CN102807538A - Method for preparing propylene oxide - Google Patents
Method for preparing propylene oxide Download PDFInfo
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- CN102807538A CN102807538A CN2011101514511A CN201110151451A CN102807538A CN 102807538 A CN102807538 A CN 102807538A CN 2011101514511 A CN2011101514511 A CN 2011101514511A CN 201110151451 A CN201110151451 A CN 201110151451A CN 102807538 A CN102807538 A CN 102807538A
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Abstract
The invention discloses a method for preparing propylene oxide. The method comprises the step: in the presence of a catalyst and a first organic solvent, enabling propylene and organic peroxide to be subjected to a contact reaction, wherein the catalyst is a modified Ti-MCM (Mesoporous Molecular Sieve)-48 obtained by a contact reaction of a Ti-mcm-48 and an organosilicon compound under the silanization condition and in the presence of second organic solvent. According to the method for preparing propylene oxide, which is provided by the invention, the selectivity and the yield of propylene oxide can be improved.
Description
Technical field
The present invention relates to a kind of method for preparing propylene oxide.
Background technology
Propylene oxide (PO) is a kind of important organic chemical industry's midbody, is widely used in industries such as petrochemical complex, light industry, medicine, food and weaving, and demand increases day by day.At present, chlorohydrination and organo-peroxide oxidation style (being mainly the ethylbenzene hydroperoxide oxidation style) are the major techniques of industrial production propylene oxide, but the former is seriously polluted, and the latter will receive the restriction of the co-product market requirement.Calendar year 2001, SUMITOMO CHEMICAL chemical company discloses the novel process that the cumene hydroperoxide oxidation style prepares propylene oxide in patent US6512128, US6639085 and US6639086, and isopropyl benzene can recycle, avoided the generation of co-product.
The Halcon method epoxidation of propylene technological process of U.S. Arco company exploitation is to realize the organo-peroxide method propylene oxide production process (US3351635) of industrial applications the earliest, and the epoxidation catalyst of employing is homogeneous phase Mo catalyst based (US3507809, US3666777).The advantage of this type catalyzer is to be easy to preparation, stable performance, but has product and catalyst separating problem, and the selectivity of propylene oxide is not high.Later 1960s, Shell company begins to research and develop loading type Ti/SiO
2Catalyzer, this is the report the earliest (US3829392, US3923843, US4021454, US4367342) about the epoxidation of propylene heterogeneous catalyst.But because the silica supports specific surface area and the pore volume that are adopted are less, the charge capacity of titanium is difficult to improve, and activity of such catalysts is difficult for improving.2000, Arco company also disclosed the heterogeneous catalyst result of study of oneself in patent US6114552.They are with SiO
2Or the MCM-41 mesopore molecular sieve impregnated in TiCl
4Solution or two (acetylacetone based) metatitanic acid diisopropyl ester solution, it is catalyst based to be prepared into loading type Ti through steps such as super-dry, roasting, silylanizations then.But in propylene ring oxidation reaction, transformation efficiency and selectivity are all lower when being oxygenant with the ethylbenzene hydroperoxide with this type catalyst applications.
1994, people such as Corma adopted the Direct Water thermal synthesis method to prepare Ti-MCM-41 molecular sieve (Chem.Commun., 1994, (2): 147-148), and find that it shows good catalytic performance in the oxidizing reaction of macromole alkene.From then on, people begin mesoporous titanium-silicon molecular screen is applied to organo-peroxide method propylene ring oxidation reaction.2000, it was oxygenant that sumitomo chemical company discloses with the ethylbenzene hydroperoxide in patent CN1248579A and CN1250775A, and Ti-MCM-41 molecular sieve catalytic propylene ring oxidation reaction is produced the process of propylene oxide.2004, it was oxygenant that sumitomo chemical company discloses with the isopropyl benzene hydroperoxide in patent CN1500004A again, and the Ti-MCM-41 molecular sieve is the technology of Preparation of Catalyst propylene oxide.Though the Ti-MCM-41 mesoporous material has shown catalytic activity preferably in the organo-peroxide oxidation style prepares the reaction of propylene oxide; But because its structure is two dimension six side's straight hole roads; Active sites utilization ratio in the duct is lower, and the diffusion of macromolecular reactant in molecular sieve pore passage also is restricted.
1996, Zhang (Catal.Lett., 1996,38 (3-4): 261-265) and Morey (Micropor.Mater., 1996,6 (2): 99-104) wait and to have reported the synthetic of Ti-MCM-48 mesopore molecular sieve per capita.Same year, people such as Koyano (Chem.Commun., 1996, (2): 145-146) also adopt tetraethoxy and tetrabutyl titanate two step hydrolyzation method successfully to prepare Ti-MCM-48, and be applied to the macromole epoxidation Reaction of Alkenes.Compare with the MCM-41 series molecular sieve with two dimension six side's straight hole roads, MCM-48 has the continuous three-dimensional cubic structure that interweaves, and structural symmetry is very high, and its duct is very beneficial for the diffusion of reactant and product, and is difficult for obstruction.Therefore, under identical condition, Ti-MCM-48 very likely shows the better catalytic performance than Ti-MCM-41.Known can be in the presence of Ti-MCM-41, react through propylene and organo-peroxide and to prepare propylene oxide.But in the presence of Ti-MCM-41, propylene and organo-peroxide react the yield and the selectivity that prepare propylene oxide all to be needed to improve.Because Ti-MCM-48 has the continuous three-dimensional cubic structure that interweaves; Structural symmetry is very high; Its duct is very beneficial for the diffusion of reactant and product, and is difficult for stopping up, therefore; Under identical condition, adopt Ti-MCM-48 catalyzing propone and organo-peroxide to react to prepare propylene oxide very likely to show better catalytic performance than Ti-MCM-41.But; Contriver of the present invention finds; Adopt Ti-MCM-48 mesopore molecular sieve catalyzing propone that this prior art for preparing obtains and organo-peroxide to react when preparing propylene oxide yield and compare with Ti-MCM-41 not only with selectivity and do not improve, also reduce to some extent on the contrary.
Summary of the invention
The technical problem that the present invention will solve is to react propylene oxide yield and the not high shortcoming of selectivity when preparing propylene oxide through propylene and organo-peroxide in the prior art, and the method for a kind of high yield and highly-selective preparation propylene oxide is provided.
Although reacting when preparing propylene oxide with adopting Ti-MCM-41 mesopore molecular sieve catalyzing propone and organo-peroxide to react to prepare propylene oxide, the Ti-MCM-48 mesopore molecular sieve catalyzing propone and the organo-peroxide that prepare in the employing prior art compare; The yield of propylene oxide and selectivity not only do not improve; Descend to some extent on the contrary; But; The inventor is surprised to find that; The Ti-MCM-48 molecular sieve is carried out after silylanization handles, when the Ti-MCM-48 molecular sieve of gained modification is used for propylene and organo-peroxide prepared in reaction propylene oxide, not only react the yield and the selectivity that can improve propylene oxide when preparing propylene oxide significantly than employing Ti-MCM-48 mesopore molecular sieve catalyzing propone and organo-peroxide; And, can improve the yield and the selectivity of propylene oxide significantly than adopting modification Ti-MCM-41 mesopore molecular sieve catalyzing propone and organo-peroxide behind Ti-MCM-41 and the silylanization to react when preparing propylene oxide.
The present invention provides a kind of method for preparing propylene oxide; This method is included in catalyzer and first organic solvent exists down; With propylene and organo-peroxide contact reacts; Said catalyzer is in the presence of the silylanization condition and second organic solvent, the modification Ti-MCM-48 molecular sieve that Ti-MCM-48 molecular sieve and silicoorganic compound contact reacts are obtained.
The invention has the beneficial effects as follows:
(1) with in the presence of unmodified Ti-MCM-48 molecular sieve; Propylene is prepared propylene oxide with the organo-peroxide contact reacts to be compared; When the Ti-MCM-48 molecular sieve of silylanization modification of the present invention is used for propylene and organo-peroxide prepared in reaction propylene oxide, can obviously improve the selectivity of the transformation efficiency and the propylene oxide of organo-peroxide, for example; See from embodiment 1 and Comparative Examples 1 result; Through silylanization, propylene oxide (PO) yield of modification Ti-MCM-48 molecular sieve improves 23.3%, and PO improves 18.4% to isopropyl benzene hydroperoxide (CHP) selectivity; See that from embodiment 2 and Comparative Examples 4 results handle through silylanization, the PO yield of modification Ti-MCM-48 molecular sieve improves 26.9%, PO improves 21.8% to the CHP selectivity.
(2) with prior art in the presence of the Ti-MCM-41 molecular sieve of Ti-MCM-41 molecular sieve and silylanization modification; Propylene is prepared propylene oxide with the organo-peroxide contact reacts to be compared; When the Ti-MCM-48 molecular sieve of silylanization modification of the present invention is used for propylene and organo-peroxide prepared in reaction propylene oxide; Can improve the selectivity of the transformation efficiency and the propylene oxide of organo-peroxide; Under the condition that keeps identical titanium content and catalyst levels, have higher propylene oxide yield and selectivity.For example, see that improve approximately 19.1% than the PO yield of Ti-MCM-41 molecular sieve through the modification Ti-MCM-48 molecular sieve behind the silylanization, PO improves about 16.5% to the CHP selectivity from embodiment 1 and Comparative Examples 3 results; See that from embodiment 1 and Comparative Examples 2 results improve approximately 6.5% than the PO yield through silylanization post-modification Ti-MCM-41 molecular sieve through silylanization post-modification Ti-MCM-48 molecular sieve, PO improves about 4.0% to the CHP selectivity.
(3) under a kind of preferable case of the present invention; The template of preparation Ti-MCM-48 molecular sieve is a composite mould plate agent; Except using conventional quaternary ammonium cation tensio-active agent; Can also use nonionogenic tenside, thereby can when reducing the pollution of quaternary ammonium cation amount of surfactant minimizing, keep the CHP transformation efficiency and the PO selectivity of modification Ti-MCM-48 molecular sieve like this environment.For example; See from embodiment 1 and embodiment 6 results; Adopting the PO yield rate through silylanization Ti-MCM-48 molecular sieve of single template among the embodiment 6 is 83.4%; PO is 96.2% to the CHP selectivity, compares with the Ti-MCM-48 molecular sieve of composite mould plate agent preparation among the embodiment 1, and PO yield and selectivity are suitable.
(4) under a kind of preferable case of the present invention, when the Ti-MCM-48 molecular sieve exists, be that oxygenant carries out propylene ring oxidation reaction when producing propylene oxide with the cumene hydroperoxide, this reaction yield can further improve, selectivity is better.For example; See from embodiment 1 and embodiment 7 results, adopt employed catalyzer among the embodiment 1 among the embodiment 7, with ethylbenzene hydroperoxide as oxygenant; The yield of PO is 73.6%; PO is 91.8% to the ethylbenzene hydroperoxide selectivity, and PO is 95.4% to the propylene selectivity, all is lower than embodiment 1.In addition,, avoided the generation of co-product, made the production of propylene oxide fully no longer receive the restriction of the co-product market requirement because isopropyl benzene can recycle.
Description of drawings
Fig. 1 is the X-ray diffractogram of 1 synthetic Ti-MCM-48 of embodiment molecular sieve.
Fig. 2 is the N of 1 synthetic Ti-MCM-48 of embodiment molecular sieve
2The adsorption isotherm line chart.
Fig. 3 is the pore size distribution curve figure of 1 synthetic Ti-MCM-48 of embodiment molecular sieve.
Fig. 4 is the ultraviolet-visible light spectrogram of 1 synthetic Ti-MCM-48 of embodiment molecular sieve.
Embodiment
According to the method for preparing propylene oxide of the present invention; This method is included in catalyzer and first organic solvent exists down; Make propylene and organo-peroxide contact reacts; Said catalyzer is in the presence of the silylanization condition and second organic solvent, the modification Ti-MCM-48 molecular sieve that Ti-MCM-48 molecular sieve and silicoorganic compound contact reacts are obtained.
According to the method for preparing propylene oxide according to the invention, wherein, propylene and organo-peroxide contact reacts temperature can be 50-120 ℃, are preferably 50-100 ℃, more preferably 70-90 ℃.Reaction pressure can be 0.5-6.0MPa, is preferably 0.5-4.0MPa, more preferably 0.7-3.0MPa.Reaction times can be 0.5-2.5 hour, is preferably 1-2 hour, more preferably 1.2-1.8 hour.
Propylene: first organic solvent: the mol ratio of organic hydroperoxide can be 2-30: 1-10: 1, be preferably 5-20: 1-5: 1.
The sieve catalyst consumption can be preferably 10%-30% for the 5%-40% of organo-peroxide weight.
According to the method for preparing propylene oxide of the present invention, wherein, preferred said organo-peroxide is an isopropyl benzene hydroperoxide.Adopt isopropyl benzene hydroperoxide as oxygenant, compare with other organo-peroxides, can obtain better effects, for example: propylene oxide is 100% to the selectivity of propylene; The yield of propylene oxide is also higher.
According to the method for preparing propylene oxide of the present invention; Wherein, Said first organic solvent can be the various organic solvents that can be used in preparing epoxypropane by epoxidation of propene; For example said first organic solvent can be selected from one or more in ethylbenzene, isopropyl benzene, Trimethylmethane and the hexanaphthene, preferred isopropyl benzene.
According to the method for preparing propylene oxide of the present invention, wherein, the consumption of said silicoorganic compound can be preferably 30%-90% for the 10%-100% of Ti-MCM-48 molecular sieve weight.The consumption of said second organic solvent can be 2-20 times of Ti-MCM-48 molecular sieve weight, is preferably 5-15 doubly.
According to the method for preparing propylene oxide of the present invention, wherein, said silicoorganic compound can be selected from the R that general formula is
1R
2R
3The halosilanes of SiX, general formula are [R
4R
5R
6Si]
2The silazane of NH, general formula are R
7R
8R
9Si [N
2C
3H
3] silyl imidazoles and general formula be (R
10)
3SiN (R
11)
2One or more of silylamine, R wherein
1, R
2And R
3Identical or different, be respectively C separately
1-C
4Saturated alkyl or phenyl; R
4, R
5And R
6Identical or different, be respectively C separately
1-C
4Alkyl, alkylhalide group or phenyl; R
7-R
11Be respectively C separately
1-C
3Saturated alkyl, preferred said silicoorganic compound are one or more in hexamethyldisilazane, silylamine, trimethylchlorosilane, the N-trimethyl-silyl-imidazole.
According to the method for preparing propylene oxide of the present invention, wherein, said second organic solvent can be identical or different with first organic solvent, can be selected from C
6-C
16Aromatic hydrocarbon or C
6-C
16In the saturated alkane one or more are preferably in toluene, benzene, hexanaphthene, the isopropyl benzene one or more, more preferably toluene, isopropyl benzene.
According to the method for preparing propylene oxide of the present invention, wherein, said Ti-MCM-48 molecular sieve and the catalytic temperature of silicoorganic compound are 50-350 ℃, are preferably 70-180 ℃.Time is 1-24 hour, is preferably 1-6 hour.
According to the present invention, when preparation modification Ti-MCM-48 molecular sieve, under the preferable case, also comprise and remove after Ti-MCM-48 molecular sieve and the silicoorganic compound contact reacts solvent in the products therefrom like second organic solvent.The method of removing said second organic solvent for example can be for carrying out solid-liquid separation and with solid drying, also can directly products therefrom after the contact reacts being carried out reduction vaporization.
Modification Ti-MCM-48 molecular sieve according to the present invention is made up of silicon-oxy tetrahedron and titanyl tetrahedron, has the adjustable three-dimensional cubic meso-hole structure in 2.0-4.0nm aperture, even aperture distribution, the higher (900-1500m of specific surface area
2/ g), the big (0.6-2.0cm of pore volume
3/ g).In the ultraviolet-visible spectrum of this modification Ti-MCM-48 molecular sieve; Wavelength has very strong absorption band between 210-230nm; Skeleton titanium species corresponding to four-coordination; Proof Ti species have entered into framework of molecular sieve, but not near skeleton titanium species content few (absorption band of non-skeleton titanium oxide is 340nm).
According to the method for preparing propylene oxide of the present invention; Wherein, Said Ti-MCM-48 molecular sieve can obtain through the whole bag of tricks well known in the art; For example can make by means commonly known in the art, under the preferable case, said Ti-MCM-48 molecular sieve makes through the method that may further comprise the steps:
A, under hydrolysis glue condition, template, alkali, silicon source, titanium source, water are hydrolyzed, obtain gel mixture;
B, under crystallization condition, after above-mentioned gel mixture crystallization, filter, drying obtains the Ti-MCM-48 molecular screen primary powder;
C, the Ti-MCM-48 molecular screen primary powder is removed template, obtain the Ti-MCM-48 molecular sieve; Wherein, said template contains quaternary ammonium cation tensio-active agent and nonionogenic tenside.
Thereby aforesaid method adopts quaternary ammonium cation tensio-active agent and nonionogenic tenside can when reducing the pollution of quaternary ammonium cation amount of surfactant minimizing to environment, keep the PO yield and the selectivity of modification Ti-MCM-48 molecular sieve as template.
The method of the above-mentioned Ti-MCM-48 of preparation molecular sieve relates generally to the improvement to template, so other steps and condition can adopt step well known in the art and condition to carry out.Under the preferable case, according to the method for preparing propylene oxide of the present invention, wherein, alkali described in the step a is that sodium hydroxide, general formula are (R
16)
4In the alkyl ammonium hydroxide of NOH one or more, wherein R
16Be C
1-C
4The straight or branched alkyl, be preferably C
1-C
3Straight chained alkyl, methyl more preferably.
Under the preferable case, said silicon source is that general formula is R
17R
18R
19R
20The alkoxyl silicone of Si, R
17-R
20Can be respectively C separately
1-C
4Straight chain alkoxyl group or branched alkoxy, be preferably methylsiloxane or ethylsiloxane.R
17-R
20Can be identical or different, preferred R
17-R
20Identical.
Under the preferable case, said titanium source can be organic titanium source and/or inorganic ti sources.The organic titanium source can in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate, tetrabutyl titanate, metatitanic acid four isobutylates, the diisopropoxy diacetyl acetone acid titanium one or more; Inorganic ti sources can be in titanous chloride, titanium tetrachloride, dichloro oxygen titanium, Titanium Nitrate, the titanium sulfate one or more.Be preferably the organic titanium source, more preferably one or more in tetraethyl titanate, titanium isopropylate, the tetrabutyl titanate.
According to the method for preparing propylene oxide of the present invention, under hydrolysis glue condition, template, alkali, silicon source, titanium source, water are hydrolyzed; The condition that obtains gel mixture does not have particular requirement, can carry out with reference to prior art, for example can for; Under 5-35 ℃ of condition; Template, the quaternary ammonium cation tensio-active agent that comprises aforementioned proportion and nonionogenic tenside and alkali are dissolved in deionized water, stirred 10-120 minute, obtain the alkaline solution of template.Under 5-35 ℃ of condition, in the alkaline solution of template, add the silicon source, stirred 0.5-1 hour.Then, under 5-35 ℃ of condition, in the mixing solutions in above-mentioned template and silicon source, add the titanium source, stirred 1-3 hour.
According to the method for preparing propylene oxide of the present invention, the present invention does not have particular requirement to said crystallization condition, can be the crystallization condition of the preparation Ti-MCM-48 molecular sieve of routine, and for example, the temperature of crystallization is 100-150 ℃; The time of crystallization is 24-96 hour.Those skilled in the art are known, and said crystallization is generally carried out in water heating kettle, repeats no more at this.Obtain containing the solid of Ti-MCM-48 molecular sieve composition and template after the crystallization.
According to the method for preparing propylene oxide of the present invention; Wherein said crystallization after-filtration, exsiccant condition do not have particular requirement; Can carry out with reference to prior art; For example, said crystallization after-filtration, exsiccant condition generally comprise, and the solid that will contain Ti-MCM-48 molecular sieve composition and template separates with mother liquor; To neutral, obtain the former powder of titanium-containing meso-porous molecular sieve Ti-MCM-48 with the solid of deionized water wash Ti-MCM-48 molecular sieve composition and template 70 ℃-120 ℃ air drying 3-10 hour.
According to the method for preparing propylene oxide of the present invention, wherein step c comprises the former powder removal of Ti-MCM-48 template, obtains the Ti-MCM-48 mesopore molecular sieve.The removal template can adopt any one in roasting method or the extracting process.Adopt roasting method comprise with the former powder of Ti-MCM-48 400 ℃-650 ℃ roasting 2-24 hour, be preferably 4-12 hour; Adopt extracting process to comprise the reflux extraction in extraction agent of the former powder of Ti-MCM-48, extraction temperature is 50 ℃-90 ℃, and the extraction time is 5-36 hour, is preferably 8-16 hour.Said extraction agent is acidifying methyl alcohol or acidifying ethanol.
According to the method for preparing propylene oxide of the present invention, wherein, the mol ratio of quaternary ammonium cation tensio-active agent and nonionogenic tenside is 2-40: 1, be preferably 4-10: 1.Among the present invention, when said nonionogenic tenside was polymkeric substance, the molar weight of said nonionogenic tenside calculated according to the weight-average molecular weight of polymkeric substance.
According to the method for preparing propylene oxide of the present invention, wherein, it is [NR that said template contains general formula
12R
13R
14R
15]
+X
-The quaternary ammonium cation tensio-active agent, R
12Represent C
12-C
30The straight or branched alkyl, be preferably C
12-C
20The straight or branched alkyl, C more preferably
16Alkyl; R
13, R
14And R
15Can be respectively C separately
1-C
4The straight or branched alkyl, preferably be respectively methyl separately, X is a halogen.The example of template can be preferably cetyl trimethylammonium bromide for cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, benzyltrimethylammonium bromide, docosyl dimethyl-brometo de amonio and analogue.Said nonionogenic tenside can or gather oxyethylene ether-gather propylene oxide ether-gather oxyethylene ether triblock copolymer for Soxylat A 25-7, preferably can be triton x-100, Triton X-10, Triton X-114, P123 (EO
20PO
70EO
20), F108 (EO
132PO
50EO
132) or F127 (EO
106PO
70EO
106) in one or more, triton x-100 more preferably.
According to the method for preparing propylene oxide of the present invention; Wherein, In Siliciumatom, the alkali among the step a: water: silicon source: the mol ratio of quaternary ammonium cation tensio-active agent can be 1.0-4.0: 200-600: 3-20: 1, be preferably 1.0-3.0: 200-300: 3-10: 1; The mol ratio of the titanium atom in the silicon source in Siliciumatom and the titanium source can be 15-1000: 1, be preferably 20-200: 1.
Further describe the present invention below in conjunction with embodiment.Scope of the present invention is not limited by these embodiment.
In following examples, the XRD of sample test is carried out on X ' the Pert MPD type x-ray powder diffraction instrument that Dutch Philips company produces; N
2The adsorption-desorption experiment is carried out on the ASAP2020-M+C type absorption appearance that U.S. Micromeritics company produces, and the sample specific surface area is calculated the BET method that adopts; Ultraviolet-visible spectrum (UV-Vis) experiment is carried out on Nicolet Evolution 600 ultraviolet-visible pectrophotometers that U.S. Thermo company produces.In the catalyst performance evaluation experiment; Employing is furnished with 3420 type gas chromatographs (north, Beijing divides sky general technical device ltd to produce) the assay products composition of HP-INNOWax capillary column and fid detector, and the organo-peroxide transformation efficiency is calculated by iodometric titrationiodimetry titration.
Among the present invention, adopt gc to carry out each analysis of forming in the system, carry out quantitatively all can carrying out, calculate the evaluation indexes such as yield and selectivity of transformation efficiency, the product of reactant on this basis with reference to prior art through proofreading and correct normalization method.
Among the present invention, the transformation efficiency calculation formula of organo-peroxide is following:
Propylene oxide (PO) is following to the optionally calculation formula of organo-peroxide:
The calculation formula of propylene oxide yield is following:
Y
Propylene oxide=S
Propylene oxide* X
Organo-peroxide
Propylene oxide (PO) is following to the optionally calculation formula of propylene:
Wherein, X is a transformation efficiency; S and S ' are selectivity; M is the quality of component; N is the molar weight of component; M wherein
0And n
0Represent quality and molar weight that component reaction is preceding respectively.
(1) preparation of Ti-MCM-48 molecular sieve
With the 9.95g cetyl trimethylammonium bromide, 3.79g triton x-100 and 27.8g concentration are that tetramethylammonium hydroxide aqueous solution and the 300ml deionized water of 25 weight % mixes, and stir 1 hour down for 20 ℃ in room temperature; The 43.5g tetraethoxy is dropwise added in the above-mentioned solution, stirred 1 hour; The 1.7g tetrabutyl titanate is dropwise added in the above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 135 ℃ of hydrothermal crystallizings 24 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, with the deionized water wash solid product to neutrality, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-48 mesopore molecular sieve then.
(2) modification of Ti-MCM-48 molecular sieve
The above-mentioned Ti-MCM-48 mesopore molecular sieve that obtains of 10.0g is mixed with 6.0g hexamethyldisilazane and 80.0g toluene, and 130 ℃ of reflux are after 2 hours, and the remaining liquid of evaporated in vacuo under uniform temp obtains modification Ti-MCM-48 molecular sieve.This molecular sieve specific surface area is 1152m
2/ g; Its X-ray diffraction spectrogram (XRD) is as shown in Figure 1,110 spacing d
110Be 3.5nm; Its N
2The adsorption isotherm line chart is as shown in Figure 2, and pore size distribution curve figure is as shown in Figure 3, and mean pore size is 2.4nm, and pore volume is 0.8cm
3/ g; Its ultraviolet-visible light spectrogram is as shown in Figure 4, and titanium species mainly is present on the framework of molecular sieve with the four-coordination form.
(3) propylene oxide (PO) is synthetic
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g reacts.Temperature of reaction is 70 ℃, and reaction pressure is 2.0MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.5 hours.Reaction result is seen table 1.
Comparative Examples 1
According to the method synthesizing epoxypropane (PO) of embodiment 1, different is, does not comprise step (2), and promptly the Ti-MCM-48 molecular sieve is through silylanization and directly be not used for the synthetic of propylene oxide, and reaction result is seen table 1.
Comparative Examples 2
(1) preparation of Ti-MCM-41 molecular sieve
With 24.0g cetyl trimethylammonium bromide and 24.3g concentration is that tetramethylammonium hydroxide aqueous solution and the 90ml deionized water of 25 weight % mixes, and stirs 30 minutes down for 20 ℃ in room temperature; In this mixture, add 30.4g methyl silicate and 1.4g titanium isopropylate, stir 5 hours after-filtration, be neutral with deionized water wash solid product to washings.70 ℃ of drying under reduced pressure solid products 5 hours, obtained the Ti-MCM-41 mesopore molecular sieve in 8 hours 530 ℃ of roastings then.
(2) modification of Ti-MCM-41 molecular sieve
The above-mentioned Ti-MCM-41 mesopore molecular sieve that obtains of 10.0g is mixed with 6.0g hexamethyldisilazane and 80.0g toluene, and 130 ℃ of reflux are after 2 hours, and the remaining liquid of evaporated in vacuo under uniform temp obtains modification Ti-MCM-41 molecular sieve.This catalyzer has typical MCM-41 meso-hole structure, and specific surface area is 1084m
2/ g, mean pore size is 3.1nm, pore volume is 0.8cm
3/ g.
(3) propylene oxide (PO) is synthetic
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-41 molecular sieve 2.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g reacts.Temperature of reaction is 70 ℃, and reaction pressure is 2.0MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.5 hours.Reaction result is seen table 1.
Comparative Examples 3
According to the method synthesizing epoxypropane (PO) of Comparative Examples 2, different is, does not comprise step (2), and promptly the Ti-MCM-41 molecular sieve is through silylanization and directly be not used for the synthetic of propylene oxide, and reaction result is seen table 1.
(1) preparation of Ti-MCM-48 molecular sieve
With the 26.3g cetyl trimethylammonium bromide, 10.5gP123 (EO
20PO
70EO
20) mix with 3.8g sodium hydroxide and 280ml deionized water, stirred 1 hour down at 5-35 ℃; The 31.8g methyl silicate is dropwise added in the above-mentioned solution, stirred 1 hour; The 1.4g titanium isopropylate is dropwise added above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 110 ℃ of hydrothermal crystallizings 72 hours.Hydro-thermal reaction is separated solid product after finishing with mother liquor, with deionized water that the solid product washing is extremely neutral, obtains the former powder of Ti-MCM-48 in 5 hours at 110 ℃ air dryings.The former powder of the Ti-MCM-48 of 20.0g is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with the concentrated hydrochloric acid volume ratio), 80 ℃ of reflux extractions 18 hours, then through filtering, wash, obtaining the Ti-MCM-48 mesopore molecular sieve in 3 hours 100 ℃ of vacuum-dryings.
(2) modification of Ti-MCM-48 molecular sieve
The 10.0g mesopore molecular sieve is mixed with 9.0gN-trimethyl-silyl-imidazole and 100.0g isopropyl benzene, and 200 ℃ of reflux are after 1 hour, and the remaining liquid of evaporated in vacuo under uniform temp obtains modification Ti-MCM-48 molecular sieve.This modification Ti-MCM-48 molecular sieve specific surface area is 1136m
2/ g, 110 spacing d
110Be 3.7nm, mean pore size is 2.6nm, and pore volume is 0.7cm
3/ g; Its X-ray diffraction spectrogram, N
2Adsorption isotherm line chart, pore size distribution curve figure and ultraviolet-visible light spectrogram all with embodiment 1 in the sample chromatogram characteristic consistent.
(3) propylene oxide (PO) is synthetic
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 6.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, ethylbenzene 20.17g and propylene 165.8g reacts.Temperature of reaction is 80 ℃, and reaction pressure is 0.7MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.8 hours.Reaction result is seen table 1.
Comparative Examples 4
According to the method synthesizing epoxypropane (PO) of embodiment 2, different is, does not comprise step (2), and promptly the Ti-MCM-48 molecular sieve is through silylanization and directly be not used for the synthetic of propylene oxide, and reaction result is seen table 1.
Embodiment 3
(1) preparation of Ti-MCM-48 molecular sieve
With the 4.06g cetyl trimethylammonium bromide, 2.99g Triton X-114 mixes with 3.8g sodium hydroxide and 280ml deionized water, stirs 1 hour down at 5-35 ℃; The 31.8g methyl silicate is dropwise added in the above-mentioned solution, stirred 1 hour; The 1.1g tetraethyl titanate is dropwise added in the above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 110 ℃ of hydrothermal crystallizings 72 hours.Hydro-thermal reaction is separated solid product after finishing with mother liquor, with deionized water that the solid product washing is extremely neutral, obtains the former powder of Ti-MCM-48 in 5 hours at 110 ℃ air dryings.The former powder of the Ti-MCM-48 of 20.0g is mixed with 200ml acidifying ethanol (ethanol is 20: 1 with the concentrated hydrochloric acid volume ratio), 80 ℃ of reflux extractions 18 hours, then through filtering, wash, obtaining the Ti-MCM-48 mesopore molecular sieve in 3 hours 100 ℃ of vacuum-dryings.
(2) modification of Ti-MCM-48 molecular sieve
The 10.0g mesopore molecular sieve is mixed with 3.0g silylamine and 50.0g hexanaphthene, and 90 ℃ of reflux are after 6 hours, and the remaining liquid of evaporated in vacuo obtains the Ti-MCM-48 molecular sieve under uniform temp.This molecular sieve specific surface area is 1161m
2/ g, 110 spacing d
110Be 3.8nm, mean pore size is 2.7nm, and pore volume is 0.8cm
3/ g; Its X-ray diffraction spectrogram, pore size distribution curve figure and ultraviolet-visible light spectrogram all with embodiment 1 in the sample chromatogram characteristic consistent.
(3) propylene oxide (PO) is synthetic
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 9.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, hexanaphthene 80.0g and propylene 41.47g reacts.Temperature of reaction is 90 ℃, and reaction pressure is 3.0MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.2 hours.Reaction result is seen table 1.
According to the method synthesizing epoxypropane (PO) of embodiment 1, different is that step (3) is changed as follows:
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide 30.0g, isopropyl benzene 70.0g and propylene 82.9g reacts.Temperature of reaction is 50 ℃, and reaction pressure is 0.7MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.5 hours.Reaction result is seen table 1.
According to the method synthesizing epoxypropane (PO) of embodiment 1, different is that step (3) is changed as follows:
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide 30.0g, isopropyl benzene 70.0g and propylene 82.9g reacts.Temperature of reaction is 120 ℃, and reaction pressure is 3.0MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.5 hours.Reaction result is seen table 1.
(1) preparation of Ti-MCM-48 molecular sieve
The 28.0g cetyl trimethylammonium bromide is mixed with TMAH and the 300ml deionized water of 27.8g 25%, stirred 1 hour down at 5-35 ℃; The 43.2g tetraethoxy is dropwise added above-mentioned solution, stirred 1 hour; The 1.7g tetrabutyl titanate is dropwise added in the above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 135 ℃ of hydrothermal crystallizings 24 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, with the deionized water wash solid product to neutrality, 110 ℃ air dryings 5 hours; 550 ℃ of roastings 6 hours, obtain the Ti-MCM-48 mesopore molecular sieve then.
(2) modification of Ti-MCM-48 molecular sieve
The 10.0g mesopore molecular sieve is mixed with 6.0g hexamethyldisilazane and 80.0g toluene, and 120 ℃ of reflux are after 2 hours, and the remaining liquid of evaporated in vacuo obtains the Ti-MCM-48 molecular sieve under uniform temp.This molecular sieve specific surface area is 1098m
2/ g, 110 spacing d
110Be 3.4nm, mean pore size is 2.3nm, and pore volume is 0.8cm
3/ g; Its X-ray diffraction spectrogram, pore size distribution curve figure and ultraviolet-visible light spectrogram all with embodiment 1 in the sample chromatogram characteristic consistent.
(3) propylene oxide (PO) is synthetic
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g reacts.Temperature of reaction is 70 ℃, and reaction pressure is 2.0MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.5 hours.Reaction result is seen table 1.
Embodiment 7
According to the method synthesizing epoxypropane (PO) of embodiment 1, different is that step (3) is changed as follows:
In the autoclave of induction stirring is housed, adding above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, ethylbenzene hydroperoxide 27.6g, ethylbenzene 64.4g and propylene 82.9g reacts.Temperature of reaction is 70 ℃, and reaction pressure is 2.0MPa, and stirring velocity is 300 rev/mins, and the reaction times is 1.5 hours.Reaction result is seen table 1.
Table 1
Can find out from table 1; Although comparing when being used for that through the Ti-MCM-48 molecular sieve of silylanization propylene prepared propylene oxide with the organo-peroxide contact reacts in the Ti-MCM-41 of silylanization modification and the Comparative Examples 1 in the Comparative Examples 3; PO yield and selectivity difference high 4.2% and 1.9%; But; The Ti-MCM-41 through passing through silylanization in the Ti-MCM-41 of silylanization and the Comparative Examples 3 through in the Ti-MCM-48 of silylanization and the Comparative Examples 2 from embodiment 1 compares when being used for that propylene prepared propylene oxide with the organo-peroxide contact reacts, and the PO yield has improved 6.5%, 19.1% respectively, and the PO selectivity has improved 4.0%, 16.5% respectively.In addition; Embodiment 1 is compared with Comparative Examples 1; Embodiment 2 compares with Comparative Examples 4, no matter is embodiment 1 or embodiment 2, when the Ti-MCM-48 molecular sieve is used for that propylene and organo-peroxide contact reacts prepared propylene oxide after silylanization is handled; It is about 25% that the PO yield improves, and the PO selectivity improves about 20%.See from embodiment 1 and the result of embodiment 6; When adopting compound masterplate agent of the present invention and the Ti-MCM-48 molecular sieve that adopts traditional single mode version agent to prepare gained to be used for that propylene and organo-peroxide contact reacts prepared propylene oxide, PO yield and selectivity are suitable.See from embodiment 7; The PO yield is merely 73.6% when adopting ethylbenzene hydroperoxide to be used for that as oxygenant propylene and organo-peroxide contact reacts prepared propylene oxide; PO is merely 95.4% to the selectivity of propylene; And embodiment 1 employing CHP is 83.5% as oxygenant PO yield, and PO is 100% to the selectivity of propylene.
Claims (12)
1. method for preparing propylene oxide; This method is included in catalyzer and first organic solvent exists down; Make propylene and organo-peroxide contact reacts; It is characterized in that said catalyzer is in the presence of the silylanization condition and second organic solvent, the modification Ti-MCM-48 molecular sieve that Ti-MCM-48 molecular sieve and silicoorganic compound contact reacts are obtained.
2. method according to claim 1, wherein, the catalytic temperature of propylene and organo-peroxide is 50-120 ℃, and pressure is 0.5-6.0MPa, and the time is 0.5-2.5 hour; Propylene: first organic solvent: the mol ratio of organo-peroxide is 2-30: 1-10: 1; Catalyst consumption is the 5%-40% of organo-peroxide weight.
3. method according to claim 1 and 2, wherein, said organo-peroxide is an isopropyl benzene hydroperoxide.
4. method according to claim 1 and 2, wherein, said first organic solvent is one or more in ethylbenzene, isopropyl benzene, Trimethylmethane and the hexanaphthene, preferred isopropyl benzene.
5. method according to claim 1, wherein, the consumption of said silicoorganic compound is the 10%-100% of Ti-MCM-48 molecular sieve weight, is preferably 30%-90%.
6. according to claim 1 or 5 described methods, wherein, it is R that said silicoorganic compound are selected from general formula
1R
2R
3The halosilanes of SiX, general formula are [R
4R
5R
6Si]
2The silazane of NH, general formula are R
7R
8R
9Si [N
2C
3H
3] silyl imidazoles and general formula be (R
10)
3SiN (R
11)
2One or more of silylamine, R wherein
1, R
2And R
3Identical or different, be respectively C separately
1-C
4Saturated alkyl or phenyl; R
4, R
5And R
6Identical or different, be respectively C separately
1-C
4Alkyl, alkylhalide group or phenyl; R
7-R
11Be respectively C separately
1-C
3Saturated alkyl, preferred said silicoorganic compound are one or more in hexamethyldisilazane, silylamine, trimethylchlorosilane, the N-trimethyl-silyl-imidazole.
7. method according to claim 1, wherein, said second organic solvent is selected from C
6-C
16Alkane, naphthenic hydrocarbon and aromatic hydrocarbon in one or more, be preferably in toluene, benzene, hexanaphthene, the isopropyl benzene one or more.
8. method according to claim 1, wherein, said Ti-MCM-48 molecular sieve and the catalytic condition of silicoorganic compound comprise that temperature is 50-350 ℃, are preferably 70-180 ℃; Time is 1-24 hour, is preferably 1-6 hour.
9. method according to claim 1, wherein, said Ti-MCM-48 molecular sieve makes through following method: under hydrolysis glue condition, template, alkali, silicon source, titanium source, water are hydrolyzed, obtain gel mixture; Under crystallization condition, after above-mentioned gel mixture crystallization, filtration, drying obtain the Ti-MCM-48 molecular screen primary powder; Remove the template in the Ti-MCM-48 molecular screen primary powder, wherein, said template contains quaternary ammonium cation tensio-active agent and nonionogenic tenside.
10. method according to claim 9, wherein, the mol ratio of said quaternary ammonium cation tensio-active agent and nonionogenic tenside is 2-40: 1.
11. according to claim 9 or 10 described methods, wherein, the general formula of said quaternary ammonium cation tensio-active agent is [NR
12R
13R
14R
15]
+X
-, R
12Represent C
12-C
30The straight or branched alkyl, R
13, R
14And R
15Be respectively C separately
1-C
4The straight or branched alkyl, X is a halogen, is preferably cetyl trimethylammonium bromide; Said nonionogenic tenside is Soxylat A 25-7 or gathers oxyethylene ether-gather propylene oxide ether-gather oxyethylene ether triblock copolymer, is preferably triton x-100, Triton X-10, Triton X-114, EO
20PO
70EO
20, EO
132PO
50EO
132Or EO
106PO
70EO
106In one or more.
12. method according to claim 9, wherein, in Siliciumatom, alkali: water: silicon source: the mol ratio of template is 1.0-4.0: 200-600: 3-20: 1; The mol ratio of the titanium atom in Siliciumatom in the silicon source and the titanium source is 15-1000: 1.
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