CN114133313B - Method for preparing ethane by carrying out anaerobic coupling on methane based on monatomic catalyst - Google Patents
Method for preparing ethane by carrying out anaerobic coupling on methane based on monatomic catalyst Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000010168 coupling process Methods 0.000 title claims abstract description 19
- 230000008878 coupling Effects 0.000 title claims abstract description 18
- 238000005286 illumination Methods 0.000 claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 91
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 72
- 239000004408 titanium dioxide Substances 0.000 claims description 39
- 229910052763 palladium Inorganic materials 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 32
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000002135 nanosheet Substances 0.000 claims description 6
- 239000003345 natural gas Substances 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 29
- 238000001514 detection method Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011941 photocatalyst Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009616 inductively coupled plasma 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/39—
-
- 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)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing ethane by carrying out anaerobic coupling on methane based on a monatomic catalyst, which comprises the following steps: and carrying out anaerobic coupling reaction on methane gas at a first preset temperature and a first preset time in the presence of a monatomic catalyst under an illumination condition to obtain ethane.
Description
Technical Field
The invention relates to the technical field of carbon resource conversion, in particular to a method for preparing ethane by carrying out anaerobic coupling on methane based on a monatomic catalyst.
Background
With the continuous consumption of fossil energy, the development and utilization of renewable energy are in need. Methane, as a main component in natural gas, shale gas and combustible ice, is not only an important renewable energy source, but also an important chemical raw material for preparing multi-carbon alkane and olefin, and plays an important role in the industries of construction, machinery, traffic, aerospace, chemical engineering and the like. The current industrial methods for preparing multi-carbon alkane and olefin by using methane mainly adopt methane aerobic coupling and methane anaerobic coupling. Because methane has extremely high molecular stability, both methods need higher temperature to be effectively carried out and are easy to generate byproducts such as carbon dioxide or carbon black, so that the selectivity of a multi-carbon product is not ideal, and the separation and purification of the product after the reaction are needed, thereby increasing the production cost. Therefore, the development of a more environmentally friendly method for methane activation is very important for sustainable development in the energy field.
Compared with the traditional thermal catalysis methane coupling reaction, the photocatalysis methane oxygen-free coupling reaction has the advantages of milder reaction conditions, no need of high temperature and high pressure, capability of being driven by sustainable light energy, and very promising methane conversion mode. Heretofore, the oxygen-free coupling of photocatalytic methane mainly adopts an oxide semiconductor as a photocatalyst, and methane is oxidized by utilizing photogenerated holes generated by the oxide semiconductor under the condition of illumination.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing ethane by anaerobic coupling of methane based on a monatomic catalyst, so as to solve the above technical problems.
In order to achieve the technical purpose, the invention provides a method for preparing ethane by anaerobic coupling of methane based on a monatomic catalyst, which comprises the following steps:
and carrying out anaerobic coupling reaction on methane gas at a first preset temperature and a first preset time in the presence of a monatomic catalyst under an illumination condition to obtain ethane.
According to an embodiment of the present invention, the monatomic catalyst includes: a palladium monatomic supported titania catalyst.
According to an embodiment of the present invention, in the above-mentioned monatomic catalyst, the atomic molar ratio of palladium to titanium includes: 0.0005 to 0.05:1.
according to an embodiment of the present invention, in the monatomic catalyst, the shape of the titanium dioxide includes at least one of: flake, rod, sphere, rhombus; the crystal form of the titanium dioxide comprises at least one of the following substances: anatase, rutile, commercial P25.
According to an embodiment of the present invention, the light source of the illumination condition includes at least one of: xenon lamps, LED lamps, tungsten lamps, mercury lamps.
According to an embodiment of the present invention, the illumination intensity of the illumination condition includes: 10-1000 mW/cm 2 。
According to an embodiment of the present invention, the first preset temperature includes: 0 to 100 ℃.
According to an embodiment of the present invention, the first preset time includes: 30-360 min.
According to an embodiment of the present invention, the methane gas includes at least one of: natural gas, shale gas, combustible ice and methane.
The raw gas used according to the embodiment of the present invention may be in the form of pure methane gas or may be in the form of methane-containing gas. The term "methane gas" refers to a gas mixture containing methane therein, preferably a methane-containing gas having a methane content of more than 10% by volume.
According to an embodiment of the present invention, the partial pressure of the methane gas includes: 0.001 to 1MPa.
According to the embodiment of the invention, methane gas reacts under a palladium monatomic supported titanium dioxide catalyst, an illumination condition and a mild condition, and due to the special electronic structure in the palladium monatomic supported titanium dioxide, when the palladium monatomic supported titanium dioxide is used as a photocatalyst, methyl radicals formed in the reaction process are concentrated and stabilized at palladium sites, and are further directly coupled into ethane, so that extremely high ethane selectivity is obtained. The reaction generates few byproducts such as carbon monoxide or carbon dioxide, and the obtained product ethane has high selectivity and is easy to separate subsequently. In addition, the invention provides a thought for realizing the anaerobic coupling of the photocatalytic methane under mild conditions, and has wide application prospect.
Drawings
Figure 1 schematically shows a high angle annular dark field scanning transmission electron microscope picture of a palladium monatomic supported titanium dioxide catalyst.
Figure 2 schematically shows the real-time variation values during the photocatalytic anaerobic methane coupling of a palladium monatomic supported titanium dioxide catalyst.
FIG. 3 is a graph schematically illustrating the effect of the palladium monatomic supported titanium dioxide catalyst on the photocatalytic oxygen-free coupling of methane.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The oxide semiconductor in the related art serves as a photocatalyst, and generally, photogenerated holes of the oxide semiconductor are mainly concentrated on oxygen sites, so that methane is easily over-oxidized to carbon dioxide when contacting the oxygen sites, thereby reducing the selectivity of a multi-carbon product.
The development of oxide semiconductor photocatalysts to achieve efficient oxygen-free coupling of methane has therefore attracted extensive attention.
According to an embodiment of the present invention, the present invention provides a method for preparing ethane by anaerobic coupling of methane based on a monatomic catalyst, comprising:
and carrying out anaerobic coupling reaction on methane gas at a first preset temperature and a first preset time in the presence of a monatomic catalyst under an illumination condition to obtain ethane.
According to the embodiment of the invention, methane gas reacts under a palladium monatomic supported titanium dioxide catalyst, an illumination condition and a mild condition, and due to the special electronic structure in the palladium monatomic supported titanium dioxide, when the palladium monatomic supported titanium dioxide is used as a photocatalyst, methyl radicals formed in the reaction process are concentrated and stabilized at palladium sites, and are further directly coupled into ethane, so that extremely high ethane selectivity is obtained. The reaction generates few byproducts such as carbon monoxide or carbon dioxide, and the obtained product ethane has high selectivity and is easy to separate subsequently. In addition, the invention provides a thought for realizing the anaerobic coupling of the photocatalytic methane under mild conditions, and has wide application prospect.
According to an embodiment of the present invention, wherein the monatomic catalyst includes: a palladium monatomic supported titania catalyst.
According to the embodiment of the invention, the monatomic catalyst is prepared by supporting palladium on titanium oxide in a monodisperse form to prepare a palladium monatomic supported titanium dioxide catalyst, and due to the special electronic structure in the palladium monatomic supported titanium dioxide, methyl radicals formed in the reaction process when the palladium monatomic supported titanium dioxide is used as a photocatalyst are concentrated and stabilized on palladium sites rather than oxygen sites, and are further coupled to produce ethane, so that extremely high ethane selectivity is obtained.
After the reaction is complete, the product ethane and its selectivity can be determined by conventional means, including but not limited to using gas chromatography, according to embodiments of the present invention.
According to an embodiment of the present invention, in the above-mentioned single atom catalyst, the atomic molar ratio of palladium to titanium includes: 0.0005 to 0.05:1, for example, 0.0005: 1. 0.01: 1. 0.03: 1. 0.05:1.
according to an embodiment of the present invention, in the above single atom catalyst, the shape of the titanium dioxide includes at least one of: flake, rod, sphere, rhombus; the crystal form of the titanium dioxide comprises at least one of the following substances: anatase, rutile, commercial P25.
According to the embodiment of the invention, in the monatomic catalyst, the titanium dioxide used as the carrier is wide in source and low in cost, and has excellent photochemical performance, chemical stability, thermal stability and super-hydrophilicity. Meanwhile, in the preparation process of the catalyst, only palladium monoatomic atoms with extremely low content need to be loaded by a simple method, and the obtained compound can be used for converting methane in methane gas or methane-containing gas into ethane with high selectivity under specific reaction conditions. In addition, the atomic catalyst can be simply separated and recovered after being used and can be repeatedly used for many times with approximately equivalent catalytic efficiency, so that the method has great application prospect.
According to an embodiment of the present invention, the light source of the illumination condition includes at least one of: xenon lamps, LED lamps, tungsten lamps, mercury lamps.
According to the embodiment of the present invention, the light source used for the lighting condition is not particularly limited as long as it can emit light radiation.
According to an embodiment of the present invention, the illumination intensity of the illumination condition includes: 10-1000 mW/cm 2 E.g. 10mW/cm 2 、500mW/cm 2 、1000mW/cm 2 。
According to an embodiment of the present invention, the first preset temperature includes: 0 to 100 ℃ such as 0 ℃, 50 ℃, 80 ℃ and 100 ℃.
According to the present examples, heating to the desired reaction temperature is carried out by conventional means such as a water bath or oil bath, if desired.
According to an embodiment of the present invention, the first preset time includes: 30-360 min, for example, 30min, 120min, 240min, 360min.
According to an embodiment of the present invention, the methane gas includes at least one of: natural gas, shale gas, combustible ice and methane.
According to the embodiment of the present invention, the pressure of the methane gas or the methane-containing gas is not particularly limited.
According to an embodiment of the present invention, the partial pressure of the methane gas includes: 0.001 to 1MPa, for example, 0.001MPa, 0.05MPa, 0.1MPa or 1MPa.
The present invention will be explained in further detail with reference to specific examples.
Preparation of the catalyst
The monatomic catalyst (palladium monatomic supported titanium dioxide catalyst) used in the present invention was prepared as follows:
step 1) preparation of titanium dioxide nanosheet
Adding 5-10 mL of tetrabutyl titanate and 0.8-1.6 mL of hydrofluoric acid into the lining of the polytetrafluoroethylene hydrothermal kettle, stirring at room temperature for 30min, transferring into a high-pressure hydrothermal kettle, and then putting the hydrothermal kettle into an oven to react for 24h at 180 ℃. After the hydrothermal kettle is cooled to room temperature, repeatedly cleaning the obtained white solid with deionized water until the pH value is neutral, and drying to obtain anatase phase titanium dioxide nanosheets
Step 2) preparation of Palladium monatomic Supported Titania catalyst
Adding 20-200 mg of titanium dioxide nanosheets into a closed glass bottle, uniformly dispersing with 5-50 mL of deionized water, and then adjusting the pH value of the dispersion to 10-11. 20-200 mu L of palladium nitrate solution (0.21 mM) is absorbed by a liquid-transferring gun, diluted to 3-30 mL by deionized water, and injected into the dispersion liquid of the titanium dioxide nanosheet by using an injection pump at the speed of 1-10 mL/h. And then cleaning and drying the composite by using deionized water, and calcining the obtained solid in a muffle furnace at 300 ℃ for 2h to obtain the palladium monatomic supported titanium dioxide catalyst.
Detecting by an inductively coupled plasma mass spectrometer, wherein the molar ratio of the metal palladium element to the titanium element is 0.0015: about 1.
Figure 1 schematically shows a high angle annular dark field scanning transmission electron microscope picture of a palladium monatomic supported titanium dioxide catalyst.
As can be seen from fig. 1, the palladium element is supported on the titanium dioxide nanosheets mainly in the form of a monoatomic state.
Step 3) synthesis method of titanium dioxide with different shapes
1.5mL of tetrabutyl titanate was dissolved in 40mL of glacial acetic acid, stirred for 30min, transferred to an autoclave, and reacted at 180 ℃ for 20h. And washing the obtained white solid with deionized water and ethanol for multiple times, and then putting the white solid into an oven for drying to obtain the titanium dioxide nanospheres.
32mg of titanyl sulfate were weighed and dissolved in 40mM hydrofluoric acid solution, and then the solution was transferred to a high-pressure hydrothermal kettle and reacted at 180 ℃ for 2 hours. And washing the obtained white solid with deionized water and ethanol for multiple times, and then putting the white solid into an oven for drying to obtain the titanium dioxide nanorod.
Example 1
20mg of palladium monatomic supported titanium dioxide compound is added into a quartz reactor as a catalyst, and after a methane steel cylinder is filled with high-purity (the purity is more than 99.9%) methane gas through a pressure reducing valve, the reactor is sealed (the pressure in the reactor is 0.1 MPa). At room temperature (about 25 ℃ C.), using a xenon lamp as a light source at 600mW/cm 2 Under the illumination intensity of (1) for 3 hours. After the reaction was complete, a gas sample was taken and the product distribution was determined by gas chromatography, GC. The GC detection conditions of the gas chromatography are as follows: agilent 7890B GC, ar carrier gas, FID detector, capillary column, column temperature 60 ℃.
The product was predominantly ethane and its selectivity was 93% as determined by gas chromatography.
Figure 2 schematically shows the real-time values of the changes in the photocatalytic anaerobic methane coupling process with a palladium monatomic supported titanium dioxide catalyst.
As can be seen from FIG. 2, under the light condition, the titanium dioxide composite supported by palladium single atom achieves the ethane yield of 0.91mmol/g/h on average and the ethane selectivity is more than 93 percent.
Example 2
The specific reaction process and detection method are the same as those of example 1, except that the titanium dioxide nanorods are used as the carrier to prepare the palladium monatomic supported titanium dioxide composite. The yield of ethane was found to be 0.78mmol/g/h with a selectivity of 89%.
Example 3
The specific reaction procedure and detection method were the same as in example 1, except that a palladium monatomic supported titanium dioxide composite was prepared using commercial P25 as a carrier. The yield of ethane was found to be 0.83mmol/g/h with a selectivity of 89%.
Example 4
The specific reaction procedure and detection method were the same as in example 1, except that the catalyst composition was prepared using a catalyst in which the atomic molar ratio of palladium to titanium was 0.0005:1 as catalyst. The yield of ethane was found to be 0.53mmol/g/h with a selectivity of 85%.
Example 5
The specific reaction procedure and detection method were the same as in example 1 except that a solution in which the atomic molar ratio of palladium to titanium was 0.01:1 as catalyst. The yield of ethane was found to be 0.85mmol/g/h with a selectivity of 81%.
Example 6
The specific reaction process and detection method were the same as in example 1 except that the reaction time was shortened to 30min. Ethane selectivity was found to be 91.5%.
Example 7
The specific reaction process and detection method were the same as in example 1 except that the reaction time was extended to 6 hours. The ethane selectivity was determined to be 92.3%.
Example 8
The specific reaction process and detection method were the same as in example 1 except that an LED lamp was used as a light source instead of a xenon lamp. Ethane selectivity was determined to be 92%.
Example 9
The specific reaction procedure and detection method were the same as in example 1 except that a natural gas containing methane (85% by volume of methane) was used instead of the high-purity methane gas. Ethane selectivity was determined to be 84%.
Example 10
The specific reaction process and detection method were the same as in example 1 except that the reaction was carried out by keeping the temperature of the reaction cell at 60 ℃ by heating in a water bath. Ethane selectivity was measured to be 86%.
Example 11
The specific reaction procedure and detection method were the same as in example 1 except that a mixed gas containing methane (in which the partial pressure of methane was 0.001 MPa) was used instead of the high-purity methane gas. The yield of ethane was found to be 73. Mu. Mol/g/h with a selectivity of 65%.
Example 12
The specific reaction procedure and detection method were the same as in example 1 except that a mixed gas containing methane (in which the partial pressure of methane was 0.01 MPa) was used instead of the high-purity methane gas. The yield of ethane was found to be 0.36mmol/g/h with a selectivity of 65%.
Example 13
The specific reaction procedure and detection method were the same as in example 1 except that the light intensity was adjusted to 200mW/cm 2 . The yield of ethane was found to be 0.58mmol/g/h with a selectivity of 95%.
Example 14
The specific reaction procedure and detection method were the same as in example 1 except that the light intensity was adjusted to 1000mW/cm 2 . The yield of ethane was found to be 1.19mmol/g/h with a selectivity of 90%.
Example 15
The specific reaction process and detection method were the same as in example 1 except that the catalyst reacted in example 1 was dried in air at 80 ℃ for 2 hours and then reused 8 times.
FIG. 3 is a graph schematically illustrating the effect of the palladium monatomic supported titanium dioxide catalyst on the photocatalytic oxygen-free coupling of methane.
As shown in fig. 3, the abscissa is the number of times the catalyst is recycled, and the ordinate is the yield of carbonaceous product. As can be seen from FIG. 3, the efficiency of the catalyst of the present invention for photocatalytic anaerobic methane coupling is not significantly reduced after 8 times of repeated use.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. A method for preparing ethane by carrying out anaerobic coupling on methane based on a monatomic catalyst is characterized in that,
carrying out anaerobic coupling reaction on methane gas at a first preset temperature and a first preset time in the presence of a monatomic catalyst under an illumination condition to obtain ethane;
wherein the monatomic catalyst is: a palladium monatomic supported titanium dioxide catalyst;
wherein in the single-atom catalyst, the atomic mol ratio of palladium to titanium is as follows: 0.0005 to 0.01:1;
wherein, in the monatomic catalyst, the titanium dioxide used is at least one of the following: titanium dioxide nanosheets, titanium dioxide nanorods and titanium dioxide P25;
the partial pressure of methane gas was: 0.001 to 1Mpa;
the illumination intensity of the illumination conditions was: 200-1000 mW/cm 2 ；
The first preset temperature is: room temperature to 100 ℃;
the first preset time is as follows: 30-360 min.
2. The method of claim 1, wherein in the monatomic catalyst, the titanium dioxide is in the shape of at least one of: flake, rod, sphere, rhombus; the crystal form of the titanium dioxide is at least one of the following: anatase, rutile, commercial P25.
3. The method of claim 1, wherein the light source of the lighting condition is at least one of: xenon lamps, LED lamps, tungsten lamps, mercury lamps.
4. The method of claim 1, wherein the methane gas is at least one of: natural gas, shale gas, combustible ice and methane.
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| WO2000004993A1 (en) * | 1998-07-23 | 2000-02-03 | Korea Research Institute Of Chemical Technology | Photocatalyst for methane conversion, method for preparing the same and method for preparing low carbohydrates using the same |
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| CN113600162A (en) * | 2021-08-12 | 2021-11-05 | 曹洋 | Porous titanium dioxide nano material, metal nano particle modified porous titanium dioxide photocatalytic material, and preparation method and application thereof |
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| FR2840607A1 (en) * | 2002-06-10 | 2003-12-12 | Bp Lavera | Production of ethane for olefins such as ethylene, involves contacting methane with metal catalyst chosen from metal hydride and/or metal organic compound |
| US11518722B2 (en) * | 2018-02-20 | 2022-12-06 | The Johns Hopkins University | Method for preparation of nanoceria supported atomic noble metal catalysts and the application of platinum single atom catalysts for direct methane conversion |
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| WO2000004993A1 (en) * | 1998-07-23 | 2000-02-03 | Korea Research Institute Of Chemical Technology | Photocatalyst for methane conversion, method for preparing the same and method for preparing low carbohydrates using the same |
| CN112624893A (en) * | 2020-12-25 | 2021-04-09 | 南开大学 | Catalytic coupling method of light alkane |
| CN113600162A (en) * | 2021-08-12 | 2021-11-05 | 曹洋 | Porous titanium dioxide nano material, metal nano particle modified porous titanium dioxide photocatalytic material, and preparation method and application thereof |
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