CN105367540B - It is a kind of while preparing the method for propylene glycol monomethyl ether and propene carbonate - Google Patents
It is a kind of while preparing the method for propylene glycol monomethyl ether and propene carbonate Download PDFInfo
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Abstract
The invention provides a kind of while preparing the method for propylene glycol monomethyl ether and propene carbonate, this method includes：By expoxy propane, methanol, CO2Contacted with catalyst, wherein, the catalyst includes the HTS containing template.HTS containing template is used as by expoxy propane, methanol and CO by the method for the present invention2Prepare the catalyst of propylene glycol monomethyl ether and propene carbonate, even in (such as not higher than 160 DEG C relatively low of reaction temperature, be not higher than 120 DEG C even) under reacted, can also obtain high epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate is selective.
Description
Technical field
The present invention relates to a kind of while preparing the method for propylene glycol monomethyl ether and propene carbonate.
Background technology
Propylene glycol, particularly propylene glycol monomethyl ether, due to there is two bases with strong solvability in its chemical constitution
Group --- ehter bond and hydroxyl, the former belongs to hydrophobic nature, can dissolve hydrophobic class compound；The latter belongs to hydrophilic nmature, can dissolve water-soluble
Property material, therefore, propylene glycol is the versatility solvent of function admirable, also known as alembroth.Propylene glycol monomethyl ether has faint
Ether taste, but there is no strong and stimulating smell, make its purposes more safe extensively, available for numerous areas.
For example, propylene glycol monomethyl ether can be used for styrene-acrylic emulsion, acrylic emulsion and its emulsion paint system, it, which has, reduces into
Film temperature, promotion cohesion film forming, and ensure film characteristic in good order and condition.Except the solvent for a variety of high-grade paints it
Outside, propylene glycol monomethyl ether is also used in printing-ink controlling evaporation rate and viscosity modifier, it may also be used for chemical intermediate, stop
Viscosity modifier is used as in car formula of liquid.Because propylene glycol monomethyl ether can be miscible in any proportion with water, metal accordingly can be applied to clear
As solvent in lotion formulation, or for reducing freezing point in radiator anti-freeze fluid.In addition, propylene glycol monomethyl ether
It can be used as the raw material of organic synthesis.
The method of production propylene glycol uses expoxy propane to be obtained for raw material with alcohols material chemical combination substantially, but this method is deposited
In reaction temperature high (more than 100 DEG C), big pressure, catalyst activity low (60%-90%) and poor selectivity (82%-90%) etc.
Problem.A kind of synthetic method of propylene glycol monomethyl ether disclosed in CN101550069A, uses ionic liquid for catalyst, but right
Ingredient requirement is strict, and if desired for absolute methanol, cost is high.
Using propylene one-step synthesis propylene glycol also studies have reported that, as USP6239315 discloses titaniferous, vanadium, chromium, tin
Molecular sieve makees epoxidizing agent and combine catalysis propylene with the acid solid alkylation catalyst such as resin or acidic molecular sieve to synthesize the third two
Alcohol ether, but the catalyst preparation that this method is used is complicated, and the severe reaction conditions of synthesis of propylene glycol, temperature will be controlled in zero degree
Left and right, not only consumes energy but also is difficult to realize, at the same cumbersome, and product selectivity is low, it is impossible to applied in actual production.
A kind of synthetic method of propylene glycol is also disclosed in CN1944365A, is a kind of method of two-step reaction, first
Occur epoxidation reaction by propylene and hydrogen peroxide and obtain expoxy propane, then expoxy propane reacts with alcohols and obtains third again
Glycol ethers, the catalyst used in this method is HTS or HTS and bases mixture, reaction temperature and pressure
It is required that high, particularly second reactor, reaction temperature is even as high as 200 DEG C and pressure up to 8.5MPa.
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
With in carbon dioxide cycloaddition method synthesizing acrylic ester technique, conventional catalyst has：(1) homogeneous catalyst：Quaternary ammonium salt, season
Ammonium alkali, 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 in order, specific surface area it is big,
The advantages of Stability Analysis of Structures, molecular sieve is widely used in oil refining process and chemical products production.But synthesize carbon in cycloaddition method
In acid propylene ester technique, molecular sieve it is active very poor.Therefore, document report typically uses quaternary ammonium salt, quaternary ammonium base or ionic liquid
It is active to improve its Deng being modified to molecular sieve.
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, active component is immobilized in molecular sieve outer surface
The shortcomings of there is high energy consumption, complex process, environment unfriendly (using benzene, toluene etc. to be solvent in modified) in method.Therefore having must
More environmental protection, efficient molecular sieve catalyst are explored, to open up molecular sieve in cycloaddition method prepares propene carbonate
Application.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide one kind can prepare simultaneously propylene glycol monomethyl ether and
The method of propene carbonate, this method is also resulted under gentle reaction temperature (temperature such as not higher than 160 DEG C)
Higher epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity.
The present inventor is had found in research process, and the process of propylene glycol monomethyl ether is prepared in alcoholysis
In, using the conversion ratio that expoxy propane including containing the HTS of template as catalyst, can be effectively improved and
The selectivity of target product.More it was unexpectedly observed that during propylene glycol monomethyl ether is prepared, if by expoxy propane and methanol
With CO2Reactor and the HTS haptoreaction containing template are passed through, reaction temperature can be effectively reduced, also simultaneously
The conversion ratio of expoxy propane can be significantly improved, particularly can be with coproduction propene carbonate.The present invention is completed on this basis.
To realize object defined above, the invention provides a kind of while preparing the side of propylene glycol monomethyl ether and propene carbonate
Method, this method includes：By expoxy propane, methanol, CO2Contacted with catalyst, wherein, the catalyst includes containing template
HTS.
In the building-up process of HTS, organic formwork agent plays very important effect, but under normal circumstances,
Needing to remove template from the main body bore of molecular sieve before use (will for example synthesize obtained HTS to be roasted
Burn), catalysis or the absorption property of molecular sieve could be realized.The present invention method by the HTS containing template be used as by
Expoxy propane prepares the catalyst of propylene glycol monomethyl ether and propene carbonate, even in relatively low reaction temperature (such as not higher than 160
DEG C, not even higher than 120 DEG C) under reacted, can also obtain high epoxypropane conversion rate and propylene glycol monomethyl ether and carbonic acid
Propylene selectivity.
The method of the present invention has opened up the new use of the molecular sieve containing structure directing agent in HTS particularly duct
On the way.In addition, the present invention method is simple, such as pressure autoclave type reactor carry out, only need to by such as filtering separation of solid and liquid
Method can separate molecular sieve with the liquid phase mixture containing propylene glycol monomethyl ether and propene carbonate.
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 while preparing the method for propylene glycol monomethyl ether and propene carbonate, this method includes：Will
Expoxy propane, methanol, CO2Contacted with catalyst, wherein, the catalyst includes the HTS containing template.
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 the rare earth elements such as La, Ce, Y or Nd) etc..
In the present invention, the HTS containing template refers to the titanium silicon point containing the template remained in building-up process
Son sieve, that is,：HTS does not undergo the process of removed template method after composition, even if or HTS warp
The process of removed template method was gone through, 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 basis
The species of HTS and specific contact conditions are selected.Usually, in the HTS, template contains
Amount can be 0.1-25 weight %.Preferably, in the HTS, the content of template is 1-20 weight %, more preferably
For 5-15 weight %.The content of the template can be determined using thermogravimetic analysis (TGA) method, usually, can be by thermogravimetic analysis (TGA)
In percent weight loss 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 propylene glycol monomethyl ether and propene carbonate selectivity,
The HTS is the hollow HTS with MFI structure, and the crystal grain of the hollow HTS is hollow knot
Structure, the radical length of the chamber portion of the hollow-core construction is 5-300nm, and the hollow HTS is removing template
Afterwards, in 25 DEG C, P/P0=0.10, adsorption time is that the benzene adsorbance measured under conditions of 1h is at least 70mg/g, and cryogenic nitrogen is inhaled
There is hysteresis loop between attached adsorption isotherm and desorption isotherm.Hollow HTS containing template is referred to
Method disclosed in CN1132699C 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 0.1-100：1, preferably 0.5-100：1.
The method according to the invention, the contact is preferably carried out in the presence of the solvent, so can further improve anti-
Answer the mixability between each reactant in system, enhanced dispersion and more easily the severe degree to reaction is adjusted.
The species of the solvent is not particularly limited.Usually, the solvent can be selected from C3-C8Ketone, halogenated alkane be preferably C1-
C4Halogenated alkane and C2-C8Nitrile in one or more.The instantiation of the solvent can include but is not limited to：Acetone,
Butanone, dichloromethane, acetonitrile and acrylonitrile, more preferably dichloromethane.Preferably, the solvent is selected from C3-C8Ketone and C1-
C4Halogenated alkane in one or more.
The consumption of the solvent is not particularly limited, and can be conventional selection.Usually, the weight of solvent and the catalyst
Measuring ratio can be with 0.1-1000：1, preferably 0.5-200：1.
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 expoxy propane, methanol, CO2, peroxide and appoint
The solvent of choosing is contacted with catalyst.In the presence of a peroxide, by expoxy propane, methanol, CO2And optional solvent and catalysis
Agent is contacted, and results in higher epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity.Preferably, institute
The mol ratio for stating peroxide and expoxy propane is 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 propylene glycol monomethyl ether 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 %.
In the present invention, the expoxy propane, methanol and CO2Between ratio can according to need be adjusted, for this
Invention, preferably expoxy propane, methanol and CO2Mol ratio be 1：0.1-10：1-100, more preferably 1：0.2-10：2-
50.In the existing method for preparing propylene glycol monomethyl ether by expoxy propane, in order to suppress the generation of accessory substance, it is necessary to excessively make
With methanol, (mol ratio of expoxy propane and methanol is generally 1：1-100).The consumption of methanol is excessive, on the one hand the effect of reduction reaction
Rate, on the other hand aggravates the follow-up burden isolated and purified, while also increasing the amount of the useless methanol of generation.And the method for the present invention
Using the HTS of template is contained as catalyst, even if the consumption of reduction methanol, such as expoxy propane and methanol rub
You are than being 1：0.1-50, can also obtain high propylene glycol monomethyl ether selectivity.Taking into account propylene glycol monomethyl ether and propene carbonate
Under conditions of selectivity, from the angle of the consumption of further reduction methanol, the mol ratio of expoxy propane and methanol is preferably
1：0.1-10, more preferably 1：0.2-5.
The present invention it is a kind of preferred embodiment in, expoxy propane and methanol are incorporated into instead in the form of azeotropic is constituted
Answer in device, reaction involved in the present invention can be caused more steadily effectively to carry out, therefore for the present invention, preferably by ring
Contacted in the azeotropic mixture feeding reactor of Ethylene Oxide and methanol with catalyst.
In the present invention, azeotropic ratio between the expoxy propane and methanol can be selected according to the need for reaction condition
Select.With the method for the invention it is preferred to which the azeotropic mixture of the expoxy propane and methanol is is 25-210 DEG C in temperature, pressure is
The azeotropic mixture formed under conditions of 0.5-50atm；It in temperature is 50- that the azeotropic mixture of more preferably described expoxy propane and methanol, which is,
180 DEG C, pressure is the azeotropic mixture formed under conditions of 1-40atm, the azeotropic mixture of the further preferred expoxy propane and methanol
To be 80-150 DEG C in temperature, pressure is the azeotropic mixture that is formed under conditions of 5-20atm.
It is below exemplary illustration, the data such as azeotropic quality composition and azeotropic temperature and pressure of methanol and expoxy propane are such as
Under：
0.8atm, 28.39 DEG C, expoxy propane 0.9986- methanol 0.0014；
1atm, 34.47 DEG C, expoxy propane 0.9941- methanol 0.0059；
2atm, 55.22 DEG C, expoxy propane 0.9765- methanol 0.0235；
5atm, 87.7 DEG C, expoxy propane 0.9419- methanol 0.0581；
10atm, 116.77 DEG C, expoxy propane 0.9032- methanol 0.0968；
15atm, 135.77 DEG C, expoxy propane 0.8740- methanol 0.1260；
20atm, 150.19 DEG C, expoxy propane 0.8498- methanol 0.1502；
30atm, 171.86 DEG C, expoxy propane 0.8106- methanol 0.1894；
50atm, 201.4 DEG C, expoxy propane 0.7526- methanol 0.2474.
The method of the present invention by using containing the HTS of template as catalyst, while by expoxy propane and
Contacted in the azeotropic mixture feeding reactor of methanol with catalyst so that the method according to the present invention can obtain high expoxy propane and turn
Rate and propene carbonate selectivity.
The condition of the contact can be the conventional selection of this area, and such as temperature can be 10-160 DEG C；In terms of gauge pressure, pressure
Power can be 0-2.5MPa.Even if the method for the present invention is contacted under mild conditions, higher epoxy third can be also obtained
Alkane conversion ratio and propylene glycol monomethyl ether and propene carbonate selectivity.Contacted, on the one hand can under mild conditions
Energy consumption is reduced, on the other hand reaction is more easily controlled.Method in accordance with the invention it is preferred that the condition of the contact includes：Temperature
Degree can be 20-120 DEG C；In terms of gauge pressure, preferably 0.5-2MPa.
The method according to the invention can also be including isolating propylene glycol monomethyl ether and carbon from obtained mixture is contacted
Acid propylene ester.The method that propylene glycol monomethyl ether and propene carbonate are isolated in the mixture obtained from contact is not limited especially
It is fixed, can be the conventional selection of this area.Specifically, obtained mixture progress separation of solid and liquid can will be contacted, and will separation
Obtained liquid phase is distilled, so as to obtain propylene glycol monomethyl ether and propene carbonate.
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 TA951 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 propylene glycol monomethyl ether and propylene carbonate are calculated using below equation
Ester selectivity.
(formula IV)
(Formula V)
(Formula IV)
In formula IV, Formula V and Formula IV, X is epoxypropane conversion rate；For the molal quantity of the expoxy propane of addition；To be anti-
The molal quantity for the liquid phase mixture oxypropylene that should be obtained；SMMEFor propylene glycol monomethyl ether selectivity；nMMEReaction is obtained
The molal quantity of propylene glycol monomethyl ether in liquid phase mixture；SPCFor propene carbonate selectivity；nPCTo react the mixing of obtained liquid phase
The molal quantity of propene carbonate in thing.
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.
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) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, acetone as solvent and the titanium silicon molecule prepared as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 35 DEG C of stirring reactions 1 hour after being well mixed.Wherein, expoxy propane, methanol and CO2
Mol ratio be 1：1：20, the weight ratio of solvent and catalyst is 20：1, the weight ratio of expoxy propane and catalyst is 20：1, it is high
It is 2.0MPa to press the Stress control in reactor.Then, obtained mixture is filtered, is determined and obtained with gas chromatography
Liquid phase mixture composition, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, as a result
Listed in table 1.
Comparative example 1
Propylene glycol monomethyl ether and propene carbonate are prepared using method same as Example 1, unlike, without using urging
Agent.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Comparative example 2
Propylene glycol monomethyl ether and propene carbonate are prepared using method same as Example 1, unlike, step (1)
In, the HTS containing template is calcined 5 hours at 500 DEG C, so as to obtain the HTS (mould of template agent removing
The HTS is used as the catalyst in step (2) for 0) by the content of plate agent.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 2
Propylene glycol monomethyl ether and propene carbonate are prepared using method same as Example 1, unlike, in step (1),
Method with reference to disclosed in Chinese patent CN1132699C, the hollow HTS containing template is prepared using following methods
HTS；
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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 3
Propylene glycol monomethyl ether and propene carbonate are prepared using method same as Example 1, unlike, in step (1),
With reference to Corma etc., J.Chem.Soc., Chem.Commun., the method disclosed in 1994,147-148 (save last roasting
Step), prepare the HTS Ti-MCM-41 containing template using following methods.
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 Aerosil200 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 4
Propylene glycol monomethyl ether and propene carbonate are 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, use with
Lower section method prepares the HTS Ti-Beta containing template.
Specifically preparation process is：At room temperature, tetraethyl titanate and amorphous silica gel Aerosil200 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 5
Propylene glycol monomethyl ether and propene carbonate are prepared using method same as Example 1, unlike, step (2)
In, replace acetone using the dichloromethane of equivalent.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Embodiment 6
Propylene glycol monomethyl ether and propene carbonate are prepared using method same as Example 1, unlike, step (2)
In, using expoxy propane, methanol, carbon dioxide, the acetone as solvent, the titanium silicon molecule as (1) preparation the step of catalyst
Sieve in TS-1 and Peracetic acid (being 30 weight % peroxide acetate aqueous solution) feeding autoclave, at 35 DEG C after being well mixed
Stirring reaction 1 hour.Wherein, the mol ratio of expoxy propane and Peracetic acid 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 1.
Table 1
| Numbering | Epoxypropane conversion rate (%) | Propylene glycol monomethyl ether selectivity (%) | Propene carbonate selectivity (%) |
| Embodiment 1 | 69.9 | 66.6 | 25.7 |
| Comparative example 1 | 27.9 | 69.4 | 26.9 |
| Comparative example 2 | 30.4 | 63.1 | 24.2 |
| Embodiment 2 | 79.5 | 69.4 | 26.9 |
| Embodiment 3 | 54.8 | 58.9 | 22.4 |
| Embodiment 4 | 61.5 | 65.3 | 25.6 |
| Embodiment 5 | 96.9 | 65.9 | 25.4 |
| Embodiment 6 | 85.5 | 68.0 | 26.3 |
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) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2The titanium silicon molecule prepared as the acetone of solvent and as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 50 DEG C of stirring reactions 1 hour after being well mixed.Wherein, expoxy propane, methanol and CO2
Mol ratio be 1：2：10, the weight ratio of solvent and catalyst is 120：1, the weight ratio of expoxy propane and catalyst is 40：1,
Stress control in autoclave is 1.5MPa.Then, obtained mixture is filtered, determined with gas chromatography
The composition of the liquid phase mixture arrived, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, knot
Fruit is 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 5.2 weights
Measure %.
(2) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2The titanium silicon molecule prepared as the acetone of solvent and as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 60 DEG C of stirring reactions 0.5 hour after being well mixed.Wherein, expoxy propane, methanol with
CO2Mol ratio be 1：5：50, the weight ratio of solvent and catalyst is 200：1, the weight ratio of expoxy propane and catalyst is 80：
1, the Stress control in autoclave is 1.0MPa.Then, obtained mixture is filtered, determined with gas chromatography
The composition of obtained liquid phase mixture, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity,
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) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, acetonitrile as solvent and the titanium silicon molecule prepared as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 40 DEG C of stirring reactions 1 hour after being well mixed.Wherein, expoxy propane, methanol and CO2
Mol ratio be 1：4：5, the weight ratio of solvent and catalyst is 80：1, the weight ratio of expoxy propane and catalyst is 2：1, high pressure
Stress control in reactor is 0.5MPa.Then, obtained mixture is filtered, determines what is obtained with gas chromatography
The composition of liquid phase mixture, and epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity are calculated, as a result exist
Listed in table 2.
Embodiment 10
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, acrylonitrile as solvent and the titanium silicon point prepared as (1) the step of catalyst
In son sieve TS-1 feeding autoclaves, in 90 DEG C of stirring reactions 1 hour after being well mixed.Wherein, expoxy propane, methanol with
CO2Mol ratio be 1：3：2, the weight ratio of solvent and catalyst is 180：1, the weight ratio of expoxy propane and catalyst is 5：1,
Stress control in autoclave is 1.0MPa.Then, obtained mixture is filtered, determined with gas chromatography
The composition of the liquid phase mixture arrived, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether 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) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, acetonitrile as solvent and the titanium silicon molecule prepared as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 110 DEG C of stirring reactions 0.5 hour after being well mixed.Wherein, expoxy propane, methanol with
CO2Mol ratio be 5：1：1, the weight ratio of solvent and catalyst is 10：1, the weight ratio of expoxy propane and catalyst is 10：1,
Stress control in autoclave is 1.5MPa.Then, obtained mixture is filtered, determined with gas chromatography
The composition of the liquid phase mixture arrived, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, knot
Fruit is listed in table 2.
Embodiment 12
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, acetone as solvent and the titanium silicon molecule prepared as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 70 DEG C of stirring reactions 1 hour after being well mixed.Wherein, expoxy propane, methanol and CO2
Mol ratio be 3：1：15, the weight ratio of solvent and catalyst is 80：1, the weight ratio of expoxy propane and catalyst is 100：1,
Stress control in autoclave is 0.5MPa.Then, obtained mixture is filtered, determined with gas chromatography
The composition of the liquid phase mixture arrived, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, knot
Fruit is listed in table 2.
Embodiment 13
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 1.
(2) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, butanone as solvent and the titanium silicon molecule prepared as (1) the step of catalyst
Sieve in TS-1 feeding autoclaves, in 30 DEG C of stirring reactions 2 hours after being well mixed.Wherein, expoxy propane, methanol and CO2
Mol ratio be 2：1：80, the weight ratio of solvent and catalyst is 40：1, the weight ratio of expoxy propane and catalyst is 60：1, it is high
It is 1.5MPa to press the Stress control in reactor.Then, obtained mixture is filtered, is determined and obtained with gas chromatography
Liquid phase mixture composition, and calculate epoxypropane conversion rate and propylene glycol monomethyl ether 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) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2And the titanium-silicon molecular sieve TS-1 prepared as (1) the step of catalyst sends into high pressure
In reactor, in 60 DEG C of stirring reactions 1 hour after being well mixed.Wherein, expoxy propane, methanol and CO2Mol ratio be 1：10：
5, the weight ratio of expoxy propane and catalyst is 1：1, the Stress control in autoclave is 1.0MPa.Then, it will obtain
Mixture is filtered, and determines the obtained composition of liquid phase mixture with gas chromatography, and calculate epoxypropane conversion rate and
Propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 15
(1) titanium-silicon molecular sieve TS-1 containing template is prepared using method same as Example 7.
(2) propylene glycol monomethyl ether and propene carbonate are prepared
By expoxy propane, methanol, CO2, solvent acetone and as the step of catalyst (1) prepare titanium-silicon molecular sieve TS-1
Send into autoclave, in 60 DEG C of stirring reactions 3 hours after being well mixed.Wherein, expoxy propane, methanol and CO2Mole
Than for 1：4：25, the weight ratio of solvent and catalyst is 50：1, the weight ratio of expoxy propane and catalyst is 20：1, reaction under high pressure
Stress control in kettle is 0.6MPa.Then, obtained mixture is filtered, obtained liquid phase is determined with gas chromatography
The composition of mixture, and epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity are calculated, as a result in table 2
List.
Embodiment 16
Propylene glycol monomethyl ether and propene carbonate are prepared using with the identical method of embodiment 15, unlike, step (2)
In, by expoxy propane, methanol, CO2, (concentration is for the titanium-silicon molecular sieve TS-1 and hydrogen peroxide that prepare as (1) the step of catalyst
30 weight %) in feeding autoclave, in 60 DEG C of stirring reactions 3 hours after being well mixed.Wherein, expoxy propane and peroxidating
The mol ratio of hydrogen is 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 17
Propylene glycol monomethyl ether and propene carbonate are prepared using with the identical method of embodiment 16, unlike, step (2)
In, hydrogen peroxide is replaced using cumyl 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 18
Method according to embodiment 15 prepares propylene glycol monomethyl ether and propene carbonate, the difference is that what step (2) was used
Catalyst is prepared 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, 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 2.
Embodiment 19
Propylene glycol monomethyl ether and propene carbonate are prepared using with the identical method of embodiment 15, unlike, step (2)
In, temperature is 200 DEG C, is as a result listed in table 2.
Comparative example 3
Propylene glycol monomethyl ether and propene carbonate are prepared using with the step of embodiment 15 (2) identical method, unlike,
In step (1), the HTS containing template is calcined 5 hours at 500 DEG C, so as to obtain HTS (template
Content be 0), and by the HTS be used as step (2) in catalyst.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 2.
Comparative example 4
Propylene glycol monomethyl ether and propene carbonate are prepared using with the identical method of comparative example 3, unlike, contacting
Template triethanolamine is added in journey simultaneously, amount and the template in HTS in embodiment 15 of the template of addition contain
Amount 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 propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 2.
Table 2
| Numbering | Epoxypropane conversion rate (%) | Propylene glycol monomethyl ether selectivity (%) | Propene carbonate selectivity (%) |
| Embodiment 7 | 53.6 | 80.1 | 17.3 |
| Embodiment 8 | 61.2 | 63.5 | 32.1 |
| Embodiment 9 | 42.7 | 90.4 | 8.3 |
| Embodiment 10 | 51.0 | 72.3 | 23.5 |
| Embodiment 11 | 11.8 | 56.4 | 30.9 |
| Embodiment 12 | 22.4 | 58.1 | 35.6 |
| Embodiment 13 | 9.1 | 92.8 | 6.5 |
| Embodiment 14 | 89.6 | 95.2 | 4.4 |
| Embodiment 15 | 81.6 | 80.8 | 13.2 |
| Embodiment 16 | 86.2 | 82.4 | 15.6 |
| Embodiment 17 | 91.4 | 83.3 | 16.2 |
| Embodiment 18 | 65.8 | 74.6 | 8.9 |
| Embodiment 19 | 96.9 | 73.2 | 11.7 |
| Comparative example 3 | 22.4 | 80.2 | 0.1 |
| Comparative example 4 | 76.2 | 52.3 | 20.8 |
Tables 1 and 2 as a result, it was confirmed that the present invention method by the HTS containing template be used as by epoxy third
Alkane, methanol and CO2The catalyst of propylene glycol monomethyl ether and propene carbonate is prepared, high epoxypropane conversion rate and third can be obtained
Glycol monomethyl ether and propene carbonate selectivity.
Embodiment 20
Method according to embodiment 1 prepares propylene glycol monomethyl ether and propene carbonate, unlike, step (2) is by as follows
Step is carried out：
By the azeotropic mixture (20atm, 150.19 DEG C, expoxy propane 0.8498- methanol 0.1502) of expoxy propane and methanol,
CO2, acetone as solvent and the titanium-silicon molecular sieve TS-1 that is prepared as (1) the step of catalyst send into autoclave,
Remaining reaction condition and material proportion are same as Example 1.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 3.
Embodiment 21
Method according to embodiment 1 prepares propylene glycol monomethyl ether and propene carbonate, unlike, step (2) is by as follows
Step is carried out：
By the azeotropic mixture (10atm, 116.77 DEG C, expoxy propane 0.9032- methanol 0.0968) of expoxy propane and methanol,
CO2, acetone as solvent and the titanium-silicon molecular sieve TS-1 that is prepared as (1) the step of catalyst send into autoclave,
Remaining reaction condition and material proportion are same as Example 1.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 3.
Embodiment 22
Method according to embodiment 1 prepares propylene glycol monomethyl ether and propene carbonate, unlike, step (2) is by as follows
Step is carried out：
By azeotropic mixture (5atm, 87.7 DEG C, expoxy propane 0.9419- methanol 0.0581), the CO of expoxy propane and methanol2、
The titanium-silicon molecular sieve TS-1 prepared as the acetone of solvent and as (1) the step of catalyst is sent into autoclave, remaining
Reaction condition and material proportion are same as Example 1.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 3.
Embodiment 23
Method according to embodiment 22 prepares propylene glycol monomethyl ether and propene carbonate, unlike, without using azeotropic mixture,
It is 0.9419 directly according to the mass ratio of expoxy propane and methanol:0.0581 feeds intake.
Obtained mixture is filtered, the composition of obtained liquid phase mixture is determined with gas chromatography, and is calculated
Epoxypropane conversion rate and propylene glycol monomethyl ether and propene carbonate selectivity, are as a result listed in table 3.
Table 3
| Embodiment | Epoxypropane conversion rate (%) | Propylene glycol monomethyl ether selectivity (%) | Propene carbonate selectivity (%) |
| Embodiment 20 | 88.7 | 11.3 | 85.6 |
| Embodiment 21 | 82.3 | 10.6 | 86.9 |
| Embodiment 22 | 85.8 | 11.5 | 87.0 |
| Embodiment 23 | 76.1 | 16.3 | 76.9 |
Table 3 as a result, it was confirmed that the method for the present invention uses the azeotropic mixture of expoxy propane and methanol as raw material, can be relatively low
Reaction temperature under the epoxypropane conversion rate that further improves and propene carbonate selectivity.
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 (11)
1. a kind of while preparing the method for propylene glycol monomethyl ether and propene carbonate, this method includes：By expoxy propane, methanol,
CO2Contacted with catalyst, wherein, the catalyst includes the HTS containing template, the titanium containing template
In si molecular sieves, the content of template is 0.1-25 weight %, and the template is quaternary ammonium base, aliphatic amine and aliphatic hydramine
In one or more.
2. according to the method described in claim 1, wherein, the HTS be selected from MFI structure HTS,
HTS with MEL structures, the HTS with BEA structures, the HTS with MWW structures, have
The HTS of MOR structures, the HTS with TUN structures and the HTS with two-dimentional hexagonal structure.
3. method according to claim 2, wherein, the HTS is the hollow titanium silicon molecule with MFI structure
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. according to the method described in claim 1, wherein, it is described contact in the presence of peroxide carry out, the peroxidating
The mol ratio of thing and expoxy propane is 0.0001-0.1：1.
5. method according to claim 4, wherein, the peroxide is cumyl peroxide.
6. the method according to claim 1 or 4, wherein, the contact is carried out in the presence of the solvent, the solvent and institute
The weight ratio for stating catalyst is 0.1-1000：1.
7. method according to claim 6, wherein, the solvent is selected from C3-C8Ketone, C1-C4Halogenated alkane and C2-C8
Nitrile in one or more.
8. according to the method described in claim 1, wherein, expoxy propane, methanol and CO2Mol ratio be 1：0.1-10：1-100.
9. the method according to claim 1 or 8, wherein, the contact is carried out under conditions of temperature is 10-160 DEG C；Ring
The weight ratio of Ethylene Oxide and the catalyst is 0.1-100：1；In terms of gauge pressure, the contact is in the condition that pressure is 0-2.5MPa
It is lower to carry out.
10. according to the method described in claim 1, wherein, the azeotropic mixture of expoxy propane and methanol is sent into reactor with urging
Agent is contacted, and the azeotropic mixture of the expoxy propane and methanol is is 25-210 DEG C in temperature, and pressure is under conditions of 0.5-50atm
The azeotropic mixture of formation.
11. method according to claim 10, wherein, it in temperature is 80- that the azeotropic mixture of the expoxy propane and methanol, which is,
150 DEG C, pressure is the azeotropic mixture that is formed under conditions of 5-20atm.
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| CN1138500A (en) * | 1996-01-03 | 1996-12-25 | 南开大学 | Coordinate catalyst in use for CO2 for synthetizing carbonate |
| CN1485312A (en) * | 2002-09-24 | 2004-03-31 | 中国石化上海石油化工股份有限公司 | Method for preparing methyl carbonate by directly esterfying propylene oxide |
| CN1528735A (en) * | 2003-10-16 | 2004-09-15 | 华东理工大学 | Method for joint production of dialkyl carbonate and diatomic alcohol |
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| CN1138500A (en) * | 1996-01-03 | 1996-12-25 | 南开大学 | Coordinate catalyst in use for CO2 for synthetizing carbonate |
| CN1485312A (en) * | 2002-09-24 | 2004-03-31 | 中国石化上海石油化工股份有限公司 | Method for preparing methyl carbonate by directly esterfying propylene oxide |
| CN1528735A (en) * | 2003-10-16 | 2004-09-15 | 华东理工大学 | Method for joint production of dialkyl carbonate and diatomic alcohol |
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