CN105524038B - A kind of method for preparing propene carbonate - Google Patents
A kind of method for preparing propene carbonate Download PDFInfo
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- CN105524038B CN105524038B CN201410514406.1A CN201410514406A CN105524038B CN 105524038 B CN105524038 B CN 105524038B CN 201410514406 A CN201410514406 A CN 201410514406A CN 105524038 B CN105524038 B CN 105524038B
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Abstract
The invention provides a kind of method for preparing propene carbonate, this method includes：Under the conditions of cycloaddition reaction, liquid charging stock is contacted with beds, the liquid charging stock contains expoxy propane, carbon dioxide and optional solvent；The beds contain the first beds and the second beds, on the basis of the flow direction of the liquid charging stock, first beds are located at the upstream of second beds, the catalyst of the first beds filling is the catalyst containing the HTS containing template, and the catalyst of the second beds filling is the catalyst containing HTS.Propene carbonate is prepared using the method for the present invention, higher target product selectivity and reaction-ure conversion-age can be obtained, and effectively increase the single pass life of catalyst in preparation process.
Description
Technical field
The present invention relates to a kind of method for preparing propene carbonate.
Background technology
Propene carbonate is not only the higher boiling of function admirable, highly polar aprotic organic solvent, or important has
Machine synthetic intermediate.Propene carbonate has been widely used as the electrolyte of capacitor and high-energy battery, desulfurization and decarburization solvent, metal extraction
Take plasticizer of agent, binder and polymer etc.；In addition, propene carbonate can be additionally used in the important essence such as Synthesis of dimethyl carbonate
Refine chemical product.
At present, the industrial process of propene carbonate includes：Phosgenation, ester-interchange method, chloropropyl alcohol method and epoxy third
Alkane and carbon dioxide cycloaddition method.Wherein, expoxy propane and carbon dioxide cycloaddition method are due to atom utilization height
(100%) the advantages that, process is simple and green and be increasingly becoming main propene carbonate production method.
In expoxy propane and carbon dioxide cycloaddition method synthesizing acrylic ester technique, conventional catalyst has：(1)
Phase catalyst：Quaternary ammonium salt, quaternary ammonium base, organic phosphine compound, organo-metallic compound, alkali metal or alkaline-earth halide etc.；
(2) heterogeneous catalyst：Metal oxide or its mixture, molecular sieve, loaded catalyst etc..Wherein, because with duct rule
And the advantages that orderly, specific surface area is big, Stability Analysis of Structures, molecular sieve are widely used in oil refining process and chemical products production.
But in cycloaddition method synthesizing acrylic ester technique, molecular sieve it is active very poor.Therefore, document report typically uses quaternary ammonium
Salt, quaternary ammonium base or ionic liquid etc. are modified to molecular sieve to improve its activity.
Such as：CN102188999A reports the Al- that 3- r-chloropropyl trimethoxyl silanes and ionic liquid N-methylimidazole are modified
MCM-41 has an excellent performance in expoxy propane and carbon dioxide cycloaddition reaction, and under optimal conditions, expoxy propane converts
Rate is 96%, and propene carbonate is selectively 99%.
CN1775356A reports r-chloropropyl trimethoxyl silane and quaternary ammonium base (TMAH or tetraethyl hydroxide
Ammonium) modified MCM-41 can make 98% expoxy propane be converted into propene carbonate.
The MCM-41 or SBA-15 that CN101844090A report glyoxaline ion liquids are modified can be under the conditions of relatively mild
Propene carbonate is set selectively to reach 100%.
CN1151118 reports that the mixed catalyst that sylvite forms with A, X or Y type molecular sieve can efficient catalytic propene carbonate
Synthesis, under optimal conditions, epoxypropane conversion rate and propene carbonate yield are respectively up to 98.8% and 96.9%.
Jing etc. (《It is catalyzed journal》,29(7),2008:It is 589-591) then that the HTS of quaternary ammonium salt functionalization is direct
For being catalyzed propylene oxidative esterification synthesizing acrylic ester, but the yield of propene carbonate only has 48%.
Although molecular sieve, which is modified, using quaternary ammonium salt, quaternary ammonium base or ionic liquid etc. can effectively improve it in cycloaddition
Activity in method, but this method needs the step such as fired, modified, twice-modified, therefore active component is immobilized in molecular sieve appearance
The shortcomings of high energy consumption, complex process, environment unfriendly (it is solvent that benzene, toluene etc. are used in modified) be present in the method in face.Therefore
It is necessary to explore more green, efficient molecular sieve catalyst, propylene carbonate is prepared in cycloaddition method to open up molecular sieve
Application in ester.
In Zeolite synthesis, conventional method is hydrothermal synthesis method.Generally wrapped using hydrothermal synthesis method synthesis of molecular sieve
Include hydrolysis, catch up with the steps such as alcohol, plastic, crystallization, washing, drying and roast.Wherein, in the presence of structure directing agent, hydro-thermal is closed
β, ZSM-5, SAPO-34, titanium-silicon molecular sieve TS-1, Silicalite-1, MCM-22, SBA-15, AlPO are prepared into method4-11、
SAPO-102, UZM-5, have hollow-core construction HTS HTS when, between crystallization and calcination stepses, the molecule of shaping
Structure directing agent, such as TPAOH, tetraethyl ammonium hydroxide are all included in sieve aperture road.
Because duct limits, the structure directing agent being present in molecular sieve pore passage is sufficiently stable, the methods of washing and extract
It can not all be removed.Further, since the side chain of structure directing agent stretches in molecular sieve pore passage, its activated centre (such as N, P
Deng) difficult and extraneous molecule contacts, therefore have been generally acknowledged that the structure directing agent being present in molecular sieve pore passage is unserviceable.Base
In view of the above, prepared in the laboratory of molecular sieve and industrial production in, generally by high-temperature roasting method by the knot in molecular sieve
Structure directed agents are converted into removal of nitrogen oxide.
The content of the invention
It is an object of the invention to the deficiency for existing process, there is provided a kind of to be catalyzed ring using new catalyst and technique
The method that Ethylene Oxide prepares propene carbonate with carbon dioxide cycloaddition.
The present inventor has been surprisingly found that in research practice, in the cycloaddition reaction mistake of expoxy propane and carbon dioxide
Cheng Zhong, the HTS containing template, HTS are introduced as catalyst, and make containing expoxy propane, carbon dioxide
And the liquid material of optional solvent contacts with the beds containing the first beds and the second beds,
And on the basis of the flow direction of the liquid charging stock, first beds are located at the upper of second beds
Trip, the catalyst of first beds filling are the catalyst containing the HTS containing template, described second
The catalyst of beds filling is the catalyst containing HTS.Higher epoxypropane conversion rate and carbon can be obtained
The selectivity of acid propylene ester and the single trip use life-span of catalyst.More it was unexpected that introducing a small amount of peroxide in reaction system
During compound, the conversion ratio of expoxy propane further improves with the selectivity of purpose product propene carbonate.Based on this, this is completed
Invention.
To realize object defined above, the invention provides a kind of method for preparing propene carbonate, this method includes：In ring plus
Into under reaction condition, liquid charging stock is contacted with beds, the liquid charging stock contain expoxy propane, carbon dioxide and
Optional solvent；The beds contain the first beds and the second beds, with the liquid charging stock
On the basis of flow direction, first beds are located at the upstream of second beds, first catalyst
The catalyst of bed filling is the catalyst containing the HTS containing template, and the second beds filling is urged
Agent is the catalyst containing HTS.
Propene carbonate is prepared using the method for the present invention, higher target product selectivity can be obtained and reactant turns
Rate, and effectively increase the single pass life of catalyst in preparation process.
Method provided by the invention, reaction condition is gentle, and epoxypropane conversion rate and propene carbonate selectivity are high.This hair
Bright method has opened up the new application of HTS molecular sieve containing structure directing agent particularly in duct.And the present invention
Method is green synthesis process, and no special producing equipment requirement, process is simple and easy to control, beneficial to industrialized production and application.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The invention provides a kind of method for preparing propene carbonate, this method includes：, will under the conditions of cycloaddition reaction
Liquid charging stock contacts with beds, and the liquid charging stock contains expoxy propane, carbon dioxide and optional solvent；It is described
Beds contain the first beds and the second beds, on the basis of the flow direction of the liquid charging stock,
First beds are located at the upstream of second beds, the catalyst of the first beds filling
For the catalyst containing the HTS containing template, the catalyst of the second beds filling is titaniferous silicon molecule
The catalyst of sieve.
With the method for the invention it is preferred to the titanium silicon point containing template in the catalyst of the first beds filling
The weight ratio of the content of son sieve and the content of HTS in the catalyst of second beds filling is 1-20：1,
Preferably 2-10：1.
The method according to the invention, first beds and the second beds each can contain one or
Multiple beds.It is multiple to urge when the first beds and/or the second beds contain multiple beds
Can be to be connected in series between agent bed, or be connected in parallel, can also be series connection and combination in parallel, such as：Will
Multiple beds are divided into multigroup, and beds in every group are string between each group to be connected in series and/or being connected in parallel
Connection is connected and/or is connected in parallel.First beds and second beds can be arranged on same reaction
The different zones of device, it can also be arranged in different reactors.
The method according to the invention, the liquid charging stock flow through the apparent of the first beds and the second beds
Speed can be identical, or different.Preferably, the superficial velocity that the liquid charging stock flows through the first beds is
v1, the superficial velocity for flowing through the second beds is v2, wherein, v1＜ v2, so can further extend the one way of catalyst
Service life.It is highly preferred that v2/v1=1.5-10.It is further preferred that v2/v1=2-5.
In the present invention, the superficial velocity refers in the unit interval by the quality of the whole liquid charging stock of beds
The area of a certain cross section of flow (in terms of kg/s) and beds is (with m2Meter) ratio.Usually, can be by unit
The quality of the liquid charging stock of fixed bed reactors is sent into time as " by the liquid of whole beds in the unit interval
The mass flow of raw material ".In the present invention, there is no special want for superficial velocity of the liquid charging stock in the first beds
Ask, typically can be in 0.001-200kg/ (m2S) in the range of.
Method according to the invention it is possible to adjusted using various methods the liquid charging stock in the first beds and
Superficial velocity in second beds.For example, liquid original can be adjusted by the cross-sectional area of selecting catalyst bed
The superficial velocity of material.Specifically, the cross-sectional area of first beds can be made to be more than second beds
Cross-sectional area so that v1＜ v2, it is preferable that v2/v1For 1.5-10, more preferably cause v2/v1For 2-5.According to expected
Superficial velocity come determine the method for the cross-sectional area of beds be it is known in those skilled in the art, it is no longer detailed herein
State.
The method according to the invention, residence time of the liquid charging stock in the first beds are T1, it is being catalyzed
Total residence time in agent bed is T, it is preferable that T1/ T=0.4-0.95, can so in continuous running for a long time
Higher oxidant conversion ratio is obtained, and desirable oxidation selectivity of product is maintained to higher level.It is highly preferred that T1/ T=
0.5-0.9。
The method according to the invention, the HTS containing template in the catalyst of first beds filling
The filling of content and second beds catalyst in HTS content weight than preferably 2-10：1,
More preferably 2-4：1, the internal diameter of first beds and the internal diameter ratio of the second beds are 2-5：1.
The method according to the invention, as the case may be can be between the first beds and the second beds
Material is supplemented, when the first beds and/or the second beds are multiple beds, as the case may be may be used
To supplement fresh material between the first beds and/or between the second beds into the liquid charging stock.Example
Such as：Between the first beds and the second beds, between the first beds and/or the second beds
Between supplement expoxy propane, carbon dioxide and/or solvent.However, it is desirable to explanation, the liquid charging stock flow through the first catalysis
(that is, second urges for whole beds (that is, the whole process of the first beds) of agent bed and whole beds of the second beds
The whole process of agent bed), the liquid charging stock is not included between the first beds, between the second beds and
The fresh material introduced between first beds and the second beds, previously described superficial velocity is by the liquid
Whether raw material determines, not by introducing fresh material and influenceed.
The method according to the invention, the reaction condition of first beds and the second beds can phase
Together, or different.From operation terseness angle, between first beds and the second beds
Reaction condition it is identical.
The method according to the invention, the catalyst containing the HTS containing template can be containing template
HTS original powder, or the HTS containing template of shaping, the titanium silicon containing template being preferably molded
Molecular sieve.The HTS containing template of shaping typically contain as HTS of the active component containing template and
As the carrier of binding agent, wherein, the content of the HTS containing template can be conventional selection.Usually, with described
On the basis of the total amount of the HTS containing template of shaping, the content of the HTS containing template can be 5-95 weights
Measure %, more preferably preferably 10-95 weight %, 70-95 weight %；The content of the carrier can be 5-95 weight %, excellent
Elect 5-90 weight %, more preferably 5-30 weight % as.The carrier of the HTS containing template of the shaping can be
Conventional selection, such as aluminum oxide and/or silica.The method for preparing the HTS containing template of the shaping is this area
Known, no longer it is described in detail herein.The granular size of the HTS containing template of the shaping is also not particularly limited,
Appropriate selection can be carried out according to concrete shape.Such as when the HTS containing template of the shaping is spherical, institute
The average grain diameter for stating the HTS containing template of shaping can be 4-10000 microns, preferably 5-5000 microns, more excellent
40-4000 microns are elected as, such as 50-2000 microns.The average grain diameter is volume average particle size, laser particle analyzer can be used to survey
It is fixed.
The method according to the invention, the HTS can be HTS original powder, or shaping titanium silicon
Molecular sieve, preferably it is molded HTS.Shaping HTS typically contain as active component HTS and
As the carrier of binding agent, wherein, the content of HTS can be conventional selection.Usually, with the shaping titanium silicon point
On the basis of the total amount of son sieve, the content of HTS can be 5-95 weight %, preferably 10-95 weight %, be more preferably
70-95 weight %；The content of the carrier can be 5-95 weight %, and preferably 5-90 weight %, more preferably 5-30 are heavy
Measure %.The carrier of the shaping HTS can be conventional selection, such as aluminum oxide and/or silica.Prepare the shaping
The method of HTS is it is known in the art, being no longer described in detail herein.The granular size of the shaping HTS
It is not particularly limited, appropriate selection can be carried out according to concrete shape.Such as when the shaping HTS is spherical, institute
The average grain diameter for stating shaping HTS can be 4-10000 microns, preferably 5-5000 microns, more preferably 40-4000
Micron, such as 50-2000 microns.The average grain diameter is volume average particle size, laser particle analyzer can be used to determine.
The method according to the invention, first beds can be loaded only containing the HTS containing template
Catalyst, catalyst and inactive filler that can also be containing the HTS containing template.In the first catalyst bed
Filling inactive filler can be adjusted to the amount of the HTS containing template in the first beds in layer, so as to
The speed of reaction is adjusted.First beds contain containing the HTS containing template catalyst and
During inactive filler, the content of inactive filler can be 5-95 weight % in the first beds.The inactive filler
Refer to cycloaddition reaction without or the basic filler without catalytic activity, its instantiation can include but is not limited to：Quartz
One or more in sand, ceramic ring and potsherd.
The method according to the invention, second beds can only load HTS, can also contain
The catalyst and inactive filler of HTS.Loading inactive filler in beds can be to the second catalyst bed
The amount of the catalyst containing HTS is adjusted in layer, so as to which the speed of reaction be adjusted.In the described second catalysis
When agent bed contains the catalyst and inactive filler containing HTS, the content of inactive filler in the second beds
Can be 5-95 weight %.The inactive filler refer to oxidation reaction without or the basic filler without catalytic activity, its
Instantiation can include but is not limited to：One or more in quartz sand, ceramic ring and potsherd.
The method according to the invention, entered using foregoing first beds and the second beds according to preceding kind of mode
Luggage is filled out and run, and can not only further extend the single trip use life-span of HTS, and can also further improve mesh
Mark selectivity of product.
The method according to the invention, the catalyst of the HTS containing template can contain template for whole
HTS, can also contain other catalyst, for example, can also be containing part prior art cycloaddition catalyst, tool
The example of body is montmorillonite, MgO, Mg-Al hydrotalcite, MgAl2O4Spinelle, 1- normal-butyl -3- methyl imidazolium tetrafluoroborates
([bmim]BF4)、CH3ONa, TBAB, sodium methoxide, KI/ γ-Al2O3、KI-Ti(OH)4/γ-Al2O3、K2O/4A points
Sub- sieve, KOH, NaOH, KNO3And K2CO3And Lewis acid-inorganic base bicomponent catalyst, wherein Lewis acid can be LiCl,
NaCl, KCl, KI, inorganic base can be Na2CO3、K2CO3、NaHCO3、NH4HCO3。
With the method for the invention it is preferred to the titanium containing template in the catalyst of the HTS containing template
The content of si molecular sieves is more than 50 weight %, contains template in the catalyst of the more preferably described HTS containing template
The content of the HTS of agent is 60-100 weight %.The titanium silicon containing template used in a particular embodiment of the present invention
The catalyst of molecular sieve be the HTS containing template content be 100 weight % catalyst, but this not because
This limitation the scope of the present invention.Catalyst composition when content herein refers to being free of carrier.
The method according to the invention, the catalyst containing HTS can be whole HTSs, also may be used
Containing other catalyst, for example, can also be containing part prior art cycloaddition catalyst, specific example be montmorillonite,
MgO, Mg-Al hydrotalcite, MgAl2O4Spinelle, 1- normal-butyl -3- methyl imidazolium tetrafluoroborates ([bmim] BF4)、CH3ONa、
TBAB, sodium methoxide, KI/ γ-Al2O3、KI-Ti(OH)4/γ-Al2O3、K2O/4A molecular sieves, KOH, NaOH, KNO3
And K2CO3And Lewis acid-inorganic base bicomponent catalyst etc., wherein Lewis acid can be LiCl, NaCl, KCl, KI etc., nothing
Machine alkali can be Na2CO3、K2CO3、NaHCO3、NH4HCO3Deng.
With the method for the invention it is preferred to the content of HTS is 50 weights in the catalyst containing HTS
More than % is measured, the content of HTS is 60-100 weight % in the more preferably described catalyst containing HTS.At this
The content that the catalyst containing HTS used in the specific embodiment of invention is HTS is 100 weight %
Catalyst, but this and be not so limited the scope of the present invention.Catalyst composition when content herein refers to being free of carrier.
When the catalyst (including catalyst of the catalyst containing HTS and the HTS containing template)
Respectively formed body when, it each also includes carrier, wherein, carrier can be each Al2O3、ZnO、MgO、SiO2, CaO and
TiO2, rare earth oxide RE2O3(RE La, Ce, Y or Nd etc.) etc..
With the method for the invention it is preferred to contain solvent in the liquid charging stock, the optional scope of the species of the solvent
It is wider, the one or more preferably in dichloromethane, methanol, pentane, amylene, pentamethylene and cyclopentene etc..For the present invention,
It is preferred that the solvent is dichloromethane.
With the method for the invention it is preferred in the liquid charging stock, the mol ratio composition and epoxy of expoxy propane and solvent
The composition that propane forms azeotropic mixture with solvent is identical.The feed conditions of expoxy propane and solvent can be with expoxy propane and solvent shape
Condition (including temperature and pressure) into azeotropic mixture is identical.
In the present invention, the ratio between the azeotropic mixture oxypropylene and solvent can be entered according to the needs of reaction condition
Row selection.The method according to the invention, when the solvent is dichloromethane, preferably described expoxy propane and dichloromethane are total to
Thing is boiled to be 5-50 DEG C in temperature, the azeotropic mixture that pressure is formed under conditions of being 40-100kPa.
It is exemplary illustration below, dichloromethane and the azeotropic mole composition of expoxy propane and azeotropic temperature and pressure etc. count
According to as follows：
At 42.93 DEG C and 100kPa, expoxy propane is formed in binary azeotrope with dichloromethane, dichloromethane
Molar content is 0.5573, and the molar content of expoxy propane is 0.4427；
At 39.96 DEG C and 80kPa, expoxy propane is formed in binary azeotrope with dichloromethane, dichloromethane
Molar content is 0.5603, and the molar content of expoxy propane is 0.4397；
At 29.65 DEG C and 60kPa, expoxy propane is formed in binary azeotrope with dichloromethane, dichloromethane
Molar content is 0.5643, and the molar content of expoxy propane is 0.4357；
At 20.05 DEG C and 40kPa, expoxy propane is formed in binary azeotrope with dichloromethane, dichloromethane
Molar content is 0.5699, and the molar content of expoxy propane is 0.4301；
At 5.26 DEG C and 40kPa, expoxy propane is formed in binary azeotrope with dichloromethane, and dichloromethane rubs
Your content is 0.5795, and the molar content of expoxy propane is 0.4205.
The method of the present invention by using the catalyst containing the HTS containing template and contains titanium silicon molecule
The catalyst of sieve causes the beds to contain the first beds and the second catalyst bed as catalyst
Layer, on the basis of the flow direction of the liquid charging stock, first beds are located at second beds
Upstream, the catalyst of first beds filling is the catalyst containing the HTS containing template, described the
The catalyst of two beds filling is the catalyst containing HTS so that the method according to the present invention can obtain high
Propene carbonate selectivity, while the single trip use life-span of catalyst can be improved.
In the present invention, the HTS containing template refers to the titanium silicon molecule containing the template remained in building-up process
Sieve, that is,：HTS is after composition without the process of experience removed template method, or even if HTS undergoes
The process of removed template method is crossed, but template is not removed all, the content of template is more than or equal to 0.1 weight %.
The present invention is not particularly limited for the content of the template in the HTS containing template, can be according to titanium
The species of si molecular sieves and specific alcoholysis reaction condition are selected.Usually, in the HTS, template
Content can be 0.1-25 weight %.Preferably, in the HTS, the content of template is 1-20 weight %, more excellent
Elect 5-15 weight % as.The content of the template can use thermogravimetic analysis (TGA) method to determine, usually, can be by thermal weight loss point
Content of the percent weight loss as template in analysis between 200-800 DEG C.
The template can be usually used various templates during synthesis of titanium silicon molecular sieve, such as：It is described
Template can be the one or more in quaternary ammonium base, quaternary ammonium salt, aliphatic amine and aliphatic hydramine.The quaternary ammonium base can be
Various organic level Four ammonium alkali, the quaternary ammonium salt can be various organic quarternary ammonium salts, described such as halide salt and various oxysalts
Aliphatic amine can be various NH3In at least one hydrogen substituted by aliphatic alkyl (such as alkyl) after the compound that is formed, institute
It can be various NH to state aliphatic hydramine3In at least one hydrogen by hydroxyl aliphatic group (such as alkyl) substitution after formed
Compound.
Specifically, the alkaline template can be selected from formula I represent quaternary ammonium base, formula II represent quaternary ammonium salt,
One or more in the aliphatic hydramine that the aliphatic amine and general formulae IV that general formula III represents represent.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, such as：R1、R2、R3And R4Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
In Formula II, X is salt forming anion, including halide ion and various oxygen-containing acid ions, such as Cl-、F-、Br-、I-、
SO4 2-, NO3 -, PO4 3-Etc.；R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Side chain
Alkyl, such as：R1、R2、R3And R4Each can be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or
The tert-butyl group.
R5(NH2)n(formula III)
In formula III, n is 1 or 2 integer.When n is 1, R5For C1-C6Alkyl, including C1-C6Straight chained alkyl and C3-C6
Branched alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, the tert-butyl group, n-pentyl, new penta
Base, isopentyl, tertiary pentyl and n-hexyl.When n is 2, R5For 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.
(HOR6)mNH(3-m)(formula IV)
In formula IV, m R6It 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.
The template is specifically as follows but is not limited to：TMAH, tetraethyl ammonium hydroxide, tetrapropyl hydrogen-oxygen
Change ammonium (including the various isomers of TPAOH, such as four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), four
Butyl ammonium hydroxide (includes the various isomers of TBAH, such as 4-n-butyl ammonium hydroxide and four isobutyl group hydrogen-oxygens
Change ammonium), tetramethyl ammonium halide, tetraethyl ammonium halide, tetrapropyl ammonium halide, tetrabutyl ammonium halide, ethamine, n-propylamine, n-butylamine,
One or more in di-n-propylamine, butanediamine, hexamethylene diamine, MEA, diethanol amine and triethanolamine.Preferably, it is described
Template is tetraethyl ammonium hydroxide, TPAOH, 4-propyl bromide, 4-propyl ammonium chloride and tetrabutylammonium hydroxide
Ammonium.
In the present invention, HTS distinguishes with the HTS containing template, the former be without template, or
The content of template is less than 0.1 weight % HTS.
In the present invention, the HTS species of HTS and the HTS containing template can phase
It is same or different, wherein, HTS specifically refers to a kind of zeolite of a part of silicon atom in titanium atom substitution lattice framework
General name.The HTS can be the common HTS with various topological structures, such as：The titanium silicon molecule
Sieve can be selected from HTS (such as TS-1), HTS (such as TS-2), the titanium of BEA structures of MEL structures of MFI structure
Si molecular sieves (such as Ti-Beta), the HTS (such as Ti-MCM-22) of MWW structures, MOR structures HTS (such as
Ti-MOR), the HTS (such as Ti-TUN) of TUN structures, two-dimentional hexagonal structure HTS (such as Ti-MCM-41,
Ti-SBA-15) and other structures HTS (such as Ti-ZSM-48).The HTS is preferably selected from MFI structure
HTS, the HTS of MEL structures and the HTS of BEA structures, the more preferably titanium silicon of MFI structure point
Son sieve.
From the further angle for improving epoxypropane conversion rate and propene carbonate selectivity, the HTS
For the hollow HTS with MFI structure, the crystal grain of the hollow HTS is hollow-core construction, the hollow-core construction
The radical length of chamber portion is 5-300nm, and the hollow HTS is after template is removed, in 25 DEG C, P/P0=
0.10th, the benzene adsorbance that adsorption time measures under conditions of being 1h is at least 70mg/g, the adsorption isotherm of nitrogen absorption under low temperature and
Hysteresis loop between desorption isotherm be present.Hollow HTS containing template is referred to disclosed in CN1132699C
Method is prepared, simply without be finally intended to remove template calcination stepses.
In a kind of preferred embodiment of the present invention, the contact is carried out in the presence of peroxide, the mistake
The mol ratio of oxide and expoxy propane is 0.0001-0.1：1.That is, by the azeotropic mixture of expoxy propane and solvent, carbon dioxide,
Peroxide contacts with catalyst.
In the presence of a peroxide, expoxy propane is contacted with azeotropic mixture, the carbon dioxide of solvent with catalyst, can obtained
Get Geng Gao epoxypropane conversion rate and propene carbonate selectivity.Preferably, mole of the peroxide and expoxy propane
Than for 0.001-0.05：1, more preferably 0.001-0.01：1.
In the present invention, the peroxide refers to the compound for containing-O-O- keys in molecular structure, and its formula is R7-O-O-
R8(can be hydrogen peroxide and/or organic peroxide), wherein R7、R8Can be each hydrogen or organic group, preferably R7、R8In
At least one is organic group, for example, C1-C10 alkyl or C6-C10 aryl, for example, TBHP, mistake
Isopropylbenzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid are aoxidized, wherein, preferably R7And R8It is organic group, it is more excellent
Select R7And R8It is cumenyl, i.e., the preferably peroxide is cumyl peroxide.It so can further improve epoxy
Conversion of propane and propene carbonate selectivity.
When the peroxide is hydrogen peroxide, the hydrogen peroxide can be deposited in a variety of manners to be commonly used in the art
Hydrogen peroxide.From the further angle for improving security, the method according to the invention is preferably used with aqueous solution shape
Hydrogen peroxide existing for formula.The method according to the invention, when the hydrogen peroxide provides as an aqueous solution, the peroxidating
The concentration of aqueous solution of hydrogen can be the normal concentration of this area, such as：20-80 weight %.Concentration meets the peroxide of above-mentioned requirements
Changing the aqueous solution of hydrogen can use conventional method to prepare, and can also be commercially available, such as：Can be 30 weights that can be commercially available
Measure % hydrogen peroxide, 50 weight % hydrogen peroxide or 70 weight % hydrogen peroxide.
With the method for the invention it is preferred to the mol ratio of expoxy propane and carbon dioxide is 1:0.1-100.
The cycloaddition reaction condition can be the conventional selection of this area, if temperature can be 10-160 DEG C；With gauge pressure
Meter, pressure can be 0-2.5MPa.Even if the method for the present invention carries out addition under mild conditions, higher ring can be also obtained
Ethylene Oxide conversion ratio and propene carbonate selectivity.Addition is carried out under mild conditions, on the one hand can reduce energy consumption, it is another
Aspect reaction is more easily controlled.Method in accordance with the invention it is preferred that the cycloaddition reaction condition includes：Temperature can be
20-120 DEG C, more preferably 30-110 DEG C；In terms of gauge pressure, preferably 0.1-2MPa.
Propene carbonate is isolated in the mixture that the method according to the invention can also include obtaining from contact.From contact
The method that propene carbonate is isolated in obtained mixture is not particularly limited, and can be the conventional selection of this area.Specifically
Ground, obtained mixture progress separation of solid and liquid can will be contacted, and isolated liquid phase is distilled, so as to obtain carbonic acid
Propylene.
With the method for the invention it is preferred to expoxy propane is prepared as follows：In the presence of solvent, by propylene and peroxide
Change hydrogen and HTS contact, isolated expoxy propane.
With the method for the invention it is preferred to the solvent is methanol.
According to a kind of preferred embodiment of the present invention, the expoxy propane is prepared as follows：Exist in methanol
Under, propylene is contacted with hydrogen peroxide and HTS, isolated expoxy propane.
The method according to the invention, the hydrogen peroxide can be peroxidating existing in a variety of manners commonly used in the art
Hydrogen.From the further angle for improving security, the method according to the invention is preferably using existing mistake as an aqueous solution
Hydrogen oxide.The method according to the invention, when the hydrogen peroxide provides as an aqueous solution, the aqueous hydrogen peroxide solution
Concentration can be the normal concentration of this area, such as：20-80 weight %.Concentration meets the water-soluble of the hydrogen peroxide of above-mentioned requirements
Liquid can use conventional method to prepare, and can also be commercially available, such as：It can be the dioxygen for the 30 weight % that can be commercially available
The hydrogen peroxide of water, 50 weight % hydrogen peroxide or 70 weight %.
The method according to the invention, the HTS can be that HTS commonly used in the art (refers to not
HTS containing template, template agent content are less than 0.1 weight %), such as the HTS can be common
HTS with various topological structures, such as：The HTS can be MFI structure HTS (such as
TS-1), the HTS (such as TS-2) of MEL structures, HTS (such as Ti-Beta), the titanium of MWW structures of BEA structures
Si molecular sieves (such as Ti-MCM-22), the HTS (such as Ti-MOR) of MOR structures, HTS (such as Ti- of TUN structures
TUN), the HTS (such as Ti-MCM-41, Ti-SBA-15) of two-dimentional hexagonal structure and the HTS of other structures be (such as
Ti-ZSM-48 the one or more in).The HTS is preferably the HTS of MFI structure, the titanium of MEL structures
The HTS of one or more in si molecular sieves and the HTS of BEA structures, more preferably MFI structure.
With the method for the invention it is preferred to the mol ratio of propylene, methanol and hydrogen peroxide is 0.1-10:1-100:1, it is more excellent
Elect 1-5 as:5-20:1.
With the method for the invention it is preferred to which the concentration of HTS is 0.002-0.1g/mL, refer specifically to, relatively
In every mL reaction mass, the dosage of HTS is 0.002-0.1g.
With the method for the invention it is preferred to the condition of contact includes：Temperature is 30-80 DEG C, pressure 0.1-2MPa, the time
For 0.1-4h；More preferably temperature is 40-60 DEG C, pressure 0.1-1.5MPa, time 0.2-1h.
The invention will be further described for following examples, but and is not so limited the scope of the present invention.
In following examples and comparative example, if not otherwise specified, reaction is in 250mL universal autoclave
Carry out, used reagent is commercially available AR.
In following examples and comparative example, if not otherwise specified, pressure is gauge pressure.
In following examples, the content of the template in the HTS containing template, tool are determined using DTG
Body examination method for testing is：HTS is determined on the thermogravimetric analyzer commercially available from the model TA 951 of E.I.Du Pont Company in 200-
Rate of weight loss between 800 DEG C, the rate of weight loss correspond to the content of template, wherein, heating rate is 10 DEG C/min,
Tested in nitrogen atmosphere.
In following examples and comparative example, the composition of the liquid phase mixture obtained using gas chromatography measure reaction, lead to
Overcorrect normalization method is quantified, and epoxypropane conversion rate and propene carbonate selectivity are calculated using below equation.
(Formula V)
In Formula V, X is epoxypropane conversion rate；
For the molal quantity of the expoxy propane of addition；
For the molal quantity of reacted liquid phase mixture oxypropylene.
(Formula IV)
In Formula IV, S is propene carbonate selectivity；
nPCFor the molal quantity of propene carbonate in reacted liquid phase mixture；
For the molal quantity of the expoxy propane of addition；
For the molal quantity of reacted liquid phase mixture oxypropylene.
In following examples and comparative example, expoxy propane is prepared as follows：
1.1 prepare HTS
With reference to Zeolites, prepared by 1992, the Vol.12 method described in the 943-950 pages, specific method is as follows.
(20 DEG C) at room temperature, using 22.5 grams of tetraethyl orthosilicates and 7.0 grams of TPAOHs as template
Mixing, and 59.8 grams of distilled water are added, it is stirred and is hydrolyzed 1.0 hours after normal pressure and 60 DEG C, obtains tetraethyl orthosilicate
Hydrating solution.With vigorous stirring, it is slowly added into the hydrating solution anhydrous by 1.1 grams of butyl titanates and 5.0 grams
The solution that isopropanol is formed, gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid.This colloid is placed in
In stainless steel sealing reactor, constant temperature is placed 72 hours at a temperature of 170 DEG C, obtains the mixture of crystallization product.It will obtain
Mixture filtering, after collecting obtained solid matter water used wash, dried 60 minutes in 110 DEG C, so as to obtain containing template
The titanium-silicon molecular sieve TS-1 of agent (titanium oxide content is 2.5 weight %, and the content of template is 14.2 weight %).
HTS containing template is calcined 5 hours at 500 DEG C, so as to obtain the titanium silicon molecule without template
Sieve.
1.2 prepare expoxy propane
Propylene, methanol, hydrogen peroxide are contacted with the HTS (being free of template), temperature is 40 DEG C, pressure
For 1.5MPa, time 0.5h, propylene, methanol, the molar ratio of material 3 of hydrogen peroxide:10:1, the concentration of HTS is
0.05g/mL；Expoxy propane is isolated by rectifying from the material after contact.
Embodiment 1-16 is used for the method for illustrating the present invention.
Embodiment 1
(1) titanium-silicon molecular sieve TS-1 containing template is prepared
With reference to Zeolites, prepared by 1992, the Vol.12 method described in the 943-950 pages (saves the step of roasting
Suddenly), specific method is as follows.
(20 DEG C) at room temperature, 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOHs, and added
59.8 grams of distilled water, it is stirred after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C, obtains the hydrating solution of tetraethyl orthosilicate,
The solution being made up of 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols is slowly added into vigorous stirring, and gained is mixed
Compound stirs 3 hours at 75 DEG C, obtains clear colloid, this colloid is put into stainless steel sealing reactor, at 170 DEG C
At a temperature of constant temperature place 3 days, obtain the mixture of crystallization product；By the filtering of this mixture, it is washed with water, and in 110 DEG C of dryings
60 minutes.
The titanium oxide content for containing the HTS of template is 2.4 weight %, and the content of template is 14.2 weights
%, abbreviation T1-0 are measured, (volume average particle size is 200 μm of spheric catalyst to the catalyst C-T1-0 being molded using its preparation, close
Spend for 0.76g/cm3, the T1-0 containing 85 weight % and 15 weight % silica).
HTS containing template is calcined 5 hours at 500 DEG C, so as to obtain the titanium silicon molecule without template
T1-1 is sieved, (volume average particle size is 200 μm of spheric catalyst to the catalyst C-T1-1 being molded using its preparation, and density is
0.74g/cm3, the T1-1 containing 85 weight % and 15 weight % silica).
(2) propene carbonate is prepared
Loading catalyst C-T1-0, C-T1-1 form beds respectively in the fixed bed reactors of two series connection,
Wherein, the quantity of each catalyst reactor bed is 1 layer.Using the flow direction of liquid charging stock in the reactor as base
Standard, the beds in the fixed bed reactors of upstream are referred to as the first beds, the fixed bed positioned at downstream
Beds in reactor are referred to as the second beds, the loaded catalyst C-T1-0 in the first beds with
The weight ratio of catalyst C-T1-1 loadings in second beds is 2：1, the internal diameter of the first beds and second
The ratio of the internal diameter of beds is 2：1.
By the azeotropic mixture of expoxy propane and dichloromethane (expoxy propane and dichloromethane in 42.93 DEG C and 100kPa
The binary azeotrope of formation, wherein, the molar content of dichloromethane is 0.5573, and the molar content of expoxy propane is
0.4427), carbon dioxide is sent into from the bottom of the fixed bed reactors positioned at upstream and flows through the first beds, output
Liquid mixture subsequently enters in next fixed bed reactors and flows through the second beds.Wherein, expoxy propane and two
The mol ratio of carbonoxide is 1：1, the temperature in two fixed bed reactors is 85 DEG C, in course of reaction that two fixed beds are anti-
It is 2.0MPa to answer the Stress control in device, and the weight (hourly) space velocity (WHSV) of expoxy propane is 10h-1。
Then, obtained mixture is filtered, the obtained composition of liquid phase mixture is determined with gas chromatography, and
Epoxypropane conversion rate and propene carbonate selectivity are calculated, result at 240 hours lists (remaining embodiment in table 1
As a result also it is the result of 240 hours).
Comparative example 1
Propene carbonate is prepared using method same as Example 1, unlike, without using catalyst.
Obtained mixture is determined into the obtained composition of liquid phase mixture with gas chromatography, and calculates expoxy propane and turns
Rate and propene carbonate selectivity, are as a result listed in table 1.
Comparative example 2
Propene carbonate is prepared using method same as Example 1, unlike, in step (2), the first catalyst bed
Layer is identical with the catalyst of the second beds, is C-T1-1.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Comparative example 3
Propene carbonate is prepared using with the identical method of comparative example 2, unlike, add mould simultaneously in addition process
Plate agent TPAOH, the amount of the template of addition are identical by the template agent content brought in catalyst with embodiment 1.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 2
Propene carbonate is prepared using method same as Example 1, unlike, in step (1), with reference to Chinese patent
Method disclosed in CN1132699C, the hollow HTS HTS containing template is prepared using following methods；
The gained of Example 1 sieves the TS-1 molecular sieves after 550 DEG C of roasting 3h according to molecular sieve containing template molecule
(gram)：Sulfuric acid (mole)：Water (mole)=100:0.15:150 ratio is well mixed, and reacts 5.0 hours at 90 DEG C, then
It is filtered, washed and dried according to a conventional method, obtains the TS-1 molecular sieves of acid treatment.By the TS-1 molecular sieves of above-mentioned acid treatment according to
Molecular sieve (gram):Triethanolamine (mole):TPAOH (mole):Water (mole)=100:0.20:0.15:180
Ratio is well mixed, and is put into stainless steel sealing reactor, and constant temperature places 0.5 day time at 190 DEG C of temperature and self-generated pressure,
After cooling down release, filter, wash, dry according to a conventional method.
The titanium oxide content for containing the hollow HTS of template is 2.5 weight %, and the content of template is 6.3
Weight %, abbreviation T2-0, the catalyst C-T2-0 being molded using its preparation (volume average particle size is 200 μm of spheric catalyst,
Density is 0.77g/cm3, the T2-0 containing 85 weight % and 15 weight % silica).
Hollow HTS containing template is calcined 5 hours at 500 DEG C, it is hollow without template so as to obtain
HTS T2-1, the catalyst C-T2-1 being molded using its preparation (volume average particle size is 200 μm of spheric catalyst,
Density is 0.75g/cm3, the T2-1 containing 85 weight % and 15 weight % silica).
In step (2), loading catalyst C-T2-0, C-T2-1 formation is urged respectively in the fixed bed reactors of two series connection
Agent bed, remaining condition all same.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 3
Propene carbonate is prepared using method same as Example 1, unlike, in step (1), reference Corma etc.,
J.Chem.Soc., Chem.Commun., the method (saving last calcination stepses) disclosed in 1994,147-148, use with
Lower section method prepares the HTS Ti-MCM-41 containing template.
The mixed liquor that the tetramethylammonium hydroxide aqueous solutions of amorphous silica Aerosil 200 and 25% are formed is added
Enter and mixed in the mixed liquor formed to cetyl trimethylammonium bromide and 25% tetramethylammonium hydroxide aqueous solution, Ran Houjia
Enter Aerosil 200 and tetraethyl titanate, then (a mole composition is SiO by resulting material2：TiO2：SiO2：Cetyl front three
Base ammonium bromide：TMAH：Water=60:1:15.6:10.4:48) stainless steel sealing reactor is transferred to, at 140 DEG C
At a temperature of constant temperature place 28h, obtain the mixture of crystallization product；By the filtering of this mixture, it is washed with water, and in 110 DEG C of dryings
60 minutes.
The titanium oxide content for containing the HTS of template is 3 weight %, and the content of template is 19 weight %,
(volume average particle size is 200 μm of spheric catalyst, and density is by abbreviation T3-0, the catalyst C-T3-0 being molded using its preparation
0.62g/cm3, the T3-0 containing 85 weight % and 15 weight % silica).
Hollow HTS containing template is calcined 5 hours at 500 DEG C, it is hollow without template so as to obtain
HTS T3-1, the catalyst C-T3-1 being molded using its preparation (volume average particle size is 200 μm of spheric catalyst,
Density is 0.60g/cm3, the T3-1 containing 85 weight % and 15 weight % silica).
In step (2), loading catalyst C-T3-0, C-T3-1 formation is urged respectively in the fixed bed reactors of two series connection
Agent bed, remaining condition all same.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 4
Propene carbonate is prepared using method same as Example 1, unlike, in step (1), with reference to Takashi
Tasumi etc., J.Chem.Soc., Chem.Commun., the method disclosed in 1992,589-590, prepared and contained using following methods
There is the HTS Ti-Beta of template.
Specifically preparation process is：At room temperature, tetraethyl titanate and amorphous silica gel Aerosil 200 are added under agitation
Enter into tetraethyl ammonium hydroxide (TEAOH) aqueous solution, then add appropriate aluminum nitrate, the glue mole composition now formed is
A12O3:TiO2:SiO2:H2O:TEAOH=1:12:388:6000:108, the glue of formation is transferred to polytetrafluoroethyllining lining
Dynamic crystallization is carried out in autoclave, crystallization temperature is 130 DEG C, mixing speed 60rpm, and crystallization time is 3 days.Cooling
Afterwards, obtained solidliquid mixture is centrifuged, obtains solid and crystallization mother liquor.The solid isolated is washed with water to pH=
9 or so, 80 DEG C of dry 5h, obtain the HTS containing template.
The titanium oxide content for containing the HTS of template is 2.6 weight %, and the content of template is 16.7 weights
%, abbreviation T4-0 are measured, (volume average particle size is 200 μm of spheric catalyst to the catalyst C-T4-0 being molded using its preparation, close
Spend for 0.71g/cm3, the T4-0 containing 85 weight % and 15 weight % silica).
Hollow HTS containing template is calcined 5 hours at 500 DEG C, it is hollow without template so as to obtain
HTS T4-1, the catalyst C-T4-1 being molded using its preparation (volume average particle size is 200 μm of spheric catalyst,
Density is 0.70g/cm3, the T4-1 containing 85 weight % and 15 weight % silica).
In step (2), loading catalyst C-T4-0, C-T4-1 formation is urged respectively in the fixed bed reactors of two series connection
Agent bed, remaining condition all same.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 5
Propene carbonate is prepared using method same as Example 1, unlike, in step (2), use expoxy propane
Azeotropic mixture with pentane formation at 50 DEG C is as raw material.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 6
Propene carbonate is prepared using method same as Example 1, unlike, in step (2), by expoxy propane with
Azeotropic mixture, carbon dioxide and the Peracetic acid (for 30 weight % peroxide acetate aqueous solution) of dichloromethane are sent into fixed bed reaction
Haptoreaction is carried out in device, wherein, the mol ratio of Peracetic acid and expoxy propane is 0.001：1.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Table 1
| Numbering | Epoxypropane conversion rate (%) | Propene carbonate selectivity (%) |
| Embodiment 1 | 52 | 93 |
| Comparative example 1 | 13 | 4 |
| Comparative example 2 | 11 | 77 |
| Comparative example 3 | 32 | 72 |
| Embodiment 2 | 56 | 95 |
| Embodiment 3 | 42 | 85 |
| Embodiment 4 | 49 | 90 |
| Embodiment 5 | 37 | 88 |
| Embodiment 6 | 61 | 96 |
It can be seen from the data of table 1 according to the present invention method, reaction experience still be able to up to 240 hours holding compared with
High conversion ratio and selectivity, it can be seen that, method of the invention, it is possible to obtain higher conversion rate of reaction product and target production
Thing selectivity, and the method for the present invention, the single trip use long lifespan of catalyst.
Embodiment 7
(1) titanium-silicon molecular sieve TS-1 containing template is prepared
With reference to Zeolites, prepared by 1992, the Vol.12 method described in the 943-950 pages, specific method is as follows.
(20 DEG C) at room temperature, 22.5 grams of tetraethyl orthosilicates are mixed with 10.0 grams of triethanolamines, and add 59.8 grams
Distilled water, it is stirred after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C, the hydrating solution of tetraethyl orthosilicate is obtained, violent
The solution being made up of 1.0 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols is slowly added under stirring, gained mixture is existed
Stirred 3 hours at 75 DEG C, obtain clear colloid.This colloid is put into stainless steel sealing reactor, at a temperature of 170 DEG C
Constant temperature is placed 3 days, obtains the mixture of crystallization product；By the filtering of this mixture, it is washed with water, and is dried 60 minutes in 110 DEG C,
Obtain the HTS containing template.
The titanium oxide content for containing the HTS of template is 2.1 weight %, and the content of template is 13.2 weights
%, abbreviation T7-0 are measured, (volume average particle size is 200 μm of spheric catalyst to the catalyst C-T7-0 being molded using its preparation, close
Spend for 0.76g/cm3, the T7-0 containing 85 weight % and 15 weight % silica).
Hollow HTS containing template is calcined 5 hours at 500 DEG C, it is hollow without template so as to obtain
HTS T7-1, the catalyst C-T7-1 being molded using its preparation (volume average particle size is 200 μm of spheric catalyst,
Density is 0.75g/cm3, the T7-1 containing 85 weight % and 15 weight % silica).
(2) propene carbonate is prepared
In step (2), loading catalyst C-T7-0, C-T7-1 formation is urged respectively in the fixed bed reactors of two series connection
Agent bed, remaining condition all same.And in the first loaded catalyst and the second beds in beds
The weight ratio of loaded catalyst is 4：1, the ratio of the internal diameter of the first beds and the internal diameter of the second beds is
4.4：1.
By the azeotropic mixture of expoxy propane and dichloromethane (expoxy propane and dichloromethane shape in 39.96 DEG C and 80kPa
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5603, and the molar content of expoxy propane is
0.4397), carbon dioxide is sent into from the bottom of the fixed bed reactors positioned at upstream and flows through the first beds, output
Liquid mixture subsequently enters in next fixed bed reactors and flows through the second beds.Wherein, expoxy propane and two
The mol ratio of carbonoxide is 5：1, the temperature in two fixed bed reactors is 60 DEG C, in course of reaction that two fixed beds are anti-
It is 1.0MPa to answer the Stress control in device, and the weight (hourly) space velocity (WHSV) of expoxy propane is 5h-1。
Then, obtained mixture is filtered, the obtained composition of liquid phase mixture is determined with gas chromatography, and
Epoxypropane conversion rate and propene carbonate selectivity are calculated, is as a result listed in table 2.
Embodiment 8
(1) titanium-silicon molecular sieve TS-1 containing template is prepared
With reference to Zeolites, prepared by 1992, the Vol.12 method described in the 943-950 pages, specific method is as follows.
(20 DEG C) at room temperature, 25.5 grams of tetraethyl orthosilicates are mixed with 15.0 grams of n-butylamines, and add 40.8 grams of steamings
Distilled water, it is stirred after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C, obtains the hydrating solution of tetraethyl orthosilicate, acutely stirring
The solution for being slowly added into and being made up of 1.0 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols is mixed down, by gained mixture 75
Stirred 3 hours at DEG C, obtain clear colloid, this colloid is put into stainless steel sealing reactor, it is permanent at a temperature of 170 DEG C
Temperature is placed 3 days, obtains the mixture of crystallization product；By the filtering of this mixture, it is washed with water, and is dried 60 minutes in 110 DEG C, is obtained
To the HTS containing template.
The titanium oxide content for containing the HTS of template is 2.0 weight %, and the content of template is 12.7 weights
%, abbreviation T8-0 are measured, (volume average particle size is 200 μm of spheric catalyst to the catalyst C-T8-0 being molded using its preparation, close
Spend for 0.77g/cm3, the T8-0 containing 85 weight % and 15 weight % silica).
Hollow HTS containing template is calcined 5 hours at 500 DEG C, it is hollow without template so as to obtain
HTS T8-1, the catalyst C-T8-1 being molded using its preparation (volume average particle size is 200 μm of spheric catalyst,
Density is 0.75g/cm3, the T8-1 containing 85 weight % and 15 weight % silica).
(2) propene carbonate is prepared
In step (2), loading catalyst C-T8-0, C-T8-1 formation is urged respectively in the fixed bed reactors of two series connection
Agent bed, remaining condition all same.And in the first loaded catalyst and the second beds in beds
The weight ratio of loaded catalyst is 4：1, the ratio of the internal diameter of the first beds and the internal diameter of the second beds is
3.5：1.
By expoxy propane of the azeotropic mixture of expoxy propane and dichloromethane in 29.65 DEG C and 60kPa and dichloromethane shape
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5643, and the molar content of expoxy propane is
0.4357), carbon dioxide is sent into from the bottom of the fixed bed reactors positioned at upstream and flows through the first beds, output
Liquid mixture subsequently enters in next fixed bed reactors and flows through the second beds.Wherein, expoxy propane and two
The mol ratio of carbonoxide is 1：5, the temperature in two fixed bed reactors is 90 DEG C, in course of reaction that two fixed beds are anti-
It is 0.5MPa to answer the Stress control in device, and the weight (hourly) space velocity (WHSV) of expoxy propane is 2h-1。
Then, obtained mixture is filtered, the obtained composition of liquid phase mixture is determined with gas chromatography, and
Epoxypropane conversion rate and propene carbonate selectivity are calculated, is as a result listed in table 2.
Embodiment 9
It is identical with the method for embodiment 8, unlike, the azeotropic mixture of expoxy propane and dichloromethane be at 20.05 DEG C and
The binary azeotrope that expoxy propane during 40kPa is formed with dichloromethane, wherein, the molar content of dichloromethane is
0.5699,0.4301) molar content of expoxy propane is.
Then, obtained mixture is filtered, the obtained composition of liquid phase mixture is determined with gas chromatography, and
Epoxypropane conversion rate and propene carbonate selectivity are calculated, is as a result listed in table 2.
Embodiment 10
Propene carbonate is prepared using method same as Example 9, unlike, in step (2), by expoxy propane with
Azeotropic mixture, carbon dioxide and the hydrogen peroxide (concentration is 30 weight %) of dichloromethane, which are sent into fixed bed reactors, contact instead
Should, wherein, the mol ratio of hydrogen peroxide and expoxy propane is 0.01：1.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 11
Propene carbonate is prepared using method same as in Example 10, unlike, in step (2), use peroxidating
Diisopropylbenzene (DIPB) replaces hydrogen peroxide, and the water that the hydrogen peroxide for introducing equivalent is brought into, remaining condition all same.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 12
Method according to embodiment 9 prepares propene carbonate, the difference is that the HTS containing template agent is by as follows
Prepared by step, i.e., the HTS containing template changes in the catalyst of the first beds：
(20 DEG C) at room temperature, 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOHs, and added
59.8 grams of distilled water, it is stirred after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C, obtains the hydrating solution of tetraethyl orthosilicate,
The solution being made up of 1.1 grams of butyl titanates and 5.0 grams of anhydrous isopropyl alcohols is slowly added into vigorous stirring, and gained is mixed
Compound stirs 3 hours at 75 DEG C, obtains clear colloid, this colloid is put into stainless steel sealing reactor, at 170 DEG C
At a temperature of constant temperature place 3 days, obtain the mixture of crystallization product；By the filtering of this mixture, it is washed with water, and in 110 DEG C of dryings
60 minutes, in the lower 360 DEG C of roastings 3h of air atmosphere.
The titanium oxide content of the HTS containing template prepared is 2.5 weight %, and the content of template is 0.8
Weight %, abbreviation T12-0, (volume average particle size is 200 μm of spherical catalyst to the catalyst C-T12-0 being molded using its preparation
Agent, density 0.73g/cm3, the T12-1 containing 85 weight % and 15 weight % silica) and as the first beds
Catalyst, the second beds are same as Example 9.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 13
Propene carbonate is prepared using method same as Example 9, unlike, in step (2), use for epoxy
(binary azeotropic that the expoxy propane in 5.26 DEG C and 40kPa is formed with dichloromethane mixes the azeotropic mixture of propane and dichloromethane
Compound, wherein, the molar content of dichloromethane is 0.5795, and the molar content of expoxy propane is 0.4205), remaining condition is homogeneous
Together.
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 14
Prepared using method same as Example 7, unlike, in the first beds and the second beds
Catalyst type and under conditions of loadings keep constant, reduce the internal diameter of the first beds, make the first catalyst
The ratio of the internal diameter of bed and the second beds is 2：1.
Experimental result is listed in table 2.
Embodiment 15
Prepared using method same as Example 7, unlike, in the first beds and the second beds
Catalyst type and under conditions of loadings keep constant, reduce the internal diameter of the first beds, make the first catalyst
The ratio of the internal diameter of the internal diameter of bed and the second beds is 1：2.
Experimental result is listed in table 2.
Embodiment 16
Propene carbonate is prepared using method same as Example 7, unlike, in step (2), expoxy propane and two
Chloromethanes does not form azeotropic mixture, is passed directly into reaction unit respectively and is reacted, and the dosage of the two is same as Example 7；
Obtained mixture is filtered, determines the obtained composition of liquid phase mixture with gas chromatography, and calculate
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Table 2
| Numbering | Epoxypropane conversion rate (%) | Propene carbonate selectivity (%) |
| Embodiment 7 | 14 | 90 |
| Embodiment 8 | 87 | 92 |
| Embodiment 9 | 86 | 91 |
| Embodiment 10 | 90 | 95 |
| Embodiment 11 | 98 | 98 |
| Embodiment 12 | 51 | 86 |
| Embodiment 13 | 83 | 87 |
| Embodiment 14 | 7 | 70 |
| Embodiment 15 | 5 | 62 |
| Embodiment 16 | 10 | 86 |
Embodiment 14-15 is compared as can be seen that according to method of the invention, liquid charging stock is passed through the first catalysis
The superficial velocity of agent bed is less than the superficial velocity by the first beds, can obtain higher conversion ratio and target production
Thing selectivity, and further extend the single trip use life-span of HTS.
Tables 1 and 2 as a result, it was confirmed that the present invention method can be obtained under relatively low reaction temperature high expoxy propane turn
Rate and propene carbonate selectivity.Particularly in the presence of cumyl peroxide, expoxy propane is not only increased
Conversion ratio and propene carbonate selectivity, and propene carbonate selectively can be up to 98%.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
Claims (14)
1. a kind of method for preparing propene carbonate, this method include：Under the conditions of cycloaddition reaction, by liquid charging stock and catalysis
Agent bed contacts, and the liquid charging stock contains expoxy propane, carbon dioxide and optional solvent；The beds contain
First beds and the second beds, on the basis of the flow direction of the liquid charging stock, first catalyst
Bed is located at the upstream of second beds, and the catalyst of the first beds filling is containing containing template
HTS catalyst, the catalyst of second beds filling is the catalyst containing HTS, institute
State in the HTS containing template, the content of template is 0.1-25 weight %.
2. according to the method for claim 1, wherein, the superficial velocity that the liquid charging stock flows through the first beds is
v1, the superficial velocity for flowing through the second beds is v2, v1＜ v2。
3. the method according to claim 11, wherein, v2/v1=1.5-10.
4. according to the method described in any one in claim 1-3, wherein, the liquid charging stock is in the beds
Residence time be T, the residence time in first beds is T1, T1/ T=0.4-0.95.
5. according to the method described in any one in claim 1-3, wherein, the catalyst of the first beds filling
In the HTS containing template the content catalyst that is loaded with second beds in HTS contain
The weight ratio of amount is 1-20：1.
6. the method according to claim 11, wherein, containing template in the catalyst of the first beds filling
The weight ratio of the content of HTS is in the catalyst that the content of HTS is loaded with second beds
2-10：1.
7. according to the method described in any one in claim 1-3, wherein, in the liquid charging stock, expoxy propane and solvent
Mol ratio composition with expoxy propane and solvent formation azeotropic mixture composition it is identical.
8. according to the method described in any one in claim 1-3, wherein, the solvent is dichloromethane.
9. according to the method for claim 8, wherein, it in temperature is 5- that the azeotropic mixture of the expoxy propane and dichloromethane, which is,
50 DEG C, the azeotropic mixture that pressure is formed under conditions of being 40-100kPa.
10. according to the method described in any one in claim 1-3, wherein, the template be quaternary ammonium base, aliphatic amine and
One or more in aliphatic hydramine.
11. according to the method described in any one in claim 1-3, wherein, the HTS is selected from being tied with MFI
The HTS of structure, the HTS with MEL structures, the HTS with BEA structures, with MWW structures
HTS, the HTS with MOR structures, the HTS with TUN structures and with two-dimentional hexagonal structure
HTS in one or more.
12. according to the method for claim 11, wherein, the HTS is the hollow titanium silicon point with MFI structure
Son sieve, the crystal grain of the hollow HTS is hollow-core construction, and the radical length of the chamber portion of the hollow-core construction is 5-
300nm。
13. according to the method described in any one in claim 1-3, wherein, the contact is entered in the presence of peroxide
OK, the mol ratio of the peroxide and expoxy propane is 0.0001-0.1：1.
14. according to the method described in any one in claim 1-3, wherein, the cycloaddition reaction condition includes：Temperature is
10-160 DEG C, the mol ratio of expoxy propane and carbon dioxide is 1:0.1-100, pressure is counted as 0-2.5MPa using gauge pressure.
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| CN103787931A (en) * | 2012-10-29 | 2014-05-14 | 中国石油化工股份有限公司 | Production method of dimethyl sulfoxide |
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| CN102179268A (en) * | 2011-03-23 | 2011-09-14 | 天津大学 | Preparation of Ti-MCM-41 mesoporous material with functionalized ionic liquid and application thereof |
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