CN102807538B - Method for preparing propylene oxide - Google Patents
Method for preparing propylene oxide Download PDFInfo
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- CN102807538B CN102807538B CN201110151451.1A CN201110151451A CN102807538B CN 102807538 B CN102807538 B CN 102807538B CN 201110151451 A CN201110151451 A CN 201110151451A CN 102807538 B CN102807538 B CN 102807538B
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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 of preparing propylene oxide.
Background technology
Propylene oxide (PO) is a kind of important organic chemical industry's intermediate, is widely used in the 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 ethylbenzene hydroperoxide oxidation style) are the major techniques of industrial production propylene oxide, but the former is seriously polluted, and the latter will be subject to the restriction of the joint product market requirement.Calendar year 2001, SUMITOMO CHEMICAL chemical company discloses the novel process that cumene hydroperoxide oxidation style is prepared propylene oxide in patent US6512128, US6639085 and US6639086, and isopropyl benzene can recycle, avoided the generation of joint product.
The Halcon method epoxidation of propylene technological process of Arco company of U.S. exploitation is to realize the earliest the organo-peroxide method propylene oxide production process (US3351635) of industrial applications, and the epoxidation catalyst of employing is homogeneous phase Mo catalyst based (US3507809, US3666777).The advantage of this class 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 starts to research and develop loading type Ti/SiO
2catalyzer, this is the report the earliest (US3829392, US3923843, US4021454, US4367342) about epoxidation of propylene heterogeneous catalyst.But because adopted silica supports specific surface area and pore volume are less, the charge capacity of titanium is difficult to improve, and the activity of catalyzer is difficult for improving.2000, Arco company also disclosed the heterogeneous catalyst result of study of oneself in patent US6114552.They are by SiO
2or MCM-41 mesopore molecular sieve impregnated in TiCl
4solution or two (acetylacetone based) metatitanic acid diisopropyl ester solution, is then prepared into loading type Ti through steps such as super-dry, roasting, silanizations catalyst based.But this class catalyzer is applied to propylene ring oxidation reaction, and during taking ethylbenzene hydroperoxide as oxygenant, transformation efficiency and selectivity are all lower.
1994, the people such as Corma adopt Direct Hydrothermal 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 start mesoporous titanium-silicon molecular screen to be applied to organo-peroxide method propylene ring oxidation reaction.2000, sumitomo chemical company disclosed taking ethylbenzene hydroperoxide as oxygenant in patent CN1248579A and CN1250775A, and Ti-MCM-41 molecular sieve catalytic propylene ring oxidation reaction is produced the process of propylene oxide.2004, sumitomo chemical company disclosed taking isopropyl benzene hydroperoxide as oxygenant again in patent CN1500004A, and Ti-MCM-41 molecular sieve is the technique that catalyzer is prepared propylene oxide.Although Ti-MCM-41 mesoporous material has shown good catalytic activity in organo-peroxide oxidation style is prepared the reaction of propylene oxide, but because its structure is two-dimentional six side's straight hole roads, active sites utilization ratio in duct is lower, and the diffusion of macromolecular reactant in molecular sieve pore passage is also restricted.
1996, Zhang (Catal.Lett., 1996,38 (3-4): 261-265) and Morey (Micropor.Mater., 1996,6 (2): 99-104) etc. reported per capita the synthetic of Ti-MCM-48 mesopore molecular sieve.Same year, the 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 are applied to the epoxidation reaction of macromole alkene.Compared with having the MCM-41 Series Molecules sieve in two-dimentional 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 stopping up.Therefore,, under identical condition, Ti-MCM-48 very likely shows the better catalytic performance than Ti-MCM-41.Knownly can, under the existence of Ti-MCM-41, react to prepare propylene oxide with organo-peroxide by propylene.But under Ti-MCM-41 exists, propylene reacts to prepare propylene oxide yield and selectivity with organo-peroxide all need raising.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 be difficult for stopping up, therefore, under identical condition, adopt Ti-MCM-48 catalyzing propone to react to prepare propylene oxide with organo-peroxide and very likely show the better catalytic performance than Ti-MCM-41.But, the present inventor finds, while adopting Ti-MCM-48 mesopore molecular sieve catalyzing propone that this prior art prepares to react to prepare propylene oxide with organo-peroxide, yield does not only improve compared with Ti-MCM-41 with selectivity, also decreases on the contrary.
Summary of the invention
The technical problem to be solved in the present invention is propylene oxide yield and the not high shortcoming of selectivity while reacting to prepare propylene oxide with organo-peroxide by propylene in prior art, provides a kind of high yield and highly selective to prepare the method for propylene oxide.
Although compared with reacting to prepare propylene oxide with employing Ti-MCM-41 mesopore molecular sieve catalyzing propone with organo-peroxide when the Ti-MCM-48 mesopore molecular sieve catalyzing propone of preparing in employing prior art reacts to prepare propylene oxide with organo-peroxide, yield and the selectivity of propylene oxide not only do not improve, decline to some extent on the contrary, but, the inventor is surprised to find that, Ti-MCM-48 molecular sieve is carried out after silanization processing, the Ti-MCM-48 molecular sieve of gained modification reacts with organo-peroxide while preparing propylene oxide for propylene, while not only reacting to prepare propylene oxide with organo-peroxide than employing Ti-MCM-48 mesopore molecular sieve catalyzing propone, can improve significantly yield and the selectivity of propylene oxide, and when adopting modification Ti-MCM-41 mesopore molecular sieve catalyzing propone after Ti-MCM-41 and silanization to react to prepare propylene oxide with organo-peroxide, can improve significantly yield and the selectivity of propylene oxide.
The invention provides a kind of method of preparing propylene oxide, the method is included under catalyzer and the existence of the first organic solvent, by propylene and organo-peroxide contact reacts, described catalyzer is under silanization condition and the second organic solvent exist, 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 under unmodified Ti-MCM-48 molecular sieve existence, compared with propylene is prepared to propylene oxide with organo-peroxide contact reacts, the Ti-MCM-48 molecular sieve of silanization modification of the present invention reacts with organo-peroxide while preparing propylene oxide for propylene, can obviously improve the selectivity of transformation efficiency and the propylene oxide of organo-peroxide, for example, from embodiment 1 and comparative example 1 result, through silanization, propylene oxide (PO) yield of modification Ti-MCM-48 molecular sieve improves 23.3%, PO improves 18.4% to isopropyl benzene hydroperoxide (CHP) selectivity, from embodiment 2 and comparative example 4 results, through silanization processing, the PO yield of modification Ti-MCM-48 molecular sieve improves 26.9%, PO CHP selectivity is improved to 21.8%.
(2) with prior art under the Ti-MCM-41 molecular sieve of Ti-MCM-41 molecular sieve and silanization modification exists, compared with propylene is prepared to propylene oxide with organo-peroxide contact reacts, the Ti-MCM-48 molecular sieve of silanization modification of the present invention reacts with organo-peroxide while preparing propylene oxide for propylene, can improve the selectivity of transformation efficiency and the propylene oxide of organo-peroxide, keeping, under the condition of identical titanium content and catalyst levels, thering is higher propylene oxide yield and selectivity.For example, from embodiment 1 and comparative example 3 results, the modification Ti-MCM-48 molecular sieve after silanization improves approximately 19.1% than the PO yield of Ti-MCM-41 molecular sieve, and PO improves approximately 16.5% to CHP selectivity; From embodiment 1 and comparative example 2 results, improve approximately 6.5% through silanization post-modification Ti-MCM-48 molecular sieve than through the PO yield of silanization post-modification Ti-MCM-41 molecular sieve, PO improves approximately 4.0% to CHP selectivity.
(3) under a kind of preferable case of the present invention, the template of preparation Ti-MCM-48 molecular sieve is composite mould plate agent, except using conventional quaternary ammonium cation tensio-active agent, can also use nonionogenic tenside, can, when thereby the consumption that reduces quaternary ammonium cation tensio-active agent reduces the pollution of environment, keep CHP transformation efficiency and the PO selectivity of modification Ti-MCM-48 molecular sieve like this.For example, from embodiment 1 and embodiment 6 results, in embodiment 6, adopting the PO yield rate through silanization Ti-MCM-48 molecular sieve of single template is 83.4%, PO is 96.2% to CHP selectivity, compared with the Ti-MCM-48 molecular sieve of preparing with composite mould plate agent in embodiment 1, PO yield and selectivity are suitable.
(4), under a kind of preferable case of the present invention, in the time that Ti-MCM-48 molecular sieve exists, carry out propylene ring oxidation reaction production propylene oxide during taking cumene hydroperoxide as oxygenant, this reaction yield can further improve, selectivity is better.For example, from embodiment 1 and embodiment 7 results, in embodiment 7, adopt the catalyzer using in embodiment 1, using ethylbenzene hydroperoxide as oxygenant, the yield of PO is 73.6%, PO is that 91.8%, PO is 95.4% to Propylene Selectivity to ethylbenzene hydroperoxide selectivity, all lower than embodiment 1.In addition, because isopropyl benzene can recycle, avoided the generation of joint product, made the production of propylene oxide completely no longer be subject to the restriction of the joint product market requirement.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the Ti-MCM-48 molecular sieve of embodiment 1 synthesized.
Fig. 2 is the N of the Ti-MCM-48 molecular sieve of embodiment 1 synthesized
2adsorption isotherm line chart.
Fig. 3 is the pore size distribution curve figure of the Ti-MCM-48 molecular sieve of embodiment 1 synthesized.
Fig. 4 is ultraviolet-visible ray spectrogram of the Ti-MCM-48 molecular sieve of embodiment 1 synthesized.
Embodiment
According to the method for preparing propylene oxide of the present invention, the method is included under catalyzer and the existence of the first organic solvent, make propylene and organo-peroxide contact reacts, described catalyzer is under silanization condition and the second organic solvent exist, 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 of the present invention, wherein, propylene and organo-peroxide contact reacts temperature can be 50-120 DEG C, are preferably 50-100 DEG C, more preferably 70-90 DEG C.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: the first organic solvent: the mol ratio of organic hydroperoxide can be 2-30: 1-10: 1, be preferably 5-20: 1-5: 1.
Molecular sieve catalyst consumption can be the 5%-40% of organo-peroxide weight, is preferably 10%-30%.
According to the method for preparing propylene oxide of the present invention, wherein, preferred described organo-peroxide is isopropyl benzene hydroperoxide.Adopt isopropyl benzene hydroperoxide as oxygenant, compared 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, described the first organic solvent can be the various organic solvents that can be used in preparing epoxypropane by epoxidation of propene, for example described the first organic solvent can be selected from one or more in ethylbenzene, isopropyl benzene, Trimethylmethane and hexanaphthene, preferably isopropyl benzene.
According to the method for preparing propylene oxide of the present invention, wherein, the consumption of described silicoorganic compound can be the 10%-100% of Ti-MCM-48 molecular sieve weight, is preferably 30%-90%.The consumption of described the 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, described 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, wherein R
1, R
2and R
3identical or different, be respectively separately C
1-C
4saturated alkyl or phenyl; R
4, R
5and R
6identical or different, be respectively separately C
1-C
4alkyl, alkylhalide group or phenyl; R
7-R
11be respectively separately C
1-C
3saturated alkyl, preferred described silicoorganic compound are one or more in hexamethyldisilazane, silylamine, trimethylchlorosilane, N-trimethyl-silyl-imidazole.
According to the method for preparing propylene oxide of the present invention, wherein, described the second organic solvent can be identical or different with the first organic solvent, can be selected from C
6-C
16aromatic hydrocarbon or C
6-C
16one or more in saturated alkane, are preferably one or more in toluene, benzene, hexanaphthene, isopropyl benzene, more preferably toluene, isopropyl benzene.
According to the method for preparing propylene oxide of the present invention, wherein, described Ti-MCM-48 molecular sieve and the catalytic temperature of silicoorganic compound are 50-350 DEG C, are preferably 70-180 DEG C.Time is 1-24 hour, is preferably 1-6 hour.
According to the present invention, in the time of preparation modification Ti-MCM-48 molecular sieve, under preferable case, also comprise and remove after Ti-MCM-48 molecular sieve and silicoorganic compound contact reacts the solvent in products therefrom as the second organic solvent.The method of removing described the second organic solvent for example can be for carrying out solid-liquid separation and by solid drying, also can directly products therefrom after contact reacts being carried out to 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 large (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, corresponding to the skeleton titanium species of four-coordination, prove that Ti species have entered into framework of molecular sieve, but not near skeleton titanium species content few (absorption band of non-skeleton titanium dioxide is 340nm).
According to the method for preparing propylene oxide of the present invention, wherein, described Ti-MCM-48 molecular sieve can obtain by the whole bag of tricks well known in the art, for example can make by means commonly known in the art, under preferable case, described Ti-MCM-48 molecular sieve makes by the method comprising the following steps:
A, under hydrolysis glue condition, template, alkali, silicon source, titanium source, water are hydrolyzed, obtain gel mixture;
B, under crystallization condition, by after above-mentioned gel mixture crystallization, filter, the dry Ti-MCM-48 molecular screen primary powder that obtains;
C, to Ti-MCM-48 molecular screen primary powder remove template, obtain Ti-MCM-48 molecular sieve; Wherein, described template contains quaternary ammonium cation tensio-active agent and nonionogenic tenside.
Aforesaid method adopts quaternary ammonium cation tensio-active agent and nonionogenic tenside can, when thereby the consumption that reduces quaternary ammonium cation tensio-active agent reduces the pollution of environment, keep 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, and therefore other steps and condition can adopt step well known in the art and condition to carry out.Under preferable case, according to the method for preparing propylene oxide of the present invention, wherein, alkali described in step a is that sodium hydroxide, general formula are (R
16)
4one or more in the alkyl ammonium hydroxide of NOH, wherein R
16for C
1-C
4straight or branched alkyl, be preferably C
1-C
3straight chained alkyl, more preferably methyl.
Under preferable case, described silicon source is that general formula is R
17r
18r
19r
20the alkoxyl silicone of Si, R
17-R
20can be respectively separately C
1-C
4straight chain alkoxyl group or branched alkoxy, be preferably methylsiloxane or ethylsiloxane.R
17-R
20can be identical or different, preferably R
17-R
20identical.
Under preferable case, described titanium source can be organic titanium source and/or inorganic ti sources.Organic titanium source can be in metatitanic acid tetramethyl ester, tetraethyl titanate, metatitanic acid orthocarbonate, titanium isopropylate, tetrabutyl titanate, tetrabutyl titanate, diisopropoxy diacetyl acetone acid titanium one or more; Inorganic ti sources can be one or more in titanous chloride, titanium tetrachloride, dichloro oxygen titanium, Titanium Nitrate, titanium sulfate.Be preferably organic titanium source, more preferably one or more in tetraethyl titanate, titanium isopropylate, 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 be, under 5-35 DEG C of condition, template, the quaternary ammonium cation tensio-active agent that comprises aforementioned proportion and nonionogenic tenside and alkali are dissolved in to deionized water, stir 10-120 minute, obtain the alkaline solution of template.Under 5-35 DEG C of condition, in the alkaline solution of template, add silicon source, stir 0.5-1 hour.Then, under 5-35 DEG C of condition, in the mixing solutions in above-mentioned template and silicon source, add titanium source, stir 1-3 hour.
According to the method for preparing propylene oxide of the present invention, the present invention without particular requirement, can be the crystallization condition of conventional preparation Ti-MCM-48 molecular sieve to described crystallization condition, and for example, the temperature of crystallization is 100-150 DEG C; The time of crystallization is 24-96 hour.Those skilled in the art are known, and described crystallization is generally carried out in water heating kettle, does not repeat them here.After crystallization, obtain the solid that contains Ti-MCM-48 molecular sieve composition and template.
According to the method for preparing propylene oxide of the present invention, after wherein said crystallization, filtration, dry condition do not have particular requirement, can carry out with reference to prior art, for example, after described crystallization, filtration, dry condition generally comprise, the solid that contains Ti-MCM-48 molecular sieve composition and template is separated with mother liquor, to neutral, obtain titanium-containing meso-porous molecular sieve Ti-MCM-48 former powder at the air drying 3-10 hour of 70 DEG C-120 DEG C with the solid of deionized water wash Ti-MCM-48 molecular sieve composition and template.
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 Ti-MCM-48 mesopore molecular sieve.Removal template can adopt any one in roasting method or extracting process.Adopt roasting method to comprise former Ti-MCM-48 powder at 400 DEG C of-650 DEG C of 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 DEG C-90 DEG C, and extraction time is 5-36 hour, is preferably 8-16 hour.Described 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.In the present invention, in the time that described nonionogenic tenside is polymkeric substance, the molar weight of described nonionogenic tenside calculates 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 described template contains general formula
12r
13r
14r
15]
+x
-quaternary ammonium cation tensio-active agent, R
12represent C
12-C
30straight or branched alkyl, be preferably C
12-C
20straight or branched alkyl, more preferably C
16alkyl; R
13, R
14and R
15can be respectively separately C
1-C
4straight or branched alkyl, be preferably respectively separately methyl, X is halogen.The example of template can be cetyl trimethylammonium bromide, Trimethyllaurylammonium bromide, benzyltrimethylammonium bromide, docosyl dimethyl brometo de amonio and analogue, is preferably cetyl trimethylammonium bromide.Described nonionogenic tenside can be Soxylat A 25-7 or Pluronic F-127 ether-poly-propylene oxide ether-Pluronic F-127 ether triblock copolymer, can be preferably 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, more preferably triton x-100.
According to the method for preparing propylene oxide of the present invention, wherein, in Siliciumatom, the alkali in 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 silicon source in Siliciumatom and 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, on X ' the Pert MPD type x-ray powder diffraction instrument that the XRD of sample test is produced in Dutch Philips company, carry out; N
2on the ASAP2020-M+C type adsorption instrument that adsorption-desorption experiment is produced in Micromeritics company of the U.S., carry out, sample specific surface area is calculated the BET method that adopts; On Nicolet Evolution 600 ultraviolet-visible pectrophotometers that ultraviolet-visible spectrum (UV-Vis) experiment is produced in Thermo company of the U.S., carry out.In catalyst performance evaluation experiment, employing is furnished with 3420 type gas chromatographs (production of Beijing North Fen Tianpu technical device company limited) the assay products composition of HP-INNOWax capillary column and fid detector, and organo-peroxide transformation efficiency is calculated by iodometric titrationiodimetry titration.
In the present invention, adopt gas-chromatography to carry out the analysis of each composition in system, undertaken quantitatively, all can carrying out with reference to prior art by proofreading and correct normalization method, calculate on this basis the transformation efficiency of reactant, the evaluation index such as yield and selectivity of product.
In the present invention, the transformation efficiency calculation formula of organo-peroxide is as follows:
Propylene oxide (PO) is as follows to the optionally calculation formula of organo-peroxide:
The calculation formula of propylene oxide yield is as follows:
Y
propylene oxide=S
propylene oxide× X
organo-peroxide
Propylene oxide (PO) is as follows to the optionally calculation formula of propylene:
Wherein, X is transformation efficiency; S and S ' are selectivity; M is the quality of component; N is the molar weight of component; Wherein m
0and n
0represent respectively quality and molar weight before component reaction.
Embodiment 1
(1) preparation of Ti-MCM-48 molecular sieve
By 9.95g cetyl trimethylammonium bromide, 3.79g triton x-100 mixes with tetramethylammonium hydroxide aqueous solution and 300ml deionized water that 27.8g concentration is 25 % by weight, at 20 DEG C of room temperatures, stirs 1 hour; 43.5g tetraethoxy is dropwise added in above-mentioned solution, stir 1 hour; 1.7g tetrabutyl titanate is dropwise added in above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 135 DEG C of hydrothermal crystallizings 24 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, with deionized water wash solid product to neutral, the air dryings of 110 DEG C 5 hours; Then 550 DEG C of roastings 6 hours, obtain Ti-MCM-48 mesopore molecular sieve.
(2) modification of Ti-MCM-48 molecular sieve
Ti-MCM-48 mesopore molecular sieve obtained above 10.0g is mixed with 6.0g hexamethyldisilazane and 80.0g toluene, and 130 DEG C of reflux are after 2 hours, and the remaining liquid of evaporated in vacuo at the same temperature, obtains modification Ti-MCM-48 molecular sieve.This molecular sieve specific surface area is 1152m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1,110 spacing d
110for 3.5nm; Its N
2as shown in Figure 2, as shown in Figure 3, mean pore size is 2.4nm to pore size distribution curve figure to adsorption isotherm line chart, and pore volume is 0.8cm
3/ g; As shown in Figure 4, titanium species is mainly present on framework of molecular sieve with four-coordination form its ultraviolet-visible ray spectrogram.
(3) propylene oxide (PO) is synthetic
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g to react.Temperature of reaction is 70 DEG C, and reaction pressure is 2.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.5 hours.Reaction result is in table 1.
Comparative example 1
According to the method synthesizing epoxypropane (PO) of embodiment 1, different, do not comprise step (2), Ti-MCM-48 molecular sieve is not directly used in the synthetic of propylene oxide through silanization, and reaction result is in table 1.
Comparative example 2
(1) preparation of Ti-MCM-41 molecular sieve
The tetramethylammonium hydroxide aqueous solution and the 90ml deionized water that are 25 % by weight by 24.0g cetyl trimethylammonium bromide and 24.3g concentration mix, and at 20 DEG C of room temperatures, stir 30 minutes; In this mixture, add 30.4g methyl silicate and 1.4g titanium isopropylate, stir after 5 hours and filter, be neutral with deionized water wash solid product to washings.70 DEG C of drying under reduced pressure solid products 5 hours, then within 8 hours, obtain Ti-MCM-41 mesopore molecular sieve 530 DEG C of roastings.
(2) modification of Ti-MCM-41 molecular sieve
Ti-MCM-41 mesopore molecular sieve obtained above 10.0g is mixed with 6.0g hexamethyldisilazane and 80.0g toluene, and 130 DEG C of reflux are after 2 hours, and the remaining liquid of evaporated in vacuo at the same temperature, 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 that induction stirring is housed, add above-mentioned modification Ti-MCM-41 molecular sieve 2.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g to react.Temperature of reaction is 70 DEG C, and reaction pressure is 2.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.5 hours.Reaction result is in table 1.
Comparative example 3
According to the method synthesizing epoxypropane (PO) of comparative example 2, different, do not comprise step (2), Ti-MCM-41 molecular sieve is not directly used in the synthetic of propylene oxide through silanization, and reaction result is in table 1.
Embodiment 2
(1) preparation of Ti-MCM-48 molecular sieve
By 26.3g cetyl trimethylammonium bromide, 10.5gP123 (EO
20pO
70eO
20) mix with 3.8g sodium hydroxide and 280ml deionized water, at 5-35 DEG C, stir 1 hour; 31.8g methyl silicate is dropwise added in above-mentioned solution, stir 1 hour; 1.4g titanium isopropylate is dropwise added to above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 110 DEG C of hydrothermal crystallizings 72 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, with deionized water, solid product washing is extremely neutral, within 5 hours, obtain the former powder of Ti-MCM-48 at the air dryings of 110 DEG C.Former the Ti-MCM-48 of 20.0g powder is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 18 hours, then after filtration, washing, within 3 hours, obtain Ti-MCM-48 mesopore molecular sieve 100 DEG C of vacuum-dryings.
(2) modification of Ti-MCM-48 molecular sieve
10.0g mesopore molecular sieve is mixed with 9.0gN-trimethyl-silyl-imidazole and 100.0g isopropyl benzene, and 200 DEG C of reflux are after 1 hour, and the remaining liquid of evaporated in vacuo at the same temperature, obtains modification Ti-MCM-48 molecular sieve.This modification Ti-MCM-48 molecular sieve specific surface area is 1136m
2/ g, 110 spacing d
110for 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 ray spectrogram are all consistent with sample chromatogram characteristic in embodiment 1.
(3) propylene oxide (PO) is synthetic
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 6.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, ethylbenzene 20.17g and propylene 165.8g to react.Temperature of reaction is 80 DEG C, and reaction pressure is 0.7MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.8 hours.Reaction result is in table 1.
Comparative example 4
According to the method synthesizing epoxypropane (PO) of embodiment 2, different, do not comprise step (2), Ti-MCM-48 molecular sieve is not directly used in the synthetic of propylene oxide through silanization, and reaction result is in table 1.
Embodiment 3
(1) preparation of Ti-MCM-48 molecular sieve
By 4.06g cetyl trimethylammonium bromide, 2.99g Triton X-114 mixes with 3.8g sodium hydroxide and 280ml deionized water, stirs 1 hour at 5-35 DEG C; 31.8g methyl silicate is dropwise added in above-mentioned solution, stir 1 hour; 1.1g tetraethyl titanate is dropwise added in above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 110 DEG C of hydrothermal crystallizings 72 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, with deionized water, solid product washing is extremely neutral, within 5 hours, obtain the former powder of Ti-MCM-48 at the air dryings of 110 DEG C.Former the Ti-MCM-48 of 20.0g powder is mixed with 200ml acidifying ethanol (ethanol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 18 hours, then after filtration, washing, within 3 hours, obtain Ti-MCM-48 mesopore molecular sieve 100 DEG C of vacuum-dryings.
(2) modification of Ti-MCM-48 molecular sieve
10.0g mesopore molecular sieve is mixed with 3.0g silylamine and 50.0g hexanaphthene, and 90 DEG C of reflux are after 6 hours, and the remaining liquid of evaporated in vacuo, obtains Ti-MCM-48 molecular sieve at the same temperature.This molecular sieve specific surface area is 1161m
2/ g, 110 spacing d
110for 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 ray spectrogram are all consistent with sample chromatogram characteristic in embodiment 1.
(3) propylene oxide (PO) is synthetic
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 9.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, hexanaphthene 80.0g and propylene 41.47g to react.Temperature of reaction is 90 DEG C, and reaction pressure is 3.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.2 hours.Reaction result is in table 1.
Embodiment 4
According to the method synthesizing epoxypropane (PO) of embodiment 1, different, step (3) change is as follows:
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide 30.0g, isopropyl benzene 70.0g and propylene 82.9g to react.Temperature of reaction is 50 DEG C, and reaction pressure is 0.7MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.5 hours.Reaction result is in table 1.
Embodiment 5
According to the method synthesizing epoxypropane (PO) of embodiment 1, different, step (3) change is as follows:
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide 30.0g, isopropyl benzene 70.0g and propylene 82.9g to react.Temperature of reaction is 120 DEG C, and reaction pressure is 3.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.5 hours.Reaction result is in table 1.
Embodiment 6
(1) preparation of Ti-MCM-48 molecular sieve
28.0g cetyl trimethylammonium bromide is mixed with Tetramethylammonium hydroxide and the 300ml deionized water of 27.8g 25%, at 5-35 DEG C, stir 1 hour; 43.2g tetraethoxy is dropwise added to above-mentioned solution, stir 1 hour; 1.7g tetrabutyl titanate is dropwise added in above-mentioned solution, continue to stir 1 hour; Said mixture is transferred to water heating kettle, 135 DEG C of hydrothermal crystallizings 24 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, with deionized water wash solid product to neutral, the air dryings of 110 DEG C 5 hours; Then 550 DEG C of roastings 6 hours, obtain Ti-MCM-48 mesopore molecular sieve.
(2) modification of Ti-MCM-48 molecular sieve
10.0g mesopore molecular sieve is mixed with 6.0g hexamethyldisilazane and 80.0g toluene, and 120 DEG C of reflux are after 2 hours, and the remaining liquid of evaporated in vacuo, obtains Ti-MCM-48 molecular sieve at the same temperature.This molecular sieve specific surface area is 1098m
2/ g, 110 spacing d
110for 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 ray spectrogram are all consistent with sample chromatogram characteristic in embodiment 1.
(3) propylene oxide (PO) is synthetic
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g to react.Temperature of reaction is 70 DEG C, and reaction pressure is 2.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.5 hours.Reaction result is in table 1.
Embodiment 7
According to the method synthesizing epoxypropane (PO) of embodiment 1, different, step (3) change is as follows:
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 2.0g, ethylbenzene hydroperoxide 27.6g, ethylbenzene 64.4g and propylene 82.9g to react.Temperature of reaction is 70 DEG C, and reaction pressure is 2.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.5 hours.Reaction result is in table 1.
Table 1
As can be seen from Table 1, although compared with when the Ti-MCM-41 without silanization modification in comparative example 3 is used for propylene to prepare propylene oxide with organo-peroxide contact reacts with the Ti-MCM-48 molecular sieve that does not pass through silanization in comparative example 1, PO yield and selectivity difference high 4.2% and 1.9%, but, compared with while being used for propylene to prepare propylene oxide with organo-peroxide contact reacts with the Ti-MCM-41 that does not pass through silanization in comparative example 3 with the Ti-MCM-41 of the process silanization in comparative example 2 from the Ti-MCM-48 that passes through silanization embodiment 1, PO yield has improved respectively 6.5%, 19.1%, PO selectivity has improved respectively 4.0%, 16.5%.In addition, by embodiment 1 compared with comparative example 1, embodiment 2 is compared with comparative example 4, no matter be embodiment 1 or embodiment 2, after silanization is processed, Ti-MCM-48 molecular sieve is when preparing propylene oxide by propylene and organo-peroxide contact reacts, PO yield improves approximately 25%, and PO selectivity improves approximately 20%.Result from embodiment 1 with embodiment 6, adopt compound masterplate agent of the present invention and the Ti-MCM-48 molecular sieve that adopts traditional single mode version agent to prepare gained when propylene and organo-peroxide contact reacts are prepared to propylene oxide, PO yield and selectivity are suitable.From embodiment 7, adopting ethylbenzene hydroperoxide is only 73.6% as oxygenant PO yield when propylene and organo-peroxide contact reacts are prepared to propylene oxide, PO is only 95.4% to the selectivity of propylene, be 83.5% and embodiment 1 adopts CHP as oxygenant PO yield, PO is 100% to the selectivity of propylene.
Claims (17)
1. prepare the method for propylene oxide for one kind, the method is included under catalyzer and the existence of the first organic solvent, make propylene and organo-peroxide contact reacts, it is characterized in that, described catalyzer is under silanization condition and the existence of the second organic solvent, the modification Ti-MCM-48 molecular sieve that Ti-MCM-48 molecular sieve and silicoorganic compound contact reacts are obtained, described Ti-MCM-48 molecular sieve makes by the following method: under hydrolysis glue condition, template, alkali, silicon source, titanium source, water are hydrolyzed, obtain gel mixture; Under crystallization condition, by after above-mentioned gel mixture crystallization, filter, be dried, obtain Ti-MCM-48 molecular screen primary powder; Remove the template in Ti-MCM-48 molecular screen primary powder, wherein, described template contains quaternary ammonium cation tensio-active agent and nonionogenic tenside.
2. method according to claim 1, wherein, the catalytic temperature of propylene and organo-peroxide is 50-120 DEG C, and pressure is 0.5-6.0MPa, and the time is 0.5-2.5 hour; Propylene: the first organic solvent: the mol ratio of organo-peroxide is 2-30:1-10:1; The consumption of catalyzer is the 5%-40% of organo-peroxide weight.
3. method according to claim 1 and 2, wherein, described organo-peroxide is isopropyl benzene hydroperoxide.
4. method according to claim 1 and 2, wherein, described the first organic solvent is one or more in ethylbenzene, isopropyl benzene, Trimethylmethane and hexanaphthene.
5. method according to claim 4, wherein, described the first organic solvent is isopropyl benzene.
6. method according to claim 1, wherein, the consumption of described silicoorganic compound is the 10%-100% of Ti-MCM-48 molecular sieve weight.
7. method according to claim 6, wherein, the consumption of described silicoorganic compound is the 30%-90% of Ti-MCM-48 molecular sieve weight.
8. according to the method described in any one in claim 1,6 and 7, wherein, it is R that described 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, wherein R
1, R
2and R
3identical or different, be respectively separately C
1-C
4saturated alkyl or phenyl; R
4, R
5and R
6identical or different, be respectively separately C
1-C
4alkyl, alkylhalide group or phenyl; R
7-R
11be respectively separately C
1-C
3saturated alkyl.
9. method according to claim 8, wherein, described silicoorganic compound are one or more in hexamethyldisilazane, silylamine, trimethylchlorosilane, N-trimethyl-silyl-imidazole.
10. method according to claim 1, wherein, described the second organic solvent is selected from C
6-C
16alkane, naphthenic hydrocarbon and aromatic hydrocarbon in one or more.
11. methods according to claim 9, wherein, described the second organic solvent is selected from one or more in toluene, benzene, hexanaphthene and isopropyl benzene.
12. methods according to claim 1, wherein, described Ti-MCM-48 molecular sieve and the catalytic condition of silicoorganic compound comprise that temperature is 50-350 DEG C; Time is 1-24 hour.
13. methods according to claim 12, wherein, described Ti-MCM-48 molecular sieve and the catalytic condition of silicoorganic compound comprise that temperature is 70-180 DEG C; Time is 1-6 hour.
14. methods according to claim 1, wherein, the mol ratio of described quaternary ammonium cation tensio-active agent and nonionogenic tenside is 2-40:1.
15. according to the method described in claim 1 or 14, and wherein, the general formula of described quaternary ammonium cation tensio-active agent is [NR
12r
13r
14r
15]
+x
-, R
12represent C
12-C
30straight or branched alkyl, R
13, R
14and R
15be respectively separately C
1-C
4straight or branched alkyl, X is halogen; Described nonionogenic tenside is Soxylat A 25-7 or Pluronic F-127 ether-poly-propylene oxide ether-Pluronic F-127 ether triblock copolymer.
16. methods according to claim 15, wherein, described quaternary ammonium cation tensio-active agent is cetyl trimethylammonium bromide; Described nonionogenic tenside is triton x-100, Triton X-10, Triton X-114, EO
20pO
70eO
20, EO
132pO
50eO
132and EO
106pO
70eO
106in one or more.
17. methods according to claim 1, 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 the Siliciumatom in silicon source and titanium source is 15-1000:1.
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