen into 28-40 weight %.
14. a kind of Titanium Sieve Molecular Sieve of the preparation of the method as described in any one of claim 1-13.
15. a kind of cyclohexanone oxamidinating reaction method, this method are included under the conditions of Ammoximation reaction, by cyclohexanone, ammonia and mistake
Hydrogen oxide is contacted with Titanium Sieve Molecular Sieve, which is characterized in that the Titanium Sieve Molecular Sieve is Titanium Sieve Molecular Sieve described in claim 14.
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| CN110420134B (en) * | 2019-08-28 | 2022-04-15 | 广州骏朗生物科技有限公司 | Flaky silica/nano TiO2 composite material and preparation method thereof |
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