CN116199647A - Method for producing epoxypropane - Google Patents
Method for producing epoxypropane Download PDFInfo
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- CN116199647A CN116199647A CN202111456735.1A CN202111456735A CN116199647A CN 116199647 A CN116199647 A CN 116199647A CN 202111456735 A CN202111456735 A CN 202111456735A CN 116199647 A CN116199647 A CN 116199647A
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000004519 manufacturing process Methods 0.000 title description 13
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 41
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000001294 propane Substances 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052719 titanium Inorganic materials 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 14
- 239000012298 atmosphere Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 10
- 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 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910001867 inorganic solvent Inorganic materials 0.000 claims description 6
- 239000003049 inorganic solvent Substances 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002048 multi walled nanotube Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000000047 product Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 4
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 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
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- JRNXSPIOMZDAQR-UHFFFAOYSA-N ethylperoxybenzene Chemical compound CCOOC1=CC=CC=C1 JRNXSPIOMZDAQR-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- 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 present invention relates to a process for producing propylene oxide, which comprises: (1) Under the anaerobic condition, enabling propane to contact with the nano carbon-based material at 550-750 ℃ and 0-10 MPa to perform a first reaction to obtain a first mixed product; (2) The first mixed product is contacted with hydrogen peroxide at 30-65 ℃ and 0.4-7 MPa in the presence of a catalyst and an optional solvent to carry out a second reaction. The method can directly produce propylene oxide by taking propane and hydrogen peroxide as raw materials, and has higher conversion rate of the raw materials and selectivity of target products.
Description
Technical Field
The present invention relates to a process for producing propylene oxide.
Background
Propylene oxide, also known as Propylene Oxide (PO), is a large number of chemical raw materials, and is the second largest organic chemical product with the yield inferior to that of polypropylene in propylene derivatives, and among 50 chemicals with the largest global yield are listed. PO has very active chemical property and wide application, has profound effects on the development of chemical industry and national economy, and is widely applied to the industries of chemical industry, light industry, medicine, food, textile and the like.
At present, the industrial production of propylene oxide mainly adopts a chlorohydrin method and a co-oxidation method, and the production capacity of the two methods accounts for more than 80% of the total world production capacity. The chlorohydrin method is applied to production earlier, and the method uses chlorine gas, has serious corrosion, and is used for improving the conversion rate, and a large amount of water is added in the reaction process, so that a large amount of chlorine-containing wastewater polluting the environment can be generated after the reaction, and the requirements of green chemistry and clean production are not met. Thus, as environmental protection requirements increase, the process will eventually be eliminated. The co-oxidation process uses ethylbenzene peroxide, tert-butyl hydroperoxide, cumene peroxide, or the like as an oxygen source to indirectly oxidize propylene to PO. The co-oxidation method overcomes the defects of environmental pollution, equipment corrosion and the like of the chlorohydrin method, is a relatively cleaner production process than the chlorohydrin method, but co-produces a large amount of low-cost byproducts such as styrene or tertiary butanol, and the like, and the byproduct market is difficult to digest.
The method which takes hydrogen peroxide as an oxidant and takes a heteroatom molecular sieve, particularly a titanium silicalite molecular sieve as a catalyst can obtain higher propylene conversion rate and PO selectivity. The method is simple and convenient, the byproduct is mainly water, the process is clean, the environment is not polluted, the method is a PO production process with great competitiveness, meets the requirements of modern green chemistry and atomic economy development concepts, is considered as a green new process for producing PO, and is the most promising PO production method at present. However, the economy is still to be improved and the technical maturity is to be increased.
Disclosure of Invention
The invention aims to provide a method for producing propylene oxide, which can directly produce propylene oxide by taking propane and hydrogen peroxide as raw materials.
In order to achieve the above object, the present invention provides a method for producing propylene oxide, comprising:
(1) Under the anaerobic condition, enabling propane to contact with the nano carbon-based material at 550-750 ℃ and 0-10 MPa to perform a first reaction to obtain a first mixed product;
(2) The first mixed product is contacted with hydrogen peroxide at 30-65 ℃ and 0.4-7 MPa in the presence of a catalyst and an optional solvent to carry out a second reaction.
Optionally, in step (1), the conditions of the first reaction include: the temperature is 600-700 ℃, the time is 1-5 MPa, and the volume airspeed of propane is 1-100 h -1 。
Optionally, in step (2), the molar ratio of the first mixed product to the hydrogen peroxide is 1: (0.1 to 2), preferably 1: (0.2-1).
Optionally, in step (2), the conditions of the second reaction include: the temperature is 35-60 ℃ and the pressure is 0.5-6 MPa.
Optionally, the nanocarbon-based material is prepared by a method comprising the following steps: roasting the multi-wall carbon nano tube for 1-24h at 200-1000 ℃ in ammonia gas atmosphere with the concentration of 0.1-5 vol%.
Optionally, the catalyst contains titanium silicalite molecular sieve, and the content of the titanium silicalite molecular sieve is 70-100 wt% based on the total weight of the catalyst.
Optionally, the titanium silicalite molecular sieve has a silicon-titanium molar ratio of 30-60 and a total specific surface area of 250-600m 2 Per gram, mesoporous specific surface area of 30-100m 2 /g。
Optionally, in step (2), the second reaction is carried out in the presence of a catalyst and a solvent; the weight ratio of the solvent to the catalyst is (10-1000): 1, preferably (20 to 500): 1.
optionally, the solvent is selected from an inorganic solvent and/or an organic solvent; the inorganic solvent is deionized water; the organic solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile, preferably methanol and/or deionized water.
Optionally, aThe total volume space velocity of the second reaction is 1 to 1000h -1 Preferably 5 to 500h -1 。
Through the technical scheme, the propylene oxide can be directly produced by taking the propane and the hydrogen peroxide as raw materials through the coupled first reaction and the coupled second reaction, the first mixed product obtained through the first reaction is directly contacted with the hydrogen peroxide to carry out the second reaction, the preparation process is simple and easy to implement, and the conversion rate of the raw materials and the selectivity of the propylene oxide ring are high.
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 producing propylene oxide, the process comprising:
(1) Under the anaerobic condition, enabling propane to contact with the nano carbon-based material at 550-750 ℃ and 0-10 MPa to perform a first reaction to obtain a first mixed product;
(2) The first mixed product is contacted with hydrogen peroxide at 30-65 ℃ and 0.4-7 MPa in the presence of a catalyst and an optional solvent to carry out a second reaction.
In the present invention, the anaerobic condition means that the first reaction is carried out in an atmosphere containing no oxygen, and may be, for example, a nitrogen atmosphere, a helium atmosphere, a mixed atmosphere of nitrogen and helium, or an atmosphere in which propane is formed alone. In an atmosphere containing no oxygen, the molar ratio of the gas other than propane to propane may be (0 to 10): 1. the method directly takes propane and hydrogen peroxide as raw materials to produce the propylene oxide, is simple and easy to operate, has low cost, can produce the propylene oxide with higher conversion rate and selectivity, and is particularly suitable for the industrialized production of the propylene oxide taking propane as an initial raw material.
In one embodiment of the present invention, in step (1), theThe conditions of the first reaction include: the temperature is 600-700 ℃, the time is 1-5 MPa, and the volume airspeed of propane is 1-100 h -1 。
In one embodiment of the present invention, in step (2), the molar ratio of the first mixed product to the amount of hydrogen peroxide may vary within a wide range, for example, may be 1: (0.1 to 2), preferably 1: (0.2-1).
In one embodiment of the present invention, in step (2), the conditions of the second reaction include: the temperature is 35-60 ℃ and the pressure is 0.5-6 MPa; preferably, the temperature is 40-50 ℃ and the pressure is 1-4 MPa.
The apparatus used for the first reaction and the second reaction according to the present invention is not particularly limited, and the apparatus used for the first reaction and the second reaction may each be independently a fixed bed reactor, a moving bed reactor, a micro reactor or other various types of reactors. In a preferred embodiment, the first reaction is carried out in a fixed bed microreactor and the second reaction is carried out in a slurry bed reactor, with the above process further increasing the conversion of the feedstock and the selectivity to propylene oxide.
According to the invention, the nano carbon-based material is a nano carbon-based material with good thermal stability. In a specific embodiment of the present invention, the nanocarbon-based material may be a commercially available product, or may be a modified product obtained by modifying a commercially available product, and preferably, the nanocarbon-based material is a carbon nanotube modified by activation with ammonia nitrogen. In one embodiment, the modified carbon nanotubes are produced by a process comprising the steps of: the multi-walled carbon nanotubes are calcined at 200-1000 c, preferably 400-600 c, under an ammonia atmosphere of 0.1-5% by volume, preferably 1-2.5% by volume, for 1-24 hours. Preferably, the carbon nanotubes are carbon nanotubes. The ammonia atmosphere may also contain nitrogen and/or an inert gas, which is well known to those skilled in the art, and may be, for example, helium, argon, etc.
According to the invention, the catalyst comprises a titanium silicalite molecular sieve, which is well known to the person skilled in the art and may be, for example, of MFI structure, MOR structure, BEAThe titanium silicalite content of the catalyst may vary within a relatively large range, for example, from 70 to 100% by weight, preferably from 40 to 55% by weight, based on the total weight of the catalyst, and the titanium silicalite molar ratio of the titanium silicalite may also vary within a relatively large range, for example, from 15 to 60, preferably from 20 to 55, and the total specific surface area of the titanium silicalite may be from 250 to 600m 2 Per gram, mesoporous specific surface area of 25-100m 2 And/g. The titanium silicalite molecular sieve of the type described above can be employed to further increase the feedstock conversion and propylene oxide selectivity in the process of the present invention. The titanium-silicon molecular sieve is well known to those skilled in the art, and can be obtained by self-synthesis or commercial route, and the specific preparation method is not described again.
According to the invention, in step (2), the second reaction is carried out in the presence of a catalyst and a solvent; the solvent is selected from inorganic solvents and/or organic solvents; the inorganic solvent may be deionized water; the organic solvent can be selected from one or more of alcohol, ketone and nitrile, for example, one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile, preferably methanol and/or deionized water. The weight ratio of the solvent to the catalyst amount may vary within a wide range, for example (10 to 1000): 1, preferably (20 to 500): 1.
in one embodiment of the invention, the total space velocity of the second reaction may be from 1 to 1000 hours -1 Preferably 5 to 500h -1 。
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 modified by ammonia nitrogen (CNT is modified by activation). The specific production method comprises the following steps: the multi-walled carbon nanotubes were baked at 600℃for 4 hours in an ammonia atmosphere of 1% by volume (the balance being nitrogen gas) using a tube furnace.
Titanium silicalite (TS-1) is a process as described in the prior art Zeolite, 1992, vol.12, pages 943-950The molecular sieve sample (TS-1) produced by the method has the silicon-titanium molar ratio of 24 and the total specific surface area of 402m 2 /g, mesoporous specific surface area of 27m 2 /g。
The contents of the components in the obtained reaction product were analyzed by gas chromatography, and on the basis of this, the conversion of propane and the selectivity of propylene oxide were calculated using the following formulas, respectively:
propane conversion = [ (molar amount of propane added-molar amount of unreacted propane)/molar amount of propane added ] ×100%;
propylene oxide selectivity= [ molar amount of propylene oxide produced by reaction/(molar amount of propane added-molar amount of unreacted propane) ]x100%.
Example 1
The process for producing propylene oxide is as follows:
(1) In nitrogen atmosphere, 0.1MPa, 600 ℃ and 100h of propane volume space velocity -1 Under the condition of (1) passing propane (the molar ratio of nitrogen to propane is 1:1) through a fixed bed micro-reactor taking a nano carbon-based material as a catalyst bed layer to perform a first reaction to obtain a first mixed product;
(2) The first mixed product is mixed with hydrogen peroxide, solvent methanol and catalyst in a slurry bed reactor according to a mole ratio of the first mixed product to hydrogen peroxide of 1:1, the weight ratio of the solvent methanol to the catalyst is 50, the temperature is 60 ℃, the pressure is 0.5MPa, and the total volume space velocity is 500h -1 The lower contact carries out the second reaction. The reaction mixture obtained after the completion of the second reaction was subjected to gas chromatography, and the conversion of propane and the selectivity of propylene oxide were calculated. The reaction results for 2 hours are listed in table 1.
Example 2
Propylene oxide was produced in the same manner as in example 1 except that in step (1), the temperature was 550℃and the propane volume space velocity was 5 hours -1 ；
In the step (2), the molar ratio of the first mixed product to the hydrogen peroxide is 2:1, the weight ratio of the solvent methanol to the catalyst is 20, the reaction temperature is 40 ℃ and the pressure is 2.5MPa, and the total reaction is carried outThe product space velocity is 200h -1 。
Example 3
Propylene oxide was produced in the same manner as in example 1 except that in step (1), the volume space velocity of propane was 25h -1 ；
In step (2), the molar ratio of the first mixed product to the hydrogen peroxide solution (calculated as hydrogen peroxide) is 10:1, the weight ratio of the solvent methanol to the catalyst is 40, the temperature is 50 ℃, the pressure is 1.5MPa, and the total volume space velocity is 100h -1 。
Example 4
Propylene oxide was produced in the same manner as in example 1 except that in step (1), the pressure was 6MPa, the temperature was 550℃and the propane volume space velocity was 8h -1 。
Example 5
Propylene oxide was produced in the same manner as in example 1 except that in step (2), the temperature of the second reaction was 30, the pressure was 0.45MPa, and the molar ratio of the first mixed product to the hydrogen peroxide solution (in terms of hydrogen peroxide) was 1:1.2.
example 6
Propylene oxide was produced in the same manner as in example 1, except that the nanocarbon-based material used in step (1) was different, and the nanocarbon-based material used in this example was prepared by calcining a multiwall carbon nanotube at 800℃for 3 hours in an ammonia atmosphere having a concentration of 3% by volume.
Comparative example 1
Propylene oxide was produced in the same manner as in example 1 except that the nanocarbon-based material was not used.
Comparative example 2
Propylene oxide was produced in the same manner as in example 1 except that no catalyst was used.
Comparative example 3
Propylene oxide was produced in the same manner as in example 1 except that the nanocarbon-based material and the catalyst were not used.
Comparative example 4
Propylene oxide was produced in the same manner as in example 1 except that the reaction temperature in step (1) was 400 ℃.
TABLE 1
| Numbering device | Propane conversion (%) | Propylene oxide Selectivity (%) |
| Example 1 | 58 | 94 |
| Example 2 | 31 | 92 |
| Example 3 | 35 | 89 |
| Example 4 | 41 | 83 |
| Example 5 | 47 | 87 |
| Example 6 | 39 | 84 |
| Comparative example 1 | 3 | 82 |
| Comparative example 2 | 51 | 2 |
| Comparative example 3 | 1 | 3 |
| Comparative example 4 | 14 | 52 |
As can be seen from the results of the comparative examples and examples, the present invention can directly produce propylene oxide from propane and hydrogen peroxide, and the process is simple and easy to operate, has low cost, and has high propane conversion rate and propylene oxide selectivity.
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 method of producing propylene oxide, the method comprising:
(1) Under the anaerobic condition, enabling propane to contact with the nano carbon-based material at 550-750 ℃ and 0-10 MPa to perform a first reaction to obtain a first mixed product;
(2) The first mixed product is contacted with hydrogen peroxide at 30-65 ℃ and 0.4-7 MPa in the presence of a catalyst and an optional solvent to carry out a second reaction.
2. The method of claim 1, wherein in step (1), the conditions of the first reaction comprise: the temperature is 600-700 ℃, the time is 1-5 MPa, and the volume airspeed of propane is 1-100 h -1 。
3. The method of claim 1, wherein in step (2), the molar ratio of the first mixed product to the amount of hydrogen peroxide is 1: (0.1 to 2), preferably 1: (0.2-1).
4. The method of claim 1, wherein in step (2), the conditions of the second reaction comprise: the temperature is 35-60 ℃ and the pressure is 0.5-6 MPa.
5. The method of claim 1, wherein the nanocarbon-based material is prepared by a method comprising: roasting the multi-wall carbon nano tube for 1-24h at 200-1000 ℃ in ammonia gas atmosphere with the concentration of 0.1-5 vol%.
6. The process of claim 1 or 5, wherein the catalyst comprises titanium silicalite in an amount of 70-100 wt.%, based on the total weight of the catalyst.
7. The method according to claim 6, wherein the titanium silicalite molecular sieve has a molar ratio of silicon to titanium of 30-60 and a total specific surface area of 250-600m 2 Per gram, mesoporous specific surface area of 30-100m 2 /g。
8. The process of claim 1, wherein in step (2), the second reaction is performed in the presence of a catalyst and a solvent; the weight ratio of the solvent to the catalyst is (10-1000): 1, preferably (20 to 500): 1.
9. the method according to claim 8, wherein the solvent is selected from inorganic solvents and/or organic solvents; the inorganic solvent is deionized water; the organic solvent is selected from one or more of methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile, preferably methanol and/or deionized water.
10. The process according to claim 1, wherein the total volume space velocity of the second reaction is from 1 to 1000h -1 Preferably 5 to 500h -1 。
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| US5973171A (en) * | 1998-10-07 | 1999-10-26 | Arco Chemical Technology, Lp | Propylene oxide production |
| CN101274922A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Preparation for epoxypropane |
| CN105817242A (en) * | 2015-01-27 | 2016-08-03 | 中国石油化工股份有限公司 | Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons |
| CN110437178A (en) * | 2019-09-05 | 2019-11-12 | 淄博恒亿化工科技有限公司 | A kind of method of green high-efficient synthesizing epoxypropane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5973171A (en) * | 1998-10-07 | 1999-10-26 | Arco Chemical Technology, Lp | Propylene oxide production |
| CN101274922A (en) * | 2007-03-30 | 2008-10-01 | 中国石油化工股份有限公司 | Preparation for epoxypropane |
| CN105817242A (en) * | 2015-01-27 | 2016-08-03 | 中国石油化工股份有限公司 | Nanometer carbon material containing heteroatoms and preparation method and application thereof, and dehydrogenation reaction method for hydrocarbons |
| CN110437178A (en) * | 2019-09-05 | 2019-11-12 | 淄博恒亿化工科技有限公司 | A kind of method of green high-efficient synthesizing epoxypropane |
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