CN109721066A - 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 condensation reaction is hydrolyzed in the raw mixture containing template, titanium source, organic silicon source and water, in reaction process, the steam of generation is drawn and condensed, when the quality of condensate liquid and the ratio of raw mixture gross mass are 0.1-0.4:1, condition in reaction kettle is simultaneously adjusted to hydrothermal crystallizing condition by sealing reaction kettle, is carried out hydrothermal crystallizing, is obtained hydrothermal crystallizing mixture；Optionally, spray shaping is carried out after hydrothermal crystallizing mixture being mixed with supplement Titanium Sieve Molecular Sieve.The invention also discloses the Ammoximation reaction methods using the Titanium Sieve Molecular Sieve as catalyst.According to the method for the present invention, separation of solid and liquid and washing process is omitted, considerably reduces wastewater flow rate；And the mixture that hydrothermal crystallizing obtains can not use additional bonding agent to be directly used in spray shaping, and obtained Titanium Sieve Molecular Sieve particle has preferable catalytic activity.
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) existing method titanium sieve molecular sieve product as obtained from separating, washing, drying, roast is used, separates and washes
The process of washing can generate a large amount of ammonia nitrogen waste waters, and the COD value of these ammonia nitrogen waste waters is high, need to carry out just to be able to satisfy after purified treatment
The requirement discharged and/or recycled, the purified treatment of a large amount of ammonia nitrogen waste waters have aggravated the production of Titanium Sieve Molecular Sieve manufacturer
Burden；
(2) using existing method preparation Titanium Sieve Molecular Sieve when being formed, not only need to additionally introduce bonding agent or
Its precursor, and need to mix Titanium Sieve Molecular Sieve with bonding agent or its precursor, cost of material is on the one hand improved,
On the other hand operational sequence is increased.
In view of the above-mentioned problems, the present inventor has made intensive studies, discovery: will be produced during hydrolysis-condensation reaction
Raw steam is drawn and is condensed, and when controlling the amount of the condensate liquid of formation in a certain range, terminates hydrolysis-condensation reaction
And hydrothermal crystallizing is carried out, the mixture that hydrothermal crystallizing obtains is used directly for spray shaping, and the titanium silicon that spray shaping obtains
The catalytic performance and application performance stable homogeneous of sieve particle, while separation of solid and liquid and washing process is omitted, avoid ammonia
The generation of nitrogen waste water.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) under the conditions of hydrolysis-condensation reaction, by the raw mixture containing template, titanium source, organic silicon source and water into
Row hydrolysis-condensation reaction obtains hydrolytic condensation mixture, and obtained hydrolytic condensation mixture is carried out hydrothermal crystallizing, obtains hydro-thermal
Crystallization mixture；
(2) optionally, hydrothermal crystallizing mixture is mixed with supplement Titanium Sieve Molecular Sieve, obtains slurry；
(2) the hydrothermal crystallizing mixture or the slurry are subjected to spray shaping；
Wherein, during hydrolysis-condensation reaction, the steam of generation is drawn and is condensed, condensate liquid is obtained, it is described
When the ratio of the quality of condensate liquid and the raw mixture gross mass is 0.1-0.4:1, sealing reaction kettle simultaneously will be in reaction kettle
Condition be adjusted to hydrothermal crystallizing condition, carry out hydrothermal crystallizing.
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 cyclohexanone oxamidinating reaction method, this method packets
It includes under the conditions of Ammoximation reaction, cyclohexanone, ammonia and hydrogen peroxide is contacted with Titanium Sieve Molecular Sieve, wherein the titanium silicon molecule
Sieve is Titanium Sieve Molecular Sieve described in the second aspect of the present invention.
Titanium Sieve Molecular Sieve is produced using method of the invention, the mixture for obtaining hydrothermal crystallizing on the one hand can be omitted and carry out
The process for being separated by solid-liquid separation and washing considerably reduces the wastewater flow rate of production process generation；Another aspect hydrothermal crystallizing obtains
Mixture can not use additional bonding agent or its precursor, and be directly used in spray shaping, obtained Titanium Sieve Molecular Sieve
When grain is used as catalyst, show that good catalytic activity and selectivity can obtain when being especially used for the catalyst of Ammoximation reaction
Obtain higher catalytic activity and selectivity.
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) under the conditions of hydrolysis-condensation reaction, by the raw mixture containing template, titanium source, organic silicon source and water into
Row hydrolysis-condensation reaction obtains hydrolytic condensation mixture, and obtained hydrolytic condensation mixture is carried out hydrothermal crystallizing, obtains hydro-thermal
Crystallization mixture；
(2) optionally, hydrothermal crystallizing mixture is mixed with supplement Titanium Sieve Molecular Sieve, obtains slurry；
(3) the hydrothermal crystallizing mixture or the slurry 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:(0.2-6): (5-
25): (800-4000), further preferably 100:(1-5): (10-20): (1500-3000), the organic silicon source is with SiO2
Meter, the titanium source is with TiO2Meter, the template is with NH3Meter.
In step (1), the aqueous solution containing template can be mixed with the mixture containing titanium source and organic silicon source, from
And obtain the raw mixture.The mixture containing titanium source and organic silicon source can be by mixing titanium source and organic silicon source
It closes and obtains.Preferably, 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.
Aqueous solution containing template and the mixture containing titanium source and organic silicon source can be at 15-60 DEG C, preferably 20-40
DEG C, it is 20-30 DEG C more preferable at a temperature of mix 1-2 hours, to obtain the raw mixture.
In step (1), during hydrolysis-condensation reaction, hydrolysis-condensation reaction occurs for titanium source and organic silicon source, discharges simultaneously
Small molecule compound, usually alcohol.These small molecule compounds, which are volatilized, to be formed steam and escapes from reaction system.According to the present invention
Method, the steam that will escape out is condensed, and collects condensate liquid.
In step (1), when the ratio of the quality of the condensate liquid and the raw mixture gross mass is 0.1-0.4:1,
Condition in reaction kettle is simultaneously adjusted to hydrothermal crystallizing condition by sealing reaction kettle, carries out hydrothermal crystallizing.Preferably, the condensate liquid
Quality and the ratio of raw mixture gross mass when being 0.14-0.3:1, seal reaction kettle and by the condition in reaction kettle
It is adjusted to hydrothermal crystallizing condition, carries out hydrothermal crystallizing.It can be by controlling catalytic temperature and/or duration, to cold
The quality of lime set is regulated and controled.Preferably, the hydrolysis-condensation reaction can 80-98 DEG C at a temperature of carry out.More preferably
Ground, the hydrolysis-condensation reaction 85-95 DEG C (such as 89-95 DEG C) at a temperature of carry out.The hydrolysis-condensation reaction it is lasting when
Between can be 4-36 hours, preferably 6-28 hours, more preferably 10-24 hours, further preferably 12-16 hours.It is described
Hydrolysis-condensation reaction normal pressure (that is, the pressure of 1 normal atmosphere carries out), can also usually carry out under conditions of reducing pressure.Tool
Body, the hydrolysis-condensation reaction can carry out under the pressure of -0.2MPa to 0MPa, and the pressure is gauge pressure.
When preparing Titanium Sieve Molecular Sieve using existing method, template is easily decomposed in hydrothermal crystallization process, is not only influenced
The quality of Titanium Sieve Molecular Sieve, and template is that higher raw material is worth in Titanium Sieve Molecular Sieve production process, and template divides in vain
Solution is difficult to recycle, to guarantee that the quality of molecular sieve need to increase the inventory of template, it is clear that can improve Titanium Sieve Molecular Sieve
Production cost；In addition, the template decomposed forms oily phase, the crystallization of molecular sieve is not only influenced, and hydro-thermal can be swum in after standing
The upper layer of crystallization slurry, part oil phase substance can be attached to reaction kettle inner surface, pollute to reaction kettle, increase reaction kettle
Cleaning difficulty.The present inventor has found in the course of the research, if by hydrolytic condensation mixture at least partly condense
Hydrothermal crystallizing is carried out after liquid mixing, the decomposition of template in hydrothermal crystallization process can be effectively inhibited.
Therefore, according to the method for the present invention, in a preferred embodiment, before sealing reaction kettle, preferably also
Including will at least partly condensate liquid mix with the hydrolytic condensation mixture.
According to the preferred embodiment, the condensate liquid contains water and alcohol, and on the basis of the total amount of condensate liquid, alcohol contains
Amount can be 80-96 weight %, preferably 83-95 weight %, more preferably 88-92 weight %, and 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,
The nitrogen is typically derived from template.In the condensate liquid, the concentration of nitrogen can be 0.01-50mmol/L, preferably
For 0.02-20mmol/L, more preferably 0.04-5mmol/L, further preferably 0.05-3mmol/L.It is particularly preferred that described
In condensate liquid, the concentration of nitrogen is 0.5-1.5mmol/L, can preferably inhibit point of template in hydrothermal crystallization process in this way
Solution.
According to the preferred embodiment, whole condensate liquids can be mixed with hydrolytic condensation mixture, it can also be by portion
Condensate liquid is divided to mix with hydrolytic condensation mixture.Preferably, relative to 100 parts by weight hydrolytic condensation mixtures, the condensate liquid
Dosage can be 1-50 parts by weight, preferably 1.5-40 parts by weight.It is highly preferred that mixed relative to 100 parts by weight hydrolytic condensations
Object is closed, the dosage of the condensate liquid is 5-30 parts by weight.It is further preferred that relative to 100 parts by weight hydrolytic condensation mixtures,
The dosage of the condensate liquid is 10-25 parts by weight, can inhibit in hydrothermal crystallization process the decomposition of template in this way and into one
Step improves the quality that hydrothermal crystallizing obtains ground molecular sieve.
According to the preferred embodiment, can by the hydrolytic condensation mixture and the condensate liquid 20-80 DEG C, it is excellent
It is mixed 1-6 hours, preferably 1-3 hours at a temperature of selecting 40-60 DEG C.The mixing can be carried out by way of stirring.
According to the preferred embodiment, can be in the ratio of the quality and the raw mixture gross mass of condensate liquid
It when 0.1-0.4:1, preferably 0.14-0.3:1, will at least partly condensate liquid be mixed with hydrolytic condensation mixture, then sealing is anti-
Kettle is answered to carry out hydrothermal crystallizing.
In step (1), 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 120-180 DEG C, it is 140-175 DEG C more preferable, 160-175 DEG C further preferred at a temperature of carry out.The hydrothermal crystallizing
Duration is preferably 6-48 hours, more preferably 8-36 hours, further preferably 10-24 hours.The hydrothermal crystallizing is logical
It often carries out at autogenous pressures, can also additionally apply pressure in hydrothermal crystallization process.Preferably, the hydrothermal crystallizing is certainly
It is carried out under raw pressure.The hydrothermal crystallizing can carry out in conventional reaction kettle.
According to the method for the present invention, step (2) be can selection operation, step (2) can be carried out, can also be without step
(2)。
In one embodiment, the ratio of the quality of the condensate liquid and the raw mixture gross mass is 0.1-
When 0.4:1, preferably 0.14-0.3:1, directly seals reaction kettle and the condition in reaction kettle is adjusted to hydrothermal crystallizing condition
(that is, hydrothermal crystallizing does not carry out in the presence of condensate liquid), carries out hydrothermal crystallizing, and obtained hydrothermal crystallizing mixture is directly entered
In step (3), spray shaping is carried out.According to the embodiment, without adding supplement Titanium Sieve Molecular Sieve, additional without addition
Bonding agent or its precursor.According to the embodiment, hydrolytic condensation mixture preferably directly carries out hydrothermal crystallizing, and hydrothermal crystallizing is mixed
Object is closed without being separated by solid-liquid separation and being washed i.e. progress spray shaping, significantly reduces the ammonia nitrogen waste water amount of generation.
In a kind of more preferably embodiment, the ratio of the quality of the condensate liquid and the raw mixture gross mass
When value is 0.1-0.4:1, preferably 0.14-0.3:1, by hydrolytic condensation mixture with after at least partly condensate liquid mixes, seal
Condition in reaction kettle is simultaneously adjusted to hydrothermal crystallizing condition by reaction kettle, is carried out hydrothermal crystallizing, by hydrothermal crystallizing mixture and is mended
Titanium Sieve Molecular Sieve mixing is filled, slurries are obtained, the slurries are subjected to spray shaping.
According to the more preferably embodiment, the decomposition of template in hydrothermal crystallization process can be effectively inhibited, simultaneously
Hydrothermal crystallizing mixture can be carried out directly without being separated by solid-liquid separation and being washed, but after mixing with supplement Titanium Sieve Molecular Sieve
Spray shaping significantly reduces the ammonia nitrogen waste water amount of generation, while the Titanium Sieve Molecular Sieve particle prepared is used as catalyst
When, show the catalytic activity of more stable homogeneous.
According to this, more preferably embodiment, the supplement Titanium Sieve Molecular Sieve of addition can be and be prepared by step (1)
The consistent Titanium Sieve Molecular Sieve of the topological structure of Titanium Sieve Molecular Sieve, or with opening up for the Titanium Sieve Molecular Sieve that is prepared by step (1)
Flutter the different Titanium Sieve Molecular Sieve of structure.Preferably, by the topological structure and supplement titanium silicon point of the Titanium Sieve Molecular Sieve of step (1) preparation
The topological structure of son sieve is consistent, it is highly preferred that by the topological structure and supplement titanium silicon molecule of the Titanium Sieve Molecular Sieve of step (1) preparation
The topological structure of sieve is the Titanium Sieve Molecular Sieve of MFI structure, such as titanium-silicon molecular sieve TS-1.
According to the embodiment, the weight ratio for supplementing Titanium Sieve Molecular Sieve and hydrothermal crystallizing mixture is preferably 0.01-10:1,
More preferably 0.05-8:1.It is further preferred that supplement Titanium Sieve Molecular Sieve and the weight ratio of hydrothermal crystallizing mixture are 0.2-5:
1.It is further preferred that supplement Titanium Sieve Molecular Sieve and the weight ratio of hydrothermal crystallizing mixture are 0.4-3:1, it in this way can be further
Improve the particle diameter distribution of the Titanium Sieve Molecular Sieve particle finally prepared, obtains the narrower Titanium Sieve Molecular Sieve particle of particle diameter distribution.It is described
Hydrothermal crystallizing mixture is in terms of butt.In the present invention, butt refers to hydrothermal crystallizing mixture in 120 DEG C of matter after dry 8 hours
Amount.
According to the 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.
According to the 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
Hydrothermal crystallizing mixture is uniformly mixed with supplement Titanium Sieve Molecular Sieve.The mixed duration is can mix hydrothermal crystallizing
Subject to object and supplement Titanium Sieve Molecular Sieve are uniformly mixed.Generally, the mixed duration can be 0.1-12 hours, preferably
It is 0.5-6 hours, more preferably 1-3 hours.
According to the method for the present invention, in step (3), the condition of spray shaping can be conventional selection, and the present invention does not have this
It is particularly limited to.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 450-600 DEG C at a temperature of carry out.The duration of the roasting can be 2-12 hours, preferably 2-4
Hour.The roasting can carry out in air atmosphere, can also carry out in inert 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 bulk density of the Titanium Sieve Molecular Sieve prepared using first aspect the method for the present invention is 0.3-0.6g/mL's
In range, preferably in the range of 0.35-0.55g/mL.Bulk density using the Titanium Sieve Molecular Sieve of conventional method preparation is usual
In the range of 0.62-0.8g/mL.D50 using the Titanium Sieve Molecular Sieve of first aspect the method for the present invention preparation is general
It is 15-80 microns, preferably 25-70 microns, more preferably 30-60 microns.In the present invention, D50 is all made of laser particle analyzer survey
It is fixed, it is numerical value obtained from the Titanium Sieve Molecular Sieve for obtaining spray shaping is directly measured without screening separation.
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 of alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, the tert-butyl alcohol, methyl tertiary butyl ether(MTBE), acetonitrile, acrylonitrile and water or
It is two or more.Preferably, the solvent is the tert-butyl alcohol.The dosage of solvent is not particularly limited in the present invention, can be conventional
Selection.Generally, relative to 100 parts by weight cyclohexanone, the dosage of the solvent can be 10-5000 parts by weight, preferably
100-4000 parts by weight, 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.Pressure in reactor can be 0-3MPa, preferably
0.2-2MPa, the pressure are gauge pressure.The contact can carry out in fixed bed reactors, can also be in paste state bed reactor
Middle progress.When being contacted in fixed bed reactors, volume space velocity can be 0.1-50h when the liquid of cyclohexanone-1, preferably
0.2-25h-1, more preferably 1-20h-1, further preferably 2-15h-1.When being contacted in paste state bed reactor, cyclohexanone
Weight ratio with 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.
It is prepared in embodiment and preparation comparative example below, infrared spectrum analysis is in 8210 type fourier infrared light of Nicolet
It is carried out on spectrometer.
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.
It is prepared in embodiment and preparation comparative example below, the D50 of Titanium Sieve Molecular Sieve particle is had using Britain's Malvern instrument
The laser fineness gage of limit company measures.
It is prepared in embodiment and preparation comparative example below, bulk density is surveyed using method specified in GB/T 6286-1986
It is fixed.
It is prepared in embodiment and preparation comparative example below, total specific surface area and Kong Rong are measured using BET method.
It is prepared in embodiment and preparation comparative example below, it is strong to measure radial crushing using method specified in RIPP 25-90
Degree.
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.
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 and calculates yclohexanone conversion ratio and caprolactam selectivity for 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, condensation reaction is hydrolyzed with stirring, obtains hydrolytic condensation mixture,
Wherein, the mass ratio of raw mixture total amount is accounted for (that is, condensate liquid accounts for the aqueous solution containing template and contains titanium using condensate liquid
The mass ratio of the total amount of the mixture of source and organic silicon source) determine hydrolysis-condensation reaction terminal, specific value is listed in table 1.
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) after the completion of hydrolysis-condensation reaction, condensate liquid step (1) collected is added into reaction kettle, in 40 DEG C of temperature
Lower stirring 3 hours.Wherein, condensate liquid arranges in table 3 relative to the dosage of 100 parts by weight hydrolytic condensation mixtures (in terms of butt)
Out.Then, reaction kettle is sealed, the temperature in reaction kettle is increased to hydrothermal crystallizing temperature, it is brilliant to carry out hydro-thermal at autogenous pressures
Change, 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 reaction kettle is down to 30 DEG C naturally, reaction kettle is opened, is added into reaction kettle
Titanium-silicon molecular sieve TS-1 (preparing using method identical with reference example 1) is added to export obtained slurry after stirring 2 hours.Its
In, the additive amount of titanium-silicon molecular sieve TS-1 is listed in table 3.
(3) obtained slurry is subjected to spray shaping, obtained particle is roasted 3 in 550 DEG C of temperature in air atmosphere
Hour, sieve particle is obtained, the condition of spray shaping 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.The nature parameters of obtained sieve particle are listed in table 4.
Prepare embodiment 2
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 1, unlike, in step (2), not to reaction
Condensate liquid step (1) collected is added in kettle, but after the completion of hydrolysis-condensation reaction, directly it is brilliant to carry out hydro-thermal for sealing reaction kettle
Change；And in step (2), titanium-silicon molecular sieve TS-1 is not added into the mixture that hydrothermal crystallizing obtains.
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 1
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 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 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 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 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 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 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 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 as the tetraisopropyl titanate of titanium source and as organic silicon source
Ethyl orthosilicate (estersil 40, purchased from Zhangjagang City west stand Kate's Chemical trade Co., Ltd) mixing 1.5 hours, contained
The mixture of 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, condensation reaction is hydrolyzed with stirring, obtains hydrolytic condensation mixture,
Wherein, the mass percent of raw mixture total amount is accounted for (that is, condensate liquid accounts for the aqueous solution containing template and contains using condensate liquid
Have the mass percent of the total amount of the mixture of titanium source and organic silicon source) determine hydrolysis-condensation reaction terminal, specific value is in table 1
In list.
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) after the completion of hydrolysis-condensation reaction, condensate liquid step (1) collected is added into reaction kettle, in 50 DEG C of temperature
Lower stirring 2 hours.Wherein, condensate liquid arranges in table 3 relative to 100 parts by weight hydrolytic condensation mixture (in terms of butt) dosages
Out.
Then, reaction kettle is sealed, the temperature in reaction kettle is increased to hydrothermal crystallizing temperature, carries out water at autogenous pressures
Thermal crystallisation, 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 reaction kettle is down to 40 DEG C naturally, reaction kettle is opened, is added into reaction kettle
Titanium-silicon molecular sieve TS-1 (preparing using method identical with reference example 1) is added to export obtained slurry after stirring 1 hour.Its
In, the additive amount of titanium-silicon molecular sieve TS-1 is listed in table 3.
(3) obtained slurry is subjected to spray shaping, obtained particle is roasted 4 in 500 DEG C of temperature in air atmosphere
Hour, sieve particle is obtained, the condition of spray shaping 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.The nature parameters of obtained sieve particle are listed in table 4.
Prepare embodiment 6
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 5, unlike, in step (2), not to reaction
Condensate liquid step (1) collected is added in kettle, but after the completion of hydrolysis-condensation reaction, directly it is brilliant to carry out hydro-thermal for sealing reaction kettle
Change；And in step (2), titanium-silicon molecular sieve TS-1 is not added into the mixture that hydrothermal crystallizing obtains.
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 5
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 7
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 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, condensation reaction is hydrolyzed with stirring, obtains hydrolytic condensation mixture,
Wherein, the mass percent of raw mixture total amount is accounted for (that is, condensate liquid accounts for the aqueous solution containing template and contains using condensate liquid
Have the mass percent of the total amount of the mixture of titanium source and organic silicon source) determine hydrolysis-condensation reaction terminal, specific value is in table 1
In list.
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) after the completion of hydrolysis-condensation reaction, condensate liquid step (1) collected is added into reaction kettle, in 60 DEG C of temperature
Lower stirring 1 hour.Wherein, condensate liquid arranges in table 3 relative to 100 parts by weight hydrolytic condensation mixture (in terms of butt) dosages
Out.Then, reaction kettle is sealed, the temperature in reaction kettle is increased to hydrothermal crystallizing temperature, it is brilliant to carry out hydro-thermal at autogenous pressures
Change, 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 reaction kettle is down to 40 DEG C naturally, reaction kettle is opened, is added into reaction kettle
Titanium-silicon molecular sieve TS-1 (preparing using method identical with reference example 1) is added to export obtained slurry after stirring 3 hours.Its
In, the additive amount of titanium-silicon molecular sieve TS-1 is listed in table 3.
(3) obtained slurry is subjected to spray shaping, obtained particle is roasted 6 in 480 DEG C of temperature in air atmosphere
Hour, sieve particle is obtained, the condition of spray shaping 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.The nature parameters of obtained sieve particle are listed in table 4.
Prepare embodiment 9
Titanium Sieve Molecular Sieve is produced using method identical with preparation embodiment 8, unlike, in step (2), not to reaction
Condensate liquid step (1) collected is added in kettle, but after the completion of hydrolysis-condensation reaction, directly it is brilliant to carry out hydro-thermal for sealing reaction kettle
Change；And in step (2), titanium-silicon molecular sieve TS-1 is not added into the mixture that hydrothermal crystallizing obtains.
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 6
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 7
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 anti-
The hydrolytic condensation mixture answered and add condensate liquid in kettle, but step (1) is obtained is sent into reaction kettle, 60 DEG C at a temperature of
Sealing reaction kettle carries out hydrothermal crystallizing after stirring 1 hour.
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, 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.
Table 1
Table 2
| Number | Alcohol content (weight %) | Nitrogen element content (mmol/L) |
| Prepare embodiment 1 | 91 | 1.25 |
| Prepare comparative example 3 | 91 | 0 |
| Prepare comparative example 4 | 91 | 1.25 |
| Prepare embodiment 3 | 83 | 2.32 |
| Prepare embodiment 4 | 94 | 0.08 |
| Prepare embodiment 5 | 88 | 0.87 |
| Prepare comparative example 5 | 88 | 0.88 |
| Prepare embodiment 8 | 92 | 0.53 |
| Prepare comparative example 6 | 92 | 0.55 |
Table 3
1: relative to the additive amount of 1 parts by weight hydrothermal crystallizing mixture, the hydrothermal crystallizing mixture is in terms of butt, butt
Refer to the quality after hydrothermal crystallizing mixture is 8 hours dry at 120 DEG C.
Table 4
1: relative to the additive amount of 1 parts by weight hydrothermal crystallizing mixture, the hydrothermal crystallizing mixture is in terms of butt, butt
Refer to the quality after hydrothermal crystallizing mixture is 8 hours dry at 120 DEG C.
Prepare embodiment 2,6 and 9 as a result, it was confirmed that using method of the invention, during control hydrolysis-condensation reaction from
The amount for the condensate liquid being discharged in system, the hydrothermal crystallizing mixture that hydrothermal crystallizing obtains without additional addition Titanium Sieve Molecular Sieve and
Bonding agent or its precursor can directly carry out spray shaping.
Prepare embodiment 1,5 and 8 as a result, it was confirmed that Titanium Sieve Molecular Sieve is produced using method of the invention, by hydrolytic condensation
At least partly condensate liquid that reaction process generates carries out hydrothermal crystallizing after mixing with hydrolytic condensation mixture, can effectively inhibit water
The decomposition of template during thermal crystallisation, improves the amount of the template of recycling, reduces the consumption of template, in turn
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 that (pressure in table 5 is under the reaction condition that table 5 is listed
Gauge pressure).It is carried out continuously reaction in 80 hours.The reaction product exported from fixed bed reactors is collected, its composition is measured, calculates ring
Hexanone conversion ratio and caprolactam 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 1-7
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 1-7 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, the system of reference example 1 is respectively adopted
Standby 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 (13)
1. a kind of production method of Titanium Sieve Molecular Sieve, this method comprises:
(1) under the conditions of hydrolysis-condensation reaction, water will be carried out containing the raw mixture of template, titanium source, organic silicon source and water
Condensation reaction is solved, hydrolytic condensation mixture is obtained, obtained hydrolytic condensation mixture is subjected to hydrothermal crystallizing, obtains hydrothermal crystallizing
Mixture；
(2) optionally, hydrothermal crystallizing mixture is mixed with supplement Titanium Sieve Molecular Sieve, obtains slurry；
(3) the hydrothermal crystallizing mixture or the slurry are subjected to spray shaping；
It is characterized in that, the steam of generation is drawn and condensed, condensate liquid is obtained during hydrolysis-condensation reaction, institute
When the ratio of the quality and the raw mixture gross mass of stating condensate liquid is 0.1-0.4:1, preferably 0.14-0.3:1, sealing
Condition in reaction kettle is simultaneously adjusted to hydrothermal crystallizing condition by reaction kettle, carries out hydrothermal crystallizing.
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:(0.2-6): (5-25): (800-4000), further preferably 100:(1-5): (10-20):
(1500-3000), 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. method described in any one of -5 according to claim 1, wherein before sealing reaction kettle, this method further includes
At least partly condensate liquid is mixed with the hydrolytic condensation mixture；
Preferably, relative to 100 parts by weight hydrolytic condensation mixtures, the dosage of the condensate liquid is 1-50 parts by weight, preferably
1.5-40 parts by weight, more preferably 2-30 parts by weight, further preferably 10-25 parts by weight；
Preferably, with stirring, the hydrolytic condensation mixture is mixed with the condensate liquid in 20-80 DEG C, preferably 40-60 DEG C
1-6 hours.
7. method according to claim 1 or 6, wherein the condensate liquid contains water and alcohol, with the total amount of the condensate liquid
On the basis of, the content of alcohol is 80-96 weight %, preferably 83-95 weight %, more preferably 88-92 weight %, and the content of water is
4-20 weight %, preferably 5-17 weight %, more preferably 8-12 weight %.
8. according to claim 1, method described in any one of 6 and 7, 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.
9. the method according to any one of claim 6-8, wherein the method comprising the steps of (2), supplements titanium silicon molecule
Sieve and the weight ratio of hydrothermal crystallizing mixture are 0.01-10:1, preferably 0.05-8:1, more preferably 0.2-5:1, further excellent
It is selected as 0.4-3:1, the hydrothermal crystallizing mixture is in terms of butt.
10. method described in any one of -9 according to claim 1, wherein in step (1), the hydrolysis-condensation reaction exists
Carried out at a temperature of 80-98 DEG C, preferably 85-95 DEG C at a temperature of carry out；
Preferably, in step (1), the duration of the hydrolysis-condensation reaction is 4-36 hours, preferably 6-28 hours, more excellent
It is selected as 12-16 hours.
11. method described in any one of -10 according to claim 1, wherein in step (1), the hydrothermal crystallizing is in 120-
180 DEG C, preferably 140-175 DEG C, it is 160-175 DEG C more preferable at a temperature of carry out；
Preferably, in step (1), duration of the hydrothermal crystallizing is 6-48 hours, preferably 8-36 hours, more preferably
10-24 hours.
12. a kind of Titanium Sieve Molecular Sieve of the preparation of the method as described in any one of claim 1-11.
13. 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 12.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711050925.7A CN109721066B (en) | 2017-10-31 | 2017-10-31 | Method for producing titanium silicalite molecular sieve, titanium silicalite molecular sieve produced by method and ammoximation reaction method |
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| CN114425438A (en) * | 2020-09-22 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method of titanium-containing catalyst, titanium-containing catalyst and method for preparing epoxy compound |
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