CN110759875B - Preparation method of propylene oxide - Google Patents
Preparation method of propylene oxide Download PDFInfo
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- CN110759875B CN110759875B CN201911094191.1A CN201911094191A CN110759875B CN 110759875 B CN110759875 B CN 110759875B CN 201911094191 A CN201911094191 A CN 201911094191A CN 110759875 B CN110759875 B CN 110759875B
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- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 41
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 40
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052786 argon Inorganic materials 0.000 claims abstract description 11
- 239000012495 reaction gas Substances 0.000 claims abstract description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 32
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 239000012498 ultrapure water Substances 0.000 claims description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- FXXMDJFRMDVSCF-RXSVEWSESA-N (2r)-2-[(1s)-1,2-dihydroxyethyl]-3,4-dihydroxy-2h-furan-5-one;hydrate Chemical compound O.OC[C@H](O)[C@H]1OC(=O)C(O)=C1O FXXMDJFRMDVSCF-RXSVEWSESA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 16
- 230000001590 oxidative effect Effects 0.000 abstract description 15
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 238000006735 epoxidation reaction Methods 0.000 abstract description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001882 dioxygen Inorganic materials 0.000 abstract description 3
- 239000002159 nanocrystal Substances 0.000 description 27
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 22
- 230000003197 catalytic effect Effects 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000007254 oxidation reaction Methods 0.000 description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 8
- 238000010586 diagram Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 5
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 229940112669 cuprous oxide Drugs 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XENVCRGQTABGKY-ZHACJKMWSA-N chlorohydrin Chemical compound CC#CC#CC#CC#C\C=C\C(Cl)CO XENVCRGQTABGKY-ZHACJKMWSA-N 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000002124 flame ionisation detection Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DOKHEARVIDLSFF-UHFFFAOYSA-N prop-1-en-1-ol Chemical compound CC=CO DOKHEARVIDLSFF-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epoxy Compounds (AREA)
Abstract
The invention provides a preparation method of propylene oxide, which comprises the following steps: introducing mixed reaction gas of propylene, oxygen and argon into the reactor filled with Cu2Reacting in a reactor of an O catalyst to obtain propylene oxide; the Cu2The O catalyst has regular cubic morphology; the Cu2The size of the O catalyst is 20-120 nm. The present invention uses small-sized Cu with cubic micro-morphology2The O is used as a catalyst to catalyze the propylene epoxidation reaction directly using molecular oxygen as an oxidant, so that the catalyst has high propylene oxide selectivity, is simple to prepare and has mild catalytic reaction conditions. Experimental results show that the selectivity of the preparation method disclosed by the invention to a target product propylene oxide is as high as about 80%.
Description
Technical Field
The invention belongs to the technical field of nano catalysis, and particularly relates to a preparation method of propylene oxide.
Background
Propylene oxide is a high value-added commodity chemical used in the manufacture of various products. The main routes to commercial propylene oxide are the chlorohydrin process and the two variants of the hydroperoxide process, which produce tert-butanol or styrene monomer as by-products. These two variants use isobutylene and ethylbenzene as reactants, respectively. These methods have substantial drawbacks. The chlorohydrin process is the oldest and most traditional process, requires expensive oxidizing agents and produces a large amount of waste salts, is seriously polluted, is not green and environment-friendly, and has low atom utilization rate. Byproduct flows suffer from plant complexity and inefficient marketing/generation. The formation of by-products is particularly problematic because their price and capacity requirements may not match those of propylene oxide, making it difficult to optimize the process.
Direct utilization of O2The selective catalytic partial oxidation of propylene to propylene oxide is an ideal green process. Many researchers have been working on achieving high selectivity to propylene oxide in propylene epoxidation reactions. Cu-based catalysts are relatively inexpensive materials, in the direct fieldWith O2The catalytic performance of propylene oxide to propylene oxide is very good, so that it is considered as a promising catalyst for propylene epoxidation. Since propylene oxide formed during the reaction is readily isomerized to propenol at elevated temperatures and then further oxidized to acrolein or completely burned to CO2Resulting in a decrease in propylene oxide selectivity, Cu-based catalysts catalyze the epoxidation of propylene to propylene oxide with generally low selectivity, most not exceeding 50%, at high temperatures.
Disclosure of Invention
The invention aims to provide a preparation method of propylene oxide, which has high selectivity, simple preparation of a catalyst and mild catalytic reaction conditions.
The invention provides a preparation method of propylene oxide, which comprises the following steps:
introducing mixed reaction gas of propylene, oxygen and argon into the reactor filled with Cu2Reacting in a reactor of an O catalyst to obtain propylene oxide;
the Cu2The O catalyst has regular cubic morphology; the Cu2The size of the O catalyst is 20-120 nm.
Preferably, the Cu2The O catalyst is prepared according to the following steps:
mixing CuSO4Adding the solution into ultrapure water, keeping the temperature of 25-30 ℃ for 5-10 min, then adding NaOH solution, keeping the temperature of 25-30 ℃ for 5-10 min, then adding ascorbic acid water solution, reacting the obtained mixed solution at the constant temperature of 25-30 ℃ for 30-60 min to obtain Cu2And (3) an O catalyst.
Preferably, after adding the sodium citrate into the ultrapure water, adding the CuSO4A solution;
the mass of the sodium citrate and the CuSO4CuSO in solution4The amount ratio of (0.24 to 0.28) g: (1-1.2) mmol.
Preferably, the CuSO4The concentration of the solution is 1-2 mol/L;
the concentration of the NaOH solution is 4-5 mol/L;
the concentration of the ascorbic acid aqueous solution is 1-2 mol/L.
Preferably, the CuSO4The dosage relation of the solution, the NaOH solution, the ascorbic acid and the ultrapure water is as follows: (1-1.5) mL: (1-1.5) mL: (0.20-0.30 g): (400-600) mL.
Preferably, the Cu2The ratio of the mass of the O catalyst to the flow rate of propylene is (200 to 400) mg: (2-10) mL/min.
Preferably, the molar ratio of the propylene to the oxygen to the argon is (1-5): 1: (20-25).
Preferably, the reaction time is 30-50 min;
the reaction temperature is 90-150 ℃.
Preferably, the flow rate of the mixed reaction gas is 50-200 mL/min.
The invention provides a preparation method of propylene oxide, which comprises the following steps: introducing mixed reaction gas of propylene, oxygen and argon into the reactor filled with Cu2Reacting in a reactor of an O catalyst to obtain propylene oxide; the Cu2The O catalyst has regular cubic morphology; the Cu2The size of the O catalyst is 20-120 nm. The present invention uses small-sized Cu with cubic micro-morphology2The O is used as a catalyst to catalyze the propylene epoxidation reaction directly using molecular oxygen as an oxidant, so that the catalyst has high propylene oxide selectivity, is simple to prepare and has mild catalytic reaction conditions. Experimental results show that the selectivity of the preparation method disclosed by the invention to a target product propylene oxide is as high as about 80%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a cube in example 1 of the present inventionCu2SEM image of O nanocrystal;
FIG. 2 shows cubic Cu in example 2 of the present invention2SEM image of O nanocrystal;
FIG. 3 shows cubic Cu in example 3 of the present invention2SEM image of O nanocrystal;
FIG. 4 is an XRD pattern of three sizes of cubic cuprous oxide nanocrystals prepared in examples 1-3 of the present invention;
FIG. 5 shows cubic Cu in example 1 of the present invention2A catalytic performance diagram of the O nanocrystal in a propylene selective oxidation reaction directly taking oxygen as an oxidant;
FIG. 6 shows cubic Cu in example 2 of the present invention2A catalytic performance diagram of the O nanocrystal in a propylene selective oxidation reaction directly taking oxygen as an oxidant;
FIG. 7 shows cubic Cu in example 3 of the present invention2A catalytic performance diagram of the O nanocrystal in a propylene selective oxidation reaction directly taking oxygen as an oxidant;
FIG. 8 shows cubic Cu in examples 1 to 3 of the present invention2A comparison graph of catalytic performance of O nanocrystals in propylene selective oxidation reactions directly using oxygen as the oxidant.
Detailed Description
The invention provides a preparation method of propylene oxide, which comprises the following steps:
introducing mixed reaction gas of propylene, oxygen and argon into the reactor filled with Cu2Reacting in a reactor of an O catalyst to obtain propylene oxide;
the Cu2The O catalyst has regular cubic morphology; the Cu2The size of the O catalyst is 20-120 nm.
In the present invention, Cu is preferable2And (3) filling the O catalyst into a reactor, detecting the reaction temperature by a thermocouple arranged in the middle of the catalyst bed, introducing mixed reaction gas of propylene, oxygen and argon into the reactor, and reacting to obtain the propylene oxide.
In the invention, the propylene, the oxygen and the argon are all commercial products, and the molar ratio of the propylene to the oxygen to the argon is (1-5): 1:(20 to 25), specifically, in the embodiment of the present invention, the ratio of 2:1: 22; the flow rate of the mixed reaction gas is preferably 50-200 mL/min, and more preferably 100-150 mL/min. The Cu2The ratio of the mass of the O catalyst to the flow rate of propylene is preferably (200 to 400) mg: (2-10) mL/min, more preferably 200 mg: 4 mL/min.
The Cu2The O catalyst has regular cubic morphology, and the Cu2The size of the O catalyst is 20-120 nm, and more preferably 30-100 nm; in the present invention, the Cu2The dimensions of the O catalyst refer to the side length of the cube.
In the present invention, Cu having a size of 20 to 50nm2The O catalyst is preferably prepared according to the following steps:
mixing CuSO4Adding the solution into ultrapure water, keeping the temperature of 25-30 ℃ for 5-10 min, then adding NaOH solution, keeping the temperature of 25-30 ℃ for 5-10 min, then adding ascorbic acid water solution, reacting the obtained mixed solution at 25-30 ℃ for 30-60 min to obtain Cu with the size of 20-50 nm2And (3) an O catalyst.
In the present invention, the CuSO4The dosage relation of the solution, the NaOH solution, the ascorbic acid and the ultrapure water is as follows: (1-1.5) mL: (1-1.5) mL: (0.20-0.30) g: (400-600) mL, specifically, in the embodiment of the present invention, the volume may be 1 mL: 1mL of: 0.21 g: 400 mL; the CuSO4The concentration of the solution is preferably 1-2 mol/L, and more preferably 1.2-1.8 mol/L; the concentration of the NaOH solution is preferably 4-5 mol/L, and more preferably 4.5-4.8 mol/L; the concentration of the ascorbic acid is preferably 1-2 mol/L, and more preferably 1.2-1.8 mol/L.
The Cu prepared by the preparation method is 20-50 nm in size2O catalyst, Cu with the size of 80-120 nm2Adding sodium citrate into ultrapure water, and then adding CuSO into the ultrapure water4Solution, subsequent preparation steps and preparation of Cu with size of 20-50 nm as described above2The O catalyst step is the same. And will not be described in detail herein.
In the invention, the mass of the sodium citrate is equal to that of CuSO4CuSO in solution4The amount ratio of (2) is preferably (0.24 to 0.28) g: (1-1.2) mmol, specifically, 0.2647 g: 1.2 mmol.
In the invention, the reaction time is preferably 30-50 min, more preferably 35-45 min, and most preferably 40 min; the reaction temperature is preferably 90-130 ℃, more preferably 100-120 ℃, and specifically, the reaction temperature can be 90 ℃, 110 ℃, 130 ℃ or 150 ℃.
The invention provides a preparation method of propylene oxide, which comprises the following steps: introducing mixed reaction gas of propylene, oxygen and argon into the reactor filled with Cu2Reacting in a reactor of an O catalyst to obtain propylene oxide; the Cu2The O catalyst has regular cubic morphology; the Cu2The size of the O catalyst is 20-120 nm. The present invention uses small-sized Cu with cubic micro-morphology2The O is used as a catalyst to catalyze the propylene epoxidation reaction directly using molecular oxygen as an oxidant, so that the catalyst has high propylene oxide selectivity, is simple to prepare and has mild catalytic reaction conditions. Experimental results show that the selectivity of the preparation method disclosed by the invention to a target product propylene oxide is as high as about 80%.
In order to further illustrate the present invention, the following examples are provided to describe the preparation method of propylene oxide of the present invention in detail, but should not be construed as limiting the scope of the present invention.
Examples 1c-Cu2Synthesis of O-30 nanocrystals
400mL of ultrapure water is taken out of a 500mL single-neck flask and placed in an oil bath kettle at 25 ℃ for stirring at constant temperature for half an hour, and then 1mL of CuSO with the concentration of 1.2mol/L is added4The aqueous solution is rapidly added, after the completion, the constant temperature of 25 ℃ is continued for 5min, and then 1mL of NaOH solution with the concentration of 4.8mol/L is rapidly added into the solution. After 5min, 1mL of ascorbic acid aqueous solution with the concentration of 1.2mol/L is rapidly added into the mixed solution, the obtained mixed solution continues to react for 30min at the constant temperature of 25 ℃, and is repeatedly centrifuged and washed by ultrapure water and absolute ethyl alcohol for multiple times and dried for 12 h.
Detecting the shape of the filmSee FIG. 1, cubic Cu with dimensions around 30nm2SEM image of O nanocrystals.
Example 2c-Cu2Synthesis of O-100 nanocrystals
Cu was synthesized according to the procedure in example 12O catalyst except that 0.2647g of sodium citrate was added to 400mL of ultrapure water before synthesis to give cubic Cu of about 100nm in size2And (4) O nanocrystals.
The morphology of the Cu alloy is detected, as shown in FIG. 2, and the Cu alloy is cubic Cu with the size of about 100nm2SEM image of O nanocrystals.
Example 3c-Cu2Synthesis of O-1000 nanocrystal
100mL of 0.01mol/L CuCl is taken out of a 250mL three-neck flask2Placing the aqueous solution in oil bath pan, maintaining the temperature in oil bath at 55 deg.C for 30min, and sequentially adding 10ml2mol/L NaOH solution and 10ml
0.6mol/L ascorbic acid solution and reacting for 5 hours. Finally, centrifugally washing and vacuum drying for 12h to obtain cubic Cu2And (4) O nanocrystals.
The shape of the Cu-Cu alloy is detected, as shown in figure 3, and the size of the Cu-Cu alloy is about 1000nm2SEM image of O nanocrystals.
Cubic cuprous oxide nanocrystals (30 nm, 100nm, and 1000nm in size, respectively, and labeled as c-Cu) of three sizes prepared in examples 1 to 32O-30、c-Cu2O-100 and c-Cu2O-100), and the results are shown in fig. 4, and fig. 4 is an XRD pattern of cubic cuprous oxide nanocrystals of three sizes prepared by the present invention.
Example 4
Three small-sized cubic cuprous oxide nanocrystals (sizes of about 30nm, 100nm and 1000nm, respectively labeled as c-Cu)2O-30、c-Cu2O-100 and c-Cu2O-1000) testing of the catalytic Performance in the Selective Oxidation of propylene directly with oxygen as oxidant
Taking fresh cube Cu2Placing 200mg of O nanocrystal in a catalytic reaction device, and adopting C with a fixed proportion3H6+O2+Ar(C3H6:O2Ar 2:1:22) transAnd (3) taking a point every 20 ℃ from 90 ℃ at a heating rate of 2 ℃/min by using gas with a flow rate of 50mL/min, preserving the temperature for 30min, and detecting the gas components in the tail gas by using an online gas chromatograph.
The on-line gas chromatograph is Shimadzu GC-2014 gas chromatograph, which is provided with an automatic sample injection device, 2 FID detectors, 1 TCD detector and a methane converter. One of the FIDs is a Stabilwax-DA capillary column (0.53mm multiplied by 60m), can be used for detecting a series of organic matters such as propylene, acetone, propylene oxide, acrolein and the like, and has the detection precision of 1 ppm. Another FID is primarily intended to detect constituents in the methanator, primarily due to CO generated2The concentration is too low and the error of TCD detection is too large, so that the concentration is detected by FID of a methane reformer. In addition, TCD equipped with PorapakQ (3 mm. times.3 m) and C13x packed columns (3 mm. times.3 m) can be used to detect H2，O2，CO，N2And the like. Because the product Propylene Oxide (PO) is liquid at normal temperature, the distance from the outlet of the reaction furnace to the chromatographic sample inlet is wound with a heating band (the heating band is connected with a transformer) so that the temperature of the section can be kept above the liquefaction point temperature of the PO, and the product PO can be ensured to be vaporized and enter the chromatogram to be detected. Wherein the conversion and selectivity are given by the following two formulae:
conversion (propylene oxide formation amount + acrolein formation amount + carbon dioxide formation amount/3)/propylene amount in the reaction gas;
propylene oxide selectivity is propylene oxide production/(propylene oxide production + acrolein production + carbon dioxide production/3);
acrolein selectivity is acrolein formation/(propylene oxide formation + acrolein formation + carbon dioxide formation/3);
the carbon dioxide selectivity is (carbon dioxide formation amount/3)/(propylene oxide formation amount + acrolein formation amount + carbon dioxide formation amount/3).
The detection of the invention takes place as follows:
CH2CHCH3(propylene) +1/2O2→CH3CHCH2O (propylene oxide)
CH2CHCH3(propylene) + O2→CH2CHCHO (acrolein) + H2O
CH2CHCH3(propylene) +9/2O2→3CO2+3H2O
c-Cu in example 12The catalytic performance of O-30 nanocrystals in the selective oxidation of propylene directly using oxygen as the oxidant is shown in FIG. 5, c-Cu2A catalytic performance diagram for O-30; the specific data are detailed in table 1,
TABLE 1c-Cu in inventive example 12Data on catalytic performance of O-30 nanocrystal in selective oxidation reaction of propylene directly using oxygen as oxidant
| 90℃ | 110℃ | 130℃ | 150℃ | |
| Selectivity to propylene oxide% | 79.7 | 83.7 | 54.1 | 26.3 |
| |
0 | 0 | 5.6 | 10.0 |
| Carbon dioxide selectivity% | 20.3 | 16.3 | 37.3 | 61.1 |
| Conversion/. mu.molPropylene (PA)h-1g-1 Catalyst and process for preparing same | 20.0 | 34.2 | 75.5 | 89.1 |
c-Cu in example 22The catalytic performance of O-100 nanocrystal in propylene selective oxidation reaction directly using oxygen as oxidant is shown in FIG. 6, c-Cu2A catalytic performance diagram for O-100;
TABLE 2c-Cu in inventive example 22Data on catalytic performance of O-100 nanocrystals in propylene selective oxidation reactions using oxygen directly as the oxidant
| 90℃ | 110℃ | 130℃ | 150℃ | |
| Selectivity to propylene oxide% | 74.2 | 70.1 | 38.8 | 18.8 |
| |
0 | 0 | 14.3 | 17.9 |
| Carbon dioxide selectivity% | 25.8 | 29.9 | 46.9 | 63.3 |
| Conversion/. mu.molPropylene (PA)h-1g-1 Catalyst and process for preparing same | 7.5 | 11.5 | 25.3 | 60.6 |
c-Cu in example 32The catalytic performance diagram of the O-1000 nanocrystal in the selective oxidation reaction of propylene by directly using oxygen as an oxidant is shown in figure 7, and c-Cu2A catalytic performance diagram of O-1000;
TABLE 3c-Cu in inventive example 32Data on catalytic performance of O-1000 nanocrystals in propylene selective oxidation reactions directly using oxygen as the oxidant
c-Cu2O-30、c-Cu2O-100 and c-Cu2A comparative plot of the catalytic activity of O-1000 nanocrystals in the selective oxidation of propylene directly with oxygen as the oxidant is shown in FIG. 8, small cubic Cu2O relative large size Cu2And O has better catalytic activity and selectivity of the target product propylene oxide.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A method for preparing propylene oxide comprises the following steps:
introducing mixed reaction gas of propylene, oxygen and argon into the reactor filled with Cu2Reacting in a reactor of an O catalyst to obtain propylene oxide;
the Cu2The ratio of the mass of the O catalyst to the flow rate of propylene is (200 to 400) mg: (2-10) mL/min of the Cu2The ratio of the mass of the O catalyst to the flow rate of propylene is (200 to 400) mg: (2-10) mL/min;
the mol ratio of the propylene to the oxygen to the argon is (1-5): 1: (20-25);
the reaction time is 30-50 min; the reaction temperature is 90-150 ℃; the flow rate of the mixed reaction gas is 50-200 mL/min;
the Cu2The O catalyst has regular cubic morphology; the Cu2The size of the O catalyst is 20-120 nm;
the Cu2The O catalyst is prepared according to the following steps:
mixing CuSO4Solution additionAdding the mixture into ultrapure water, keeping the temperature of 25-30 ℃ for 5-10 min, adding NaOH solution, keeping the temperature of 25-30 ℃ for 5-10 min, adding ascorbic acid water solution, reacting the obtained mixed solution at the constant temperature of 25-30 ℃ for 30-60 min, repeatedly centrifuging and washing the mixed solution with ultrapure water and absolute ethyl alcohol for multiple times to obtain Cu2And (3) an O catalyst.
2. The method of claim 1, wherein the ultrapure water is added with sodium citrate and then with CuSO4A solution;
the mass of the sodium citrate and the CuSO4CuSO in solution4The amount ratio of (0.24 to 0.28) g: (1-1.2) mmol.
3. The method of claim 1, wherein the CuSO is applied to a substrate4The concentration of the solution is 1-2 mol/L;
the concentration of the NaOH solution is 4-5 mol/L;
the concentration of the ascorbic acid aqueous solution is 1-2 mol/L.
4. The method of claim 3, wherein the CuSO is applied to a substrate4The dosage relation of the solution, the NaOH solution, the ascorbic acid and the ultrapure water is as follows: (1-1.5) mL: (1-1.5) mL: (0.20-0.30 g, (400-600) mL.
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| CN102502772A (en) * | 2011-11-03 | 2012-06-20 | 中国科学技术大学 | Removing method of cuprous oxide nanocrystal surface protective agent, and catalytic application thereof |
| CN105085438A (en) * | 2015-07-31 | 2015-11-25 | 中山大学惠州研究院 | Preparation method of propylene epoxide |
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| CN102502772A (en) * | 2011-11-03 | 2012-06-20 | 中国科学技术大学 | Removing method of cuprous oxide nanocrystal surface protective agent, and catalytic application thereof |
| CN105085438A (en) * | 2015-07-31 | 2015-11-25 | 中山大学惠州研究院 | Preparation method of propylene epoxide |
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