CN103030612B - Method for producing epoxypropane through reaction between cumyl hydroperoxide and propylene - Google Patents
Method for producing epoxypropane through reaction between cumyl hydroperoxide and propylene Download PDFInfo
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- CN103030612B CN103030612B CN201110300422.7A CN201110300422A CN103030612B CN 103030612 B CN103030612 B CN 103030612B CN 201110300422 A CN201110300422 A CN 201110300422A CN 103030612 B CN103030612 B CN 103030612B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to a method for producing epoxypropane through reaction between cumyl hydroperoxide and propylene, mainly aiming at solving the problems of low catalyst activity, low epoxypropane selectivity and poor reaction stability existing in the prior art. Reaction raw materials are in contact with catalyst to produce the epoxypropane by using the cumyl hydroperoxide and the propylene as the raw materials under the conditions that the molar ratio of the cumyl hydroperoxide to the propylene is 1:1 to 1:10, the reaction temperature is 50-100DEG C, the reaction pressure is 1-5MPa and the mass space velocity of the cumyl hydroperoxide is 1-30h<-1>. The catalyst is prepared by adopting a method which comprises the following steps of: a) evenly mixing organic silicon sources, inorganic silicon sources, titanium sources and organic templates with water, and filtering, water-washing, drying and roasting the product to obtain precursors I, wherein the inorganic silicon sources are selected from at least one of silica sol, silicate ester and solid silicon oxide, and the organic silicon sources are methyltrimethoxysilane; and b) by taking inert gas as carriers, feeding silanization agent into the precursors I for reaction to obtain the catalyst, wherein the silanization agent is selected from at least one of organic silane, organic silicylamine, organic silicylamide and organic silazane. By adopting the technical scheme, the problems are better solved and the method can be used for the industrial production of the epoxypropane.
Description
Technical field
The present invention relates to a kind of hydrogen phosphide cumene and react the method for producing propylene oxide with propylene.
Background technology
The mesoporous material such as HMS, MCM-41 surface is metamict, is rich in great amount of hydroxy group, and surface hydrophilicity is strong, has a strong impact on the performance of catalyzer.Therefore, wish to eliminate hydroxyl by modified method, increase surface hydrophobicity, to improve its epoxidation performance.The work of this respect more and more causes the concern of chemist.
Bhaumik (Organically Modified Titanium-Rich Ti-MCM-41, Efficient Catalysts for Epoxidation Reactions) [J.Catal., 2000,189 (1): 31-39] adopt original position condensation method, on Ti-MCM-41 surface respectively grafting methyl, vinyl, allyl group, chloropropyl, amyl group and phenyl.Kapoor etc. (Titanium containing inorganic-organic hybrid mesoporous materials with exceptional activity in epoxidation of alkenes using hydrogen peroxide) [Mater.Chem., 2002,12:3078-3083] with 1, two (Trimethoxy silane) ethane of 2-is grafting agent, adopts the original position condensation method bridging dimethylene (CH that synthesized surface grafting
2cH
2-) Ti-MCM-41, by regulating the ingredient proportion of tetraethoxy and bridging silane, reach the rational Match of the electric density of organosilicate and surfactant interface, structure-porousness relation of control material.Pena etc. (Elucidating the local environment of Ti (IV) active sites in Ti-MCM-48:a comparison between silylated and calcined catalysts) [Micropor.Mesopor.Mater., 2001,44-45:345-356] with hexamethyldisilazane, Ti-MCM-48 is carried out to methyl graft modification by liquid phase method at 120 DEG C, on the Si-OH on surface and Ti-OH-H quilt-Si (CH simultaneously
3)
3replace.Lin etc. (Formation of better catalytically active titanium species in Ti-MCM-41byvapor-phase silylation) [J.Catal., 2005,235 (2): 423-427] the synthetic Ti-MCM-41 mesoporous material of hydrothermal method has been carried out to the research of the gas phase methyl graft modification of different time.
But, after above-mentioned document intermediary hole material modification, for the reacting of hydrogen phosphide cumene and propylene, still exist catalyst activity low, product propylene oxide selectivity is low, the problem that reaction stability is poor.
Summary of the invention
Technical problem to be solved by this invention is in prior art, to exist catalyst activity low, and product propylene oxide selectivity is low, and the problem that reaction stability is poor provides a kind of new hydrogen phosphide cumene to react the method for producing propylene oxide with propylene.It is high that the method has catalyst activity, and product propylene oxide selectivity is high, the feature that reaction stability is good.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene, taking hydrogen phosphide cumene and propylene as raw material, it is 1: 1～1: 10 at hydrogen phosphide cumene and propylene mol ratio, temperature of reaction is 50～100 DEG C, reaction pressure is 1～5MPa, and hydrogen phosphide cumene mass space velocity is 1～30 hour
-1under condition, reaction raw materials contacts with catalyzer and generates propylene oxide; Wherein catalyzer used is HMS structure titanium silicon molecular sieve, prepares by the following method:
A) organosilicon source, inorganic silicon source, titanium source, organic formwork agent and water are mixed, in raw material, each component mol ratio is: organosilicon source: inorganic silicon source: titanium source: organic formwork agent: water=1: (1～30): (0.001～0.005): (0.01～0.05): (1～5); Mixture stirs after 0.1～5 hour at 30～70 DEG C, product after filtration, washing, dry, roasting, obtain precursor I; Wherein inorganic silicon source is selected from least one in silicon sol, silicon ester or solid oxidation silicon, and organosilicon source is methyltrimethoxy silane; Titanium source is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4or general formula is (R
2o)
4at least one in the organic titanate of Ti, wherein R
2be the alkyl of 1～4 carbon atom, organic formwork agent is selected from C
10～C
20primary amine;
B) at 50～400 DEG C, taking rare gas element as carrier gas, silylating reagent is passed in precursor I, react 0.5～10 hour, obtain described HMS structure titanium silicon molecular sieve; Wherein, described silylating reagent is selected from least one in organosilane, Organosilyl amine, Organosilyl acid amides or organosilazanes, and the weight ratio of silylating reagent and precursor I is 0.001～0.05.
In technique scheme, the each component mol ratio of raw material preferable range is: organosilicon source: inorganic silicon source: titanium source: organic formwork agent: water=1: (2～19): (0.002～0.004): (0.02～0.04): (1.5～4.5).Organosilane is selected from trimethylchlorosilane, dichlorodimethylsilane, one chlorine monobromo dimethylsilane, nitrotrimethylolmethane methyl-monosilane, chlorotriethyl silane, dimethylbutyl iodine silane, at least one in 3,5-dimethylphenyl chlorosilane or dimethyl chloride bromo-silicane, Organosilyl amine is selected from N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine, N-trimethyl silyl diethylamide, at least one in N-trimethyl silyl pyrroles or N-trimethyl silyl piperidines, Organosilyl acid amides is selected from N, the two trimethyl silyl ethanamides of 0-, N, the two trimethyl silyl trifluoroacetamides of 0-, N-trimethyl silyl ethanamide, at least one in N-methyl-N-trimethyl silyl trifluoroacetamide or N-methyl-N-trimethyl silyl hexafluoro butyramide, organosilazanes is selected from hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-divinyl-1, at least one in 1,3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane.Described silylating reagent preferred version is at least one being selected from organosilane or organosilazanes.Described organic formwork agent preferred version is at least one being selected from hexadecylamine, octadecyl amine or n-dodecylamine.The weight ratio preferable range of silylating reagent and precursor I is 0.005～0.4.Described rare gas element is nitrogen.Step b) in, temperature of reaction preferable range is 80～300 DEG C, more preferably 100～250 DEG C of scopes; Reaction times preferable range is 1～8 hour, and more preferably scope is 1.5～7 hours.Hydrogen phosphide cumene and propylene reaction, wherein hydrogen phosphide cumene and propylene mol ratio preferable range are 1: 1～1: 8, temperature of reaction preferable range is 50～90 DEG C, and reaction pressure preferable range is 1～3MPa, and hydrogen phosphide cumene mass space velocity preferable range is 1～20 hour
-1.
The HMS structure titanium silicon molecular sieve that the inventive method adopts two-step approach to prepare is catalyzer, first in synthetic Ti-HMS glue, add the molecular sieve of the synthetic situ-formed graft methyl of organosilicon source methyltrimethoxy silane, introduce organic group by the hydrolysis cocondensation in organosilicon source and inorganic silicon source on surface, duct; Then adopt vapor phase process grafting methyl, obtain rich methylic Ti-HMS molecular sieve.Ti-HMS meso-porous molecular sieve material prepared by two-step approach can reduce the quantity of hydroxyl and B acid position better, increases the hydrophobicity on molecular sieve surface, improves the catalytic performance of molecular sieve.Adopting the inventive method, on fixed bed device, is 5 at propylene and hydrogen phosphide cumene CHP mol ratio, temperature is to react 24 hours under 70 DEG C of conditions, the transformation efficiency of hydrogen phosphide cumene can reach 99%, and the selectivity of product propylene oxide can reach 98%, has obtained good technique effect.
Brief description of the drawings
Fig. 1 is catalyzer in the inventive method
29si CP/MAS NMR spectrogram.
Sample in δ=-90 ,-100 and-110ppm place has occurred
29the nuclear magnetic resonance peak of Si, they belong to respectively following three kinds of Siliciumatoms in different chemical environment: Q
2((SiO)
2si
*-(OH)
2), Q
3((SiO)
3si
*-OH) and Q
4((SiO)
4si
*), after silanization, there is a new resonance peak at δ=14.7ppm place, should belong to (SiO)
3si-OSi
*(CH
3)
3, this explanation is trimethyl silicon based there is effect with surperficial Si-hydroxyl carrier, and grafting, to the surface of catalyzer, has formed Si-O-Si (CH
3)
3group.This has confirmed that organosilicon grafting, to support of the catalyst surface, has formed Si-O-Si key.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
7.23 grams of hexadecylamines are dropped in solution form by 63 grams of deionized waters and 32.2 grams of ethanol to stirring and dissolving formation solution A at 50 DEG C.The methyltrimethoxy silane of 1 mole and 0.68 gram of butyl (tetra) titanate are splashed in the mixing solutions being made up of 6 grams of Virahols and 19 moles of tetraethoxys, stir 30 minutes, form solution B.Solution B is poured in solution A, stirred 18 hours, filter, washing is dry, and at 350 DEG C, roasting 8 hours, obtains precursor I.Then precursor I is contained in quartz tube reactor, 100 DEG C of temperature, under nitrogen atmosphere, pass into N-trimethyl-silyl-imidazole reaction 1.5 hours, then under nitrogen atmosphere, purge 2 hours, obtain HMS structure titanium silicon molecular sieve.Wherein, in raw material, each component mol ratio is: methyltrimethoxy silane: tetraethoxy: butyl (tetra) titanate: cetylamine: water=1: 19: 0.002: 0.03: 3.5, and the weight ratio of hexamethyldisilazane and precursor I is 0.01.Make catalyzer
29siCP/MAS NMR spectrogram as shown in Figure 1.
[embodiment 2]
With [embodiment 1], just in raw material, each component mol ratio is: methyltrimethoxy silane: tetraethoxy: butyl (tetra) titanate: cetylamine: water=1: 19: 0.004: 0.04: 3.5, under nitrogen atmosphere, the temperature of reaction of precursor I and hexamethyldisilazane is 200 DEG C, reaction times is 3 hours, and the weight ratio of hexamethyldisilazane and precursor I is 0.05.The product obtaining its
29si CP/MAS NMR spectrogram is similar to [embodiment 1].
[embodiment 3]
With [embodiment 1], just in raw material, each component mol ratio is: methyltrimethoxy silane: tetraethoxy: butyl (tetra) titanate: stearylamine: water=1: 5: 0.003: 0.04: 4.5, under nitrogen atmosphere, the temperature of reaction of precursor I and hexamethyldisilazane is 250 DEG C, reaction times is 5 hours, N, the weight ratio of the two trimethyl silyl ethanamides of 0-and precursor I is 0.005.The product obtaining its
29si CP/MAS NMR spectrogram is similar to [embodiment 1].
[embodiment 4]
With [embodiment 1], just in raw material, each component mol ratio is: methyltrimethoxy silane: tetraethoxy: butyl (tetra) titanate: cetylamine: water=1: 10: 0.003: 0.02: 1.5, under nitrogen atmosphere, the temperature of reaction of precursor I and trimethylchlorosilane is 100 DEG C, reaction times is 7 hours, and the weight ratio of hexamethyldisilazane and precursor I is 0.03.The product obtaining its
29si CP/MAS NMR spectrogram is similar to [embodiment 1].
[embodiment 5]
The sieve peg-raking catalyst of preparing with [embodiment 1～4], carries out hydrogen phosphide cumene and propylene reaction.
On fixed bed device, add 1 gram of catalyzer, 30wt% hydrogen phosphide cumene (CHP) flow is 0.28 ml/min, and propylene flow is 0.21 ml/min, and after constant temperature to 70 DEG C, reaction pressure 3MPa, reacts 24 hours.After reaction finishes, carry out the water absorption of saturated aqueous common salt and investigate, record the hydrophobic performance that water-intake rate shows this catalyzer.Concrete outcome is in table 1.
[comparative example 1]
7.23 grams of hexadecylamines are dropped in solution form by 63 grams of deionized waters and 32.2 grams of ethanol to stirring and dissolving formation solution A at 50 DEG C.0.68 gram of butyl (tetra) titanate is splashed in the mixing solutions being made up of 6 grams of Virahols and 19 moles of tetraethoxys, stir 30 minutes, form solution B.Solution B is poured in solution A, stirred 18 hours, filter, washing is dry, then roasting 8 hours at 350 DEG C.Wherein, in raw material, each component mol ratio is: tetraethoxy: butyl (tetra) titanate: hexadecylamine: water=1: 0.0003: 0.002: 0.15.
The sample obtaining carries out hydrogen phosphide cumene and propylene reaction with [embodiment 5], the results are shown in Table 1.
[comparative example 2]
7.23 grams of hexadecylamines are dropped in solution form by 63 grams of deionized waters and 32.2 grams of ethanol to stirring and dissolving formation solution A at 50 DEG C.The methyltrimethoxy silane of 1 mole and 0.68 gram of butyl (tetra) titanate are splashed in the mixing solutions being made up of 6 grams of Virahols and 19 moles of tetraethoxys, stir 30 minutes, form solution B.Solution B is poured in solution A, stirred 18 hours, filter, washing is dry, then roasting 8 hours at 350 DEG C.Wherein, in raw material, each component mol ratio is: methyltrimethoxy silane: tetraethoxy: butyl (tetra) titanate: hexadecylamine: water=1: 5: 0.003: 0.04: 4.5.
The sample obtaining is carried out to hydrogen phosphide cumene and propylene reaction with [embodiment 5], the results are shown in Table 1.
Table 1
[embodiment 6]
With [embodiment 5], just, on fixed bed device, 30% hydrogen phosphide cumene (CHP) flow is 0.28 ml/min, propylene flow is 0.21 ml/min, and temperature of reaction is 90 DEG C, and reaction pressure is 2MPa, catalyst levels is 1 gram, and the reaction times is 240 hours.The results are shown in Table 2.
Table 2
Claims (8)
1. a hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene, taking hydrogen phosphide cumene and propylene as raw material, be 1:1～1:10 at hydrogen phosphide cumene and propylene mol ratio, temperature of reaction is 50～100 DEG C, reaction pressure is 1～5MPa, and hydrogen phosphide cumene mass space velocity is 1～30 hour
-1under condition, reaction raw materials contacts with catalyzer and generates propylene oxide; Wherein catalyzer used is HMS structure titanium silicon molecular sieve, prepares by the following method:
A) organosilicon source, inorganic silicon source, titanium source, organic formwork agent and water are mixed, in raw material, each component mol ratio is: organosilicon source: inorganic silicon source: titanium source: organic formwork agent: water=1: (1～30): (0.001～0.005): (0.01～0.05): (1～5); Mixture stirs after 0.1～5 hour at 30～70 DEG C, product after filtration, washing, dry, roasting, obtain precursor I; Wherein inorganic silicon source is selected from least one in silicon sol, silicon ester or solid oxidation silicon, and organosilicon source is methyltrimethoxy silane; Titanium source is selected from TiCl
4, TiCl
3, TiOCl
2, TiOSO
4or general formula is (R
2o)
4at least one in the organic titanate of Ti, wherein R
2be the alkyl of 1～4 carbon atom, organic formwork agent is selected from C
10～C
20primary amine;
B) at 50～400 DEG C, taking rare gas element as carrier gas, silylating reagent is passed in precursor I, react 0.5～10 hour, obtain described HMS structure titanium silicon molecular sieve; Wherein, the weight ratio of silylating reagent and precursor I is 0.001～0.05;
Described silylating reagent is selected from least one in organosilane or organosilazanes;
Organosilane is selected from trimethylchlorosilane, dichlorodimethylsilane, one chlorine monobromo dimethylsilane, nitrotrimethylolmethane methyl-monosilane, chlorotriethyl silane, dimethylbutyl iodine silane, at least one in 3,5-dimethylphenyl chlorosilane or dimethyl chloride bromo-silicane, Organosilyl amine is selected from N-trimethyl-silyl-imidazole, N-dimethylethylsilyl imidazoles, N-dimethyl sec.-propyl silyl imidazoles, N-trimethyl silyl dimethyl amine, N-trimethyl silyl diethylamide, at least one in N-trimethyl silyl pyrroles or N-trimethyl silyl piperidines, Organosilyl acid amides is selected from N, the two trimethyl silyl ethanamides of 0-, N, the two trimethyl silyl trifluoroacetamides of 0-, N-trimethyl silyl ethanamide, at least one in N-methyl-N-trimethyl silyl trifluoroacetamide or N-methyl-N-trimethyl silyl hexafluoro butyramide, organosilazanes is selected from hexamethyldisilazane, heptamethyldisilazane, 1,1,3,3-tetramethyl-disilazane, 1,3-divinyl-1, at least one in 1,3,3-tetramethyl-disilazane or 1,3-phenylbenzene tetramethyl-disilazane.
2. hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene according to claim 1, it is characterized in that the each component mol ratio of raw material is: organosilicon source: inorganic silicon source: titanium source: organic formwork agent: water=1: (2～19): (0.002～0.004): (0.02～0.04): (1.5～4.5).
3. hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene according to claim 1, it is characterized in that described organic formwork agent is selected from least one in hexadecylamine, octadecyl amine or n-dodecylamine.
4. hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene according to claim 1, and the weight ratio that it is characterized in that silylating reagent and precursor I is 0.005～0.4.
5. hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene according to claim 1, it is characterized in that described rare gas element is nitrogen.
6. hydrogen phosphide cumene reacts with propylene and produces the method for propylene oxide according to claim 1, it is characterized in that step b), and temperature of reaction is 80～300 DEG C, and the reaction times is 1～8 hour.
7. hydrogen phosphide cumene reacts with propylene and produces the method for propylene oxide according to claim 6, it is characterized in that step b), and temperature of reaction is 100～250 DEG C, and the reaction times is 1.5～7 hours.
8. hydrogen phosphide cumene reacts the method for producing propylene oxide with propylene according to claim 1, it is characterized in that hydrogen phosphide cumene and propylene mol ratio are 1:1～1:8, temperature of reaction is 50～90 DEG C, reaction pressure is 1～3MPa, and hydrogen phosphide cumene mass space velocity is 1～20 hour
-1.
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| CN104230854A (en) * | 2013-06-17 | 2014-12-24 | 中国石油化工股份有限公司 | Cumyl hydroperoxide and propylene epoxidation method for preparing epoxypropane |
| CN104437618B (en) * | 2013-09-24 | 2017-06-20 | 中国石油化工股份有限公司 | Propylene prepares the catalyst of expoxy propane, preparation method and applications |
| CN104437635B (en) * | 2013-09-24 | 2017-02-08 | 中国石油化工股份有限公司 | Catalyst for preparing epoxy propane and preparation method and application thereof |
| CN104557779A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of epoxy propane |
| CN104557780A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of epoxypropane |
| CN104557783A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing epoxypropane from cumene hydroperoxide and propylene |
| CN104557781A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN104844493B (en) * | 2015-04-01 | 2017-03-15 | 中石化上海工程有限公司 | Cumyl peroxide DCP and the method for expoxy propane CHPPO coproduction |
| CN107224993B (en) * | 2017-05-25 | 2019-12-13 | 万华化学集团股份有限公司 | preparation method of olefin epoxidation catalyst |
| CN110270382B (en) * | 2018-03-13 | 2021-09-21 | 中国石油化工股份有限公司 | Hydrophobically modified hydrogenation catalyst, and preparation method and application thereof |
| CN111097512B (en) * | 2018-10-25 | 2023-05-02 | 中国石油化工股份有限公司 | Method for producing propylene oxide |
| CN111318299B (en) * | 2018-12-14 | 2022-07-12 | 万华化学集团股份有限公司 | Modified molecular sieve catalyst and preparation method thereof, and preparation method of styrene oxide |
| EP4036084A4 (en) * | 2019-09-25 | 2023-10-18 | Sumitomo Chemical Company, Limited | Method for producing propylene oxide |
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