CN105367539A - Synthetic method of propylene carbonate - Google Patents
Synthetic method of propylene carbonate Download PDFInfo
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- CN105367539A CN105367539A CN201410413556.3A CN201410413556A CN105367539A CN 105367539 A CN105367539 A CN 105367539A CN 201410413556 A CN201410413556 A CN 201410413556A CN 105367539 A CN105367539 A CN 105367539A
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Abstract
The invention provides a synthetic method of propylene carbonate. The method is characterized in that an epoxypropane and solvent azeotrope and carbon dioxide are in contact with a catalyst under cycloaddition reaction conditions, wherein the catalyst comprises a template-containing titanium silicalite molecular sieve. The method has the advantages of mild reaction conditions, high epoxypropane conversion rate and high propylene carbonate selectivity. The method develops new uses of the titanium silicalite molecular sieve, especially the molecular sieve with tunnels containing a structure directing agent. The method is a green synthesis technology, and also has the advantages of no special production device requirements, simple control of the process, and facilitation of industrial production and application.
Description
Technical field
The present invention relates to a kind of synthetic method of propylene carbonate.
Background technology
Propylene carbonate is not only the high boiling point of excellent property, the aprotic organic solvent of high polarity, or important organic synthesis intermediate.Propylene carbonate has been widely used as the softening agent etc. of the electrolytic solution of electrical condenser and high tension battery, desulfurization and decarburization solvent, metal extraction agent, tamanori and polymkeric substance; In addition, propylene carbonate also can be used for the important fine chemical product such as Synthesis of dimethyl carbonate.
At present, the industrial process of propylene carbonate comprises: phosgenation, ester-interchange method, propylene chlorohydrin method and propylene oxide and carbonic acid gas cycloaddition method.Wherein, propylene oxide and carbonic acid gas cycloaddition method become main propylene carbonate production method gradually owing to having the advantages such as the simple and environmental protection of atom utilization high (100%), process.
In propylene oxide and carbonic acid gas cycloaddition method synthesizing acrylic ester technique, conventional catalyzer has: (1) homogeneous catalyst: quaternary ammonium salt, quaternary ammonium hydroxide, organic phosphine compound, organometallic compound, basic metal or alkaline earth metal halide etc.; (2) heterogeneous catalyst: metal oxide or its mixture, molecular sieve, loaded catalyst etc.
Summary of the invention
The object of the present invention is to provide a kind of method using new catalyst propylene oxide and carbonic acid gas cycloaddition to prepare propylene carbonate.
The present inventor is in the favorite outer discovery of research practice, in the cycloaddition reaction process of propylene oxide and carbonic acid gas, introducing contains the HTS of template as catalyzer, and use the azeotrope of propylene oxide and solvent as raw material, higher epoxypropane conversion rate and the selectivity of propylene carbonate can be obtained.More surprisingly, when introducing a small amount of superoxide in reaction system, the transformation efficiency of propylene oxide and the selectivity of object product propylene carbonate improve further.Based on this, complete the present invention.
For realizing aforementioned object, the invention provides a kind of synthetic method of propylene carbonate, the method comprises: under cycloaddition reaction condition, by the azeotrope of propylene oxide and solvent, carbonic acid gas and catalyst exposure, wherein, described catalyzer contains the HTS containing template.
Method provided by the invention, reaction conditions is gentle, epoxypropane conversion rate and propylene carbonate selectivity high.Method of the present invention has opened up the novelty teabag of the molecular sieve of HTS particularly containing structure directing agent in duct.And method of the present invention is green synthesis process, without special producing equipment requirements, process is simple and easy to control, is beneficial to suitability for industrialized production and application.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of synthetic method of propylene carbonate, the method comprises: under cycloaddition reaction condition, and by the azeotrope of propylene oxide and solvent, carbonic acid gas and catalyst exposure, wherein, described catalyzer contains the HTS containing template.
According to method of the present invention, described catalyzer can be whole HTS containing template, also can containing other catalyzer, such as can also contain the cycloaddition catalyzer of part prior art, concrete example is montmorillonite, MgO, Mg-Al hydrotalcite, MgAl
2o
4spinel, 1-normal-butyl-3-methyl imidazolium tetrafluoroborate ([bmim] BF
4), CH
3oNa, Tetrabutyl amonium bromide, sodium methylate, KI/ γ-Al
2o
3, KI-Ti (OH)
4/ γ-Al
2o
3, K
2o/4A molecular sieve, KOH, NaOH, KNO
3and K
2cO
3and Lewis acid-mineral alkali bicomponent catalyst, wherein Lewis acid can be LiCl, NaCl, KCl, KI, and mineral alkali can be Na
2cO
3, K
2cO
3, NaHCO
3, NH
4hCO
3.
According to method of the present invention, the content of the HTS containing template in preferred described catalyzer is more than 50 % by weight, and the content of the HTS more preferably containing template in described catalyzer is 60-100 % by weight.The content being the HTS containing template used in a particular embodiment of the present invention is the catalyzer of 100 % by weight, but therefore this do not limit the scope of the invention.Content herein refers to not containing catalyzer composition during carrier.
When described catalyzer is formed body, described catalyzer also comprises carrier, and wherein, carrier can be Al
2o
3, ZnO, MgO, SiO
2, CaO and TiO
2, rare earth oxide RE
2o
3(RE is La, Ce, Y or Nd etc.).
According to method of the present invention, the range of choices of the kind of described solvent is wider, as long as can form azeotrope with propylene oxide, such as, can be one or more in methylene dichloride, methyl alcohol, pentane, amylene, pentamethylene and cyclopentenes etc.For the present invention, preferred described solvent is methylene dichloride.
In the present invention, the ratio between described azeotrope oxypropylene and solvent can be selected according to the needs of reaction conditions.According to method of the present invention, when described solvent is methylene dichloride, the azeotrope of preferred described propylene oxide and methylene dichloride is for being 5-50 DEG C in temperature, and pressure is the azeotrope formed under the condition of 40-100kPa.
Be below exemplary illustration, the azeotropic mole of methylene dichloride and propylene oxide form and the data such as azeotropic temperature and pressure as follows:
When 42.93 DEG C and 100kPa, propylene oxide and methylene dichloride are formed in binary azeotrope, and the molar content of methylene dichloride is 0.5573, and the molar content of propylene oxide is 0.4427;
When 39.96 DEG C and 80kPa, propylene oxide and methylene dichloride are formed in binary azeotrope, and the molar content of methylene dichloride is 0.5603, and the molar content of propylene oxide is 0.4397;
When 29.65 DEG C and 60kPa, propylene oxide and methylene dichloride are formed in binary azeotrope, and the molar content of methylene dichloride is 0.5643, and the molar content of propylene oxide is 0.4357;
When 20.05 DEG C and 40kPa, propylene oxide and methylene dichloride are formed in binary azeotrope, and the molar content of methylene dichloride is 0.5699, and the molar content of propylene oxide is 0.4301;
When 5.26 DEG C and 40kPa, propylene oxide and methylene dichloride are formed in binary azeotrope, and the molar content of methylene dichloride is 0.5795, and the molar content of propylene oxide is 0.4205.
Method of the present invention by use containing containing the HTS of template as catalyzer, the azeotrope of propylene oxide and solvent is sent into simultaneously in reactor with catalyst exposure, make obtain high propylene carbonate selectivity according to method of the present invention.
In the present invention, HTS containing template refers to the HTS containing template residual in building-up process, namely: HTS does not experience the process of removed template method after composition, even if or HTS lives through the process of removed template method, but template is not all removed.
The present invention is not particularly limited for the content containing the template in the HTS of template, can select according to the kind of HTS and concrete alcoholysis reaction condition.Usually, in described HTS, the content of template can be 0.1-25 % by weight.Preferably, in described HTS, the content of template is 1-20 % by weight, is more preferably 5-15 % by weight.The content of described template can adopt thermogravimetic analysis (TGA) method to measure, usually, and can using the content of the percent weight loss in thermogravimetic analysis (TGA) between 200-800 DEG C as template.
Described template can be normally used various template in the process of synthesis of titanium silicon molecular sieve, such as: described template can be one or more in quaternary ammonium hydroxide, fatty amine and aliphatics hydramine.Described quaternary ammonium hydroxide can be various organic level Four ammonium alkali, and described fatty amine can be various NH
3in at least one hydrogen by aliphatic alkyl (as alkyl) replace after formed compound, described aliphatics hydramine can be various NH
3in at least one hydrogen by the aliphatic group of hydroxyl (as alkyl) replace after formed compound.
Particularly, described alkaline template can one or more for being selected from quaternary ammonium hydroxide that general formula I represents, in fatty amine that general formula I I represents and the aliphatics hydramine that general formula III represents.
In formula I, R
1, R
2, R
3and R
4be C separately
1-C
4alkyl, comprise C
1-C
4straight chained alkyl and C
3-C
4branched-chain alkyl, such as: R
1, R
2, R
3and R
4can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-or the tertiary butyl separately.
R
5(NH
2)
n(formula II)
In formula II, n is the integer of 1 or 2.When n is 1, R
5for C
1-C
6alkyl, comprise C
1-C
6straight chained alkyl and C
3-C
6branched-chain alkyl, as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, neo-pentyl, isopentyl, tert-pentyl and n-hexyl.When n is 2, R
5for C
1-C
6alkylidene group, comprise C
1-C
6straight-chain alkyl-sub-and C
3-C
6branched alkylidene, as methylene radical, ethylidene, sub-n-propyl, sub-normal-butyl, sub-n-pentyl or sub-n-hexyl.
(HOR
6)
mnH
(3-m)(formula III)
In formula III, m R
6identical or different, be C separately
1-C
4alkylidene group, comprise C
1-C
4straight-chain alkyl-sub-and C
3-C
4branched alkylidene, as methylene radical, ethylidene, sub-n-propyl and sub-normal-butyl; M is 1,2 or 3.
Described template is specifically as follows but is not limited to: Tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, TPAOH (comprise the various isomer of TPAOH, as four n-propyl ammonium hydroxide and tetra isopropyl ammonium hydroxide), TBAH (comprising the various isomer of TBAH, as 4-n-butyl ammonium hydroxide and four isobutyl-ammonium hydroxide), one or more in ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, di-n-propylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine and trolamine.Preferably, described template is tetraethyl ammonium hydroxide, TPAOH and TBAH.
Described HTS refers to that titanium atom replaces the general name of a class zeolite of a part of Siliciumatom in lattice framework.Described HTS can for the common HTS with various topological framework, such as: described HTS can be selected from the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, and the HTS of other structure (as Ti-ZSM-48) etc. Ti-SBA-15).Described HTS is preferably selected from the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure, is more preferably the HTS of MFI structure.
From improving epoxypropane conversion rate and propylene carbonate optionally angle further, described HTS is the hollow HTS with MFI structure, the crystal grain of described hollow HTS is hollow structure, the radical length of the chamber portion of this hollow structure is 5-300nm, and described hollow HTS is after removing template, at 25 DEG C, P/P
0=0.10, adsorption time is the benzene adsorptive capacity that records under the condition of 1h is at least 70mg/g, there is hysteresis loop between the adsorption isothermal line of nitrogen absorption under low temperature and desorption isotherm.Hollow HTS containing template can prepare with reference to method disclosed in CN1132699C, is not just finally intended to the calcination steps removing template.
The consumption of described catalyzer is as the criterion can realize catalysis.Usually, the weight ratio of propylene oxide and described catalyzer can be 0.1-200:1, is preferably 1-100:1.
One of the present invention preferred embodiment in, described contact is carried out under the existence of superoxide, and the mol ratio of described superoxide and propylene oxide is 0.0001-0.1:1.That is, by the azeotrope of propylene oxide and solvent, carbonic acid gas, superoxide and catalyst exposure.
In the presence of a peroxide, by the azeotrope of propylene oxide and solvent, carbonic acid gas and catalyst exposure, higher epoxypropane conversion rate and propylene carbonate selectivity can be obtained.Preferably, the mol ratio of described superoxide and propylene oxide is 0.001-0.05:1, is more preferably 0.001-0.01:1.
Described superoxide refers to the compound containing-O-O-key in molecular structure, and its general formula is R
7-O-O-R
8(can be hydrogen peroxide and/or organo-peroxide), wherein R
7, R
8can be hydrogen or organic group separately, preferred R
7, R
8in at least one is organic group, being such as the alkyl of C1-C10 or the aryl of C6-C10, such as, is tertbutyl peroxide, dicumyl peroxide, cyclohexyl hydroperoxide, Peracetic Acid and Perpropionic Acid, wherein, preferred R
7and R
8be organic group, more preferably R
7and R
8be cumyl, namely preferred described superoxide is dicumyl peroxide.Epoxypropane conversion rate and propylene carbonate selectivity can be improved further like this.
When described superoxide is hydrogen peroxide, the hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.From the angle improving security further, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
According to method of the present invention, the mol ratio of preferred propylene oxide and carbonic acid gas is 1:0.1-100.
Described cycloaddition reaction condition can be that the routine of this area is selected, if temperature can be 10-160 DEG C; In gauge pressure, pressure can be 0-2.5MPa.Even if method of the present invention carries out addition under mild conditions, higher epoxypropane conversion rate and propylene carbonate selectivity also can be obtained.Carry out addition under mild conditions, can reduce energy consumption on the one hand, reaction is easier to control on the other hand.According to method of the present invention, preferably, described cycloaddition reaction condition comprises: temperature can be 20-120 DEG C, is more preferably 30-110 DEG C; In gauge pressure, be preferably 0.1-2MPa.
Can also comprise the mixture obtained from contact according to method of the present invention and isolate propylene carbonate.The method isolating propylene carbonate from the mixture that contact obtains is not particularly limited, and can be that the routine of this area is selected.Particularly, solid-liquid separation can be carried out by contacting the mixture obtained, and distill being separated the liquid phase obtained, thus obtain propylene carbonate.
According to method of the present invention, preferred propylene oxide is prepared as follows: in the presence of solvent, is contacted by propylene with hydrogen peroxide with HTS, is separated and obtains propylene oxide.
According to method of the present invention, preferred described solvent is methyl alcohol.
According to one of the present invention preferred embodiment, described propylene oxide is prepared as follows: in presence of methyl alcohol, is contacted by propylene with hydrogen peroxide with HTS, is separated and obtains propylene oxide.
According to method of the present invention, the hydrogen peroxide existed in a variety of manners that described hydrogen peroxide can be commonly used for this area.From the angle improving security further, preferably use the hydrogen peroxide existed as an aqueous solution according to method of the present invention.According to method of the present invention, when described hydrogen peroxide provides as an aqueous solution, the concentration of described aqueous hydrogen peroxide solution can be the normal concentration of this area, such as: 20-80 % by weight.The aqueous solution that concentration meets the hydrogen peroxide of above-mentioned requirements can adopt ordinary method to prepare, and also can be commercially available, such as: can for can be commercially available the hydrogen peroxide of 30 % by weight, the hydrogen peroxide of 50 % by weight or 70 % by weight hydrogen peroxide.
According to method of the present invention, described HTS can (refer to not containing the HTS of template for the HTS that this area is conventional, template content is lower than 0.1 % by weight), such as described HTS can for the common HTS with various topological framework, such as: described HTS can be the HTS (as TS-1) of MFI structure, the HTS (as TS-2) of MEL structure, the HTS (as Ti-Beta) of BEA structure, the HTS (as Ti-MCM-22) of MWW structure, the HTS (as Ti-MOR) of MOR structure, the HTS (as Ti-TUN) of TUN structure, the HTS of two dimension hexagonal structure is (as Ti-MCM-41, Ti-SBA-15) one or more and in the HTS of other structure (as Ti-ZSM-48).Described HTS be preferably in the HTS of the HTS of MFI structure, the HTS of MEL structure and BEA structure one or more, be more preferably the HTS of MFI structure.
According to method of the present invention, the mol ratio of preferred propylene, methyl alcohol and hydrogen peroxide is 0.1-10:1-100:1, is more preferably 1-5:5-20:1.
According to method of the present invention, the concentration of preferred HTS is 0.002-0.1g/mL, specifically refers to the reaction mass relative to every mL, and the consumption of HTS is 0.002-0.1g.
According to method of the present invention, the condition of preferably contact comprises: temperature is 30-80 DEG C, and pressure is 0.1-2MPa, and the time is 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 therefore do not limit the scope of the invention.
In following examples and comparative example, if not otherwise specified, reaction is all carry out in the universal autoclave of 250mL, and used reagent is commercially available analytical reagent.
In following examples and comparative example, if not otherwise specified, pressure is gauge pressure.
In following examples, thermogravimetry is adopted to measure the content of the template in the HTS containing template, concrete testing method is: on the thermogravimetric analyzer that the model of E.I.Du Pont Company is TA951, measure the rate of weight loss of HTS between 200-800 DEG C being purchased, this rate of weight loss corresponds to the content of template, wherein, temperature rise rate is 10 DEG C/min, tests in nitrogen atmosphere.
In following examples and comparative example, the composition of the liquid phase mixture adopting gas chromatography determination to be obtained by reacting, is undertaken quantitatively, adopting following formulae discovery epoxypropane conversion rate and propylene carbonate selectivity by correcting normalization method.
In formula IV, X is epoxypropane conversion rate;
for the mole number of propylene oxide added;
for the mole number of reacted liquid phase mixture oxypropylene.
In formula V, S is propylene carbonate selectivity;
N
pCfor the mole number of propylene carbonate in reacted liquid phase mixture;
for the mole number of propylene oxide added;
for the mole number of reacted liquid phase mixture oxypropylene.
In following examples and comparative example, propylene oxide prepares all as follows:
1.1 preparation HTS
With reference to the method preparation described in Zeolites, 1992, Vol.12 943-950 page, concrete grammar is as follows.
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOH as template, and add 59.8 grams of distilled water, be hydrolyzed 1.0 hours in normal pressure and 60 DEG C after being uniformly mixed, obtain the hydrating solution of tetraethyl orthosilicate.With vigorous stirring, in described hydrating solution, add the solution be made up of 1.1 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid.This colloid is placed in stainless steel sealed reactor, and at the temperature of 170 DEG C, constant temperature places 72 hours, obtains the mixture of crystallization product.The mixture obtained is filtered, after collecting the solid matter water used wash obtained, in 110 DEG C of dryings 60 minutes, thus obtains the titanium-silicon molecular sieve TS-1 (titanium oxide content is 2.5 % by weight, and the content of template is 14.2 % by weight) containing template.
By the HTS containing template 500 DEG C of roastings 5 hours, thus obtain not containing the HTS of template.
1.2 prepare propylene oxide
Propylene, methyl alcohol, hydrogen peroxide are contacted with described HTS (not containing template), temperature is 40 DEG C, pressure is 1.5MPa, the time is 0.5h, the molar ratio of material 3:10:1 of propylene, methyl alcohol, hydrogen peroxide, and the concentration of HTS is 0.05g/mL; Propylene oxide is gone out by rectifying separation from the material after contact.
Embodiment 1-19 is for illustration of method of the present invention.
Embodiment 1
(1) titanium-silicon molecular sieve TS-1 of preparation containing template
With reference to method preparation (saving the step of roasting) described in Zeolites, 1992, Vol.12 943-950 page, concrete grammar is as follows.
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOH, and add 59.8 grams of distilled water, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after being uniformly mixed, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.1 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtain clear colloid, this colloid is put into stainless steel sealed reactor, at the temperature of 170 DEG C, constant temperature places 3 days, obtain the mixture of crystallization product, this mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes.
The titanium oxide content that should contain the HTS of template is 2.4 % by weight, and the content of template is 14.2 % by weight.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 42.93 DEG C and 100kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5573, the molar content of propylene oxide is 0.4427), the titanium-silicon molecular sieve TS-1 containing template prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 85 DEG C of stirring reactions 4 hours after mixing.Wherein, the weight ratio of propylene oxide and catalyzer is 20:1, and the mol ratio of propylene oxide and carbonic acid gas is 1:1, and the pressure-controlling in autoclave is 2MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Comparative example 1
The method identical with embodiment 1 is adopted to prepare propylene carbonate, unlike, do not use catalyzer.
By the composition of the liquid phase mixture that the mixture gas chromatography determination obtained obtains, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Comparative example 2
The method identical with embodiment 1 is adopted to prepare propylene carbonate, unlike, in step (1), by the HTS containing template 500 DEG C of roastings 5 hours, thus obtain the HTS (content of template is 0) removing template, and this HTS is used as the catalyzer in step (2).
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Embodiment 2
Adopt and prepare propylene carbonate with embodiment 1 same procedure, unlike, in step (1), with reference to method disclosed in Chinese patent CN1132699C, adopt the hollow HTS HTS of following methods preparation containing template;
The template molecule that contains of Example 1 gained sieves the TS-1 molecular sieve after 550 DEG C of roasting 3h according to molecular sieve (gram): sulfuric acid (mole): the ratio of water (mole)=100:0.15:150 mixes, react 5.0 hours at 90 DEG C, then filter according to a conventional method, wash and drying, obtain acid-treated TS-1 molecular sieve.By above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): trolamine (mole): TPAOH (mole): the ratio of water (mole)=100:0.20:0.15:180 mixes, put into stainless steel sealed reactor, at the temperature of 190 DEG C and autogenous pressure, constant temperature places 0.5 day time, after cooling release, filter according to a conventional method, wash, dry.
The titanium oxide content that should contain the hollow HTS of template is 2.5 % by weight, and the content of template is 6.3 % by weight.
In step (2), using the hollow HTS HTS containing template as catalyzer.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Embodiment 3
Adopt and prepare propylene carbonate with embodiment 1 same procedure, unlike, in step (1), with reference to Corma etc., J.Chem.Soc., Chem.Commun., 1994, method disclosed in 147-148 (saving last calcination steps), adopts the HTS Ti-MCM-41 of following methods preparation containing template.
The mixed solution that soft silica Aerosil200 and 25% tetramethylammonium hydroxide aqueous solution are formed is joined in the mixed solution that cetyl trimethylammonium bromide and 25% tetramethylammonium hydroxide aqueous solution formed and mix, then add Aerosil200 and tetraethyl titanate, then gained material (mole is consisted of SiO
2: TiO
2: SiO
2: cetyl trimethylammonium bromide: Tetramethylammonium hydroxide: water=60:1:15.6:10.4:48) proceed to stainless steel sealed reactor, at the temperature of 140 DEG C, constant temperature places 28h, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes.
The titanium oxide content that should contain the HTS of template is 3 % by weight, and the content of template is 19 % by weight.
In step (2), using the HTS Ti-MCM-41 containing template as catalyzer.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Embodiment 4
Adopt and prepare propylene carbonate with embodiment 1 same procedure, unlike, in step (1), with reference to TakashiTasumi etc., J.Chem.Soc., Chem.Commun., 1992, method disclosed in 589-590, adopts the HTS Ti-Beta of following methods preparation containing template.
Concrete preparation process is: at room temperature, tetraethyl titanate and amorphous silica gel Aerosil200 is under agitation joined in tetraethyl ammonium hydroxide (TEAOH) aqueous solution, then adds appropriate aluminum nitrate, and the glue mole now formed consists of A1
2o
3: TiO
2: SiO
2: H
2o:TEAOH=1:12:388:6000:108, proceeded to by the glue of formation in band teflon-lined autoclave and carry out dynamic crystallization, crystallization temperature is 130 DEG C, and stirring velocity is 60rpm, and crystallization time is 3 days.After cooling, the solidliquid mixture obtained is carried out centrifugation, obtains solid and crystallization mother liquor.Isolated solid washed with water is to about pH=9, and 80 DEG C of dry 5h, obtain the HTS containing template.
The titanium oxide content that should contain the HTS of template is 2.6 % by weight, and the content of template is 16.7 % by weight.
In step (2), using the HTS Ti-Beta containing template as catalyzer.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Embodiment 5
The method identical with embodiment 1 is adopted to prepare propylene carbonate, unlike, in step (2), use propylene oxide and pentane at 50 DEG C of azeotropes formed as raw material.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Embodiment 6
The method identical with embodiment 1 is adopted to prepare propylene carbonate, unlike, in step (2), the azeotrope of propylene oxide and methylene dichloride, carbonic acid gas, the titanium-silicon molecular sieve TS-1 prepared as the step (1) of catalyzer and Peracetic Acid (being the peroxide acetate aqueous solution of 30 % by weight) are sent in autoclave, 85 DEG C of stirring reactions 1 hour after mixing.Wherein, the mol ratio of Peracetic Acid and propylene oxide is 0.001:1.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in Table 1.
Table 1
| Numbering | The kind of catalyzer | Epoxypropane conversion rate (%) | Propylene 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 of preparation containing template
With reference to the method preparation described in Zeolites, 1992, Vol.12 943-950 page, concrete grammar is as follows.
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 10.0 grams of trolamines, and add 59.8 grams of distilled water, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after being uniformly mixed, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.0 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtains clear colloid.This colloid is put into stainless steel sealed reactor, and at the temperature of 170 DEG C, constant temperature places 3 days, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes, obtains the HTS containing template.
The titanium oxide content that should contain the HTS of template is 2.1 % by weight, and the content of template is 13.2 % by weight.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 39.96 DEG C and 80kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5603, the molar content of propylene oxide is 0.4397), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 60 DEG C of stirring reactions 1 hour after mixing.The mol ratio of propylene oxide and carbonic acid gas is 5:1, and the weight ratio of propylene oxide and catalyzer is 40:1, and the pressure-controlling in autoclave is 1.0MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 8
(1) titanium-silicon molecular sieve TS-1 of preparation containing template
With reference to the method preparation described in Zeolites, 1992, Vol.12 943-950 page, concrete grammar is as follows.
At room temperature (20 DEG C), 25.5 grams of tetraethyl orthosilicates are mixed with 15.0 grams of n-Butyl Amine 99s, and add 40.8 grams of distilled water, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after being uniformly mixed, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.0 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtain clear colloid, this colloid is put into stainless steel sealed reactor, at the temperature of 170 DEG C, constant temperature places 3 days, obtains the mixture of crystallization product; This mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes, obtains the HTS containing template.
The titanium oxide content that should contain the HTS of template is 2.0 % by weight, and the content of template is 12.7 % by weight.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 29.65 DEG C and 60kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5643, the molar content of propylene oxide is 0.4357), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 40 DEG C of stirring reactions 0.5 hour after mixing.The mol ratio of propylene oxide and carbonic acid gas is 1:5, and the weight ratio of propylene oxide and catalyzer is 80:1, and the pressure-controlling in autoclave is 0.5MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 9
(1) method identical with embodiment 1 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 20.05 DEG C and 40kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5699, the molar content of propylene oxide is 0.4301), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 40 DEG C of stirring reactions 2 hours after mixing.The mol ratio of propylene oxide and carbonic acid gas is 1:10, and the weight ratio of propylene oxide and catalyzer is 2:1, and the pressure-controlling in autoclave is 0.5MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 10
(1) method identical with embodiment 1 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 29.65 DEG C and 60kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5643, the molar content of propylene oxide is 0.4357), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 90 DEG C of stirring reactions 1 hour after mixing.The mol ratio of propylene oxide and carbonic acid gas is 2:1, and the weight ratio of propylene oxide and catalyzer is 5:1, and the pressure-controlling in autoclave is 2.0MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 11
(1) method identical with embodiment 1 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 20.05 DEG C and 40kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5699, the molar content of propylene oxide is 0.4301), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 110 DEG C of stirring reactions 0.5 hour after mixing.The mol ratio of propylene oxide and carbonic acid gas is 1:10, and the weight ratio of propylene oxide and catalyzer is 10:1, and the pressure-controlling in autoclave is 1.5MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 12
(1) method identical with embodiment 1 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
Titanium-silicon molecular sieve TS-1 prepared by the azeotrope (identical with embodiment 1) of propylene oxide and methylene dichloride, carbonic acid gas and the step (1) as catalyzer is sent in autoclave, 70 DEG C of stirring reactions 1 hour after mixing.The mol ratio of propylene oxide and carbonic acid gas is 1:20, and the weight ratio of propylene oxide and catalyzer is 100:1, and the pressure-controlling in autoclave is 0.8MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 13
(1) method identical with embodiment 1 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 39.96 DEG C and 80kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5603, the molar content of propylene oxide is 0.4397), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 30 DEG C of stirring reactions 2 hours after mixing.The mol ratio of propylene oxide and carbonic acid gas is 1:50, and the weight ratio of propylene oxide and catalyzer is 60:1, and the pressure-controlling in autoclave is 1.5MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 14
(1) method identical with embodiment 1 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 39.96 DEG C and 80kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5603, the molar content of propylene oxide is 0.4397) and send in autoclave as titanium-silicon molecular sieve TS-1 prepared by the step (1) of catalyzer, 90 DEG C of stirring reactions 1 hour after mixing.The mol ratio of propylene oxide and carbonic acid gas is 1:80, and the weight ratio of propylene oxide and catalyzer is 50:1, and the pressure-controlling in autoclave is 1.0MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 15
(1) method identical with embodiment 7 is adopted to prepare the titanium-silicon molecular sieve TS-1 containing template.
(2) propylene carbonate is prepared
By the azeotrope of propylene oxide and the methylene dichloride (binary azeotrope that the propylene oxide when 20.05 DEG C and 40kPa and methylene dichloride are formed, wherein, the molar content of methylene dichloride is 0.5699, the molar content of propylene oxide is 0.4301), the titanium-silicon molecular sieve TS-1 prepared of carbonic acid gas and the step (1) as catalyzer sends in autoclave, 110 DEG C of stirring reactions 3 hours after mixing.Wherein, the mol ratio of propylene oxide and carbonic acid gas is 1:1, and the weight ratio of propylene oxide and catalyzer is 20:1, and the pressure-controlling in autoclave is 0.6MPa.Then, filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 16
The method identical with embodiment 15 is adopted to prepare propylene carbonate, unlike, in step (2), the azeotrope of propylene oxide and methylene dichloride, the titanium-silicon molecular sieve TS-1 prepared as the step (1) of catalyzer and hydrogen peroxide (concentration is 30 % by weight) are sent in autoclave, 110 DEG C of stirring reactions 3 hours after mixing.Wherein, the mol ratio of hydrogen peroxide and propylene oxide is 0.01:1.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 17
The method identical with embodiment 16 is adopted to prepare propylene carbonate, unlike, in step (2), use dicumyl peroxide to replace hydrogen peroxide, all the other conditions are all identical.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 18
Prepare propylene carbonate according to the method for embodiment 15, the catalyzer used unlike step (2) is prepared as follows:
At room temperature (20 DEG C), 22.5 grams of tetraethyl orthosilicates are mixed with 7.0 grams of TPAOH, and add 59.8 grams of distilled water, at normal pressure and 60 DEG C, 1.0 hours are hydrolyzed after being uniformly mixed, obtain the hydrating solution of tetraethyl orthosilicate, add the solution be made up of 1.1 grams of tetrabutyl titanates and 5.0 grams of anhydrous isopropyl alcohols with vigorous stirring lentamente, gained mixture is stirred 3 hours at 75 DEG C, obtain clear colloid, this colloid is put into stainless steel sealed reactor, at the temperature of 170 DEG C, constant temperature places 3 days, obtain the mixture of crystallization product, this mixture is filtered, washes with water, and in 110 DEG C of dryings 60 minutes, in the lower 360 DEG C of roasting 3h of air atmosphere.
The titanium oxide content of the HTS containing template of preparation is 2.5 % by weight, and the content of template is 0.8 % by weight.All the other conditions are all identical.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Embodiment 19
The method identical with embodiment 15 is adopted to prepare propylene carbonate, unlike, in step (2), what use is that the azeotrope of propylene oxide and methylene dichloride is (in the binary azeotrope that 5.26 DEG C are formed with propylene oxide during 40kPa and methylene dichloride, wherein, the molar content of methylene dichloride is 0.5795, and the molar content of propylene oxide is 0.4205), all the other conditions are all identical.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Comparative example 3
The method identical with embodiment 15 step (2) is adopted to prepare propylene carbonate, unlike, in step (1), by the HTS containing template 500 DEG C of roastings 5 hours, thus obtain HTS (template content is 0), and this HTS is used as the catalyzer in step (2).
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Comparative example 4
The method identical with comparative example 3 is adopted to prepare propylene carbonate, unlike, in addition process, add template trolamine, the amount of the template added is identical with the template content in HTS in embodiment 15 simultaneously.
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Comparative example 5
The method identical with embodiment 15 is adopted to prepare propylene carbonate, unlike, in step (2), propylene oxide and methylene dichloride do not form azeotrope, directly pass into reaction unit respectively and react, and the consumption of the two is identical with embodiment 15;
Filtered by the mixture obtained, the composition of the liquid phase mixture obtained with gas chromatography determination, and calculate epoxypropane conversion rate and propylene carbonate selectivity, result is listed in table 2.
Table 2
| Numbering | The kind of catalyzer | Epoxypropane conversion rate (%) | Propylene 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 |
The result of table 1 and table 2 confirms, HTS containing template is used as the catalyzer being prepared propylene carbonate by propylene oxide by method of the present invention, and use the azeotrope of propylene oxide and solvent as raw material, high epoxypropane conversion rate and propylene carbonate selectivity can be obtained under lower temperature of reaction.Particularly deposit in case at dicumyl peroxide, not only increase epoxypropane conversion rate and propylene carbonate selectivity, and propylene carbonate selectivity can reach 98%.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
Claims (13)
1. a synthetic method for propylene carbonate, the method comprises: under cycloaddition reaction condition, and by the azeotrope of propylene oxide and solvent, carbonic acid gas and catalyst exposure, wherein, described catalyzer contains the HTS containing template.
2. synthetic method according to claim 1, wherein, described solvent is methylene dichloride.
3. synthetic method according to claim 2, wherein, the azeotrope of described propylene oxide and methylene dichloride is for being 5-50 DEG C in temperature, and pressure is the azeotrope formed under the condition of 40-100kPa.
4. according to the synthetic method in claim 1-3 described in any one, wherein, described containing in the HTS of template, the content of template is 0.1-25 % by weight.
5. according to the synthetic method in claim 1-3 described in any one, wherein, described template is one or more in quaternary ammonium hydroxide, fatty amine and aliphatics hydramine.
6. according to the synthetic method in claim 1-3 described in any one, wherein, described HTS be selected from the HTS with MFI structure, the HTS with MEL structure, have BEA structure HTS, have MWW structure HTS, have MOR structure HTS, have TUN structure HTS and have in the HTS of two-dimentional hexagonal structure one or more.
7. synthetic method according to claim 6, wherein, described HTS is the hollow HTS with MFI structure, and the crystal grain of described hollow HTS is hollow structure, and the radical length of the chamber portion of this hollow structure is 5-300nm.
8. according to the synthetic method in claim 1-3 described in any one, wherein, described contact is carried out under the existence of superoxide, and the mol ratio of described superoxide and propylene oxide is 0.0001-0.1:1.
9. according to the synthetic method in claim 1-3 described in any one, wherein, the mol ratio of propylene oxide and carbonic acid gas is 1:0.1-100.
10. according to the synthetic method in claim 1-3 described in any one, wherein, described cycloaddition reaction is carry out under the condition of 10-160 DEG C in temperature.
11. according to the synthetic method in claim 1-3 described in any one, and wherein, the weight ratio of propylene oxide and described catalyzer is 1-100:1, and in gauge pressure, described cycloaddition reaction is carry out under the condition of 0-2.5MPa at pressure.
12. according to the synthetic method in claim 1-3 described in any one, and wherein, described propylene oxide is prepared as follows: in presence of methyl alcohol, is contacted by propylene with hydrogen peroxide with HTS, is separated and obtains propylene oxide.
13. synthetic method according to claim 12, wherein, the mol ratio of propylene, methyl alcohol and hydrogen peroxide is 1-5:5-20:1; The condition that propylene contacts with HTS with hydrogen peroxide comprises: temperature is 40-60 DEG C, and pressure is 0.1-1.5MPa, and the time is 0.2-1h, and the concentration of HTS is 0.002-0.1g/mL.
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