CN113912574A - Method for preparing propylene oxide by directly epoxidizing propylene under alkaline condition - Google Patents
Method for preparing propylene oxide by directly epoxidizing propylene under alkaline condition Download PDFInfo
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- CN113912574A CN113912574A CN202010663791.1A CN202010663791A CN113912574A CN 113912574 A CN113912574 A CN 113912574A CN 202010663791 A CN202010663791 A CN 202010663791A CN 113912574 A CN113912574 A CN 113912574A
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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 111
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 64
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 239000007789 gas Substances 0.000 claims abstract description 169
- 238000006243 chemical reaction Methods 0.000 claims abstract description 130
- 239000003054 catalyst Substances 0.000 claims abstract description 74
- 239000003085 diluting agent Substances 0.000 claims abstract description 70
- 238000006735 epoxidation reaction Methods 0.000 claims abstract description 50
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 239000000126 substance Substances 0.000 claims abstract description 31
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- 239000000945 filler Substances 0.000 claims description 20
- 230000008569 process Effects 0.000 claims description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 238000004458 analytical method Methods 0.000 claims description 18
- 239000010931 gold Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 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
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution 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
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 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
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- -1 alkaline earth metal carbonates Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Chemical group 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
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- 239000002904 solvent Substances 0.000 claims description 3
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 239000006004 Quartz sand Substances 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
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 150000001412 amines Chemical class 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
- 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
- 229910052593 corundum Inorganic materials 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
- 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
- 150000003222 pyridines Chemical class 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
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 150000003573 thiols Chemical class 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
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 150000002429 hydrazines Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 239000012495 reaction gas Substances 0.000 abstract description 13
- 238000002360 preparation method Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000004576 sand Substances 0.000 description 12
- 238000011068 loading method Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 230000007423 decrease Effects 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000000243 solution Substances 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
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000012808 vapor phase 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
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 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
- 239000002360 explosive Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 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
- 230000001737 promoting effect Effects 0.000 description 2
- 239000001294 propane 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 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
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000005474 detonation Methods 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
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
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- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 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
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
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
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: under the propylene epoxidation reaction condition and in the presence of alkaline substances, carrying out contact reaction on a mixed gas of a reaction raw material gas and a 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 of the invention can effectively reduce the consumption of the diluent gas when used for preparing the propylene oxide, thereby relatively improving the concentration of the reaction gas and the utilization rate of the raw materials and further improving the reaction selectivity and the conversion rate.
Description
Technical Field
The invention relates to the field of propylene oxide preparation, and in particular relates to a method for preparing propylene oxide by directly epoxidizing propylene under an alkaline condition.
Background
Propylene oxide, also known as propylene oxide, methyl ethylene oxide, is a very important organic compound starting material, second only to polypropylene and acrylonitrile, the third largest propylene derivative. The epoxy propane is colorless ether liquid, low boiling point and inflammable. With chirality, the commercial product is typically a racemic mixture of two enantiomers. Mixing with water, ethanol and diethyl ether. Form binary azeotropic mixtures with pentane, pentene, cyclopentane, cyclopentene, dichloromethane.
The 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 engineering, pesticides, textile, daily chemicals and the like. Meanwhile, propylene oxide is also an important basic chemical raw material.
Propylene oxide was first synthesized in the laboratory in 1860 by Orschel, 1931 United states Union carbide built the world' 1 st plant for producing propylene oxide by the chlorohydrin process, and indirect oxidation was developed in Spain and the United states in the 60 th 20 th century. Both of these methods are currently being produced, 50% each, but the latter has a tendency to be up to date.
Subsequently, researchers have developed a direct oxygen oxidation process, i.e., over a catalyst and diluent gas N2In the presence of oxygen, propylene, hydrogen and oxygen to propylene oxideThe method simultaneously develops the research of the bifunctional catalyst loaded by the noble metal. The reaction process is simple, economical, green and environment-friendly, and has great advantages compared with the existing process flow, but generally, for safety, inert diluent gas with the volume percent of 70-95% is selected to avoid the explosion of the system. However, the use of a large amount of diluent gas leads to 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 for effectively reducing the amount of the diluent gas is urgently sought.
Disclosure of Invention
The invention aims to overcome the defects that the reaction selectivity and the conversion rate are affected due to high diluent gas consumption in the prior art, and provides a method for preparing propylene oxide by directly epoxidizing propylene under alkaline conditions. The method of the invention can effectively reduce the consumption of the diluent gas, thereby relatively improving the concentration of the reaction gas and the utilization rate of the raw materials, and further improving the reaction selectivity and the conversion rate of propylene.
In order to achieve the above object, the present invention provides a method for preparing propylene oxide by epoxidation of propylene, the method comprising: under the propylene epoxidation reaction condition and in the presence of alkaline substances, carrying out contact reaction on a mixed gas of a reaction raw material gas and a 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 1-10000 ppm.
Preferably, the catalyst and the inert filler are packed in the reactor in a layered manner.
Preferably, the space velocity of the propylene epoxidation reaction is 500-30000ml gcat -1h-1。
Preferably, at 0.1-10 deg.C for min-1The rate of (a) raises the temperature of the reaction system to a temperature required for the epoxidation of propylene.
Preferably, the method further comprises pre-mixing and/or pre-heating the mixed gas.
Through the technical scheme, the invention can obtain the following beneficial effects:
1. the reaction system effectively reduces the consumption of the diluent gas under the alkaline condition and the condition that propylene is used as the diluent gas (for example, the consumption of the solution of the invention in a tubular reactor can be reduced to below 57.5 volume percent); propylene is used as a diluent gas and a reaction gas, the concentration of the reaction gas is further improved, the forward progress of the target reaction is promoted, and other two kinds of raw material gases (H) are improved2、O2) The utilization rate of (2) is high, no redundant impurity gas is 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 under the alkaline condition and takes propylene as diluent gas, changes the original reaction path, inhibits the occurrence of side reaction, obviously improves the selectivity of propylene oxide, the conversion rate of propylene, the space-time yield and the utilization rate of hydrogen, 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 the conventional 100 hours).
3. The detonation tube explosion experiment shows that compared with N2As the diluent gas or propylene is used as the diluent gas without controlling the alkaline environment, the method system of the invention can tolerate higher limit oxygen content and has wider operable range of the raw material gas proportion, thereby being safer without burning and exploding risks and further realizing the intrinsic safety of the reaction flow.
Drawings
FIG. 1 shows a manner of filling the catalyst according to the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should 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: under the propylene epoxidation reaction condition and in the presence of alkaline substances, carrying out contact reaction on a mixed gas of a reaction raw material gas and a 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 invention, the basic substance can be a basic gas or a basic substance present in gaseous form under the conditions of the epoxidation of propene.
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 epoxidation reaction of propylene. Preferably, the basic substance is a compound having a lone electron pair and/or a substance capable of accepting a proton.
Examples of the compound having a lone electron pair may include at least one of ammonia, pyridines, hydrazine, cyanogen, amine, alcohol, ether, and thiol.
Examples of the proton-accepting substance may include Cl-、[Al(H2O)5OH]2+、Ac-、HPO4 2-、PO4 3-At least one of (1).
According to a preferred embodiment of the invention, the alkaline substance is ammonia.
According to the present invention, the form of introducing the basic 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) a certain amount of alkaline substances are added in the preparation process of the reaction raw material gas without changing a gas path. As in H2Mixing with alkaline gas to prepare H2And alkaline gas mixture, by passing H2The gas path enters the reaction system without changing the pipeline layout of the original reaction device.
(2) A new gas pipeline is added, connected into the reaction system, and fully mixed with the original reaction raw gas in the mixer and then enters the reactor.
(3) The reaction raw material gas or the dilution gas path is modified, so that the reaction raw material gas or the dilution gas passes through an alkaline medium environment, and alkaline substances enter a reactor along with the reaction raw material gas or the dilution gas.
According to the present invention, the amount of the basic substance to be added may vary within a wide range, and preferably, the amount of the basic substance to be doped in the mixed gas of the reaction raw material gas and the diluent gas is 1 to 10000ppm, for example, 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, 10000 ppm; preferably 10 to 1000ppm, and more preferably 100 to 800 ppm.
Generally, in the direct epoxidation of propylene, an inert gas is usually used as a diluent gas, which makes the reaction safer and less explosive. However, in the course of research, the inventors of the present invention found that when propylene is used as the diluent gas and the reaction is carried out in an alkaline environment, the reaction of propylene oxide can significantly reduce the amount of the diluent gas and improve the oxygen tolerance of the reaction system, so that the present invention reduces the risk of explosion while reducing the subsequent separation pressure of the reaction product (without separation, propylene is used as the reactant gas and also as the diluent gas). Meanwhile, the forward progress of the reaction can be effectively promoted due to the increase of the concentration of the oxygen serving as the reaction gas, and the reaction selectivity and the propylene conversion rate are improved. Furthermore, the inventors of the present invention have also surprisingly found that the service life of the catalyst is also extended in the case of using propylene as a diluent gas and carrying out the reaction in an alkaline environment. Furthermore, the driving energy consumption of the diluent gas is reduced due to the reduction of the using amount of the diluent gas.
It should be noted that, in the case of propylene as the diluent gas, it means that the diluent gas is completely replaced by propylene, resulting in a large excess of propylene in the reaction feed gas, which is beyond the extent that the reaction is promoted to proceed in the forward direction by increasing the amount of the reaction raw material in the ordinary case, and therefore, in this case, it cannot be simply said that propylene is in excess, which is different from the excess in the conventionally understood sense.
The improvement in propylene conversion described herein is calculated with respect to the amount of propylene as the reactant gas and does not take into account the amount of propylene as the diluent gas.
According to the present invention, generally, in order to ensure the safety of the reaction, the concentration of oxygen in the mixed gas is not 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, it is more than 22 vol%, and still more preferably, it is more than 25 vol%.
According to the invention, the concentration of oxygen is preferably not higher than 60% by volume.
According to the present invention, in general, in order to ensure the safety of the reaction, the proportion of the diluent gas in the mixed gas should not be less than 70% by volume. However, according to the method of the present invention, the proportion of the dilution gas in the mixed gas is less than 57.5 vol%, and 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 vol%, and still more preferably less than 33.5 vol%.
It can be seen from the above that the method of the present invention can reduce the amount of the diluent gas and increase the amount of the oxygen, thereby increasing the concentration of the reaction gas, promoting the forward progress of the reaction, and reducing the amount of the diluent gas and 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 conventional reactor in the field, and as long as the propylene is selected and combined with an alkaline substance environment, the consumption of diluent gas can be effectively reduced, the safe concentration of oxygen can be improved, the service life of the catalyst for the direct propylene epoxidation reaction can be prolonged, the reaction selectivity and the propylene conversion rate can be improved, and the energy consumption can be reduced.
According to a particular embodiment of the invention, the propylene epoxidation reaction is carried out in a tubular reactor. The tubular reactor may be any tubular reactor conventional in the art, for example, a quartz tube reactor.
According to another preferred embodiment of the present invention, to further achieve the object of the present invention, the epoxidation reaction is carried out in a microchannel reactor. In the 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 explosive limit, the limitation of the oxygen concentration may not be considered, that is, the diluent gas may not be used. However, in general, since the diluent gas has the function of a purge gas, propylene oxide, which is a reaction product, can be separated from the catalytic active sites in time, thereby promoting the forward shift of the reaction equilibrium. Therefore, in order to ensure the reaction efficiency, a proportion of the diluent gas is generally used, and for example, the proportion of the diluent gas in the proportion of the mixed gas is generally not less than 40% by volume. However, under the technical scheme of the invention, even if the proportion of the diluent gas is reduced to be less than 20% by volume, the reaction can be effectively ensured to have equivalent or higher propylene conversion rate and product selectivity.
The microchannel reactor according to the present invention may be any conventional one, and the present invention is not particularly limited thereto, and for example, it has a length of 1 to 1000mm, preferably 10 to 500 mm.
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 in the radial direction is 10-1000 microns at the minimum and 100-3000 microns at the maximum.
According to the present invention, the microchannel reactor may be made of 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 examples thereof include organic glass, ceramic glass, stainless steel, quartz, and resin materials.
According to the present 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 produce propylene oxide, and preferably, the catalyst is a supported metal catalyst. Wherein, the metal can be at least one selected from gold, silver, copper, ruthenium, palladium, platinum, rhodium, cobalt, nickel, tungsten, bismuth, molybdenum and oxides thereof, and is preferably gold; the carrier for supporting the metal may be at least one of carbon black, activated carbon, silica, alumina, cerium oxide, a titanium silicalite, zeolite, a resin, a polymer and an alkaline earth metal carbonate, and is preferably a titanium silicalite.
According to the invention, the content of metal in the supported metal catalyst, calculated as metal element, can vary within wide limits, for example the content of metal in the catalyst, calculated as metal element, can 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.%, can be 0.01 wt.%, 0.9 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 1.1.2 wt.%, 1.2 wt.%, 1, 45 wt%, 50 wt%, preferably 0.05 to 5 wt%, more preferably 0.1 to 2 wt%.
According to a preferred embodiment of the present invention, the catalyst is titanium silicalite supported with gold (A)Au@TS-1) (Wherein, the TS-1 molecular sieve can be prepared by a hydrothermal synthesis mode, and the active metal Au can be loaded by a deposition and precipitation method) Wherein the loading amount in terms of gold element is 0.1-2% by weight.
According to the present invention, the catalyst can be filled in the reactor for propylene epoxidation reaction (as shown in fig. 1 a) alone or in combination with other inert substances. However, in order to further reduce the amount of diluent gas used, to increase the service life of the catalyst, to 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 a catalyst and an inert packing. Wherein the inert filler can be an inert solid phase material which is conventionally used in the field, and preferably, the inert filler is selected from quartz sand and Al2O3At least one of porous silica gel and ceramic rings.
The amount of the inert filler may be varied 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 may be designed into a sandwich structure (as shown in fig. 1b), wherein the catalyst or the inert filler is located in the middle. However, the inventors of the present invention found in their research that the catalyst and the inert filler are packed in the reactor in a layered manner (as shown in fig. 1 c), which can further reduce the amount of the diluent gas, improve the life of the catalyst, and improve the selectivity, conversion, space-time yield, and hydrogen utilization rate of the reaction. Wherein, in this mode, the height of the catalyst layer and the inert filler layer can be selected within a wide range, they can be layered in a manner of equal height or in a manner of unequal height, preferably, the catalyst layer and the inert filler layer are each independently 1 to 2000 layers/m, for example, 1 layer/m, 2 layers/m, 3 layers/m, 4 layers/m, 5 layers/m, 6 layers/m, 7 layers/m, 8 layers/m, 9 layers/m, 10 layers/m, 15 layers/m, 18 layers/m, 20 layers/m, 50 layers/m, 100 layers/m, 200 layers/m, 300 layers/m, 400 layers/m, 500 layers/m, 600 layers/m, 700 layers/m, 800 layers/m, 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 be changed in a wide range, and it is preferable to further improve the effect of the present invention that the layer height ratio of the catalyst layer and the inert filler layer is 1:1 to 10, for example, 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 more preferably 1:1.5 to 2.5.
According to the present invention, the manner of filling the catalyst in the reactor may not be particularly limited, and for example, a coating method, an electrodeposition method, a solution plating method, a mechanical filling method, or the like may be employed.
According to the invention, it is preferred that the catalyst is used in an amount of 0.1 to 0.5g relative to a 10ml reactor. Usually, the amount of catalyst used is at least 1g, and it can be seen that the amount of catalyst used can also be reduced by the solution of the invention.
According to the present invention, the temperature of the epoxidation reaction of propylene 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 used, improve the conversion, selectivity, space-time yield and hydrogen utilization rate of the reaction, and improve 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 inventor of the invention finds in research that the temperature rise speed of the system can further influence the dosage of the diluent gas, the conversion rate, the selectivity, the space-time yield, the hydrogen utilization rate and the service life of the catalyst when the temperature is 0.1-10 ℃ for min-1Preferably 0.5-5 ℃ for min-1More preferably 0.5-2 ℃ for min-1(for example, it 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-1More preferably 0.8 to 1.5 ℃ for min-1) When the temperature of the reaction system is raised to the temperature required by the propylene epoxidation reaction at the rate, the using amount of the diluent gas can be further reduced, the conversion rate, the selectivity, the space-time yield and the hydrogen utilization rate of the reaction are improved, the service life of the catalyst is prolonged, and the using amount of the catalyst and the using amount of the diluent gas are reduced.
According to the present invention, in order to further improve the efficiency of the reaction, the mixed gas is preferably pre-mixed and/or preheated before entering the reactor.
According to the invention, the degree of preheating is preferably at least 50% of the target reaction temperature, for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, preferably at least 80%.
According to the present invention, the pressure of the epoxidation reaction of propylene 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 used, improve the conversion, selectivity, space-time yield and hydrogen utilization rate of the reaction, and improve 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, 0.25 MPa.
According to the present invention, the space velocity of the propylene epoxidation reaction may be a reaction space velocity conventional in the art, but in order to further reduce the amount of diluent gas used, improve the conversion, selectivity, space-time yield and hydrogen utilization rate of the reaction, and to improve the service life of the catalyst, it is preferable that the reaction space velocity is 500-30000ml gcat -1h-1More preferably 1000-cat -1h-1More preferably 2000-15000ml gcat -1h-1For example, it may be 2000ml gcat -1h-1、3000ml gcat - 1h-1、4000ml gcat -1h-1、5000ml gcat -1h-1、6000ml gcat -1h-1、7000ml gcat -1h-1、8000ml gcat -1h-1、9000ml gcat -1h-1、10000ml gcat -1h-1、12000ml gcat -1h-1、13000ml gcat -1h-1、14000ml gcat -1h-1、15000ml gcat -1h-1。
According to the invention, the ratio of the quantities of propylene, oxygen and hydrogen is preferably between 0.1 and 3: 0.1-3: 1.
according to the present invention, the flow rates of propylene, oxygen, hydrogen and the diluent gas are not particularly limited as long as mixing in the above amount by volume ratio can be ensured.
According to the invention, the method of the invention may also comprise the analysis of the composition of the reaction product, for example by gas chromatography, in particular by introducing the reaction product into a gas chromatograph equipped with TCD and FID detectors.
More preferably, in order to ensure the analysis effect, the reaction product is delivered to the component analysis equipment under the heating condition of 50-200 ℃, and specifically, a heating belt can be arranged between the outlet of the reactor and the inlet of the component analysis equipment to maintain the temperature of 50-200 ℃, preferably 80-150 ℃, for example, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃.
According to the present invention, the epoxidation reaction of propene provided by the process of the present invention is preferably not carried out in the presence of a solvent. Wherein the solvent comprises any exogenously introduced liquid phase.
The present invention will be described in detail below by way of examples.
The tubular reactor is a quartz tube reactor with a diameter of 3 cm.
Product analysis using 2 gas chromatographs, the product was sampled for gas chromatographic analysis. The two analytical chromatographic types are Agilent 7890B, wherein the chromatographic columns of the gas chromatograph A are (1) a HayeSep Q column (SFt 0.9m, OD1/8, ID 2mm), (2) a Molsieve5A column (SFt 2.44m, OD1/8, ID 2mm), (3) a PoraBOND U column (25m, 0.32mm, 7 μm); with TCD and FID detectors for analysis of H2、O2And permanent gases such as diluent gas and propylene, propane, propylene oxide, acrolein, acetone, propionaldehyde, acetaldehyde and the like, wherein the peak positions of the propylene and the 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 column of the gas chromatography B is (1) a HayeSep Q column (SFt 1.83m, OD1/8, ID 2mm), (2) a Molsieve5A column (SFt 2.44m, OD1/8, ID 2mm), (3) an HP-AL \ S column (25m, 0.32mm, 8 μm); with TCD and FID detectors for analysis of H2、O2Permanent gases such as diluent gas, propylene and propane.
In the Au @ TS-1 molecular sieve catalyst, a TS-1 molecular sieve is prepared in a hydrothermal synthesis mode, and active metal Au is loaded by a deposition and precipitation method.
Burst test
1) In a tubular reactor, 0.3g of Au @ TS-1 molecular sieve catalyst (Au loading of 1 wt%) was packed in a 10ml reactor, and layered with 30g of silica sand as shown in FIG. 1 (c), wherein the layer height ratio of the catalyst layer and the silica sand layer was 1:2, and the catalyst layer and the inert filler layer were each independently 15 layers/cm, to conduct the vapor phase direct epoxidation reaction of propylene.
Wherein the raw material gas is in proportion H2:O2:C3H6:C3H6(as a diluent gas) 26%: 26%: 26%: 22% was introduced into a mixer, in which ammonia gas was added by doping with hydrogen gas, and the final doping amount in the system was 500 ppm. And (3) feeding the obtained mixed system into a preheater, preheating to 160 ℃, and then feeding into a reactor.
Reaction space velocity 4000ml gcat -1h-1Controlling the reaction pressure of the system to be 0.2MPa and the temperature to be 1.5 ℃ for min-1The rate of (2) was programmed to 200 ℃.
Wherein, the reaction system is not exploded within 20min of reaction. However, when the diluent gas is nitrogen, it cannot be safely used.
Among them, it is impossible to carry out the reaction safely in the case where the diluent gas is nitrogen gas without introducing an alkaline gas.
Examples 1-9 below are given by H2:O2:C3H6:C3H6The other effects were verified at a ratio of 25%: 25%: 25% (as a dilution gas).
Example 1
This example illustrates the process for the direct epoxidation of propylene according to the present invention
In a tubular reactor, 0.20g of Au @ TS-1 molecular sieve catalyst (loading of Au: 1% by weight) and 20g of silica sand were packed in layers in the reactor relative to a 10ml reactor as shown in (c) of FIG. 1, wherein the layer height ratio of the catalyst layer and the silica sand layer was 1:2, and the catalyst layer and the inert filler layer were each independently 15 layers/cm, to conduct the vapor phase direct epoxidation of propylene.
Wherein, the raw material gas H2、O2、C3H6(as a reaction gas) C3H6(as dilution gas) enters a mixer, is mixed and then enters a preheater, is preheated to 160 ℃ and then enters a tubular reactor, wherein ammonia gas is added by doping hydrogen gas, and the ammonia gas is opposite to the ammonia gasThe doping amount of ammonia gas is 800ppm according to the mixed gas of the raw material gas and the diluent gas. Reaction space velocity 9000ml gcat -1h-1Controlling the reaction pressure of the system to be 0.15MPa and the temperature to be 0.8 ℃ for min-1The temperature was programmed to 200 c and after 20 minutes of reaction stabilization, the analysis of the gas phase direct epoxidation of propylene was as shown in table 1 and the approximate time at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decline was recorded (every 50 hours).
Example 2
This example illustrates the process for the direct epoxidation of propylene according to the present invention
In a tubular reactor, 0.20g of Au @ TS-1 molecular sieve catalyst (Au loading of 1% by weight) and 18g of silica sand were packed in layers in the reactor as shown in (c) in FIG. 1, with respect to a 10ml reactor, wherein the layer height ratio of the catalyst layer and the silica sand layer was 1:1.5, the catalyst layer and the inert filler layer are respectively 10 layers/cm independently, and the propylene gas phase direct epoxidation reaction is carried out.
Wherein, the raw material gas H2、O2、C3H6(as a reaction gas) C3H6The diluted gas (used as the diluent gas) enters a mixer, is mixed and then enters a preheater, is preheated to 130 ℃, and then enters a tubular reactor, wherein ammonia gas is added by doping hydrogen gas, and the doping amount of the ammonia gas is 500ppm relative to the mixed gas of the reaction raw material gas and the diluted gas. Reaction space velocity 4000ml gcat -1h-1Controlling the reaction pressure of the system to be 0.05MPa and the temperature to be 1.5 ℃ for min-1The temperature was programmed to 170 c and 20 minutes after the reaction was stable, the analysis of the gas phase direct epoxidation of propylene was as shown in table 1 and the approximate time at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decline was recorded (every 50 hours).
Example 3
This example illustrates the process for the direct epoxidation of propylene according to the present invention
In a tubular reactor, 0.20g of Au @ TS-1 molecular sieve catalyst (Au loading of 1 wt%) and 22g of silica sand were packed in layers in the reactor as shown in (c) of FIG. 1, with respect to a 10ml reactor, wherein the layer height ratio of the catalyst layer and the silica sand layer was 1:2.5, and the catalyst layer and the inert filler layer were each independently 20 layers/cm, to conduct a propylene gas phase direct epoxidation reaction.
Wherein, the raw material gas H2、O2、C3H6(as a reaction gas) C3H6The diluted gas (as the diluent gas) enters a mixer, is mixed and then enters a preheater, is preheated to 100 ℃ and then enters a tubular reactor, wherein ammonia gas is added by doping hydrogen gas, and the doping amount of the ammonia gas is 100ppm relative to the mixed gas of the reaction raw material gas and the diluted gas. Reaction space velocity 13000ml gcat -1h-1Controlling the reaction pressure of the system to be 0.25MPa and the temperature to be 1.2 ℃ for min-1The temperature was programmed to 120 c and after 20 minutes of reaction stabilization, the analysis of the gas phase direct epoxidation of propylene was as shown in table 1 and the approximate time at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decline was recorded (every 50 hours).
Example 4
This example illustrates the process for the direct epoxidation of propylene according to the present invention
In a tubular reactor, 0.20g of Au @ TS-1 molecular sieve catalyst (Au loading: 1% by weight) and 16g of silica sand were packed in layers in the reactor relative to a 10ml reactor, as shown in (c) of FIG. 1, in which the layer height ratio of the catalyst layer and the silica sand layer was 1:1, to conduct the propylene gas phase direct epoxidation reaction.
Wherein, the raw material gas H2、O2、C3H6(as a reaction gas) C3H6The pyridine is added by doping hydrogen, and the doping amount of ammonia gas is 5ppm relative to the mixed gas of the reaction raw material gas and the diluent gas. The reaction space velocity is 1000ml gcat -1h-1Controlling the reaction pressure of the system to be 0.5MPa and the temperature to be 0.5 ℃ for min-1The temperature is programmed to 100 ℃, and after the reaction is stable for 20 minutes, the propylene gas phase is directly epoxidizedThe analysis is shown in table 1 and the approximate time (every 50 hours) at which the indices of propylene conversion, propylene oxide selectivity, etc. begin to decline is recorded.
Example 5
This example illustrates the process for the direct epoxidation of propylene according to the present invention
In a tubular reactor, 0.20g of Au @ TS-1 molecular sieve catalyst (Au loading: 1% by weight) and 30g of silica sand were packed in layers in the reactor relative to a 10ml reactor, as shown in (c) of FIG. 1, in which the layer height ratio of the catalyst layer and the silica sand layer was 1:3, to conduct the vapor phase direct epoxidation of propylene.
Wherein, the raw material gas H2、O2、C3H6(as a reaction gas) C3H6The diluted gas (used as the diluent gas) enters a mixer, is mixed and then enters a preheater, and enters a tubular reactor after being preheated to 100 ℃, wherein the ethylenediamine is added by doping hydrogen, and the doping amount of ammonia gas is 1500ppm relative to the mixed gas of the reaction raw material gas and the diluted gas. Reaction space velocity 20000ml gcat -1h-1Controlling the reaction pressure of the system to be 0.01MPa and the temperature to be 2.0 ℃ for min-1The temperature was programmed to 250 c and after 20 minutes of reaction stabilization, the analysis of the gas phase direct epoxidation of propylene is shown in table 1 and the approximate time at which the indicators of propylene conversion, propylene oxide selectivity, etc. began to decline is recorded (every 50 hours).
Example 6
This example illustrates the process for the direct epoxidation of propylene according to the present invention
Propylene oxide was prepared by direct epoxidation of propylene according to the procedure of example 1, except that the catalyst was packed as shown in (b) of FIG. 1. The analysis is shown in table 1.
Example 7
This example illustrates the process for the direct epoxidation of propylene according to the present invention
Propylene oxide was prepared by direct epoxidation of propylene according to the procedure of example 1, except that the catalyst was packed as shown in (a) of FIG. 1. The analysis is shown in table 1.
Example 8
This example illustrates the process for the direct epoxidation of propylene according to the present invention
Propylene oxide was prepared by direct epoxidation of propylene as in example 1 except that no preheating was performed prior to entering the tubular reactor unit. The analysis is shown in table 1.
Comparative example 1
This comparative example serves to illustrate a process for the direct epoxidation of propylene to reference
Propylene oxide was prepared by direct epoxidation of propylene as in example 1, except that the diluent gas was replaced with nitrogen and no alkaline gas was introduced, but H was adjusted to ensure safe and smooth reaction2:O2:C3H6The dilution gas was 1:1:1:7, and the catalyst loading was 0.3 g. The analysis is shown in table 1.
TABLE 1
Note: the propylene conversion is calculated only for propylene as the reaction gas and does not take into account the amount of propylene as the diluent gas, that is, when the propylene conversion is calculated by analyzing the amounts of the respective components of the gas after the reaction, it is necessary to subtract the amount of propylene as the diluent gas, and it is considered that the diluent gas does not participate in the reaction.
As shown in Table 1, the diluent gas used in the invention can reduce the use amount of the diluent gas, and can improve the propylene conversion rate and the space-time yield of propylene oxide selectivity, so that the service life of the catalyst can be prolonged.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (18)
1. A method for preparing propylene oxide by propylene epoxidation is characterized in that the method comprises the following steps: under the propylene epoxidation reaction condition and in the presence of alkaline substances, carrying out contact reaction on a mixed gas of a reaction raw material gas and a 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.
2. The method of claim 1, wherein the alkaline substance is an alkaline gas or an alkaline substance present in a gaseous state under reaction conditions.
3. The method according to claim 2, wherein the basic substance is a compound having a lone electron pair and/or a substance capable of accepting a proton.
4. The method of claim 3, wherein the compound with a lone pair of electrons is selected from at least one of ammonia, pyridines, hydrazines, cyanides, amines, alcohols, ethers, and thiols; and/or
The substance capable of accepting protons is selected from Cl-、[Al(H2O)5OH]2+、Ac-、HPO4 2-、PO4 3-At least one of (1).
5. The method according to any one of claims 1 to 4, wherein the doping amount of the basic substance is 1 to 10000ppm, preferably 10 to 1000ppm, with respect to the mixed gas.
6. The method according to any one of claims 1 to 5, wherein the basic substance can be introduced into the reaction system by any one of:
(1) adding the alkaline substance in the process of mixing the raw material gas for reaction;
(2) after the reaction raw gas is mixed, adding the alkaline substance into the reaction raw gas;
(3) and (3) leading the reaction raw material gas or the diluent gas 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 diluent gas.
7. The method according to any one of claims 1 to 6, wherein the proportion of oxygen in the mixed gas is more than 16 vol.%, more preferably more than 22 vol.%, even more preferably more than 25 vol.%.
8. The method according to any one of claims 1 to 7, wherein the proportion of the dilution gas in the mixed gas is less than 57.5 vol%; more preferably less than 40 vol%, and still more preferably less than 33.5 vol%.
9. The process of any of claims 1-8, wherein the epoxidation reaction is carried out in a microchannel reactor or a tubular reactor.
10. The process according to any one of claims 1 to 9, wherein the catalyst is a supported metal catalyst, wherein the metal is at least one selected from the group consisting of gold, silver, copper, ruthenium, palladium, platinum, rhodium, cobalt, nickel, tungsten, bismuth, molybdenum and oxides thereof, and the support is at least one selected from the group consisting of carbon black, activated carbon, silica, alumina, ceria, titanium silicalite, zeolites, resins, polymers and alkaline earth metal carbonates, and the metal concentration in the catalyst is 0.01 to 50 wt% by weight;
preferably, the catalyst is a titanium silicalite molecular sieve loaded with gold.
11. The process according to any one of claims 1 to 10, wherein the catalyst is packed in the reactor in combination with an inert packing;
preferably, the inert filler is selected from quartz sand and Al2O3At least one of porous silica gel and ceramic ring;
preferably, the inert filler is used in an amount of 1 to 200 parts by weight, relative to 1 part by weight of the catalyst.
12. The method of claim 11, wherein the catalyst and inert packing are packed in a layered stack in the reactor;
preferably, the catalyst layer and the inert filler layer are each independently 1 to 2000 layers/m;
preferably, the layer height ratio of the catalyst layer to the inert filler layer is 1: 1-10.
13. The process of any of claims 1-12, wherein the propylene epoxidation reaction conditions comprise: the reaction temperature is 20-300 ℃, preferably 50-250 ℃; the reaction pressure is 0 to 5MPa, preferably 0 to 1.5 MPa.
14. The process as claimed in claim 1 or 13, wherein the space velocity of the propylene epoxidation reaction is 500-30000ml gcat -1h-1Preferably 1000-cat -1h-1。
15. The method of claim 1, 13 or 14, wherein the method further comprises a step of heating the mixture at 0.1-10 ℃ for min-1Preferably 0.5-5 ℃ for min-1The rate of (a) raises the temperature of the reaction system to a temperature required for the epoxidation of propylene.
16. The method of any one of claims 1-15, further comprising pre-mixing and/or pre-heating the mixed gas.
17. The method of any one of claims 1-16, wherein the method further comprises performing a compositional analysis on the reaction product;
preferably, the reaction product is fed to the component analyzing apparatus under heating at 50 to 200 ℃.
18. The process of any of claims 1-17, wherein the propylene epoxidation reaction is not carried out in the presence of a solvent.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010663791.1A CN113912574B (en) | 2020-07-10 | 2020-07-10 | Method for preparing epoxypropane by directly epoxidation of propylene under alkaline condition |
| 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 |
| US18/005,001 US20230339875A1 (en) | 2020-07-10 | 2021-01-26 | Method for preparing propylene oxide by means of direct epoxidation of propylene |
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