CN113912574B - Method for preparing epoxypropane by directly epoxidation of propylene under alkaline condition - Google Patents
Method for preparing epoxypropane by directly epoxidation of propylene under alkaline condition Download PDFInfo
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- CN113912574B CN113912574B CN202010663791.1A CN202010663791A CN113912574B CN 113912574 B CN113912574 B CN 113912574B CN 202010663791 A CN202010663791 A CN 202010663791A CN 113912574 B CN113912574 B CN 113912574B
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- propylene
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- epoxidation
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- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 105
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 61
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 52
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000007789 gas Substances 0.000 claims abstract description 170
- 238000006243 chemical reaction Methods 0.000 claims abstract description 131
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- 239000003085 diluting agent Substances 0.000 claims abstract description 64
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- 241000282326 Felis catus Species 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000004458 analytical method Methods 0.000 claims description 21
- 239000010931 gold Substances 0.000 claims description 21
- 238000010790 dilution Methods 0.000 claims description 19
- 239000012895 dilution Substances 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 239000006004 Quartz sand Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 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 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkaline earth metal carbonate Chemical class 0.000 claims description 3
- 239000000919 ceramic Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 abstract description 14
- 238000002360 preparation method Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 11
- 102000020897 Formins Human genes 0.000 description 9
- 108091022623 Formins Proteins 0.000 description 9
- 238000011068 loading method Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000004880 explosion Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920005372 Plexiglas® Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- UHZZMRAGKVHANO-UHFFFAOYSA-M chlormequat chloride Chemical compound [Cl-].C[N+](C)(C)CCCl UHZZMRAGKVHANO-UHFFFAOYSA-M 0.000 description 1
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005474 detonation Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
-
- 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
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention relates to the field of propylene oxide preparation, in particular to a method for preparing propylene oxide by directly epoxidizing propylene under alkaline conditions. The method comprises the following steps: the method comprises the following steps: in the presence of propylene epoxidation reaction conditions and alkaline substances, carrying out contact reaction on mixed gas of reaction raw material gas and diluent gas and a catalyst to obtain propylene oxide; wherein the reaction raw material gas comprises propylene, oxygen and hydrogen, and the diluent gas is propylene. The method for preparing propylene oxide can effectively reduce the consumption of diluent gas, thereby relatively improving the concentration of reaction gas and the utilization rate of raw materials and further improving the reaction selectivity and conversion rate.
Description
Technical Field
The invention relates to the field of propylene oxide preparation, in particular to a method for preparing propylene oxide by directly epoxidizing propylene under alkaline conditions.
Background
Propylene oxide, also known as propylene oxide, methyl ethylene oxide, is a very important starting material for organic compounds, the third largest propylene derivative next to polypropylene and acrylonitrile. Propylene oxide is colorless ether liquid, low boiling point and inflammable. Chiral, industrial products are generally racemic mixtures of two enantiomers. Is partially miscible with water, and is miscible with ethanol and diethyl ether. Forms a binary azeotropic mixture with pentane, pentene, cyclopentane, cyclopentene, and dichloromethane.
Propylene oxide is mainly used for producing polyether polyol, propylene glycol, various nonionic surfactants and the like, wherein the polyether polyol is an important raw material for producing polyurethane foam, heat insulation materials, elastomers, adhesives, coatings and the like, and the various nonionic surfactants are widely applied to industries such as petroleum, chemical industry, pesticide, textile, daily chemicals and the like. Meanwhile, propylene oxide is also an important basic chemical raw material.
In 1860, france b.oshel first synthesized propylene oxide in the laboratory, 1931 united carbide company built the world 1 st chlorohydrin process plant for propylene oxide, and spanish in 20 th century 60 and the united states developed an indirect oxidation process. Both of these methods are currently produced, each accounting for 50%, but the latter has a later trend.
Subsequently, researchers have developed an oxygen direct oxidation process, i.e., in the presence of a catalyst and a diluent gas N 2 In the presence of propylene, hydrogen and oxygen to propylene oxide, and noble metal supported bifunctional catalysts have been studied. The reaction process is simple, economical, green and environment-friendly, compared with the existing process flowIn the great advantage, but in general, for safety reasons, it is chosen to be doped with, for example, 70-95% by volume of inert diluent gas to avoid explosion of the system. However, the use of a large amount of diluent gas results in a decrease in the concentration of the reaction gas, poor utilization of the raw material, and a decrease in the reaction selectivity and propylene conversion. Therefore, a method capable of effectively reducing the amount of diluent gas is eagerly sought.
Disclosure of Invention
The invention aims to overcome the defect that the selectivity and conversion rate of the reaction are affected by high consumption of diluent gas in the prior art, and provides a method for preparing propylene oxide by directly epoxidizing propylene under alkaline conditions. The method for preparing propylene oxide can effectively reduce the consumption of diluent gas, thereby relatively improving the concentration of reaction gas and the utilization rate of raw materials and further improving the reaction selectivity and the propylene conversion rate.
In order to achieve the above object, the present invention provides a process for producing propylene oxide by epoxidation of propylene, which comprises: in the presence of propylene epoxidation reaction conditions and alkaline substances, carrying out contact reaction on mixed gas of reaction raw material gas and diluent gas and a catalyst to obtain propylene oxide; wherein the reaction raw material gas comprises propylene, oxygen and hydrogen, and the diluent gas is propylene.
Preferably, the doping amount of the alkaline substance is 1-10000ppm.
Preferably, the catalyst and inert filler are packed in the reactor in a layered stack.
Preferably, the propylene epoxidation reaction has a space velocity of 500 to 30000ml g cat -1 h -1 。
Preferably, the temperature is 0.1-10deg.C for min -1 The temperature of the reaction system is raised to the temperature required for the epoxidation of propylene.
Preferably, the method further comprises premixing and/or preheating the mixed gas.
Through the technical scheme, the invention has the following beneficial effects:
1. the reaction system is under alkaline condition and propyleneUnder the condition that alkene is used as diluent gas, the dosage of the diluent gas is effectively reduced (for example, the dosage can be reduced to below 57.5 volume percent by adopting the scheme of the invention in a tubular reactor); propylene is used as diluent gas and reaction gas, so that the concentration of the reaction gas is further improved, forward progress of target reaction is promoted, and other two raw material gases (H 2 、O 2 ) The utilization rate of the catalyst is improved, excessive impurity gas is not introduced, the reaction efficiency is ensured, the difficulty of product separation is reduced, and the energy consumption is effectively reduced.
2. The reaction system improves the active center of the catalyst, changes the original reaction path, inhibits the occurrence of side reaction, obviously improves the propylene oxide selectivity, the propylene conversion rate, the space-time yield and the hydrogen utilization rate under the alkaline condition and the condition that propylene is taken as diluent gas, and prolongs the service life of the catalyst (for example, in a tubular reactor, the service life can be prolonged to at least 750 hours from conventional 100 hours).
3. Detonation tube explosion experiments show that compared with N 2 As dilution gas or not controlling alkaline environment and independently taking propylene as dilution gas, the method system of the invention has higher tolerable limit oxygen content and wider operable range of raw gas proportion, thereby being safer without explosion risk and further realizing the intrinsic safety of the reaction flow.
Drawings
Fig. 1 shows a filling manner of the catalyst provided by the invention.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a method for preparing propylene oxide by propylene epoxidation, which comprises the following steps: the method comprises the following steps: in the presence of propylene epoxidation reaction conditions and alkaline substances, carrying out contact reaction on mixed gas of reaction raw material gas and diluent gas and a catalyst to obtain propylene oxide; wherein the reaction raw material gas comprises propylene, oxygen and hydrogen, and the diluent gas is propylene.
According to the present invention, the basic substance may be an alkaline gas or an alkaline substance which exists in a gaseous form under the propylene epoxidation reaction conditions.
According to the present invention, the kind of the basic substance is not particularly limited as long as it can provide basic conditions for the propylene epoxidation reaction. Preferably, the basic substance is a compound with a lone pair of electrons and/or a substance capable of accepting protons.
Examples of the compound having a lone pair of electrons may include at least one of ammonia, pyridines, hydrazine, cyanide, amine, alcohol, ether, and thiol.
Examples of the substance capable of accepting protons may include Cl - 、[Al(H 2 O) 5 OH] 2+ 、Ac - 、HPO 4 2- 、PO 4 3- At least one of them.
According to a preferred embodiment of the present invention, the alkaline substance is ammonia.
According to the present invention, the form of introducing the alkaline substance into the reaction system is not particularly limited, and may be introduced into the reaction system by any one of the following means:
(1) The gas path is not changed, and a certain amount of alkaline substances are added in the process of preparing the reaction raw material gas. As in H 2 Adding alkaline gas to prepare H 2 And an alkaline gas mixture by H 2 The gas path enters the reaction system, and the pipeline layout of the original reaction device is not changed.
(2) And a new gas pipeline is added, connected into the reaction system, fully mixed with the original reaction raw material gas in a mixer and then fed into the reactor.
(3) The modification is carried out on the reaction raw material gas or the dilution gas, so that the reaction raw material gas or the dilution gas passes through an alkaline medium environment, and alkaline substances enter the reactor along with the reaction raw material gas or the dilution gas.
According to the present invention, the addition amount of the alkaline substance may vary within a wide range, and preferably, in the mixed gas of the reaction raw material gas and the diluent gas, the addition amount of the alkaline substance is 1 to 10000ppm, for example, may be 1ppm, 10ppm, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, 100ppm, 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm, 1000ppm, 2000ppm, 3000ppm, 4000ppm, 5000ppm, 6000ppm, 7000ppm, 8000ppm, 9000ppm, 10000ppm; preferably 10 to 1000ppm, more preferably 100 to 800ppm.
Generally, in the direct epoxidation of propylene, inert gas is usually selected as diluent gas, which makes the reaction safer and the risk of explosion is lower. However, the inventor of the present invention found in the research process that propylene is adopted as a diluent gas, and propylene oxide is reacted under the condition of performing the reaction in an alkaline environment, so that the usage amount of the diluent gas can be significantly reduced, and the oxygen tolerance of the reaction system can be improved, and therefore, the present invention reduces the explosion risk while reducing the subsequent separation pressure of the reaction product (propylene is used as the reactant gas and also as the diluent gas without separation). Meanwhile, as the concentration of oxygen serving as the reaction gas is improved, the forward direction of the reaction can be effectively promoted, and the reaction selectivity and the propylene conversion rate are improved. Furthermore, the inventors of the present invention have unexpectedly found that in the case where propylene is selected as the diluent gas and the reaction is carried out in an alkaline environment, the service life of the catalyst is also prolonged. Further, the driving energy consumption of the dilution gas is also reduced due to the reduction of the consumption of the dilution gas.
In the present invention, in the case of propylene as the diluent gas, it is meant that the diluent gas is completely substituted with propylene, resulting in a large excess of propylene in the reaction raw material gas, which exceeds the extent to which the forward progress of the reaction is promoted by increasing the amount of the reaction raw material in general, and therefore, in this case, propylene cannot be simply considered to be excess, which is different from that in the conventional sense.
The improvement in propylene conversion described herein was calculated for the amount of propylene as the reaction gas, and the amount of propylene as the diluent gas was not taken into account.
According to the present invention, in general, in order to secure the safety of the reaction, the concentration of oxygen in the mixed gas generally must not be higher than 5 vol%, however, according to the method of the present invention, the proportion of oxygen in the mixed gas may be more than 16 vol%, for example, the proportion of oxygen may be 16 vol%, 17 vol%, 18 vol%, 19 vol%, 20 vol%, 21 vol%, 22 vol%, 23 vol%, 24 vol%, 25 vol%, 26 vol%, 27 vol%, 28 vol%, 29 vol%, 30 vol%, 31 vol%, 32 vol%, 33 vol%, 34 vol%, 35 vol%. More preferably greater than 22% by volume, still more preferably greater than 25% by volume.
According to the invention, the concentration of oxygen is preferably not higher than 60% by volume.
According to the present invention, in general, the proportion of the diluent gas in the mixed gas should not be lower than 70% by volume in order to secure safety of the reaction. However, according to the method of the present invention, the proportion of the dilution gas in the mixed gas is lower than 57.5 vol%, for example, may be 10 vol%, 12 vol%, 15 vol%, 20 vol%, 22 vol%, 23 vol%, 24 vol%, 25 vol%, 30 vol%, 35 vol%, 40 vol%, 45 vol%, 50 vol%, 55 vol%, 57.5 vol%; more preferably less than 40% by volume, still more preferably less than 33.5% by volume.
From the above, the method of the invention can reduce the consumption of the diluent gas and increase the consumption of the oxygen, thereby increasing the concentration of the reaction gas, promoting the forward progress of the reaction, reducing the consumption of the diluent gas and reducing the pressure of the separation process of the subsequent reaction products.
Further, the amount of the diluent gas to which the alkaline gas is added can be further reduced as compared with the amount of the diluent gas when the alkaline gas is not added.
According to the invention, the propylene epoxidation reaction can be carried out in a reactor conventional in the art, so that the dosage of diluent gas can be effectively reduced, the safe concentration of oxygen can be improved, the service life of a catalyst for the direct epoxidation reaction of propylene can be prolonged, the reaction selectivity and the propylene conversion rate can be improved, and the energy consumption can be reduced as long as the propylene is selected and combined with an alkaline substance environment.
According to a specific embodiment of the present invention, the propylene epoxidation reaction is carried out in a tubular reactor. The tubular reactor may be various tubular reactors conventional in the art, for example, a quartz tube reactor.
According to another preferred embodiment of the present invention, the epoxidation reaction is carried out in a microchannel reactor in order to further achieve the object of the invention. In a microchannel reactor, although flame propagation may be quenched due to the wall effect of the microchannel, so that the reactant concentration is no longer limited by the explosion limit, the limitation of oxygen concentration may not be considered, i.e., a dilution gas may not be used. However, in general, because the diluent gas has the effect of the purge gas, propylene oxide which is a reaction product can be timely separated from the catalytic active center, and the forward movement of the reaction balance is promoted. Therefore, in order to ensure the reaction efficiency, a dilution gas is generally used in a proportion, for example, the proportion of the dilution gas in the mixed gas proportion is generally not less than 40% by volume. However, under the technical scheme of the invention, the reaction can be effectively ensured to have equivalent or higher propylene conversion rate and product selectivity under the condition that the proportion of the diluent gas is reduced to below 20 volume percent.
The microchannel reactor may be any of conventional reactors according to the present invention, and the present invention is not particularly limited thereto, and for example, it has a length of 1 to 1000mm, preferably 10 to 500mm.
According to the present invention, the width of the microchannel reactor in the radial direction is not particularly limited as long as it meets the standards of the microchannel reactor, and the width thereof in the radial direction is the same or different along the length of the microchannel reactor, and according to a preferred embodiment of the present invention, the width thereof in the radial direction is 20 to 2000 μm when the same; meanwhile, the width of the radial direction is 10-1000 micrometers at the minimum and 100-3000 micrometers at the maximum.
According to the present invention, the material of the microchannel reactor may be any material that can withstand the reaction temperature of the present invention and does not react with the raw materials and products of the present invention, and may be, for example, plexiglas, ceramic glass, stainless steel metal, quartz, resin material, or the like.
According to the invention, the catalyst may have any size and shape suitable for the tubular reactor or the microchannel reactor.
According to the present invention, the catalyst may be any catalyst disclosed in the prior art capable of catalytically reacting propylene, oxygen, hydrogen and a diluent gas to form propylene oxide, and preferably the catalyst is a supported metal catalyst. Wherein the metal may be selected from at least one of gold, silver, copper, ruthenium, palladium, platinum, rhodium, cobalt, nickel, tungsten, bismuth, molybdenum and oxides thereof, preferably gold; the carrier for supporting the metal may be at least one of carbon black, activated carbon, silica, alumina, cerium oxide, titanium silicalite, zeolite, resin, polymer and alkaline earth metal carbonate, preferably titanium silicalite.
According to the present invention, in the supported metal catalyst, the content of the metal in terms of the metal element may be changed within a wide range, for example, the content of the metal in terms of the metal element in the catalyst may be 0.01 to 50 wt%, for example, 0.01 wt%, 0.05 wt%, 0.06 wt%, 0.07 wt%, 0.08 wt%, 0.09 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, 1 wt%, 1.1 wt%, 1.2 wt%, 1.3 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.7 wt%, 1.8 wt%, 1.9 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, preferably 0.05 wt%, more preferably 0.05 to 2 wt%.
According to a preferred embodiment of the invention, the catalyst is a titanium silicalite molecular sieve loaded with goldAu@TS-1) (Wherein, the TS-1 molecular sieve can be prepared by hydrothermal synthesis, and the active metal Au can be loaded by a deposition and precipitation method) Wherein the loading amount calculated by gold element is 0.1-2% by weight.
According to the invention, the catalyst may be packed in the reactor of propylene epoxidation reaction alone (as shown in fig. 1 a) or in combination with other inert substances. However, in order to further reduce the amount of dilution gas used, increase the service life of the catalyst, increase the selectivity of the reaction, the conversion, the space-time yield and the hydrogen utilization, it is preferred that the catalyst is packed in the reactor in combination with the catalyst and inert packing. Wherein the inert filler can be inert solid phase material conventionally used in the art, preferably, the inert filler is selected from quartz sand, al 2 O 3 At least one of porous silica gel and ceramic ring.
The amount of the inert filler may vary within a wide range, but is preferably 1 to 200 parts by weight (for example, 1 part by weight, 10 parts by weight, 20 parts by weight, 50 parts by weight, 80 parts by weight, 90 parts by weight, 95 parts by weight, 100 parts by weight, 105 parts by weight, 110 parts by weight, 115 parts by weight, 120 parts by weight, 125 parts by weight, 130 parts by weight, 135 parts by weight, 140 parts by weight, 145 parts by weight, 150 parts by weight, 160 parts by weight, 170 parts by weight, 180 parts by weight, 190 parts by weight, 200 parts by weight, preferably 80 to 150 parts by weight, more preferably 90 to 110 parts by weight) relative to 1 part by weight of the catalyst.
According to the present invention, the combination form of the catalyst and the inert filler is not particularly limited, for example, the catalyst and the inert filler may be directly mixed and then filled in the reactor, or the catalyst and the inert filler may be designed into a sandwich structure (as shown in fig. 1 b), wherein the catalyst or the inert filler is located in the middle. However, the present inventors have found in the study that the catalyst and inert filler are packed in the reactor in a layered stack (as shown in fig. 1 c), which can further reduce the amount of diluent gas, increase the catalyst lifetime, selectivity of reaction, conversion, space-time yield, and hydrogen utilization. Wherein in this manner the heights of the catalyst layers and inert filler layers may be chosen within a wide range, they may be stacked in layers, either at equal heights or at unequal heights, preferably the catalyst layers and inert filler layers are each independently 1-2000 layers/meter, for example, 1 layer/meter, 2 layers/meter, 3 layers/meter, 4 layers/meter, 5 layers/meter, 6 layers/meter, 7 layers/meter, 8 layers/meter, 9 layers/meter, 10 layers/meter, 15 layers/meter, 18 layers/meter, 20 layers/meter, 50 layers/meter, 100 layers/meter, 200 layers/meter, 300 layers/meter, 400 layers/meter, 500 layers/meter, 600 layers/meter, 700 layers/meter, 800 layers/meter, 900 layers/meter, 1000 layers/meter, 1200 layers/meter, 1400 layers/meter, 1600 layers/meter, 1800 layers/meter, 2000 layers/meter; preferably 1000-2000 layers/m, or 10-20 layers/m.
According to the present invention, the layer height ratio of the catalyst layer and the inert filler layer may vary within a wide range, and preferably, in order to further enhance the effect of the present invention, the layer height ratio of the catalyst layer and the inert filler layer is 1:1 to 10, for example, may be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, preferably 1:1 to 3, and further preferably 1:1.5 to 2.5.
The manner of filling the catalyst in the reactor according to the present invention is not particularly limited, and for example, a coating method, an electrodeposition method, a solution plating method, a mechanical filling method, and the like may be employed.
According to the invention, the catalyst is preferably used in an amount of 0.1 to 0.5g relative to 10ml of the reactor. In general, the amount of catalyst is at least 1g, and it can be seen that the catalyst can be reduced according to the technical scheme of the invention.
The temperature of the propylene epoxidation reaction according to the present invention may be a reaction temperature conventional in the art, for example, may be 20 to 300 ℃, but in order to further reduce the amount of diluent gas, increase the conversion, selectivity, space-time yield and hydrogen utilization of the reaction, and increase the service life of the catalyst, it is preferable that the temperature of the reaction is 50 to 250 ℃, more preferably 120 to 200 ℃, for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃.
The inventors of the present invention have found in the study that the rate of temperature rise of the system can also further influence the amount of diluent gas, the conversion rate of the reaction, the selectivity, the space-time yield and the hydrogen utilization rate, the service life of the catalyst, when the catalyst is used at 0.1-10 ℃ for min -1 Preferably at 0.5-5deg.C for min -1 More preferably 0.5-2deg.C for min -1 (e.g., may be 0.5 ℃ C. Min -1 、0.8℃min -1 、1.0℃min -1 、1.2℃min -1 、1.5℃min -1 、2.0℃min -1 Further preferably 0.8-1.5℃min -1 ) When the temperature of the reaction system is raised to the temperature required by propylene epoxidation reaction, the dosage of diluent gas can be further reduced, the conversion rate, selectivity, space-time yield and hydrogen utilization rate of the reaction are improved, the service life of the catalyst is prolonged, and the dosage of the catalyst and the dosage of the diluent gas are reduced.
According to the invention, it is also preferred to pre-mix and/or preheat the mixed gas before it enters the reactor in order to further increase the efficiency of the reaction.
According to the invention, the extent of preheating preferably amounts to at least 50%, for example 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, preferably at least 80% of the target reaction temperature.
The pressure of the propylene epoxidation reaction according to the present invention may be a reaction pressure conventional in the art, for example, may be 0 to 5MPa, but in order to further reduce the amount of diluent gas, increase the conversion, selectivity, space time yield and hydrogen utilization of the reaction, and increase the service life of the catalyst, it is preferable that the pressure of the reaction is 0 to 1.5MPa, more preferably 0.05 to 0.25MPa, for example, may be 0.05MPa, 0.07MPa, 0.09MPa, 0.11MPa, 0.13MPa, 0.15MPa, 0.17MPa, 0.19MPa, 0.21MPa, 0.23MPa, 0.25MPa.
The space velocity of the propylene epoxidation reaction according to the present invention may be the reaction space velocity conventional in the art, but in order to further reduce the amount of diluent gas, increase the conversion, selectivity, space-time yield and hydrogen utilization of the reaction, and increase the service life of the catalyst, it is preferable that the reaction space velocity is 500 to 30000ml g cat -1 h -1 More preferably 1000-20000ml g cat -1 h -1 Further preferably 2000-15000ml g cat -1 h -1 For example, 2000ml g may be used cat -1 h -1 、3000ml g cat - 1 h -1 、4000ml g cat -1 h -1 、5000ml g cat -1 h -1 、6000ml g cat -1 h -1 、7000ml g cat -1 h -1 、8000ml g cat -1 h -1 、9000ml g cat -1 h -1 、10000ml g cat -1 h -1 、12000ml g cat -1 h -1 、13000ml g cat -1 h -1 、14000ml g cat -1 h -1 、15000ml g cat -1 h -1 。
According to the invention, the ratio of the amount of propylene, oxygen and hydrogen is preferably 0.1-3:0.1-3:1.
according to the present invention, the flow rates of propylene, oxygen, hydrogen and diluent gas are not particularly limited as long as mixing in the above-described ratio of the amount by volume can be ensured.
According to the invention, the method of the invention may further comprise subjecting the reaction product to a component analysis, for example, a gas chromatography analysis, in particular, the reaction product may be introduced into a gas chromatograph equipped with TCD and FID detectors for analysis.
More preferably, in order to secure the effect of the analysis, the reaction product is fed to the component analysis apparatus under heating conditions of 50 to 200 ℃, and in particular, a heating belt may be provided between the outlet of the reactor and the inlet of the component analysis apparatus to maintain a temperature of 50 to 200 ℃, preferably 80 to 150 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.
According to the present invention, the propylene epoxidation reaction provided by the process of the present invention is preferably not carried out in the presence of a solvent. Wherein the solvent comprises any liquid phase introduced by external assistance.
The present invention will be described in detail by examples.
The tubular reactor was a quartz tube reactor with a diameter of 3cm.
Product analysis the product was sampled using 2 gas chromatographs and analyzed by gas chromatography. Both analytical chromatographic models were Agilent 7890B, with the columns of gas chromatograph A being (1) HayeSep Q column (SFt 0.9m, OD1/8, ID 2 mm), (2) Molsieve5A column (SFt 2.44m, OD1/8, ID 2 mm), (3) PoraBOND U column (25 m,0.32mm,7 μm); equipped with TCD and FID detectors for analysis of H 2 、O 2 And permanent gases such as diluent gas, propylene, propane, epoxypropane, acrolein, acetone, propionaldehyde, acetaldehyde and the like, wherein the peak positions of propylene and hydrogen are similar, and the mutual influence of the propylene and the hydrogen cannot be accurately distinguished, so that the gas chromatography B is used for assisting analysis. The chromatographic columns of the gas chromatograph B are (1) a HayeSep Q column (SFt 1.83m, OD1/8, ID 2 mm), (2) a Molsieve5A column (SFt 2.44m, OD1/8, ID 2 mm), (3) an HP-AL/S column (25 m,0.32mm,8 μm); equipped with TCD and FID detectors for analysis of H 2 、O 2 Permanent gases such as diluent gases, propylene and propane.
In the Au@TS-1 molecular sieve catalyst, the TS-1 molecular sieve is prepared by a hydrothermal synthesis mode, and active metal Au is loaded by a deposition and precipitation method.
Explosion experiment
1) In a tubular reactor, 0.3g of Au@TS-1 molecular sieve catalyst (the loading amount of Au is 1% by weight) was packed with 30g of quartz sand in a layered manner as shown in FIG. 1 (c), wherein the layer height ratio of the catalyst layer and the quartz sand layer, each independently being 15 layers/cm, was 1:2, and propylene gas phase direct epoxidation was carried out.
Wherein the raw material gas is in proportion of H 2 :O 2 :C 3 H 6 :C 3 H 6 (as dilution gas) =26%: 26%:22% was fed into the mixer, wherein ammonia was added by incorporation into the hydrogen gas, the final doping amount in the system being 500ppm. The obtained mixed system enters a preheater, is preheated to 160 ℃ and then enters a reactor.
Reaction space velocity 4000ml g cat -1 h -1 Controlling the reaction pressure of the system to be 0.2MPa and the temperature to be 1.5 ℃ for min -1 Is programmed to a temperature of 200 ℃.
Wherein the reaction system does not explode within 20min of reaction time. In the case of nitrogen, the dilution gas cannot be safely conducted.
However, if the alkaline gas is not introduced and the diluent gas is nitrogen, the process cannot be safely performed.
Examples 1 to 9 below are described as H 2 :O 2 :C 3 H 6 :C 3 H 6 Verification of other effects was performed (as dilution gas) =25%: 25% ratio.
Example 1
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
In a tubular reactor, 0.20g of Au@TS-1 molecular sieve catalyst (loading of Au is 1% by weight) and 20g of quartz sand were packed in layers in the reactor with respect to 10ml of the reactor, as shown in FIG. 1 (c), wherein the layer height ratio of the catalyst layer and the quartz sand layer was 1:2, and the catalyst layer and the inert packing layer were each independently 15 layers/cm, and a propylene gas phase direct epoxidation reaction was carried out.
Wherein the feed gas H 2 、O 2 、C 3 H 6 (as a reaction gas), C 3 H 6 The mixture (as a diluent gas) was fed into a mixer, then fed into a preheater, preheated to 160℃and fed into a tubular reactor, wherein ammonia was added by being incorporated into hydrogen gas in an amount of 800ppm relative to the mixed gas of the reaction raw material gas and the diluent gas. 9000ml g of reaction space velocity cat -1 h -1 Control systemThe reaction pressure of (2) was 0.15MPa at 0.8℃for min -1 After the reaction was stabilized for 20 minutes at 200℃with a programmed temperature, the analysis of the propylene gas phase direct epoxidation reaction was shown in Table 1, and the approximate time (recorded every 50 hours) at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decrease was recorded.
Example 2
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
In a tubular reactor, 0.20g of au@ts-1 molecular sieve catalyst (loading of Au is 1 wt%) and 18g of quartz sand were layered in the reactor with respect to 10ml of the reactor, as shown in fig. 1 (c), wherein the layer height ratio of the catalyst layer and the quartz sand layer was 1:1.5, the catalyst layer and the inert filler layer are each independently 10 layers/cm, and the propylene gas phase direct epoxidation reaction is carried out.
Wherein the feed gas H 2 、O 2 、C 3 H 6 (as a reaction gas), C 3 H 6 The mixture (as a diluent gas) was fed into a mixer, then fed into a preheater, preheated to 130℃and fed into a tubular reactor, wherein ammonia was added by being incorporated into hydrogen gas in an amount of 500ppm relative to the mixed gas of the reaction raw material gas and the diluent gas. Reaction space velocity 4000ml g cat -1 h -1 Controlling the reaction pressure of the system to be 0.05MPa and 1.5 ℃ for min -1 After the reaction was stabilized for 20 minutes at 170℃and the analysis of the propylene gas phase direct epoxidation reaction was shown in Table 1, the approximate time (recorded every 50 hours) at which the propylene conversion, propylene oxide selectivity, etc. began to decrease was recorded.
Example 3
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
In a tubular reactor, 0.20g of Au@TS-1 molecular sieve catalyst (loading of Au is 1% by weight) and 22g of quartz sand were packed in layers in the reactor with respect to 10ml of the reactor, as shown in FIG. 1 (c), wherein the layer height ratio of the catalyst layer and the quartz sand layer was 1:2.5, and the catalyst layer and the inert packing layer were each independently 20 layers/cm, and a propylene gas phase direct epoxidation reaction was carried out.
Wherein the feed gas H 2 、O 2 、C 3 H 6 (as a reaction gas), C 3 H 6 The mixture (as a diluent gas) was fed into a mixer, mixed and fed into a preheater, preheated to 100℃and fed into a tubular reactor, wherein ammonia was added by being incorporated into hydrogen gas in an amount of 100ppm relative to the mixed gas of the reaction raw material gas and the diluent gas. Reaction space velocity 13000ml g cat -1 h -1 Controlling the reaction pressure of the system to be 0.25MPa and the temperature to be 1.2 ℃ for min -1 After the reaction was stabilized for 20 minutes at 120℃and the analysis of the propylene gas phase direct epoxidation reaction was shown in Table 1, the approximate time (recorded every 50 hours) at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decrease was recorded.
Example 4
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
In a tubular reactor, 0.20g of Au@TS-1 molecular sieve catalyst (loading of Au is 1% by weight) and 16g of quartz sand were packed in layers in the reactor with respect to 10ml of the reactor, as shown in FIG. 1 (c), wherein the layer height ratio of the catalyst layer and the quartz sand layer was 1:1, and a propylene gas phase direct epoxidation reaction was carried out.
Wherein the feed gas H 2 、O 2 、C 3 H 6 (as a reaction gas), C 3 H 6 The mixture (as a diluent gas) was fed into a mixer, then into a preheater, preheated to 100℃and fed into a tubular reactor, wherein pyridine was added by doping with hydrogen gas in an amount of 5ppm with respect to the mixed gas of the reaction raw material gas and the diluent gas. Reaction space velocity 1000ml g cat -1 h -1 Controlling the reaction pressure of the system to be 0.5MPa and the temperature to be 0.5 ℃ for min -1 After the reaction was stabilized for 20 minutes at 100℃with the rate programmed to increase, the analysis of the propylene gas phase direct epoxidation reaction is shown in Table 1, and the approximate time (recorded every 50 hours) at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decrease was recorded.
Example 5
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
In a tubular reactor, 0.20g of Au@TS-1 molecular sieve catalyst (loading of Au is 1% by weight) and 30g of quartz sand were packed in layers in the reactor with respect to 10ml of the reactor, as shown in FIG. 1 (c), wherein the layer height ratio of the catalyst layer to the quartz sand layer was 1:3, and a propylene gas phase direct epoxidation reaction was carried out.
Wherein the feed gas H 2 、O 2 、C 3 H 6 (as a reaction gas), C 3 H 6 Mixing (as diluent gas) in a mixer, preheating to 100 ℃, and introducing into a tubular reactor, wherein ethylenediamine is added by doping into hydrogen, and the doping amount of ammonia is 1500ppm relative to the mixed gas of reaction raw material gas and diluent gas. Reaction space velocity 20000ml g cat -1 h -1 Controlling the reaction pressure of the system to be 0.01MPa and 2.0 ℃ for min -1 After the reaction was stabilized for 20 minutes at 250 c, the analysis of the propylene gas phase direct epoxidation reaction was as shown in table 1, and the approximate time (recorded every 50 hours) at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decrease was recorded.
Example 6
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
Propylene was directly epoxidized to produce propylene oxide as in example 1, except that the catalyst was packed as shown in fig. 1 (b). The analysis is shown in table 1.
Example 7
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
Propylene was directly epoxidized to produce propylene oxide as in example 1, except that the catalyst was packed as shown in fig. 1 (a). The analysis is shown in table 1.
Example 8
This example is illustrative of the method of direct epoxidation of propylene provided by the present invention
Propylene was directly epoxidized to produce propylene oxide as in example 1, except that no preheating was performed prior to entry into the tubular reactor unit. The analysis is shown in table 1.
Comparative example 1
This comparative example is intended to illustrate the direct epoxidation of propylene in a reference
Propylene was directly epoxidized to prepare propylene oxide in the same manner as in example 1 except that the diluent gas was replaced with nitrogen gas and that no alkaline gas was introduced, but in order to ensure safe and smooth progress of the reaction, H was adjusted 2 :O 2 :C 3 H 6 Diluent gas=1:1:1:7, the loading of catalyst was 0.3g. The analysis is shown in table 1.
TABLE 1
Note that: the propylene conversion is calculated for propylene alone as the reaction gas, and the amount of propylene as the diluent gas is not taken into account, i.e., when the propylene conversion is calculated by analyzing the amount of each component of the gas after the reaction, it is necessary to subtract the amount of propylene as the diluent gas, and the diluent gas is considered not to participate in the reaction.
As shown in Table 1, the diluent gas used in the invention can reduce the dosage of the diluent gas and improve the propylene conversion rate and the hydrogen utilization rate catalyst service life of the propylene oxide selectivity space-time yield.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (16)
1. A process for the epoxidation of propylene to propylene oxide, comprising: in the presence of propylene epoxidation reaction conditions and alkaline substances, carrying out contact reaction on mixed gas of reaction raw material gas and diluent gas and a catalyst to obtain propylene oxide; wherein the reaction raw material gas is propylene, oxygen and hydrogen, and the diluent gas is propylene; the catalyst and the inert filler are filled in the reactor in a layered stacking mode; the catalyst layer and the inert filler layer are each independently 1-2000 layers/meter; the layer height ratio of the catalyst layer to the inert filler layer is 1:1-10;
wherein the propylene epoxidation reaction is not carried out in the presence of a solvent;
wherein, in the mixed gas, the proportion of oxygen is more than 25-60 volume percent, and the proportion of the dilution gas is 25-40 volume percent;
the catalyst is a supported metal catalyst, wherein the metal is at least one of gold, silver, copper, ruthenium, palladium, platinum, rhodium, cobalt, nickel, tungsten, bismuth, molybdenum and oxides thereof, the carrier is at least one of carbon black, activated carbon, silicon dioxide, aluminum oxide, cerium oxide, titanium silicalite, zeolite, resin, polymer and alkaline earth metal carbonate, and the metal concentration in the catalyst is 0.01-50 wt% based on the weight;
the alkaline substance is at least one selected from ammonia, hydrazine, pyridine and ethylenediamine; the doping amount of the alkaline substance is 1-10000ppm relative to the mixed gas.
2. The method according to claim 1, wherein the doping amount of the alkaline substance is 10 to 1000ppm with respect to the mixed gas.
3. The method according to claim 1, wherein the alkaline substance is introduced into the reaction system by any one of the following means:
(1) Adding the alkaline substance in the mixing process of the reaction raw material gas;
(2) After the reaction raw material gas is mixed, adding the alkaline substance into the reaction raw material gas;
(3) The reaction raw material gas or the dilution gas is led to pass through the environment of the alkaline substance, so that the alkaline substance enters the reaction system along with the reaction raw material gas or the dilution gas.
4. The method according to claim 1, wherein the proportion of the dilution gas in the mixed gas is 25% by volume or more and less than 33.5% by volume.
5. The process of claim 1, wherein the epoxidation reaction is carried out in a microchannel reactor or a tubular reactor.
6. The method of claim 1, wherein the catalyst is a gold-loaded titanium silicalite molecular sieve.
7. The method of claim 1, wherein the inert filler is selected from quartz sand, al 2 O 3 At least one of porous silica gel and ceramic ring;
and/or the inert filler is used in an amount of 1 to 200 parts by weight relative to 1 part by weight of the catalyst.
8. The process of any of claims 1-7, wherein the propylene epoxidation reaction conditions comprise: the reaction temperature is 20-300 ℃; the reaction pressure is 0-5MPa.
9. The process of any of claims 1-7, wherein the propylene epoxidation reaction conditions comprise: the reaction temperature is 50-250 ℃; the reaction pressure is 0-1.5MPa.
10. The process of any of claims 1-7, wherein the propylene epoxidation reaction has a space velocity of500-30000ml g cat -1 h -1 。
11. The process according to any one of claims 1 to 7, wherein the propylene epoxidation reaction has a space velocity of from 1000 to 20000ml g cat -1 h -1 。
12. The method according to any one of claims 1 to 7, wherein the method further comprises the step of heating at 0.1 to 10 ℃ for a minute -1 The temperature of the reaction system is raised to the temperature required for the epoxidation of propylene.
13. The method according to any one of claims 1-7, wherein the method further comprises the step of heating at 0.5-5 ℃ for a period of time -1 The temperature of the reaction system is raised to the temperature required for the epoxidation of propylene.
14. The method of any one of claims 1-7, further comprising premixing and/or preheating the mixed gas.
15. The method of any one of claims 1-7, wherein the method further comprises performing a component analysis of the reaction product.
16. The method of claim 15, wherein the reaction product is delivered to the component analysis device under heating conditions of 50-200 ℃.
Priority Applications (4)
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| CN202010663791.1A CN113912574B (en) | 2020-07-10 | 2020-07-10 | Method for preparing epoxypropane by directly epoxidation of propylene under alkaline condition |
| US18/005,001 US20230339875A1 (en) | 2020-07-10 | 2021-01-26 | Method for preparing propylene oxide by means of direct epoxidation of propylene |
| EP21838273.7A EP4163274A4 (en) | 2020-07-10 | 2021-01-26 | Method for preparing propylene oxide by means of direct epoxidation of propylene |
| PCT/CN2021/073750 WO2022007388A1 (en) | 2020-07-10 | 2021-01-26 | Method for preparing propylene oxide by means of direct epoxidation of propylene |
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