CN102887875B - Method for preparing epoxypropane - Google Patents
Method for preparing epoxypropane Download PDFInfo
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- CN102887875B CN102887875B CN201110206184.3A CN201110206184A CN102887875B CN 102887875 B CN102887875 B CN 102887875B CN 201110206184 A CN201110206184 A CN 201110206184A CN 102887875 B CN102887875 B CN 102887875B
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Abstract
The invention discloses a method for preparing epoxypropane. The method comprises that (1) at 10-50 DEG C, a template, an inorganic silicon source and an inorganic titanium source are hydrolyzed with water to obtain a gel mixture; (2) the gel mixture is crystallized when the pH value is between 9-11, and products after the crystallization are filtered, dried and is subjected to the template removing to obtain a Ti-MCM-41 molecular sieve; and (3) with the existence of the Ti-MCM-41 molecular sieve which is prepared in the step (2) and a first organic solvent, propylene and organic peroxide are subjected to contact reaction, wherein the template is alkyl trimethyl ammonium bromide with the formula of R1Me3NBr, and R1 is C12-C22 straight-chain alkyl groups. By the method for preparing epoxypropane, the selectivity and yield of epoxypropane 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 important basic chemical industry raw material, and purposes is very extensive, and market application quantity is very large.Propylene oxide is since 1860 synthesize first, up to now, its production technology nearly more than 20 is planted, and mainly comprises: chlorohydrination, organo-peroxide method (conjugated oxidation), electrochemical process, mistake acid system, biochemical process, cracking process and direct oxidation method etc.Wherein, only having chlorohydrination and organo-peroxide method is the technology of industrial production propylene oxide.Due to chlorohydrination, inevitably to exist the job rate high, and production cost is high, and sewage discharge is many, the environmental pollution problem such as heavily, and organo-peroxide method becomes at present the main flow technique of production of propylene oxide in the world.
The development research of organo-peroxide method oxidation catalyst of cyclopropene starts from nineteen sixties, and what receive publicity at first is to contain Mo, V, W, the homogeneous catalyst of the transition metal such as Ti.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 about epoxidation of propylene heterogeneous catalyst.In patent US3829392, US3923843, US4021454 and US4367342, Shell company discloses the preparation method of this catalyzer, that is: by TiCl
4or organic titanic compound is impregnated into business and sells SiO
2on surface, then obtain Ti/SiO through steps such as super-dry, roasting and silanization processing
2catalyzer.The appearance of loading type oxidation catalyst of cyclopropene, has solved the separation problem of product and catalyzer well, but due to Ti/SiO
2silica supports specific surface area and pore volume that catalyzer adopts are less, and the charge capacity of titanium is difficult to improve.Until 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, carried out the process of propylene ring oxidation reaction production propylene oxide taking the Ti-MCM-41 molecular sieve through silanization processing as catalyzer.Calendar year 2001, sumitomo chemical company discloses taking isopropyl benzene hydroperoxide as oxygenant again in patent US6323147, prepares equally the technique of propylene oxide taking the Ti-MCM-41 molecular sieve through silanization processing as catalyzer.
Although Ti-MCM-41 molecular sieve has shown good catalytic activity in organo-peroxide oxidation style is prepared the reaction of propylene oxide, but in prior art, this molecular sieve taking organo-silicon ester and titanium ester as raw material, quaternary ammonium cation tensio-active agent is as template, alkyl ammonium hydroxide are as auxiliary template agent, prepare by hydrothermal synthesis method, there is following problem: (1) is in synthetic, because the hydrolysis rate of titanium ester is faster than the hydrolysis rate of estersil, can cause the outer TiO of skeleton
2the generation of species even can destroy the formation of meso-hole structure in the time that titanium content is higher.In the time carrying out epoxidation reaction, the outer TiO of amorphous skeleton
2the existence of species may cause organo-peroxide decomposition, reduces its utilization ratio; (2) organic raw material using and organic auxiliary template agent are expensive, have increased the synthetic cost of molecular sieve; (3) adopt hydrothermal synthesis method not only to need comparatively high temps, and consuming time longer, also require to use high pressure resistant synthesis reactor.The above shortcoming all can restricted T i-MCM-41 molecular sieve scale operation and industrial application.In addition, adopt the Ti-MCM-41 molecular sieve prepared of prior art when reacting to prepare propylene oxide with organo-peroxide by propylene, propylene oxide yield and propylene oxide option demand further improve.
Summary of the invention
The technical problem to be solved in the present invention is propylene oxide yield and the not high shortcoming of propylene oxide selectivity while reacting to prepare propylene oxide with organo-peroxide by propylene in prior art, and a kind of method of preparing propylene oxide of high yield and highly selective is provided.
The invention provides a kind of method of preparing propylene oxide, the method comprises the following steps:
(1) at 10-50 DEG C, template, inorganic silicon source, inorganic ti sources and water are hydrolyzed, obtain gel mixture;
(2), by above-mentioned gel mixture crystallization in the time that pH value is 9-11, the product after crystallization is filtered, is dried, removes template and obtain Ti-MCM-41 molecular sieve;
(3) the Ti-MCM-41 molecular sieve of preparing in step (2) and the first organic solvent make propylene and organo-peroxide contact reacts under existing;
Wherein, described template is that general formula is R
1me
3the alkyl trimethyl ammonium bromide of NBr, wherein R
1for C
12-C
22straight chained alkyl.
Method of the present invention is by being used the Ti-MCM-41 molecular sieve being made by above-mentioned ad hoc approach as catalyzer, because even aperture distribution, the titanium active sites of this Ti-MCM-41 molecular sieve are evenly distributed, the amount of extra-framework titanium is less, there is following beneficial effect in the method for preparing propylene oxide provided by the invention:
(1) under existing with the Ti-MCM-41 molecular sieve of preparing in prior art, compared with propylene is prepared to propylene oxide with organo-peroxide contact reacts, Ti-MCM-41 molecular sieve prepared by the present invention reacts with organo-peroxide while preparing propylene oxide for propylene, can show good catalytic performance.For example, from embodiment 1 and comparative example 1 result, in the present invention, adopt inorganic silicon source, inorganic ti sources, the standby Ti-MCM-41 molecular sieve of low temperature crystallized legal system to improve 10.8%, PO than Ti-MCM-41 molecular sieve propylene oxide (PO) yield that adopts organosilicon source, organic titanium source, hydrothermal crystallization method to prepare isopropyl benzene hydroperoxide (CHP) selectivity is improved to 4.1%.
(2) under a kind of preferable case of the present invention, the process silanization of preparation Ti-MCM-41 molecular sieve, with under the Ti-MCM-41 molecular sieve of silanization does not exist, compared with propylene is prepared to propylene oxide with organo-peroxide contact reacts, the Ti-MCM-41 molecular sieve of silanization modification of the present invention reacts with organo-peroxide while preparing propylene oxide for propylene, can further obviously improve the selectivity of transformation efficiency and the propylene oxide of organo-peroxide, for example, from embodiment 1 and embodiment 4 results, through silanization, propylene oxide (PO) yield of modification Ti-MCM-41 molecular sieve improves 35.1%, PO improves 24.4% to isopropyl benzene hydroperoxide (CHP) selectivity.
(3), under a kind of preferable case of the present invention, in the time that Ti-MCM-41 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 5 results, in embodiment 5, adopt the catalyzer using in embodiment 1, using ethylbenzene hydroperoxide as oxygenant, PO yield is 84.2%, PO is that 92.7%, PO is 95.7% 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.
In addition, because the glue in the above-mentioned method of preparing molecular sieve, crystallization are all at 10-50 DEG C, crystallization does not need to use high pressure water heating kettle, under normal pressure, just can carry out, and therefore method of the present invention is simple, and condition is easy to control.In addition, the cost of material that the present invention prepares molecular sieve is cheap, has effectively reduced the cost of synthetic Ti-MCM-41 molecular sieve.
Brief description of the drawings
Fig. 1 is the X-ray diffractogram of the Ti-MCM-41 molecular sieve of embodiment 1, embodiment 2 and embodiment 3 synthesizeds.
Fig. 2 is the N of the Ti-MCM-41 molecular sieve of embodiment 1 synthesized
2adsorption isotherm line chart.
Fig. 3 is the pore size distribution curve figure of the Ti-MCM-41 molecular sieve of embodiment 1 synthesized.
Fig. 4 is the ultraviolet-visible light spectrogram of the Ti-MCM-41 molecular sieve of embodiment 1 synthesized.
Embodiment
According to the method for preparing propylene oxide of the present invention, the method comprises:
(1) at 10-50 DEG C, template, inorganic silicon source, inorganic ti sources and water are hydrolyzed, obtain gel mixture;
(2), by above-mentioned gel mixture crystallization in the time that pH value is 9-11, the product after crystallization is filtered, is dried, removes template and obtain Ti-MCM-41 molecular sieve;
(3) the Ti-MCM-41 molecular sieve that prepared by step (2) and the first organic solvent make propylene and organo-peroxide contact reacts under existing,
Wherein, described template is that general formula is R
1me
3the alkyl trimethyl ammonium bromide of NBr, wherein R
1for C
12-C
22straight chained alkyl, preferably hexadecyl.
According to the method for preparing propylene oxide of the present invention, can realize object of the present invention according to aforesaid method of the present invention, to the mol ratio of described inorganic ti sources, inorganic silicon source, water and template without particular requirement, can in wider scope, select, under preferable case, the described inorganic silicon source in silicon: the inorganic ti sources taking titanium: template: the mol ratio of water is as 1: 0.015-0.05: 0.15-0.4: 100-200, is preferably 1: 0.03-0.04: 0.2-0.3: 120-180.
According to the method for preparing propylene oxide of the present invention, the present invention without particular requirement, can be the various water-soluble or acid-soluble inorganic titanium-containing compounds of preparing molecular sieve that can be used in to the kind of described inorganic ti sources, and under preferable case, described inorganic ti sources is TiCl
3, TiCl
4, TiOCl
2, Ti (NO
3)
4and Ti (SO
4)
2in one or more, more preferably TiCl
3, TiCl
4, Ti (SO
4)
2in one or more.
According to the method for preparing propylene oxide of the present invention, the present invention to the kind in described inorganic silicon source without particular requirement, can be the various water-soluble inorganic silicon-containing compounds of preparing molecular sieve that can be used in, under preferable case, described inorganic silicon source be water glass and/or Starso.
According to the method for preparing propylene oxide of the present invention, the present invention is to described hydrolysis glue condition without particular requirement, and under preferable case, described hydrolysis glue temperature is 10-50 DEG C, and the time of hydrolysis glue is 10-60 minute.
According to the method for preparing propylene oxide of the present invention, described crystallization condition comprises: the temperature of crystallization is 10-50 DEG C, more preferably 20-40 DEG C; Time is 3-24 hour, more preferably 3-8 hour.
According to the method for preparing propylene oxide of the present invention, the reaction of step (2) is carried out for 9-11 in pH value, the acid that is used for the pH value of reaction system of regulating step (2) is organic acid and/or mineral acid, preferably mineral acid, more preferably one or more in hydrochloric acid, sulfuric acid and nitric acid, are further preferably hydrochloric acid.
According to the method for preparing propylene oxide of the present invention, the present invention is to condition dry described in step (2) without particular requirement, and under preferable case, described dry temperature is 70-120 DEG C, and the time is 3-10 hour.
According to the method for preparing propylene oxide of the present invention, the method for removing Molecular Sieves as Template agent described in step (2) is extraction process, can carry out with reference to prior art.Under preferable case, the solvent of described extraction is one or more in acidifying methyl alcohol, acidifying ethanol or tetrahydrofuran (THF), and extraction time is 8-36 hour, and extraction temperature is 70-100 DEG C.In the present invention, described acidifying methyl alcohol refers to the mixture of hydrochloric acid and methyl alcohol, and acidifying ethanol refers to the mixture of hydrochloric acid and ethanol, and those skilled in the art all can know this, not repeat them here.
According to the method for preparing propylene oxide of the present invention, wherein, under preferable case, the method is also included in the following steps that step (3) is carried out before:
(4) under silanization condition and the existence of the second organic solvent, the Ti-MCM-41 molecular sieve that step (2) is obtained and silicoorganic compound contact reacts.
By above-mentioned silanization treatment step, the hydroxyl that Ti-MCM-41 molecular sieve surface is existed is converted into alkyl siloxy, thereby can strengthen the hydrophobicity of catalyst surface, reduces acidity simultaneously, and then further improves the selectivity of target product propylene oxide.
According to the method for preparing propylene oxide of the present invention, wherein, the consumption of described silicoorganic compound can be the 30%-100% of Ti-MCM-41 molecular sieve weight, is preferably 50%-80%.The consumption of described the second organic solvent can be 5-20 times of Ti-MCM-41 molecular sieve weight, is preferably 5-10 doubly.
According to the method for preparing Ti-MCM-41 molecular sieve of the present invention, wherein, it is R that described silicoorganic compound can be selected from general formula
2r
3r
4the halosilanes of SiX, general formula are [R
5r
6r
7si]
2the silazane of NH, general formula are R
8r
9r
10si[N
2c
3h
3] silyl imidazoles and general formula be (R
11)
3siN (R
12)
2one or more of silylamine, wherein R
2, R
3and R
4identical or different, be respectively separately C
1-C
4saturated alkyl or phenyl; R
5, R
6and R
7identical or different, be respectively separately C
1-C
4alkyl, alkylhalide group or phenyl; R
8-R
12be 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 selected from C
6-C
16aromatic hydrocarbon and C
6-C
16one or more in saturated alkane, are preferably one or more in toluene, benzene, hexanaphthene, isopropyl benzene.
According to the method for preparing propylene oxide of the present invention, wherein, described Ti-MCM-41 molecular sieve and the catalytic temperature of silicoorganic compound are 110-180 DEG C, are preferably 120-150 DEG C.Time is 1-6 hour, is preferably 1-2 hour.
According to the present invention, under preferable case, the method also comprises removes after Ti-MCM-41 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.
According to the method for preparing propylene oxide of the present invention, wherein, in step (3), propylene and organo-peroxide contact reacts temperature can be 70-100 DEG C, are preferably 70-90 DEG C.Reaction pressure can be 1.0-3.0MPa, is preferably 1.5-2.5MPa.Reaction times can be 1.0-2.5 hour, is preferably 1.5-2.5 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.
A preferred embodiment of the invention, the method for preparing propylene oxide provided by the invention can be carried out in accordance with the following steps:
(1) at 10-50 DEG C, quaternary ammonium cation template is dissolved in to deionized water, form colourless transparent solution, stir 10-60 minute.Wherein the mol ratio of water and template is 200-400: 1.
(2) at 10-50 DEG C, inorganic silicon source is mixed with a certain amount of deionized water, join in above-mentioned template solution.Wherein the mol ratio of silicon source and template is 1: 0.15-0.4, in this step, the mol ratio in water and silicon source is 20-100: 1.
(3) at 10-50 DEG C, inorganic ti sources is mixed with a certain amount of deionized water, join in above-mentioned mixing solutions.Wherein the mol ratio in silicon source Yu Tai source is 1: 0.015-0.05, in this step, the mol ratio in water and titanium source is 50-2000: 1.
(4) by sour regulation system pH value to 9-11, stir crystallization 2-24 hour in 10-50 DEG C.Solid product is separated with mother liquor, to neutral, obtain Ti-MCM-41 molecular screen primary powder at the air drying 3-10 hour of 70-120 DEG C with deionized water wash.
(5) template is removed in the reflux extraction in organic extract liquid of Ti-MCM-41 molecular screen primary powder, obtains Ti-MCM-41 molecular sieve, and extraction temperature is 70-100 DEG C, and extraction time is 8-36 hour.
(6) under the temperature condition of 110-180 DEG C, Ti-MCM-41 molecular sieve is carried out to silanization processing with the silicoorganic compound that are dissolved in the second organic solvent, obtain modification Ti-MCM-41 molecular sieve, wherein the consumption of silicoorganic compound is the 30-100% of Ti-MCM-41 molecular sieve weight, and the silanization treatment time is 1-6 hour.
(7) under the above-mentioned modification Ti-MCM-41 molecular sieve preparing and the existence of the first organic solvent, make propylene and organo-peroxide contact reacts, the catalytic temperature of propylene and organo-peroxide is 70-100 DEG C, and pressure is 1.0-3.0MPa, and the time is 1.0-2.5 hour; Propylene: the first organic solvent: the mol ratio of organo-peroxide is 2-30: 1-10: 1; The consumption of Ti-MCM-41 molecular sieve is the 5-40% of organo-peroxide weight.
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:
T
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-41 molecular sieve
19.0g cetyl trimethylammonium bromide is dissolved in to 250ml deionized water, at 25 DEG C, stirs 30 minutes; By the Na of 57.6g
2siO
39H
2o is dissolved in 150ml deionized water, is added drop-wise in the cetyl trimethylammonium bromide aqueous solution, simultaneously vigorous stirring; By 5.5g 17.0wt%TiCl
3the aqueous solution is added drop-wise in above-mentioned mixing solutions after mixing with 100ml deionized water, simultaneously vigorous stirring; System pH is adjusted to 9.5 with dilute hydrochloric acid solution; Continue to stir crystallization 5 hours at 25 DEG C.Solid product is separated with mother liquor, to neutral, 5 hour obtain Ti-MCM-41 mesopore molecular sieve former powder at the air dryings of 110 DEG C with deionized water wash.The former powder of 20.0g Ti-MCM-41 mesopore molecular sieve is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 12 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 mesopore molecular sieve 70 DEG C of vacuum-dryings.
(2) modification of Ti-MCM-41 molecular sieve
10.0g Ti-MCM-41 mesopore molecular sieve is mixed with 7.2g hexamethyldisilazane and 100.0g 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 molecular sieve specific surface area is 1204m
2/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1; Its N
2adsorption isotherm line chart as shown in Figure 2; As shown in Figure 3, mean pore size is 2.8nm to its pore size distribution curve figure, and pore volume is 1.0cm
3/ g; As shown in Figure 4, titanium species is mainly present on framework of molecular sieve with four-coordination form its ultraviolet-visible light spectrogram.
(3) propylene oxide (PO) is synthetic
In the autoclave that induction stirring is housed, add above-mentioned modification Ti-MCM-48 molecular sieve 3.0g, isopropyl benzene hydroperoxide (CHP) 30.0g, isopropyl benzene 70.0g and propylene 82.9g.Temperature of reaction is 80 DEG C, and reaction pressure is 2.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 2.0 hours.Reaction result is in table 1.
Comparative example 1
(1) preparation of Ti-MCM-41 molecular sieve
19.0g cetyl trimethylammonium bromide is dissolved in to 500ml deionized water, at 25 DEG C, stirs 30 minutes; The tetraethoxy of 41.6g is added drop-wise in the cetyl trimethylammonium bromide aqueous solution, simultaneously vigorous stirring; Afterwards 2.1g tetrabutyl titanate is added drop-wise in above-mentioned mixing solutions, simultaneously vigorous stirring; System pH is adjusted to 9.5 with dilute hydrochloric acid solution; Stir, after 1 hour, said mixture is transferred to water heating kettle, 120 DEG C of hydrothermal crystallizings 72 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, to neutral, 5 hour obtain a kind of Ti-MCM-41 mesopore molecular sieve former powder at the air dryings of 110 DEG C with deionized water wash.The former powder of 20.0g Ti-MCM-41 mesopore molecular sieve is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 12 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 mesopore molecular sieve 70 DEG C of vacuum-dryings.
Step (2) is identical with embodiment 1 with step (3), and reaction result is in table 1.
Comparative example 2
(1) preparation of Ti-MCM-41 molecular sieve
19.0g cetyl trimethylammonium bromide is dissolved in to 250ml deionized water, at 25 DEG C, stirs 30 minutes; By the Na of 57.6g
2siO
39H
2o is dissolved in 150ml deionized water, drips, simultaneously vigorous stirring in the cetyl trimethylammonium bromide aqueous solution; By 5.5g 17.0wt%TiCl
3the aqueous solution mixes with 100ml deionized water, to above-mentioned mixed solution and dripping, and vigorous stirring simultaneously; System pH is adjusted to 9.5 with dilute hydrochloric acid solution; Stir, after 1 hour, said mixture is transferred to water heating kettle, 120 DEG C of hydrothermal crystallizings 72 hours.After hydro-thermal reaction finishes, solid product is separated with mother liquor, to neutral, 5 hour obtain a kind of Ti-MCM-41 mesopore molecular sieve former powder at the air dryings of 110 DEG C with deionized water wash.The former powder of 20.0g Ti-MCM-41 mesopore molecular sieve is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 12 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 mesopore molecular sieve 70 DEG C of vacuum-dryings.
Step (2) is identical with embodiment 1 with step (3), and reaction result is in table 1.
Comparative example 3
19.0g cetyl trimethylammonium bromide is dissolved in to 500ml deionized water, at 25 DEG C, stirs 30 minutes; 41.6g tetraethoxy is dripped in the cetyl trimethylammonium bromide aqueous solution, simultaneously vigorous stirring; By 2.1g tetrabutyl titanate to above-mentioned mixed solution and dripping, simultaneously vigorous stirring; System pH is adjusted to 9.5 with dilute hydrochloric acid solution; Continue to stir crystallization 5 hours at 25 DEG C.Solid product is separated with mother liquor, to neutral, 5 hour obtain a kind of Ti-MCM-41 mesopore molecular sieve former powder at the air dryings of 110 DEG C with deionized water wash.The former powder of 20.0g mi-MCM-41 mesopore molecular sieve is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 12 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 mesopore molecular sieve 70 DEG C of vacuum-dryings.
Step (2) is identical with embodiment 1 with step (3), and reaction result is in table 1.
Comparative example 4
(1) preparation of Ti-MCM-41 molecular sieve
19.0g cetyl trimethylammonium bromide is mixed with Tetramethylammonium hydroxide and the 235ml deionized water of 19.0g 25%, at 25 DEG C, stir 30 minutes; By the Na of 57.6g
2siO
39H
2o is dissolved in 150ml deionized water, drips, simultaneously vigorous stirring in the cetyl trimethylammonium bromide aqueous solution; By 5.5g17.0wt%TiCl
3the aqueous solution mixes with 100ml deionized water, to above-mentioned mixed solution and dripping, and vigorous stirring simultaneously; Continue to stir crystallization 5 hours at 25 DEG C.Solid product is separated with mother liquor, to neutral, 5 hour obtain Ti-MCM-41 mesopore molecular sieve former powder at the air dryings of 110 DEG C with deionized water wash.The former powder of 20.0g Ti-MCM-41 mesopore molecular sieve is mixed with 200ml acidifying methyl alcohol (methyl alcohol is 20: 1 with concentrated hydrochloric acid volume ratio), 80 DEG C of reflux extractions 12 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 mesopore molecular sieve 70 DEG C of vacuum-dryings.
Step (2) is identical with embodiment 1 with step (3), and reaction result is in table 1.
Comparative example 5
According to the method synthesizing epoxypropane (PO) of comparative example 1, 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-41 molecular sieve
10.9g cetyl trimethylammonium bromide is dissolved in to 280ml deionized water, at 10 DEG C, stirs 60 minutes; By 42.6g water glass (SiO
2content is 28.26wt%) be dissolved in 300ml deionized water, in the cetyl trimethylammonium bromide aqueous solution, drip, simultaneously vigorous stirring; 0.9g titanium sulfate is dissolved in to 50ml 0.1M/L dilute sulphuric acid, to above-mentioned mixed solution and dripping, vigorous stirring simultaneously; System pH is adjusted to 9 with dilution heat of sulfuric acid; Continue to stir crystallization 24 hours at 10 DEG C.Solid product is separated with mother liquor, to neutral, 5 hour obtain a kind of Ti-MCM-41 mesopore molecular sieve former powder at the air dryings of 110 DEG C with deionized water wash.The former powder of 20.0g Ti-MCM-41 mesopore molecular sieve is mixed with 400ml acidifying ethanol (ethanol is 20: 1 with concentrated hydrochloric acid volume ratio), 100 DEG C of reflux extractions 8 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 mesopore molecular sieve 70 DEG C of vacuum-dryings.
(2) modification of Ti-MCM-41 molecular sieve
Above-mentioned 10.0g Ti-MCM-41 mesopore molecular sieve is mixed with 3.0g trimethylchlorosilane and 50.0g isopropyl benzene, and 180 DEG C of reflux are after 5 hours, and the remaining liquid of evaporated in vacuo at the same temperature, obtains modification Ti-MCM-41 molecular sieve.Its specific surface area is 1182m
2/ g, mean pore size is 3.0nm, pore volume is 1.1cm
3/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1; N
2adsorption isotherm line chart, pore size distribution curve figure and ultraviolet-visible light 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 modification Ti-MCM-41 molecular sieve 1.5g, isopropyl benzene hydroperoxide 30.0g, hexanaphthene 10.0g and propylene 9.24g to react.Temperature of reaction is 70 DEG C, and reaction pressure is 1.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 2.5 hours.Reaction result is in table 1.
Embodiment 3
(1) preparation of Ti-MCM-41 molecular sieve
29.2g cetyl trimethylammonium bromide is dissolved in to 300ml deionized water, at 50 DEG C, stirs 10 minutes; By the Na of 57.6g
2siO
39H
2o is dissolved in 100ml deionized water, drips, simultaneously vigorous stirring in the cetyl trimethylammonium bromide aqueous solution; By 1.9g TiCl
4mix with 50ml deionized water, to above-mentioned mixed solution and dripping, vigorous stirring simultaneously; System pH is adjusted to 11 with dilute hydrochloric acid solution; Continue to stir crystallization 3 hours at 50 DEG C.Solid product is separated with mother liquor, to neutral, 5 hour obtain Ti-MCM-41 molecular screen primary powder at the air dryings of 110 DEG C with deionized water wash.The Ti-MCM-41 molecular screen primary powder of 10.0g is mixed with 100g tetrahydrofuran (THF), 70 DEG C of reflux extractions 36 hours, then after filtration, washing, within 5 hours, obtain Ti-MCM-41 molecular sieve 70 DEG C of vacuum-dryings.
(2) modification of Ti-MCM-41 molecular sieve
10.0gTi-MCM-41 mesopore molecular sieve is mixed with 10.0gN-trimethyl-silyl-imidazole and 200.0g toluene, and 110 DEG C of reflux are after 10 hours, and the remaining liquid of evaporated in vacuo at the same temperature, obtains modification Ti-MCM-41 molecular sieve.Its specific surface area is 1217m
2/ g, mean pore size is 2.9nm, pore volume is 1.0cm
3/ g; Its X-ray diffraction spectrogram (XRD) as shown in Figure 1; N
2adsorption isotherm line chart, pore size distribution curve figure and ultraviolet-visible light 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 modification Ti-MCM-41 molecular sieve 12.0g, isopropyl benzene hydroperoxide 30.0g, isopropyl benzene 133.41g and propylene 139.86g to react.Temperature of reaction is 100 DEG C, and reaction pressure is 3.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 1.0 hours.Reaction result is in table 1.
Embodiment 4
According to the method synthesizing epoxypropane (PO) of embodiment 1, 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 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 modification Ti-MCM-41 molecular sieve 3.0g, ethylbenzene hydroperoxide 27.6g, isopropyl benzene 70.0g and propylene 82.9g.Temperature of reaction is 80 DEG C, and reaction pressure is 2.0MPa, and stirring velocity is 300 revs/min, and the reaction times is 2.0 hours.Reaction result is in table 1.
Table 1
As can be seen from Table 1, by embodiment 1 compared with comparative example 1, adopt Ti-MCM-41 that Ti-MCM-41 prepared by inorganic silicon provided by the invention source, inorganic ti sources, low temperature crystallized method prepared with available technology adopting organosilicon source, organic titanium source, hydrothermal crystallizing method when propylene is prepared to propylene oxide with organo-peroxide contact reacts compared with, PO yield has improved 10.8%, PO the selectivity of isopropyl benzene hydroperoxide (CHP) has been improved to 4.1%.Embodiment 1 can be found out with comparative example 2 contrasts, Ti-MCM-41 prepared by the low temperature crystallized method that adopt inorganic silicon source, inorganic ti sources, provides and adopt Ti-MCM-41 prepared by inorganic silicon source, inorganic ti sources, hydrothermal crystallizing method when propylene is prepared to propylene oxide with organo-peroxide contact reacts compared with, PO yield has improved 6.6%, PO CHP selectivity has been improved to 3.4%.In addition, by embodiment 1 compared with comparative example 3, the Ti-MCM-41 molecular sieve that uses inorganic silicon source, titanium source, low temperature crystallized preparation than use organosilicon source, organic titanium source, low temperature crystallized preparation Ti-MCM-41 molecular sieve time propylene oxide (PO) yield improve 11.3%, PO isopropyl benzene hydroperoxide (CHP) selectivity improved to 3.6%; Embodiment 1 is compared with comparative example 5, in building-up process, do not use Ti-MCM-41 molecular sieve prepared by auxiliary template agent to improve 14.5%, PO to isopropyl benzene hydroperoxide (CHP) selectivity raising 5.0% than propylene oxide (PO) yield on the Ti-MCM-41 molecular sieve that uses auxiliary template agent to prepare.Embodiment 1 is compared with embodiment 4, after silanization is processed Ti-MCM-41 molecular sieve with not through the Ti-MCM-41 molecular sieve of silanization processing when propylene and organo-peroxide contact reacts are prepared to propylene oxide, PO yield improves approximately 35.1%, and PO selectivity improves approximately 24.4%.From embodiment 5, adopting ethylbenzene hydroperoxide is only 84.2% as oxygenant PO yield when propylene and organo-peroxide contact reacts are prepared to propylene oxide, PO is only 92.7% to the selectivity of propylene, be 91.1% and embodiment 1 adopts CHP as oxygenant PO yield, PO is 96.2% to the selectivity of propylene.
Claims (14)
1. a method of preparing propylene oxide, the method comprises the following steps:
(1) at 10-50 DEG C, template, inorganic silicon source, inorganic ti sources and water are hydrolyzed, obtain gel mixture;
(2) by above-mentioned gel mixture crystallization in the time that pH value is 9-11, the product after crystallization is filtered, is dried, removes template, obtain Ti-MCM-41 molecular sieve;
(3) under silanization condition and the existence of the second organic solvent, the Ti-MCM-41 molecular sieve that step (2) is obtained and silicoorganic compound contact reacts, obtain modification Ti-MCM-41 molecular sieve;
(4) the modification Ti-MCM-41 molecular sieve of preparing in step (3) and the first organic solvent make propylene and organo-peroxide contact reacts under existing;
Wherein, described template is that general formula is R
1me
3the alkyl trimethyl ammonium bromide of NBr, wherein R
1for C
12-C
22straight chained alkyl;
Wherein, in step (2), the temperature of described crystallization is 10-50 DEG C, and the time is 3-24 hour;
Wherein, described organo-peroxide is isopropyl benzene hydroperoxide.
2. in accordance with the method for claim 1, wherein, described inorganic ti sources is TiCl
3, TiCl
4, TiOCl
2, Ti (NO
3)
4and Ti (SO
4)
2in one or more.
3. in accordance with the method for claim 1, wherein, described inorganic silicon source is water glass and/or Starso.
4. method according to claim 1, wherein, the consumption of described silicoorganic compound is the 30%-100% of Ti-MCM-41 molecular sieve weight.
5. method according to claim 4, wherein, the consumption of described silicoorganic compound is the 50%-80% of Ti-MCM-41 molecular sieve weight.
6. according to the method described in claim 1,4 or 5, wherein, it is R that described silicoorganic compound are selected from general formula
2r
3r
4the halosilanes of SiX, general formula are [R
5r
6r
7si]
2the silazane of NH, general formula are R
8r
9r
10si[N
2c
3h
3] silyl imidazoles and general formula be (R
11)
3siN (R
12)
2one or more of silylamine, wherein R
2, R
3and R
4identical or different, be respectively separately phenyl or C
1-C
4saturated alkyl; R
5, R
6and R
7identical or different, be respectively separately C
1-C
4alkyl, C
1-C
4alkylhalide group or phenyl; R
8-R
12be respectively separately C
1-C
3saturated alkyl.
7. method according to claim 6, wherein, described silicoorganic compound are one or more in hexamethyldisilazane, silylamine, trimethylchlorosilane and N-trimethyl-silyl-imidazole.
8. 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.
9. method according to claim 1, wherein, described the second organic solvent is selected from one or more in toluene, benzene, hexanaphthene and isopropyl benzene.
10. method according to claim 1, wherein, in step (3), described Ti-MCM-41 molecular sieve and the catalytic condition of described silicoorganic compound comprise that temperature is 110-180 DEG C, the time is 1-10 hour.
11. methods according to claim 10, wherein, in step (3), described Ti-MCM-41 molecular sieve and the catalytic condition of described silicoorganic compound comprise that temperature is 120-150 DEG C; Time is 1-4 hour.
12. methods according to claim 1, wherein, in step (4), described propylene and the catalytic temperature of described organo-peroxide are 70-100 DEG C, and pressure is 1.0-3.0MPa, and the time is 1.0-2.5 hour; Propylene: the first organic solvent: the mol ratio of organo-peroxide is 2-30:1-10:1; The consumption of Ti-MCM-41 molecular sieve is the 5%-40% of organo-peroxide weight.
13. according to the method described in claim 1 or 12, and wherein, described the first organic solvent is one or more in ethylbenzene, isopropyl benzene, Trimethylmethane and hexanaphthene.
14. methods according to claim 13, wherein, described the first organic solvent is isopropyl benzene.
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| CN106964337B (en) * | 2016-01-14 | 2019-09-20 | 万华化学集团股份有限公司 | A kind of preparation method of epoxidation catalyst and epoxidation catalyst and its application of preparation |
| CN107442126B (en) * | 2016-05-30 | 2020-05-19 | 中国石油化工股份有限公司 | Preparation method of hydrotreating catalyst |
| CN107442161B (en) * | 2016-05-30 | 2020-05-19 | 中国石油化工股份有限公司 | Hydrogenation modification catalyst and preparation method and application thereof |
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| 于健强等.以硅溶胶和三氯化钛为原料合成Ti-MCM-41分子筛Ⅰ.Ti-MCM-41分子筛的合成.《催化学报》.2001,第22卷(第3期),第267-270页. |
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