CN105367539B - A kind of synthetic method of propene carbonate - Google Patents
A kind of synthetic method of propene carbonate Download PDFInfo
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- CN105367539B CN105367539B CN201410413556.3A CN201410413556A CN105367539B CN 105367539 B CN105367539 B CN 105367539B CN 201410413556 A CN201410413556 A CN 201410413556A CN 105367539 B CN105367539 B CN 105367539B
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Abstract
The invention provides a kind of synthetic method of propene carbonate, this method includes：Under the conditions of cycloaddition reaction, the azeotropic mixture of expoxy propane and solvent, carbon dioxide are contacted with catalyst, wherein, the catalyst contains the HTS containing template.The method that the present invention is provided, reaction condition is gentle, and epoxypropane conversion rate and propene carbonate selectivity are high.The method of the present invention has opened up the new application of the molecular sieve containing structure directing agent in HTS particularly duct.And the method for the present invention is green synthesis process, no special producing equipment requirement, process is simple and easy to control, beneficial to industrialized production and application.
Description
Technical field
The present invention relates to a kind of synthetic method of 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 capacitor and electrolyte, desulfurization and decarburization solvent, the metal of high-energy battery extract
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 high with atom utilization
(100%), process is simple and is increasingly becoming main propene carbonate production method the advantages of environmental protection.
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..
The content of the invention
New catalyst expoxy propane and carbon dioxide cycloaddition system are used it is an object of the invention to provide a kind of
The method of standby propene carbonate.
The present inventor has been surprisingly found that in research practice, in the cycloaddition reaction mistake of expoxy propane and carbon dioxide
Cheng Zhong, introduces the HTS containing template as catalyst, and uses the azeotropic mixture of expoxy propane and solvent as raw material,
Result in higher epoxypropane conversion rate and the selectivity of propene carbonate.More it was unexpected that being introduced in reaction system
During a small amount of peroxide, the conversion ratio of expoxy propane is further improved with the selectivity of purpose product propene carbonate.Based on this,
Complete the present invention.
To realize object defined above, the invention provides a kind of synthetic method of propene carbonate, this method includes：In ring plus
Into under reaction condition, the azeotropic mixture of expoxy propane and solvent, carbon dioxide are contacted with catalyst, wherein, the catalyst contains
There is the HTS containing template.
The method that the present invention is provided, 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 the molecular sieve containing structure directing agent in HTS particularly 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 embodiment part.
Embodiment
The embodiment to the present invention is described in detail below.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 synthetic method of propene carbonate, this method includes：, will under the conditions of cycloaddition reaction
Azeotropic mixture, the carbon dioxide of expoxy propane and solvent are contacted with catalyst, wherein, the catalyst contains the titanium silicon containing template
Molecular sieve.
The method according to the invention, the catalyst can be whole HTSs containing template, can also contain
Other catalyst, cycloaddition catalyst that for example can also be containing part prior art, specific example be montmorillonite, MgO,
Mg-Al hydrotalcites, MgAl2O4Spinelle, 1- normal-butyl -3- methyl imidazolium tetrafluoroborates ([bmim] BF4)、CH3ONa, four fourths
Base ammonium bromide, sodium methoxide, KI/ γ-Al2O3、KI-Ti(OH)4/γ-Al2O3、K2O/4A molecular sieves, KOH, NaOH, KNO3With
K2CO3And Lewis acid-inorganic base bicomponent catalyst, wherein Lewis acid can be LiCl, NaCl, KCl, KI, and inorganic base can
Think Na2CO3、K2CO3、NaHCO3、NH4HCO3。
With the method for the invention it is preferred to which the content of the HTS containing template is 50 weights in the catalyst
The content for measuring the HTS containing template in more than %, more preferably described catalyst is 60-100 weight %.In this hair
What is used in bright specific embodiment is that the content of the HTS containing template is 100 weight % catalyst, but
This is simultaneously not so limited the scope of the present invention.Catalyst composition when content herein refers to being free of carrier.
When the catalyst is formed body, the catalyst also includes carrier, wherein, carrier can be Al2O3、ZnO、
MgO、SiO2, CaO and TiO2, rare earth oxide RE2O3(RE is La, Ce, Y or Nd etc.).
The method according to the invention, optional wider range of the species of the solvent, as long as can be formed with expoxy propane altogether
Boil thing, such as can be dichloromethane, methanol, pentane, amylene, pentamethylene and cyclopentene in one or more.Pin
To the present invention, preferably described solvent is dichloromethane.
In the present invention, ratio between the azeotropic mixture oxypropylene and solvent can be entered according to the need for reaction condition
Row selection.The method according to the invention, when the solvent is dichloromethane, preferably described expoxy propane and dichloromethane are total to
It in temperature is 5-50 DEG C to boil thing to be, pressure is the azeotropic mixture formed under conditions of 40-100kPa.
It is below exemplary illustration, the number such as azeotropic mole composition and azeotropic temperature and pressure of dichloromethane and expoxy propane
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 during 40kPa, expoxy propane with dichloromethane formation binary azeotrope, dichloromethane rubs
Your content is 0.5795, and the molar content of expoxy propane is 0.4205.
The method of the present invention is by using containing the HTS containing template as catalyst, while by expoxy propane
Contacted with the azeotropic mixture feeding reactor of solvent with catalyst so that the method according to the present invention can obtain high propylene carbonate
Ester selectivity.
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 does not undergo the process of removed template method after composition, even if or HTS experience
The process of removed template method is crossed, but template is not removed all.
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 be determined using thermogravimetic analysis (TGA) method, usually, can be by thermal weight loss point
Percent weight loss in analysis between 200-800 DEG C as template content.
The template can be various templates usually used during synthesis of titanium silicon molecular sieve, for example：It is described
Template can be the one or more in quaternary ammonium base, aliphatic amine and aliphatic hydramine.The quaternary ammonium base can have to be various
Machine level Four ammonium alkali, the aliphatic amine can be various NH3In at least one hydrogen by aliphatic alkyl (such as alkyl) replace after
The compound of formation, the aliphatic hydramine can be various NH3In at least one hydrogen by the aliphatic group of hydroxyl (such as
Alkyl) compound that is formed after substitution.
Specifically, the aliphatic amine that the alkaline template can represent for quaternary ammonium base, the formula II represented selected from formula I
One or more in the aliphatic hydramine represented with general formula III.
In Formulas I, R1、R2、R3And R4Respectively C1-C4Alkyl, including C1-C4Straight chained alkyl and C3-C4Branched alkane
Base, for example：R1、R2、R3And R4Can be each methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group or uncle
Butyl.
R5(NH2)n(Formula II)
In Formula II, 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 III)
In formula III, m R6It is identical or different, respectively C1-C4Alkylidene, including C1-C4Straight-chain alkyl-sub and C3-
C4Branched alkylidene, such as methylene, ethylidene, sub- n-propyl and sub- normal-butyl；M is 1,2 or 3.
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), ethamine, n-propylamine, n-butylamine, di-n-propylamine, butanediamine, hexamethylene diamine, MEA, in diethanol amine and triethanolamine
One or more.Preferably, the template is tetraethyl ammonium hydroxide, TPAOH and tetrabutylammonium hydroxide
Ammonium.
The HTS refers to the general name of a class zeolite of a part of silicon atom in titanium atom substitution lattice framework.Institute
It can be the common HTS with various topological structures to state HTS, for example：The HTS can be with
HTS (such as TS-2), the titanium silicon molecule of BEA structures of HTS (such as TS-1), MEL structures selected from MFI structure
Sieve (such as Ti-Beta), the HTS (such as Ti-MCM-22) of MWW structures, the HTS (such as Ti-MOR) of MOR structures,
The HTS (such as Ti-MCM-41, Ti-SBA-15) of the HTS (such as Ti-TUN) of TUN structures, two-dimentional hexagonal structure
With the HTS (such as Ti-ZSM-48) of other structures.The HTS is preferably selected from the titanium silicon molecule of MFI structure
The HTS of the HTS, more preferably MFI structure of sieve, the HTS of MEL structures and BEA structures.
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, adsorption time is that the benzene adsorbance measured under conditions of 1h is at least 70mg/g, the adsorption isotherm of nitrogen absorption under low temperature and
There is hysteresis loop between desorption isotherm.Hollow HTS containing template is referred to disclosed in CN1132699C
Method is prepared, and is the calcination stepses without being finally intended to remove template.
The consumption of the catalyst is can realize that catalysis is defined.Usually, expoxy propane and the catalyst
Weight ratio can be 0.1-200：1, preferably 1-100：1.
The present invention it is a kind of preferred embodiment in, it is described contact in the presence of peroxide carry out, 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 is contacted 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.
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
For the aryl of organic group, for example, C1-C10 alkyl or C6-C10, for example, TBHP, peroxidating isopropyl
Benzene, cyclohexyl hydroperoxide, Peracetic acid and Perpropionic Acid, wherein, preferably R7And R8It is organic group, more preferably R7And R8
It is cumenyl, i.e., preferably the peroxide is cumyl peroxide.Expoxy propane so can be further improved to turn
Rate and propene carbonate selectivity.
When the peroxide is hydrogen peroxide, the hydrogen peroxide can in a variety of manners be deposited 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
The hydrogen peroxide that formula is present.The method according to the invention, when the hydrogen peroxide is provided as an aqueous solution, the peroxidating
The concentration of aqueous solution of hydrogen can be the normal concentration of this area, for example：20-80 weight %.Concentration meets the peroxide of above-mentioned requirements
Changing the aqueous solution of hydrogen can be prepared using conventional method, can also be commercially available, for example：Can be 30 weights that can be commercially available
Measure the hydrogen peroxide of % hydrogen peroxide, 50 weight % hydrogen peroxide or 70 weight %.
With the method for the invention it is preferred to which 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, and such as 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.
The method according to the invention can also be including isolating propene carbonate from obtained mixture is contacted.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, can will contact obtained mixture progress separation of solid and liquid, and isolated liquid phase is distilled, so as to obtain carbonic acid
Propylene.
With the method for the invention it is preferred to which 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 which the solvent is methanol.
According to one kind of the present invention preferred embodiment, 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 the peroxidating existed in a variety of manners commonly used in the art
Hydrogen.From the further angle for improving security, the method according to the invention preferably uses the mistake existed as an aqueous solution
Hydrogen oxide.The method according to the invention, when the hydrogen peroxide is provided as an aqueous solution, the aqueous hydrogen peroxide solution
Concentration can be the normal concentration of this area, for example：20-80 weight %.Concentration meets the water-soluble of the hydrogen peroxide of above-mentioned requirements
Liquid can be prepared using conventional method, can also be commercially available, for example：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 referred to not for HTS commonly used in the art
HTS containing template, template agent content is less than 0.1 weight %), such as described HTS can be common
HTS with various topological structures, for example：The HTS can for 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 which 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 consumption of HTS is 0.002-0.1g.
With the method for the invention it is preferred to which the condition of contact includes：Temperature is 30-80 DEG C, and pressure is 0.1-2MPa, time
For 0.1-4h；More preferably temperature is 40-60 DEG C, and pressure is 0.1-1.5MPa, and the time is 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 corresponds 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 for the liquid phase mixture that reaction is obtained is determined using gas chromatography, is led to
Overcorrect normalization method is quantified, and epoxypropane conversion rate and propene carbonate selectivity are calculated using below equation.
(formula IV)
In formula IV, 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 V)
In Formula V, 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, 1992, the Vol.12 method preparation described in the 943-950 page, specific method is as follows.
At room temperature (20 DEG C), 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, stirring mixing 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 constituted, gained mixture is stirred 3 hours at 75 DEG C, clear colloid is obtained.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, collect after 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
It is 0.5h, propylene, methanol, the molar ratio of material 3 of hydrogen peroxide for 1.5MPa, time:10:1, the concentration of HTS is
0.05g/mL；Expoxy propane is isolated by rectifying from the material after contact.
Embodiment 1-19 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.
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOHs, and adds
59.8 grams of distilled water, stirring mixing obtains the hydrating solution of tetraethyl orthosilicate after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C,
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 is stirred 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
Measure %.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane in 42.93 DEG C and 100kPa of expoxy propane and dichloromethane
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 and the titanium-silicon molecular sieve TS-1 containing template prepared as (1) the step of catalyst send into high pressure
In reactor, in 85 DEG C of stirring reactions 4 hours after being well mixed.Wherein, the weight ratio of expoxy propane and catalyst is 20：1, ring
The mol ratio of Ethylene Oxide and carbon dioxide is 1：1, the Stress control in autoclave is 2MPa.Then, by obtained mixing
Thing is filtered, and the composition of obtained liquid phase mixture is determined with gas chromatography, and calculates epoxypropane conversion rate and carbonic acid
Propylene selectivity, is as a result listed in table 1.
Comparative example 1
Propene carbonate is prepared using method same as Example 1, unlike, without using catalyst.
Obtained mixture gas chromatography is determined to the composition of obtained liquid phase mixture, and calculates expoxy propane and is turned
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 (1), template will be contained
HTS be calcined 5 hours at 500 DEG C, so as to obtain the HTS (content of template be 0) of template agent removing,
And the HTS is used as the catalyst in step (2).
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
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 TS-1 molecular sieves after 550 DEG C of roasting 3h are sieved according to molecular sieve containing template molecule obtained by Example 1
(gram)：Sulfuric acid (mole)：Water (mole)=100:0.15:150 ratio is well mixed, in reacting 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, constant temperature places 0.5 day time at 190 DEG C of temperature and self-generated pressure,
Cool down after 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 %.
In step (2), the hollow HTS HTS for containing template is regard as catalyst.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
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), with reference to 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 adds
Enter in the mixed liquor formed to cetyl trimethylammonium bromide and 25% tetramethylammonium hydroxide aqueous solution and mix, 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 %.
In step (2), the HTS Ti-MCM-41 for containing template is regard as catalyst.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
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 are prepared using following methods and contained
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 is 60rpm, 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
Measure %.
In step (2), the HTS Ti-Beta for containing template is regard as catalyst.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
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 in 50 DEG C of formation is used as raw material.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
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, the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst and the Peracetic acid of dichloromethane
In (be 30 weight % peroxide acetate aqueous solution) feeding autoclave, in 85 DEG C of stirring reactions 1 hour after being well mixed.Its
In, the mol ratio of Peracetic acid and expoxy propane is 0.001：1.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 1.
Table 1
| Numbering | The species of catalyst | Epoxypropane conversion rate (%) | Propene carbonate selectivity (%) |
| Embodiment 1 | TS-1 | 47 | 91 |
| Comparative example 1 | - | 13 | 4 |
| Comparative example 2 | TS-1 | 11 | 77 |
| Embodiment 2 | HTS | 51 | 93 |
| Embodiment 3 | Ti-MCM-41 | 37 | 83 |
| Embodiment 4 | Ti-Beta | 44 | 88 |
| Embodiment 5 | TS-1 | 32 | 86 |
| Embodiment 6 | TS-1 | 56 | 94 |
Embodiment 7
(1) titanium-silicon molecular sieve TS-1 containing template is prepared
With reference to Zeolites, 1992, the Vol.12 method preparation described in the 943-950 page, specific method is as follows.
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 10.0 grams of triethanolamines, and adds 59.8 grams
Distilled water, stirring mixing obtains the hydrating solution of tetraethyl orthosilicate, violent after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C
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
Measure %.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 39.96 DEG C and 80kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5603, and the molar content of expoxy propane is
0.4397), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 60 DEG C of stirring reactions 1 hour.The mol ratio of expoxy propane and carbon dioxide is 5：1, expoxy propane and catalyst
Weight ratio be 40：1, the Stress control in autoclave is 1.0MPa.Then, obtained mixture is filtered, used
Gas chromatography determines the obtained composition of liquid phase mixture, and calculates epoxypropane conversion rate and propene carbonate selectivity,
As a result listed in table 2.
Embodiment 8
(1) titanium-silicon molecular sieve TS-1 containing template is prepared
With reference to Zeolites, 1992, the Vol.12 method preparation described in the 943-950 page, specific method is as follows.
At room temperature (20 DEG C), 25.5 grams of tetraethyl orthosilicates are mixed with 15.0 grams of n-butylamines, and adds 40.8 grams of steamings
Distilled water, stirring mixing obtains the hydrating solution of tetraethyl orthosilicate, acutely stirred after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C
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
Measure %.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 29.65 DEG C and 60kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5643, and the molar content of expoxy propane is
0.4357), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 40 DEG C of stirring reactions 0.5 hour.The mol ratio of expoxy propane and carbon dioxide is 1：5, expoxy propane is with being catalyzed
The weight ratio of agent is 80：1, the Stress control in autoclave is 0.5MPa.Then, obtained mixture is filtered,
The composition of obtained liquid phase mixture is determined with gas chromatography, and calculates epoxypropane conversion rate and propene carbonate selection
Property, as a result listed in table 2.
Embodiment 9
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 20.05 DEG C and 40kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5699, and the molar content of expoxy propane is
0.4301), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 40 DEG C of stirring reactions 2 hours.The mol ratio of expoxy propane and carbon dioxide is 1：10, expoxy propane and catalyst
Weight ratio be 2：1, the Stress control in autoclave is 0.5MPa.Then, obtained mixture is filtered, uses gas
Phase chromatography determines the composition of obtained liquid phase mixture, and calculates epoxypropane conversion rate and propene carbonate selectivity, knot
Fruit is listed in table 2.
Embodiment 10
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 29.65 DEG C and 60kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5643, and the molar content of expoxy propane is
0.4357), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 90 DEG C of stirring reactions 1 hour.The mol ratio of expoxy propane and carbon dioxide is 2：1, expoxy propane and catalyst
Weight ratio be 5：1, the Stress control in autoclave is 2.0MPa.Then, obtained mixture is filtered, uses gas
Phase chromatography determines the composition of obtained liquid phase mixture, and calculates epoxypropane conversion rate and propene carbonate selectivity, knot
Fruit is listed in table 2.
Embodiment 11
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 20.05 DEG C and 40kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5699, and the molar content of expoxy propane is
0.4301), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 110 DEG C of stirring reactions 0.5 hour.The mol ratio of expoxy propane and carbon dioxide is 1：10, expoxy propane is with urging
The weight ratio of agent is 10：1, the Stress control in autoclave is 1.5MPa.Then, obtained mixture was carried out
Filter, the composition of obtained liquid phase mixture is determined with gas chromatography, and calculates epoxypropane conversion rate and propene carbonate choosing
Selecting property, is as a result listed in table 2.
Embodiment 12
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propene carbonate is prepared
Using azeotropic mixture (same as Example 1), carbon dioxide and the step as catalyst of expoxy propane and dichloromethane
Suddenly in the titanium-silicon molecular sieve TS-1 feeding autoclave that prepared by (1), in 70 DEG C of stirring reactions 1 hour after being well mixed.Epoxy
The mol ratio of propane and carbon dioxide is 1：20, the weight ratio of expoxy propane and catalyst is 100：1, the pressure in autoclave
Power control is 0.8MPa.Then, obtained mixture is filtered, the liquid phase mixture obtained with gas chromatography measure
Composition, and epoxypropane conversion rate and propene carbonate selectivity are calculated, as a result listed in table 2.
Embodiment 13
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 39.96 DEG C and 80kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5603, and the molar content of expoxy propane is
0.4397), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 30 DEG C of stirring reactions 2 hours.The mol ratio of expoxy propane and carbon dioxide is 1：50, expoxy propane and catalyst
Weight ratio be 60：1, the Stress control in autoclave is 1.5MPa.Then, obtained mixture is filtered, used
Gas chromatography determines the obtained composition of liquid phase mixture, and calculates epoxypropane conversion rate and propene carbonate selectivity,
As a result listed in table 2.
Embodiment 14
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 39.96 DEG C and 80kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5603, and the molar content of expoxy propane is
0.4397) and as the step of catalyst (1) prepare titanium-silicon molecular sieve TS-1 send into autoclave in, be well mixed after
90 DEG C of stirring reactions 1 hour.The mol ratio of expoxy propane and carbon dioxide is 1：80, the weight ratio of expoxy propane and catalyst is
50：1, the Stress control in autoclave is 1.0MPa.Then, obtained mixture is filtered, uses gas chromatography
The composition of obtained liquid phase mixture is determined, and calculates epoxypropane conversion rate and propene carbonate selectivity, as a result in table 2
List.
Embodiment 15
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 7.
(2) propene carbonate is prepared
By azeotropic mixture (expoxy propane and dichloromethane shape in 20.05 DEG C and 40kPa of expoxy propane and dichloromethane
Into binary azeotrope, wherein, the molar content of dichloromethane is 0.5699, and the molar content of expoxy propane is
0.4301), carbon dioxide and the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst are sent into autoclave, are mixed
Close it is uniform after in 110 DEG C of stirring reactions 3 hours.Wherein, the mol ratio of expoxy propane and carbon dioxide is 1：1, expoxy propane with
The weight ratio of catalyst is 20：1, the Stress control in autoclave is 0.6MPa.Then, obtained mixture was carried out
Filter, the composition of obtained liquid phase mixture is determined with gas chromatography, and calculates epoxypropane conversion rate and propene carbonate choosing
Selecting property, is as a result listed in table 2.
Embodiment 16
Propene carbonate is prepared using with the identical method of embodiment 15, unlike, in step (2), by expoxy propane
(concentration is 30 weights for azeotropic mixture with dichloromethane, the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst and hydrogen peroxide
Measure %) in feeding autoclave, in 110 DEG C of stirring reactions 3 hours after being well mixed.Wherein, hydrogen peroxide and expoxy propane
Mol ratio be 0.01：1.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 17
Propene carbonate is prepared using with the identical method of embodiment 16, unlike, in step (2), use peroxidating
Diisopropylbenzene (DIPB) replaces hydrogen peroxide, remaining condition all same.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 18
Method according to embodiment 15 prepares propene carbonate, the difference is that the catalyst that step (2) is used is by following step
It is rapid to prepare：
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOHs, and adds
59.8 grams of distilled water, stirring mixing obtains the hydrating solution of tetraethyl orthosilicate after being hydrolyzed 1.0 hours at normal pressure and 60 DEG C,
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 is stirred 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 %.Remaining condition all same.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 19
Prepare propene carbonate using with the identical method of embodiment 15, unlike, in step (2), use for ring
Azeotropic mixture (expoxy propane and the binary azeotropic of dichloromethane formation in 5.26 DEG C and 40kPa of Ethylene Oxide and dichloromethane
Mixture, wherein, the molar content of dichloromethane is 0.5795, and the molar content of expoxy propane is 0.4205), remaining condition is equal
It is identical.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Comparative example 3
Propene carbonate is prepared using with the step of embodiment 15 (2) identical method, unlike, in step (1), it will contain
The HTS for having template is calcined 5 hours at 500 DEG C, so that HTS (template agent content is 0) is obtained, and should
HTS is used as the catalyst in step (2).
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Comparative example 4
Propene carbonate is prepared using with the identical method of comparative example 3, unlike, add mould simultaneously in addition process
Plate agent triethanolamine, the amount of the template of addition is identical with the template agent content in HTS in embodiment 15.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Comparative example 5
Prepare propene carbonate using with the identical method of embodiment 15, unlike, in step (2), expoxy propane with
Dichloromethane does not form azeotropic mixture, and reaction unit is passed directly into respectively and is reacted, and the consumption of the two is identical with embodiment 15；
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propene carbonate selectivity, are as a result listed in table 2.
Table 2
| Numbering | The species of catalyst | Epoxypropane conversion rate (%) | Propene carbonate selectivity (%) |
| Embodiment 7 | TS-1 | 7 | 88 |
| Embodiment 8 | TS-1 | 12 | 92 |
| Embodiment 9 | TS-1 | 18 | 90 |
| Embodiment 10 | TS-1 | 25 | 89 |
| Embodiment 11 | TS-1 | 91 | 90 |
| Embodiment 12 | TS-1 | 83 | 92 |
| Embodiment 13 | TS-1 | 15 | 94 |
| Embodiment 14 | TS-1 | 89 | 91 |
| Embodiment 15 | TS-1 | 87 | 92 |
| Embodiment 16 | TS-1 | 91 | 93 |
| Embodiment 17 | TS-1 | 93 | 98 |
| Embodiment 18 | TS-1 | 46 | 84 |
| Embodiment 19 | TS-1 | 78 | 85 |
| Comparative example 3 | TS-1 | 42 | 68 |
| Comparative example 4 | TS-1 | 80 | 82 |
| Comparative example 5 | TS-1 | 83 | 89 |
Tables 1 and 2 as a result, it was confirmed that the present invention method by the HTS containing template be used as by expoxy propane
The catalyst of propene carbonate is prepared, and uses the azeotropic mixture of expoxy propane and solvent as raw material, can be in relatively low reaction temperature
Degree is lower to obtain high epoxypropane conversion rate and propene carbonate selectivity.Situation about particularly existing in cumyl peroxide
Under, epoxypropane conversion rate and propene carbonate selectivity are not only increased, 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 (9)
1. a kind of synthetic method of propene carbonate, this method includes：Under the conditions of cycloaddition reaction, by expoxy propane and solvent
Azeotropic mixture, carbon dioxide contacted with catalyst, wherein, the catalyst contains the HTS containing template, described to contain
In the HTS of template, the content of template is 0.1-25 weight %, and the solvent is dichloromethane, expoxy propane and
The azeotropic mixture of dichloromethane is is 5-50 DEG C in temperature, and pressure is the azeotropic mixture formed under conditions of 40-100kPa, the template
Agent is the one or more in quaternary ammonium base, aliphatic amine and aliphatic hydramine.
2. synthetic method according to claim 1, wherein, the HTS is selected from the titanium silicon with MFI structure
Molecular sieve, the HTS with MEL structures, the HTS with BEA structures, the titanium silicon molecule with MWW structures
Sieve, the HTS with MOR structures, the HTS with TUN structures and the titanium silicon point with two-dimentional hexagonal structure
One or more in son sieve.
3. synthetic method according to claim 2, wherein, the HTS is the hollow titanium silicon with MFI structure
Molecular 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。
4. synthetic method according to claim 1, wherein, 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.
5. synthetic method according to claim 1, wherein, the mol ratio of expoxy propane and carbon dioxide is 1:0.1-100.
6. synthetic method according to claim 1, wherein, the cycloaddition reaction is under conditions of temperature is 10-160 DEG C
Carry out.
7. synthetic method according to claim 1, wherein, the weight ratio of expoxy propane and the catalyst is 1-100:1,
In terms of gauge pressure, the cycloaddition reaction is carried out under conditions of pressure is 0-2.5MPa.
8. synthetic method according to claim 1, wherein, the expoxy propane is prepared as follows：Exist in methanol
Under, propylene is contacted with hydrogen peroxide and HTS, isolated expoxy propane.
9. synthetic method according to claim 8, wherein, the mol ratio of propylene, methanol and hydrogen peroxide is 1-5:5-20:
1；The condition that propylene is contacted with hydrogen peroxide and HTS includes：Temperature is 40-60 DEG C, and pressure is 0.1-1.5MPa, when
Between be 0.2-1h, the concentration of HTS is 0.002-0.1g/mL.
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