CN115724810A - Method for preparing propylene oxide - Google Patents
Method for preparing propylene oxide Download PDFInfo
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- CN115724810A CN115724810A CN202111014063.9A CN202111014063A CN115724810A CN 115724810 A CN115724810 A CN 115724810A CN 202111014063 A CN202111014063 A CN 202111014063A CN 115724810 A CN115724810 A CN 115724810A
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- Prior art keywords
- oxidative dehydrogenation
- dehydrogenation reaction
- reaction mixture
- propane
- propylene
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- 238000000034 method Methods 0.000 title claims abstract description 45
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims abstract description 60
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011541 reaction mixture Substances 0.000 claims abstract description 45
- 239000001294 propane Substances 0.000 claims abstract description 42
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000010936 titanium Substances 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 27
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000001301 oxygen Substances 0.000 claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 25
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 28
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 17
- 239000002808 molecular sieve Substances 0.000 claims description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical group CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Epoxy Compounds (AREA)
Abstract
The present invention relates to a process for the preparation of propylene oxide, which process comprises: in the presence of a nano carbon material, enabling propane to contact oxygen to carry out oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture; the oxidative dehydrogenation reaction mixture is contacted with hydrogen peroxide in the presence of a titanium silicalite catalyst and optionally a solvent to effect epoxidation. The method has higher effective utilization rate of hydrogen peroxide and selectivity of propylene oxide.
Description
Technical Field
The present invention relates to a process for the preparation of propylene oxide.
Background
Propylene Oxide (PO) is a large chemical raw material, is the second largest organic chemical product with the second yield of the propylene derivatives to polypropylene, and is the highest among 50 chemicals with the largest global yield. PO has active chemical property and wide application, is mainly used for producing polyether, propylene glycol, isopropanolamine, allyl alcohol, non-polyether polyol and the like, further produces unsaturated polyester resin, polyurethane, surfactant and the like, is widely applied to the industries of chemical industry, light industry, medicine, food, textile and the like, and has profound influence on the development of chemical industry and national economy. With the expansion of PO application and the continuous increase of the dosage of downstream products, particularly the prosperity of industries such as automobiles, buildings, home furnishing and the like, the demand of polyurethane and nonionic surfactants is greatly increased, and the market demand of PO is vigorous.
The method using hydrogen peroxide as oxidant and titanium-silicon molecular sieve as catalyst can obtain higher propane conversion rate and PO selectivity, and open up a new way for PO synthesis. The method is simple and convenient, does not pollute the environment, is a very competitive PO production process, meets the requirements of the modern green chemistry and atomic economic development concepts, and is considered as a green new process for producing PO. However, due to H 2 O 2 Are extremely unstable, subject to heat, light, rough surfaces, decomposition of heavy metals and other impurities, and are corrosive, and special safety measures are taken in packaging, storage and transportation. Subject to cost and safety concerns, and preparation of H 2 O 2 Requires separate equipment and circulation systems, is expensive, has high on-site production cost, and has no obvious economic advantages before being released by stricter environmental regulations.
Disclosure of Invention
The invention aims to provide a method for preparing propylene oxide, which has higher effective utilization rate of hydrogen peroxide and selectivity of propylene oxide.
In order to achieve the above object, the present invention provides a method for preparing propylene oxide, comprising:
s1, in the presence of a nano carbon material, enabling propane to contact oxygen to carry out oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture;
and S2, in the presence of a titanium-silicon catalyst and an optional solvent, contacting the oxidative dehydrogenation reaction mixture with hydrogen peroxide to carry out epoxidation reaction.
Alternatively, in step S1, the conditions of the oxidative dehydrogenation reaction include: the temperature is 250-600 ℃, the pressure is 0.1-2.5MPa, and the time is 0.1-48h.
Optionally, in step S1, the volume space velocity of the propane is 10-2000h -1 (ii) a The molar ratio of the propane to the oxygen is 1: (0.2-2).
Optionally, in step S1, the oxidative dehydrogenation reaction mixture comprises propane, propylene, and optionally oxygen; the propylene content is from 10 to 90% by volume, based on the total volume of the oxidative dehydrogenation reaction mixture.
Alternatively, in step S2, the epoxidation reaction conditions include: the temperature is 0-80 ℃, the pressure is 0.1-5MPa, and the time is 0.1-12h.
Alternatively, in step S2, the molar ratio of propylene to the amount of hydrogen peroxide in the oxidative dehydrogenation reaction mixture is 1: (0.1-2), preferably 1: (0.5-1.5);
the weight ratio of the oxidative dehydrogenation reaction mixture to the solvent is 100: (1-5000), preferably 100: (10-1000);
the solvent is selected from one or more of water, alcohol, ketone and nitrile; preferably, the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol and isobutanol; the ketone is acetone and/or butanone; the nitrile is acetonitrile.
Optionally, in step S2, the titanium silicalite catalyst contains titanium silicalite, the content of the titanium silicalite is 70 to 100 wt% based on the total weight of the titanium silicalite catalyst, and the molar ratio of silicon to titanium of the titanium silicalite is 20 to 80.
Optionally, in step S1, the nanocarbon material is prepared by a method including the following steps:
in the atmosphere of ammonia gas, roasting the carbon nano tube for 2-10h at 500-700 ℃ to obtain the nano carbon material;
based on the total weight of the nano-carbon material, the carbon content of the nano-carbon material is 82-99 wt%, the nitrogen content is 1-8 wt%, and the balance is oxygen;
the ammonia gas atmosphere contains ammonia gas and helium gas, and the content of the ammonia gas is 0.2-10% by volume.
Optionally, the methodThe method is continuous operation, and the total volume space velocity of the epoxidation reaction is 0.5-200h -1 Preferably 1-50h -1 。
Optionally, the method may further include: and (3) carrying out gas-liquid separation on the mixture obtained by the epoxidation reaction, and returning the obtained gas phase material flow to the step S1.
Through the technical scheme, the method is simple and feasible, can effectively improve the effective utilization rate of the hydrogen peroxide, and has higher selectivity of the propylene oxide.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
In a first aspect, the present invention provides a process for producing propylene oxide, the process comprising:
s1, in the presence of a nano carbon material, enabling propane to contact oxygen to carry out oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture;
and S2, in the presence of a titanium-silicon catalyst and an optional solvent, contacting the oxidative dehydrogenation reaction mixture with hydrogen peroxide to perform epoxidation reaction.
In the method, the mixture after the oxidative dehydrogenation of the propane is directly used for the epoxidation of the propylene by using the hydrogen peroxide as an oxidant, and the oxidative dehydrogenation reaction mixture (mainly the propylene, the water, the unreacted propane and the unreacted oxygen) can directly enter the epoxidation process without separation, so that the process is greatly simplified, and the industrial implementation is facilitated. The conversion rate of propane and the concentration of propylene in oxidative dehydrogenation are greatly improved compared with the direct dehydrogenation, the efficiency of an epoxidation reaction device is improved, and the load of a device for subsequent separation and circulation of unreacted propane is reduced; and the reaction temperature of oxidative dehydrogenation is relatively mild, which is more beneficial to the stability of the catalyst nano carbon material, prolongs the one-way operation time of the catalyst, and integrally reduces the energy consumption and the material consumption, so that the technology of the invention has more market competitiveness. The method can improve the effective utilization rate of the oxidant hydrogen peroxide in the epoxidation process and has higher selectivity of the propylene oxide.
In one embodiment of the present invention, the method of the present invention may further comprise: the reaction heat of the oxidative dehydrogenation reaction is used for the subsequent separation and purification process of the target product propylene oxide so as to improve the utilization rate of energy. In another embodiment, the oxydehydrogenation product reaction mixture is heat exchanged with propylene oxide to initially separate water from the oxydehydrogenation reaction mixture before introducing the gas phase components into step S2.
According to the present invention, in step S1, the conditions of the oxidative dehydrogenation reaction may include: the temperature is 250-600 ℃, the pressure is 0.1-2.5MPa, and the time is 0.1-48h; preferably, the temperature is 300-450 ℃, the pressure is 0.1-1.5MPa, and the time is 0.5-8h.
According to the invention, the volume space velocity of propane can be varied within a wide range, and in order to allow sufficient contact reaction of propane with the nanocarbon material, in a preferred embodiment, the volume space velocity of propane is in the range of 1 to 10000h -1 Preferably 10-2000h -1 . When the volume space velocity of propane is within the above range, the oxidative dehydrogenation reaction can be carried out more sufficiently, which is also advantageous in further improving the effective utilization rate of hydrogen peroxide and the selectivity of the final target product, propylene oxide.
According to the invention, the molar ratio of propane to oxygen used in step S1 may vary within wide limits, for example 1: (0.2-2.0), preferably 1: (0.8-1.2).
According to the present invention, in step S1, the oxidative dehydrogenation reaction mixture may contain propane, propylene and optionally oxygen. The propylene content may be from 10 to 90% by volume, based on the total volume of the oxydehydrogenation reaction mixture.
According to the present invention, in step S2, the epoxidation reaction conditions may include: the temperature is 0-80 ℃, the pressure is 0.1-5.0MPa, and the time is 0.1-12h; preferably, the temperature is 30-60, the pressure is 0.5-3.0MPa, and the time is 0.5-6h.
In one embodiment of the present invention, in step S2, the molar ratio of the amount of propylene to the amount of hydrogen peroxide in the oxidative dehydrogenation reaction mixture is 1: (0.1-2), preferably 1: (0.5-1.5); the weight ratio of the oxidative dehydrogenation reaction mixture to the solvent is 100: (1-5000), preferably 100: (10-1000).
According to the present invention, the solvent may be selected from one or more of water, alcohol, ketone and nitrile. In a preferred embodiment, the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol and isobutanol; the ketone is acetone and/or butanone; the nitrile is acetonitrile.
According to the present invention, the titanium silicalite catalyst contains titanium silicalite molecular sieves, which are well known to those skilled in the art, and can be, for example, one or more of molecular sieves having MFI structure, MOR structure and BEA structure, and the content of the titanium silicalite molecular sieves in the titanium silicalite catalyst can be varied within a relatively large range, for example, the content of the titanium silicalite molecular sieves is 70-100 wt% based on the total weight of the titanium silicalite catalyst, and the silicon-titanium molar ratio of the titanium silicalite molecular sieves can also be varied within a relatively large range, for example, 20-80, preferably 20-70.
According to the present invention, the source of the nanocarbon material is not limited, and may be commercially available or prepared by itself. In one embodiment, the preparation method comprises the following steps: and (2) roasting the carbon nano tube for 2-10h at 500-700 ℃ in an ammonia atmosphere to obtain the nano carbon material.
According to the present invention, in order to obtain a nanocarbon material having good physicochemical properties, the ammonia gas atmosphere further contains helium gas as an equilibrium gas, and the content of ammonia gas may vary within a wide range, and may be, for example, 0.2 to 10% by volume, and preferably 0.6 to 7% by volume.
According to the present invention, the carbon content of the nanocarbon material may be 82 to 99% by weight, the nitrogen content may be 1 to 8% by weight, and the balance is oxygen, based on the total weight of the nanocarbon material; preferably, the nanocarbon material has a carbon content of 95 to 99 wt%, a nitrogen content of 1 to 5 wt%, and the balance being oxygen.
According to the invention, the methodThe method is continuous operation, and the total volume space velocity of the epoxidation reaction is 0.5-200h -1 Preferably 1-50h -1 。
In a specific embodiment of the present invention, the method may further include: and (2) carrying out gas-liquid separation on the mixture obtained by the epoxidation reaction to obtain a gas-phase material flow (containing propane, propylene and oxygen) and a liquid-phase material flow (containing propylene oxide, a solvent and water), and returning the obtained gas-phase material flow to the step S1 for carrying out the oxidative dehydrogenation reaction. In the method, the gas phase material flow separated after the epoxidation reaction is returned to the oxidative dehydrogenation reaction process, so that the process flow is simplified, the operation and separation cost is reduced, and the utilization rate of the raw material propane is improved.
The invention is further illustrated by the following examples, but is not limited thereto.
All reagents used in the examples were commercially available, chemically pure reagents.
The nano carbon material is a multi-wall Carbon Nano Tube (CNT) modified by ammonia nitrogen, and the specific preparation method comprises the following steps: the CNT is calcined for 4 hours at 600 ℃ in 2% ammonia gas atmosphere, the balance gas is helium, the carbon content in the nano carbon material is 96 wt%, the nitrogen content is 3.1 wt%, and the balance is oxygen.
The titanium silicalite molecular sieve (TS-1) is a calcined molecular sieve (TS-1) prepared as described in Zeolite, 1992, vol.12, pages 943-950 of the prior art. The titanium silicalite molecular sieve (TS-1) has a silicon-titanium molar ratio of 27.
In comparative examples and examples:
propane conversion (%) = (mole amount of propane in charge-mole amount of unreacted propane)/mole amount of propane in charge × 100%;
propylene oxide selectivity (%) = moles of propylene oxide in product/moles of propylene total conversion x 100%;
hydrogen peroxide effective utilization (%) = molar amount of propylene oxide in product/molar amount of total hydrogen peroxide conversion x 100%.
Example 1
S1, at normal pressure of 400 ℃, the propane volume space velocity is 100h -1 Then, propane is reactedWith oxygen in a ratio of 1:1, firstly, carrying out oxidative dehydrogenation reaction for 6 hours by using a bed layer with a nano-carbon material as a catalyst to obtain an oxidative dehydrogenation reaction mixture, carrying out heat exchange on the oxidative dehydrogenation reaction mixture and a product of epoxidation reaction, and then preliminarily separating gas and liquid to obtain water; at this time, the oxidative dehydrogenation reaction mixture mainly contains propylene produced after the reaction, propane which does not participate in the reaction, and oxygen, wherein the content of propylene is 36% by volume;
s2, at the temperature of 40 ℃, the pressure of 0.5MPa and the space velocity of the total volume of 10h -1 Then, mixing the oxidative dehydrogenation reaction mixture with hydrogen peroxide, methanol and a titanium silicalite molecular sieve according to the molar ratio of propylene to hydrogen peroxide in the oxidative dehydrogenation reaction mixture of 1:0.5, the weight ratio of the oxidative dehydrogenation reaction mixture to methanol is 1:10, carrying out epoxidation reaction for 1h, and the results are shown in Table 1.
Example 2
S1, at normal pressure of 600 ℃, the propane volume space velocity is 10h -1 Then, propane is mixed with oxygen in a ratio of 1:2, firstly carrying out oxidative dehydrogenation reaction for 5 hours through a bed layer taking the nano carbon material as a catalyst to obtain an oxidative dehydrogenation reaction mixture, carrying out heat exchange on the oxidative dehydrogenation reaction mixture and a product of epoxidation reaction, and then carrying out primary gas-liquid separation to obtain water; at this time, the oxidative dehydrogenation reaction mixture mainly contained propane, propylene and oxygen, wherein the content of propylene was 80% by volume;
s2, at the temperature of 40 ℃, the pressure of 2.5MPa and the space velocity of the total volume of 200h -1 Then, mixing the oxidative dehydrogenation reaction mixture with hydrogen peroxide, methanol and a titanium silicalite molecular sieve according to the molar ratio of the propylene to the hydrogen peroxide in the oxidative dehydrogenation reaction mixture of 2:1, the weight ratio of the oxidative dehydrogenation reaction mixture to the methanol is 1: and 10, carrying out epoxidation reaction for 3h.
Example 3
S1, under the normal pressure of 500 ℃ and the propane volume space velocity of 100h -1 Then, propane is mixed with oxygen in a ratio of 2:1, firstly, carrying out oxidative dehydrogenation reaction for 4 hours by using a bed layer with a nano-carbon material as a catalyst to obtain an oxidative dehydrogenation reaction mixture, carrying out heat exchange on the oxidative dehydrogenation reaction mixture and a product of epoxidation reaction, and then preliminarily separating gas and liquid to obtain water; at this time, the oxidative dehydrogenation reaction mixture mainly contained propane, propylene and oxygen, wherein the content of propylene was 25% by volume；
S2, under the conditions that the temperature is 50 ℃, the pressure is 1.5MPa, and the space velocity of the total volume is 100h -1 Then, mixing the oxidative dehydrogenation reaction mixture with hydrogen peroxide, tert-butyl alcohol and a titanium silicalite molecular sieve according to the molar ratio of propylene to hydrogen peroxide in the oxidative dehydrogenation reaction mixture being 1:1, the weight ratio of the oxidative dehydrogenation reaction mixture to the tertiary butanol is 1: and 20, carrying out epoxidation reaction for 2 hours, wherein the mass ratio of the tert-butyl alcohol to the titanium silicalite molecular sieve is 40.
Example 4
Propylene oxide was produced in the same manner as in example 1, except that in step S1, the volume space velocity of propane was 100 hours -1 The molar ratio of the propane to the oxygen is 1:3, the propylene content in the oxidative dehydrogenation reaction mixture was 89% by volume.
Example 5
Propylene oxide was prepared in the same manner as in example 1, except that in step S1, the volume space velocity of propane was 500 hours -1 The molar ratio of the propane to the oxygen is 1:0.1, the content of propylene in the oxidative dehydrogenation reaction mixture was 5% by volume.
Example 6
Propylene oxide was produced in the same manner as in example 1, except that, in step S1, the time of the oxidative dehydrogenation reaction was 12 hours, the temperature was 210 ℃ and the content of propylene in the oxidative dehydrogenation reaction mixture was 3% by volume.
Example 7
Propylene oxide was produced in the same manner as in example 1, except that the molar ratio of propylene to hydrogen peroxide in the oxidative dehydrogenation reaction mixture in step S2 was 1:0.4.
example 8
Propylene oxide was produced in the same manner as in example 1, except that the temperature of the epoxidation reaction in step S2 was 100 ℃, the pressure was 0.15MPa, and the time was 1 hour.
Example 9
Propylene oxide was produced in the same manner as in example 1, except that the total volume of the epoxidation reaction was emptied in step S2The speed is 80h -1 。
Comparative example 1
Propylene oxide was prepared by the same method as in example 1, except that the nanocarbon material was not used in step S1.
Comparative example 2
Propylene oxide was prepared by the same method as in example 1, except that no titanium silicalite was used in step S2.
Comparative example 3
Propylene oxide was prepared in the same manner as in example 1, except that a nanocarbon material was not used in step S1 and a titanium silicalite molecular sieve was not used in step S2.
TABLE 1
As can be seen from Table 1, the method for preparing propylene oxide from propane provided by the invention not only has high conversion rate of propane, but also has higher effective utilization rate of hydrogen peroxide and selectivity of propylene oxide.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A process for the preparation of propylene oxide, the process comprising:
s1, in the presence of a nano carbon material, enabling propane to contact oxygen to carry out oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture;
and S2, in the presence of a titanium-silicon catalyst and an optional solvent, contacting the oxidative dehydrogenation reaction mixture with hydrogen peroxide to perform epoxidation reaction.
2. The process according to claim 1, wherein in step S1, the conditions of the oxidative dehydrogenation reaction comprise: the temperature is 250-600 ℃, the pressure is 0.1-2.5MPa, and the time is 0.1-48h.
3. The process of claim 1, wherein in step S1, the volume space velocity of propane is 10-2000h -1 (ii) a The molar ratio of the propane to the oxygen is 1: (0.2-2).
4. The process of claim 1, wherein in step S1, the oxidative dehydrogenation reaction mixture comprises propane, propylene, and optionally oxygen;
the propylene content is from 10 to 90% by volume, based on the total volume of the oxidative dehydrogenation reaction mixture.
5. The method of claim 1, wherein in step S2, the epoxidation reaction conditions comprise: the temperature is 0-80 ℃, the pressure is 0.1-5MPa, and the time is 0.1-12h.
6. The process of claim 1, wherein in step S2, the molar ratio of propene to the amount of hydrogen peroxide used in the oxidative dehydrogenation reaction mixture is 1: (0.1-2), preferably 1: (0.5-1.5); the weight ratio of the oxidative dehydrogenation reaction mixture to the solvent is 100: (1-5000), preferably 100: (10-1000);
the solvent is selected from one or more of water, alcohol, ketone and nitrile; preferably, the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol and isobutanol; the ketone is acetone and/or butanone; the nitrile is acetonitrile.
7. The method of claim 1, wherein in step S2, the titanium silicalite catalyst contains titanium silicalite molecular sieves, and the content of the titanium silicalite molecular sieves is 70-100 wt% based on the total weight of the titanium silicalite catalyst, and the molar ratio of silicon to titanium of the titanium silicalite molecular sieves is 20-80.
8. The method of claim 1, wherein, in step S1, the nanocarbon material is prepared by a method comprising:
in the atmosphere of ammonia gas, roasting the carbon nano tube for 2-10h at 500-700 ℃ to obtain the nano carbon material;
based on the total weight of the nano-carbon material, the carbon content of the nano-carbon material is 82-99 wt%, the nitrogen content is 1-8 wt%, and the balance is oxygen;
the ammonia gas atmosphere contains ammonia gas and helium gas, and the content of the ammonia gas is 0.2-10% by volume.
9. The process as claimed in claim 1, wherein the process is operated continuously, the overall space velocity of the epoxidation reaction being from 0.5 to 200h -1 Preferably 1-50h -1 。
10. The method of claim 1, wherein the method further comprises: and (3) carrying out gas-liquid separation on the mixture obtained by the epoxidation reaction, and returning the obtained gas phase material flow to the step S1.
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