CN115724810B - Method for preparing epoxypropane - Google Patents
Method for preparing epoxypropane Download PDFInfo
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- CN115724810B CN115724810B CN202111014063.9A CN202111014063A CN115724810B CN 115724810 B CN115724810 B CN 115724810B CN 202111014063 A CN202111014063 A CN 202111014063A CN 115724810 B CN115724810 B CN 115724810B
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- oxidative dehydrogenation
- dehydrogenation reaction
- reaction mixture
- titanium
- propane
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 38
- 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 63
- 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
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 27
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 27
- 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 18
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002808 molecular sieve Substances 0.000 claims description 19
- 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 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 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 4
- 239000010703 silicon Substances 0.000 claims description 4
- 230000000694 effects Effects 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 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
- 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
- 238000002156 mixing 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
- 238000002360 preparation method Methods 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
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000010276 construction 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
- 230000002035 prolonged 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
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- Epoxy Compounds (AREA)
Abstract
The present invention relates to a process for preparing propylene oxide, which comprises: in the presence of a nano carbon material, enabling propane to contact with oxygen to perform 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 preparing propylene oxide.
Background
Propylene Oxide (PO) is a large chemical raw material, and is a second largest organic chemical product with the yield of propylene derivatives being inferior to that of polypropylene among 50 chemicals with the largest global yield. The PO has very active chemical property and wide application, is mainly used for producing polyether, propylene glycol, isopropanolamine, allyl alcohol, non-polyether polyol and the like, further producing 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. Along with the expansion of the application of PO and the continuous increase of the consumption of downstream products, especially the flourishing of industries such as automobiles, construction home furnishings and the like, the demand for polyurethane and nonionic surfactant 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 have higher propane conversion rate and PO selectivity, and opens up a new way for PO synthesis. The method is simple and convenient, does not pollute the environment, is a PO production process with great competitiveness, meets the requirements of modern green chemistry and atomic economy development concepts, and is considered as a green new process for producing PO. However, H 2O2 is extremely unstable, and when exposed to heat, light, rough surfaces, heavy metals and other impurities are decomposed, and the H 2O2 is corrosive, so that special safety measures are required in packaging, storage and transportation. The preparation of H 2O2 is limited by cost and safety problems, and requires a separate device and a circulating system, so that the cost is high, the on-site production cost is high, and the economic advantage is not obvious until no stricter environmental regulations are put out.
Disclosure of Invention
The invention aims to provide a method for preparing propylene oxide, which has high 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 producing propylene oxide, comprising:
S1, in the presence of a nano carbon material, enabling propane to contact oxygen for oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture;
S2, contacting the oxidative dehydrogenation reaction mixture with hydrogen peroxide in the presence of a titanium silicon catalyst and an optional solvent to perform epoxidation reaction.
Optionally, in step S1, the oxidative dehydrogenation reaction conditions 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; the molar ratio of the propane to the oxygen is 1: (0.2-2).
Optionally, in step S1, the oxidative dehydrogenation reaction mixture contains 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.
Optionally, 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.
Optionally, 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-silicon catalyst contains a titanium-silicon molecular sieve, wherein the content of the titanium-silicon molecular sieve is 70-100 wt% based on the total weight of the titanium-silicon catalyst, and the molar ratio of silicon to titanium of the titanium-silicon molecular sieve is 20-80.
Optionally, in step S1, the nanocarbon material is prepared by a method including the following steps:
Roasting the carbon nano tube for 2-10 hours at 500-700 ℃ in an ammonia atmosphere 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.
Alternatively, the process is operated continuously, the total volume space velocity of the epoxidation reaction being in the range of from 0.5 to 200h -1, preferably from 1 to 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 easy to implement, can effectively improve the effective utilization rate of the hydrogen peroxide, and has higher selectivity of propylene oxide.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
In a first aspect, the present invention provides a process for preparing propylene oxide, the process comprising:
S1, in the presence of a nano carbon material, enabling propane to contact oxygen for oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture;
S2, contacting the oxidative dehydrogenation reaction mixture with hydrogen peroxide in the presence of a titanium silicon catalyst and an optional solvent to perform epoxidation reaction.
In the method, the mixture after the oxidative dehydrogenation of propane is directly used for propylene epoxidation reaction by taking hydrogen peroxide as an oxidant, and the oxidative dehydrogenation reaction mixture (mainly propylene, water and unreacted propane and oxygen) can directly enter the epoxidation reaction process without separation, so that the process is greatly simplified and the industrialized implementation is facilitated. Compared with the direct dehydrogenation, the oxidative dehydrogenation greatly improves the conversion rate of propane and the concentration of propylene, improves the efficiency of an epoxidation reaction device, and simultaneously reduces the load of the device for subsequent separation and circulation of unreacted propane; the reaction temperature of oxidative dehydrogenation is also relatively mild, so that the stability of the catalyst nano carbon material is facilitated, the single-pass operation time of the catalyst is prolonged, and the energy consumption and the material consumption are reduced as a whole, 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 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 that the utilization rate of energy sources is improved. In another embodiment, the oxidative dehydrogenation product reaction mixture is heat exchanged with propylene oxide to initially separate water from the oxidative dehydrogenation reaction mixture and the gas phase component is introduced 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.
The volume space velocity of propane according to the present invention may vary within a wide range, and in order to allow a sufficient contact reaction of propane with the nanocarbon material, in a preferred embodiment, the volume space velocity of propane is 1 to 10000h -1, preferably 10 to 2000h -1. When the volume space velocity of propane is within the above range, the oxidative dehydrogenation reaction can be more fully carried out, and the effective utilization rate of hydrogen peroxide and the selectivity of propylene oxide as a final target product can be further improved.
According to the invention, in step S1, the molar ratio of propane to oxygen used can vary within a wide range, for example 1: (0.2-2.0), preferably 1: (0.8-1.2).
According to the invention, in step S1, the oxidative dehydrogenation reaction mixture may comprise propane, propylene and optionally oxygen. The propylene content may be from 10 to 90% by volume, based on the total volume of the oxidative dehydrogenation reaction mixture.
According to the present invention, in step S2, the conditions of the epoxidation reaction 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 invention, in step S2, the molar ratio of propylene to 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 amount of solvent used 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, t-butanol and isobutanol; the ketone is acetone and/or butanone; the nitrile is acetonitrile.
According to the invention, the titanium-silicon catalyst contains titanium-silicon molecular sieves, which are well known to those skilled in the art, and may be, for example, one or more of molecular sieves having an MFI structure, a MOR structure, and a BEA structure, and the content of the titanium-silicon molecular sieve in the titanium-silicon catalyst may vary within a wide range, for example, 70 to 100% by weight, based on the total weight of the titanium-silicon catalyst, and the molar ratio of silicon to titanium of the titanium-silicon molecular sieve may also vary within a wide range, for example, 20 to 80, and preferably 20 to 70.
According to the present invention, the source of the nanocarbon material is not limited, and it may be commercially available or self-prepared. In one embodiment, the method comprises the following steps: and roasting the carbon nano tube for 2-10 hours 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, helium is contained in the ammonia atmosphere as a balance gas, and the content of ammonia may vary within a wide range, for example, may be 0.2 to 10% by volume, and preferably 0.6 to 7% by volume.
According to the invention, the carbon content of the nano carbon material can be 82-99 wt%, the nitrogen content can be 1-8 wt%, and the balance is oxygen, based on the total weight of the nano carbon material; preferably, the carbon content of the nanocarbon material is 95-99 wt%, the nitrogen content is 1-5 wt%, and the balance is oxygen.
According to the invention, the process is operated continuously, the total volume space velocity of the epoxidation reaction being in the range from 0.5 to 200h -1, preferably from 1 to 50h -1.
In one embodiment of the present invention, the method may further comprise: and (3) carrying out gas-liquid separation on the mixture obtained by the epoxidation reaction to obtain a gas-phase stream (containing propane, propylene and oxygen) and a liquid-phase stream (containing propylene oxide, solvent and water), and returning the obtained gas-phase stream to the step S1 for carrying out 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 separation cost is reduced, and the utilization rate of raw material propane is improved.
The invention is further illustrated by the following examples, which are not intended to be limiting in any way.
The reagents used in the examples were all commercially available chemically pure reagents.
The nano carbon material is a multiwall Carbon Nanotube (CNT) modified by ammonia nitrogen, and the specific preparation method comprises the following steps: the CNTs are calcined for 4 hours at 600 ℃ in 2% ammonia atmosphere, the balance gas is helium, the carbon content in the nano carbon material is 96% by weight, the nitrogen content is 3.1% by weight, and the balance is oxygen.
Titanium silicalite molecular sieves (TS-1) are calcined molecular sieves (TS-1) prepared as described in the prior art Zeolite, 1992, vol.12, pages 943-950. The molar ratio of silicon to titanium of the titanium silicon molecular sieve (TS-1) is 27.
In the comparative examples and examples:
Propane conversion (%) = (molar amount of propane in feed-molar amount of unreacted propane)/molar amount of propane in feed x 100%;
propylene oxide selectivity (%) = molar amount of propylene oxide in product/molar amount of total conversion of propylene x 100%;
Effective hydrogen peroxide utilization (%) = molar amount of propylene oxide in product/molar amount of total conversion of hydrogen peroxide x 100%.
Example 1
S1, enabling propane and oxygen to be mixed at a normal pressure of 400 ℃ and a propane volume space velocity of 100h -1: 1, carrying out oxidative dehydrogenation reaction for 6 hours through a bed layer with a nano carbon material as a catalyst, and carrying out heat exchange on the obtained oxidative dehydrogenation reaction mixture and an epoxidation reaction product to obtain primary gas-liquid separation water; at this time, the oxidative dehydrogenation reaction mixture mainly contains propylene produced after the reaction, and propane and oxygen which do not participate in the reaction, wherein the content of propylene is 36% by volume;
S2, under the conditions that the temperature is 40 ℃, the pressure is 0.5MPa, the total volume space velocity is 10h -1, the oxidative dehydrogenation reaction mixture and hydrogen peroxide, methanol and titanium silicalite molecular sieves are mixed according to the mole ratio of propylene to hydrogen peroxide in the oxidative dehydrogenation reaction mixture of 1:0.5, the weight ratio of oxidative dehydrogenation reaction mixture to methanol is 1:10, epoxidation reaction was carried out for 1 hour, and the results are shown in Table 1.
Example 2
S1, mixing propane and oxygen at the normal pressure 600 ℃ and the propane volume space velocity of 10h -1 according to the ratio of 1:2, carrying out oxidative dehydrogenation reaction for 5 hours through a bed layer with a nano carbon material as a catalyst to obtain an oxidative dehydrogenation reaction mixture, and carrying out heat exchange on the oxidative dehydrogenation reaction mixture and a product of the epoxidation reaction to obtain primary gas-liquid separation water; at this time, the oxidative dehydrogenation reaction mixture mainly contains propane, propylene and oxygen, wherein the content of propylene is 80% by volume;
S2, under the conditions that the temperature is 40 ℃, the pressure is 2.5MPa, the total volume space velocity is 200h -1, the oxidative dehydrogenation reaction mixture and hydrogen peroxide, methanol and titanium silicalite molecular sieves are mixed according to the mole ratio of propylene to hydrogen peroxide in the oxidative dehydrogenation reaction mixture of 2:1, the weight ratio of the oxidative dehydrogenation reaction mixture to methanol is 1:10, performing an epoxidation reaction for 3 hours.
Example 3
S1, mixing propane and oxygen at normal pressure 500 ℃ and a propane volume space velocity of 100h -1 according to a ratio of 2:1, carrying out oxidative dehydrogenation reaction for 4 hours through a bed layer with a nano carbon material as a catalyst to obtain an oxidative dehydrogenation reaction mixture, and carrying out heat exchange on the oxidative dehydrogenation reaction mixture and a product of the epoxidation reaction to obtain primary gas-liquid separation water; at this time, the oxidative dehydrogenation reaction mixture mainly contains propane, propylene and oxygen, wherein the content of propylene is 25% by volume;
S2, under the conditions that the temperature is 50 ℃, the pressure is 1.5MPa, the total volume space velocity is 100h -1, and the mol ratio of propylene to hydrogen peroxide in the oxidative dehydrogenation reaction mixture is 1:1, the weight ratio of the oxidative dehydrogenation reaction mixture to the tertiary butanol is 1:20, the mass ratio of the tertiary butanol to the titanium silicalite molecular sieve is 40, and the epoxidation reaction is carried out for 2h.
Example 4
Propylene oxide was prepared in the same manner as in example 1 except that in step S1, the volume space velocity of propane was 100h -1 and the molar ratio of propane to oxygen was 1:3 the content of propylene 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 500h -1 and the molar ratio of propane to oxygen was 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 for the oxidative dehydrogenation reaction was 12 hours, the temperature was 210℃and the propylene content in the oxidative dehydrogenation reaction mixture was 3% by volume.
Example 7
Propylene oxide was prepared 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 epoxidation reaction in step S2 was carried out at a temperature of 100℃and a pressure of 0.15MPa for a period of 1 hour.
Example 9
Propylene oxide was prepared in the same manner as in example 1 except that in step S2, the total volume space velocity of the epoxidation reaction was 80h -1.
Comparative example 1
Propylene oxide was prepared in the same manner as in example 1, except that the nanocarbon material was not used in step S1.
Comparative example 2
Propylene oxide was prepared in the same manner as in example 1 except that no titanium silicalite molecular sieve was used in step S2.
Comparative example 3
Propylene oxide was prepared in the same manner as in example 1, except that no nanocarbon material was used in step S1, and no titanium silicalite molecular sieve was 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 has high conversion rate of propane, and has high effective utilization rate of hydrogen peroxide and high selectivity of propylene oxide.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (10)
1. A process for preparing propylene oxide, the process comprising:
S1, in the presence of a nano carbon material, enabling propane to contact oxygen for oxidative dehydrogenation reaction to obtain an oxidative dehydrogenation reaction mixture;
S2, enabling the oxidative dehydrogenation reaction mixture to be in contact with hydrogen peroxide in the presence of a titanium-silicon catalyst and an optional solvent for epoxidation;
The conditions of the oxidative dehydrogenation reaction include: the temperature is 400-600 ℃, the pressure is 0.1-2.5MPa, and the time is 4-48h;
The volume airspeed of the propane is 10-100h -1; the molar ratio of the propane to the oxygen is 1: (0.5-2);
The nano carbon material is prepared by adopting a method comprising the following steps: roasting the carbon nano tube for 2-10 hours at 500-700 ℃ in an ammonia atmosphere to obtain the nano carbon material; the ammonia gas atmosphere contains ammonia gas and helium gas, and the content of the ammonia gas is 0.2-10% by volume.
2. The process according to 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.
3. The method of claim 1, wherein 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.
4. The process according to claim 1, wherein 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); the weight ratio of the oxidative dehydrogenation reaction mixture to the solvent is 100: (1-5000);
The solvent is selected from one or more of water, alcohol, ketone and nitrile; the alcohol is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tertiary butanol and isobutanol; the ketone is acetone and/or butanone; the nitrile is acetonitrile.
5. The process of claim 4, wherein in step S2 the molar ratio of propylene to the amount of hydrogen peroxide in the oxidative dehydrogenation reaction mixture is 1: (0.5-1.5); the weight ratio of the oxidative dehydrogenation reaction mixture to the solvent is 100: (10-1000).
6. The method according to claim 1, wherein in the step S2, the titanium-silicon catalyst contains a titanium-silicon molecular sieve, the content of the titanium-silicon molecular sieve is 70-100 wt% based on the total weight of the titanium-silicon catalyst, and the molar ratio of silicon to titanium of the titanium-silicon molecular sieve is 20-80.
7. The method of claim 1, wherein the nanocarbon material has a carbon content of 82-99 wt%, a nitrogen content of 1-8 wt%, and the balance oxygen, based on the total weight of the nanocarbon material.
8. The process of claim 1, wherein the process is a continuous operation and the total volume space velocity of the epoxidation reaction is from 0.5 to 200h -1.
9. The process of claim 8, wherein the total volume space velocity of the epoxidation reaction is from 1 to 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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