CN118079615A - Low-temperature plasma dielectric barrier discharge liquid film reactor and application thereof in methane selective oxidation reaction - Google Patents
Low-temperature plasma dielectric barrier discharge liquid film reactor and application thereof in methane selective oxidation reaction Download PDFInfo
- Publication number
- CN118079615A CN118079615A CN202410251360.2A CN202410251360A CN118079615A CN 118079615 A CN118079615 A CN 118079615A CN 202410251360 A CN202410251360 A CN 202410251360A CN 118079615 A CN118079615 A CN 118079615A
- Authority
- CN
- China
- Prior art keywords
- liquid film
- connecting part
- voltage electrode
- glass tube
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000007788 liquid Substances 0.000 title claims abstract description 94
- 230000004888 barrier function Effects 0.000 title claims abstract description 23
- 238000007254 oxidation reaction Methods 0.000 title abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000011521 glass Substances 0.000 claims abstract description 72
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000007789 gas Substances 0.000 claims abstract description 35
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 29
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 238000007789 sealing Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 210000005239 tubule Anatomy 0.000 claims description 11
- 239000007791 liquid phase Substances 0.000 claims description 10
- 230000002093 peripheral effect Effects 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 6
- 239000010959 steel Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 96
- 230000003647 oxidation Effects 0.000 abstract description 11
- 230000004913 activation Effects 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 210000002381 plasma Anatomy 0.000 description 40
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 235000019253 formic acid Nutrition 0.000 description 6
- 239000012263 liquid product Substances 0.000 description 6
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 5
- 230000000903 blocking effect Effects 0.000 description 5
- 238000004364 calculation method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- MEUKEBNAABNAEX-UHFFFAOYSA-N hydroperoxymethane Chemical compound COO MEUKEBNAABNAEX-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000005273 aeration Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 241000521257 Hydrops Species 0.000 description 2
- 206010030113 Oedema Diseases 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Landscapes
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a low-temperature plasma dielectric barrier discharge liquid film reactor and application of methane selective oxidation reaction thereof. The device comprises a central high-voltage electrode, a saline low-voltage electrode, a reducing glass tube, a first polytetrafluoroethylene cutting sleeve of a liquid film water inlet device and a second polytetrafluoroethylene cutting sleeve of a gas-liquid outlet device; the high-voltage electrode is arranged in the center of the reducing glass tube and is fixed by an upper clamping sleeve and a lower clamping sleeve; methane and oxygen raw material gas enter along a gap of the high-voltage electrode from a left end air inlet, water enters from a right end water inlet, flows into the inner side of the glass tube along a narrow inclined plane after flowing through the water tank, forms a liquid film which is tightly attached to the inner wall of the glass tube, and can be quickly absorbed to generate an oxygen-containing compound through a discharge region surrounded by circulating saline (the high-voltage electrode), so that the oxygen-containing compound is quickly separated from the discharge region, and excessive oxidation is inhibited. The device can realize high-efficiency activation and conversion of methane and oxygen at normal temperature and normal pressure, and remarkably improves the yield of the oxygen-containing compounds such as methanol and the like.
Description
Technical Field
The invention relates to the technical field of plasma synthesis chemistry, in particular to a low-temperature plasma dielectric barrier discharge liquid film reactor and application of methane selective oxidation reaction thereof.
Background
The environmental pollution is gradually aggravated, resources such as petroleum, coal and the like are increasingly scarce, the clean energy of natural gas, hydropower, nuclear power, wind power and the like in China occupies a huge space than the future development, and the importance and research heat of the conversion utilization of the natural gas in the field of energy catalysis are continuously increased along with the adjustment of the energy structure. Compared with an indirect conversion path (methane, synthesis gas, methanol and the like) with high energy consumption and high equipment investment, the method has the advantages that the main component methane (CH 4) of the low-cost natural gas can be directly converted into liquid-phase methanol and other oxygen-containing compounds convenient to transport by adopting a plasma technology at normal temperature and normal pressure by using molecular oxygen (O 2), so that the investment cost can be greatly reduced, and the method has remarkable advantages especially for the development of methane gas resources in remote areas. However, highly symmetrical methane molecules have four equivalent C-H bonds, and the dissociation energy of the C-H bonds is up to 439.3 kJ.mol -1 (standard condition), target products such as methanol, formaldehyde, formic acid and the like containing functional groups are more active to methane, and high-energy electrons and other species excited in a plasma field easily cause the methane and intermediate products to be excessively oxidized into CO or CO 2, so that the problem that the conversion rate and the selectivity are difficult to be compatible in the plasma catalytic methane selective oxidation is faced.
Dielectric Barrier Discharge (DBD) is the most common and simple mode of plasma-catalyzed methane selective oxidation under normal temperature and pressure conditions. In the early researches, the documents of Energy & Fuels 2000,14,459-463, catalyst, today,2001,71,211-217 and the like adopt a single cylindrical tube DBD reactor, a central iron rod is a high-voltage electrode, a quartz cylindrical tube is a blocking medium, an aluminum mesh is attached to the outside of the quartz tube and is a grounding electrode, so that the methane conversion rate of 1.7% and the methanol selectivity of 47% are realized. On the basis, the synergistic improvement of the methane selective oxidation performance by plasma and a catalyst is also a recent research hot spot ,Catalysis Science&Technology,2020,10(16):5566-5578;Applied Catalysis B:Environmental,2021,284:119735;Sustainable Energy&Fuels,2021,5(13):3351-3362;Applied Catalysis B:Environmental,2021,296:120384, a CN202310654908 patent and the like, and the catalyst such as Ni/Al 2O3、Pt/SBA-15、Fe/γ-Al2O3, ni/glass beads, a supported boron-based catalyst and the like is filled into a plasma discharge zone to catalyze methane selective oxidation, so that 13% of methane conversion rate, 37% of methanol selectivity and 73% of oxygen-containing compound selectivity can be achieved.
Ind, eng, chem, res.,2001,40,1594-1601; the literature, such as Ind.Eng.chem.Res.2001,40,5496-5506 and CATALYSIS TODAY (2001) 199-210, adopts an external circulating water cooling mode to reduce the reaction temperature of a plasma discharge zone earlier, so that the selectivity of oxygen-containing compounds is improved. The reaction gas and plasma discharge are led into the gap of the double coaxial cylinders, the inner cylinder is a glass medium with the diameter of 3.7cm and the length of 30cm, the inner iron wall metal foil is used as a high-voltage electrode, the outer cylinder is a stainless steel wall which is used as a grounding electrode, and the double coaxial cylinders are provided with circulating water cooling components. The conversion rate of methane per pass can reach 12%, the selectivity of methanol is 16%, and the selectivity of total oxygen-containing compounds is 52%. CHEMICAL ENGINEERING Journal,2011,166 (1): 288-293, et al adopts a miniature DBD reactor with external circulating water cooling (reaction temperature is 10 ℃), and the process parameters are regulated to ensure that the single-pass methane conversion rate can reach 43%, the methanol selectivity is 14%, and the total oxygenate selectivity is 40%.
According to the above studies, it has been shown that the heat generated by partial oxidation of methane is effectively removed in the microreactor structure, and that the low reaction temperature promotes condensation of liquid components on the microreactor wall, effectively increasing the selectivity of oxygenates. In addition, CHEMICAL ENGINEERING Journal,2011,167,560-566 discloses a pulsed water injection method for flushing condensed oxygen-containing compounds to inhibit excessive oxidation of liquid products. However, the water injection process requires that the plasma discharge be stopped, and the discharge and the rinsing process cannot be performed simultaneously. The J.Phys.D. Appl.Phys.2011,44,274010 literature is fed with a trace amount of water during the plasma discharge process, and intermittently generates a liquid film to wash and condense the oxygen-containing compound on the glass tube wall, but the liquid film can cause a uniform discharge mode to be converted into a local severe discharge, thereby causing multiple oxidation.
ChemSusChem 2011,4,1095-1098 and Fuel 284 (2021) 118944 literature compared single-medium plasma reactor, dual-medium plasma reactor and arc discharge plasma reactor for the first time under the condition of external cooling circulating water, found that dual-medium plasma reactor with uniform discharge characteristics has optimal methane selective oxidation performance, and achieved 66.4% methane conversion, 16.3% methanol selectivity and 57.3% oxygenate selectivity. The patent CN113713799 uses a metal supported catalyst and combines a coaxial dielectric barrier discharge plasma reactor with circulating water as a grounding electrode, and methane is oxidized to prepare methanol by taking molecular oxygen as an oxidant at normal temperature and normal pressure, wherein the methane conversion rate is 6.4%, and the methanol selectivity is up to 49.7%. Patent CN116726830a also uses a dual-medium plasma microreactor, and when the alkoxide ratio is 0.5, the methane conversion rate is 50.8%, the selectivity of the oxygen-containing compound is 60.3%, and the yield of the oxygen-containing compound is 30.6%.
The above studies indicate that low temperature, uniform discharge, catalyst co-operation, intermittent flushing, etc. are effective for increasing methane conversion and oxygenate selectivity, but liquid phase products tend to be complex. Under the condition of high methane conversion, how to improve the selectivity of methanol which is a single liquid phase product is still a problem to be solved.
Disclosure of Invention
The invention discloses a low-temperature plasma dielectric barrier discharge liquid film reactor and application of methane selective oxidation reaction thereof, so as to improve the yield of oxygen-containing compounds such as methanol and the like.
The invention provides a low-temperature plasma medium blocking discharge liquid film reactor which comprises a central high-voltage electrode, a reducing glass tube, a liquid film water inlet polytetrafluoroethylene cutting sleeve and a gas-liquid outlet polytetrafluoroethylene cutting sleeve, wherein the central high-voltage electrode sequentially penetrates through the centers of the liquid film water inlet polytetrafluoroethylene cutting sleeve, the reducing glass tube and the gas-liquid outlet polytetrafluoroethylene cutting sleeve, the diameter of a middle tube region of the reducing glass tube is smaller than two ends, the diameter of the middle tube region of the reducing glass tube is a discharge region, and a liquid film which stably flows is arranged on the inner wall of the glass tube in the discharge region.
Preferably, the high-voltage electrode is one of a thin-wall glass tube filled with NaCl solution, a metal rod with a glass shell and a glass tube filled with metal powder at the center; wherein the wall thickness of the thin-wall glass tube is 0.05-1mm.
Preferably, the liquid film water inlet device polytetrafluoroethylene cutting sleeve comprises an interface module, a water storage module and a first cutting sleeve module which are sequentially connected from top to bottom;
the middle of the interface module is provided with a threaded interface for fixing a high-voltage electrode, one side of the interface module is provided with a gas sample inlet, and the other side of the interface module is provided with a water inlet;
The water storage module is internally provided with a water delivery channel, the bottom end of the water delivery channel is provided with a gas filtering ring, and the top end of the water delivery channel is communicated with the water inlet;
The first cutting sleeve module comprises a first connecting part, a second connecting part and a first sealing gasket, the sealing gasket is arranged between the first connecting part and the second connecting part, and an inclined-plane crack is formed between the inner wall of the first connecting part and the outer wall of the water storage module;
The gas filtering ring is communicated with the inclined plane crack;
The lower end of the first cutting sleeve module is connected with the reducing glass tube;
the central high-voltage electrode is arranged in the polytetrafluoroethylene clamping sleeve of the liquid film water inlet device and is provided with a gap, and the gap is used for enabling gas to enter the inside of the reducing glass tube along a vertical gap parallel to the high-voltage electrode;
the first connecting part is connected with the water storage module through an annular steel ring and is sealed by a sealing gasket.
Preferably, the threaded interface of the fixed high voltage electrode is sealed by a polytetrafluoroethylene sealing ring and a hollow peak plastic bolt.
Preferably, the reducing glass tube is of an integrated structure and comprises two end tube areas, a middle tube area and peripheral glass tubules, wherein the diameters of the two end tube areas are larger than those of the middle tube area, the peripheral glass tubules are positioned on the outer wall of the reducing glass tube, and the two sides of the middle tube area are provided with water inlets/water outlets.
Preferably, the gas-liquid outlet polytetrafluoroethylene cutting ferrule comprises a second cutting ferrule and a fifth connecting part;
the second clamping sleeve comprises a third connecting part, a second sealing gasket and a fourth connecting part;
the second sealing gasket is arranged between the third connecting part and the fourth connecting part;
The fourth connecting part and the fifth connecting part are connected together by adopting an annular steel ring and are sealed by a sealing gasket;
one side of the fifth connecting part is provided with an outlet, and the center of the bottom end of the fifth connecting part is provided with a threaded interface;
The threaded interface is sealed by a polytetrafluoroethylene sealing ring and a hollow peak plastic bolt;
The upper end of the fifth connecting part is conical.
Preferably, the diameter of the high-voltage electrode is 1-4mm;
The diameter-variable glass tube has the outer diameter of 8-20mm, the wall thickness of 0.5-2mm and the length of 5-30cm at the two end areas; the outer diameter of the middle pipe area 19 is 5-15mm, the wall thickness is 0.5-2mm, and the length is 1-10cm; the outer diameter of the peripheral glass tubule 20 is 8-25mm, the wall thickness is 0.5-2mm, and the length is 1-10cm;
the length of the diameter-reduced part of the reducing glass tube is 0.5-4cm, and the joint is smooth.
The invention also provides application of the low-temperature plasma dielectric barrier discharge liquid film reactor, the reactor is applied to the reaction of generating oxygen-containing compounds by the reaction of methane and oxygen gas mixture, the flow rate of water introduced into a water inlet is 10-100mL/min, and the inflow mode can be single-pass inflow or circulating inflow.
The method specifically comprises the following steps:
(1) Controlling the temperature of the circulating water solution in the peripheral glass tubule to be kept at a fixed value through an external circulating water system, wherein the range is 0-90 ℃;
(2) The total flow and the mole ratio of methane and oxygen and the flow of inert gases such as argon added are controlled by adopting a flow controller, and the mixture is mixed by a mixing air chamber and then is introduced into a low-temperature plasma dielectric barrier discharge liquid film reactor device through a gas sample inlet;
(3) Starting a plasma generator, regulating a transformer, and gradually loading alternating-current high voltage on the plasma generator until uniform discharge occurs; the voltage is finely adjusted to adjust the input power, and the discharge frequency is matched to ensure the mildness and uniformity of discharge; the reaction products are carried by the unreacted mixed gas and enter a collector; collecting liquid phase products through a condensing tube; wherein the discharge power ranges from 5 to 25 watts and the discharge frequency ranges from 1 to 100 kilohertz.
The invention provides a low-temperature plasma dielectric barrier discharge liquid film reactor and application of methane selective oxidation reaction thereof.
It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosure of the invention as claimed.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the prior art will be briefly described below, and it will be obvious to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic diagram of the overall structure of a low-temperature plasma dielectric barrier discharge reactor according to an embodiment of the present disclosure;
FIG. 2 is a schematic diagram of an application process of a low-temperature plasma dielectric barrier discharge reactor applied to a methane selective oxidation reaction according to an embodiment of the present disclosure;
a three-port liquid collecting bottle (111), a water pump (112), a condensing tube (113), a gas chromatograph (114) and a plasma generator (115).
Detailed Description
The invention is further illustrated below in connection with specific embodiments, but is not intended to limit the scope of the invention.
In order to improve the selectivity of single liquid-phase product methanol, the embodiment provides a low-temperature plasma dielectric barrier discharge liquid film reactor and application of methane selective oxidation reaction thereof, and the novel low-temperature plasma dielectric barrier discharge liquid film reactor introduces a stable liquid film in a discharge region with controllable temperature. Firstly, the external circulating water and the flowing liquid film are subjected to double temperature control to maintain low-temperature reaction, secondly, the high-voltage electrode of the liquid medium and the stable liquid film enhance the uniform discharge characteristic, and the low-temperature and uniform discharge is beneficial to methane selective oxidation reaction. In addition, the important function of the liquid film is that the generated oxygen-containing compound is dissolved into the liquid film and timely separated from the plasmas rich in active oxygen species, so that excessive oxidation is inhibited, and the yield of the oxygen-containing compound such as methanol is obviously improved.
In order to realize the simultaneous stabilization of the plasma DBD discharge and the liquid film, water is required to flow stably and continuously against the inner wall of the reducing glass tube, and the low-temperature plasma medium blocking discharge liquid film reactor is shown as a figure 1 and mainly comprises a central high-voltage electrode 2, the reducing glass tube 3, a liquid film water inlet device polytetrafluoroethylene cutting ferrule 4 and a gas-liquid outlet polytetrafluoroethylene cutting ferrule 5;
The central high-voltage electrode is fixed by an upper cutting sleeve and a lower cutting sleeve and is arranged on a mandrel at the narrowest part in the middle of the reducing glass tube. The water inlet 9 is connected with an outlet pipe of the water inlet pump, and the flow speed of water is regulated and controlled according to the size of the reducing glass pipe, so that the water forms a stable and continuous flowing liquid film in the discharge zone 1. Methane and oxygen are mixed by controlling the flow rate through a mass flowmeter and then are input through a gas sample inlet 8.
Specifically, a low-temperature plasma medium blocking discharge liquid film reactor device forms a stable flowing liquid film on the inner wall of a glass tube in an intermediate discharge interval 1, and comprises a central high-voltage electrode 2, a reducing glass tube 3, a liquid film water inlet device polytetrafluoroethylene cutting sleeve 4 and a gas-liquid outlet polytetrafluoroethylene cutting sleeve 5;
the high-voltage electrode 2 consists of a thin-wall glass tube penetrating through the centers of the liquid film water inlet polytetrafluoroethylene cutting ferrule 4 and the gas-liquid outlet polytetrafluoroethylene cutting ferrule 5 and NaCl solution filled in the thin-wall glass tube, penetrates through the reducing glass tube 3 and is always positioned on the center thereof; the central high-voltage electrode 2 may be replaced with various types including, but not limited to, a metal rod of copper, iron, aluminum, alloy, etc., a metal rod with a glass envelope, a glass tube with a metal powder filled in the center, etc.
The liquid film water inlet device polytetrafluoroethylene clamping sleeve 4 is composed of four modules: the middle of the interface module 6 is provided with a threaded interface 7 for fixing a high-voltage electrode, and the interface is sealed by a polytetrafluoroethylene sealing ring and a hollow peak plastic bolt; the left side is a gas injection port 8, and gas enters the inside of the reducing glass tube 3 along a vertical gap parallel to the high-voltage electrode; on the right is a water inlet 9 through a vertical channel 10 into a water storage module 11. The water storage module 11 mainly comprises a water storage tank 12 and a plurality of water outlet holes 13, wherein the water storage tank can be filled with metal filtering rings, and when the water storage tank 12 is filled with water, the water flows out of the water outlet holes 13 simultaneously, enters into an inclined-plane crack 15 between the first connecting part 14 and the water storage module 11, so that the water gradually forms an annular liquid film to cling to the inner wall 14 of the yellow module and then flows into the inner wall of the reducing glass tube 3. The first connecting part 14, the second connecting part 16 and the first sealing gasket 17 form a cutting sleeve to connect the liquid film water inlet device polytetrafluoroethylene cutting sleeve 4 and the reducing glass tube 3. The first connection portion 14 is connected with the water storage module 11 using an annular steel ring and is sealed with a sealing gasket 18.
The reducing glass tube 3 is composed of thick tubes 18 at two ends, a middle thin tube 19 and a peripheral glass thin tube 20. Only the middle tubule 19 is nearest to the central high-voltage electrode and is a discharge zone 1, and the length of the discharge zone can be effectively regulated and controlled by controlling the length of the tubule, so that multipoint discharge is avoided. Two ends of the glass 20 are water inlet/outlet 21, which is filled with saline water, and controls the temperature of the discharge area on one hand and is used as a grounding electrode on the other hand.
The gas-liquid outlet polytetrafluoroethylene clamping sleeve 5 is composed of three modules: the third connecting part 22, the second sealing gasket 23 and the fourth connecting part 24 form a clamping sleeve to be connected with the gas-liquid outlet polytetrafluoroethylene clamping sleeve 5 and the reducing glass tube 3. The fourth connecting portion 24 and the fifth connecting portion 25 are connected together using an annular steel ring and sealed with a sealing gasket. The gas and liquid film are discharged 27 from an outlet at the lower part of the annular groove at the bottom end. A threaded interface 26 for fixing the high-voltage electrode is arranged in the middle of the fifth connecting part 25, and the interface is sealed by a polytetrafluoroethylene sealing ring and a hollow peak plastic bolt; the upper end of the fifth connecting part 25 is conical, so that the liquid film is effectively prevented from discharging with the central high-voltage electrode 2 when the liquid film is collected at the bottom.
The diameter of the high-voltage electrode 2 is 1-4mm, and when a thin-wall quartz tube is used, the wall thickness is 0.05-1mm.
The diameter-variable glass tube 3 has the outer diameter of the thick tubes 18 at the two ends of 8-20mm, the wall thickness of 0.5-2mm and the length of 5-30cm; the outer diameter of the middle tubule 19 is 5-15mm, the wall thickness is 0.5-2mm, and the length is 1-10cm; the outer diameter of the glass tube 20 is 8-25mm, the wall thickness is 0.5-2mm, and the length is 1-10cm.
The length of the discharge interval of the reducing glass tube 3 is 0.5-4cm, the interface is smooth, and the liquid film is prevented from flowing unevenly.
The depth of the water storage groove 12 is 1-3cm, and the width is 0.1-0.4cm.
The key point of forming the liquid film is that the flow rate of the introduced water is 10-100mL/min, and the water can flow in a single way or flow in a circulating way.
As shown in fig. 2, the reaction gas and the liquid film of the low-temperature plasma medium blocking discharge liquid film reactor flow into a three-port liquid accumulation bottle 1 from a water outlet at the same time, gas-liquid separation is completed, liquid is conveyed to a water inlet of a polytetrafluoroethylene cutting sleeve of a liquid film water inlet device through a water pump 2, and the stability of the liquid film is continuously maintained in a circulating way; the gas separated by the three-port hydrops bottle 1 is further subjected to gas-liquid separation through a condensing pipe 3, the components of the gas are detected and quantified through an online gas chromatograph 4, and the content of the oxygen-containing compound is measured through an ultraviolet visible spectrometer, gas chromatograph-mass spectrometer and hydrogen nuclear magnetism after the liquid in the condensing pipe is mixed with the circulating liquid in the three-port hydrops bottle.
After the air tightness is checked and the air speed and the liquid film state are maintained stable, the high-voltage line of the plasma generator 5 is connected with the central high-voltage electrode, and the grounding line is arranged in external matched circulating equipment to realize the grounding and cooling of circulating water.
As the optimization of the technical scheme, the inner diameter of the glass tube in the discharge zone is 6-10 mm, and the length is 0.5-5 cm.
As the optimization of the technical scheme, the key point of forming the liquid film is that the flow rate of the water is 30-70mL/min.
As the optimization of the technical scheme, the external circulating water system controls the temperature of the circulating water solution in the peripheral glass tube of the discharge interval to be kept between 0 and 40 ℃.
Preferably, the discharge power is in the range of 10 to 20 watts and the discharge frequency is in the range of 2 to 30 kilohertz.
After the experimental makeup is built in the above manner, the present invention will be further described with reference to specific examples;
the following examples were all tested using the above device in the following manner:
and the first step, a temperature control device for circulating water outside the glass tube in the discharge interval is arranged, and after the temperature is stable, the circulating water is sent into the glass sleeve of the reaction tube by using a circulating water pump. And opening a circulating water temperature control device of the condensing pipe to reduce the temperature of the condensed water to below 5 ℃.
And secondly, opening a water pump connected to the three-hole liquid collecting bottle, and regulating the flow speed to ensure that the liquid film is uniform and continuous.
Thirdly, the flow rates of methane, oxygen and inert gases and the molar ratio of the methane, the oxygen and the inert gases are regulated through a flowmeter, the methane, the oxygen and the inert gases are mixed through a gas mixing chamber, then the mixed gases enter a discharge area from an air inlet at the upper end of a liquid film reactor, gas and liquid are primarily separated in a three-port liquid collecting bottle, then the gas and liquid are introduced into a condensing pipe through an air duct, and the gas is introduced into gas chromatography for online detection after the gas and liquid separation.
And thirdly, starting the plasma generator, adjusting the transformer, gradually loading alternating-current high voltage on the high-voltage electrode, and finally forming uniform and stable discharge. After the reaction is completed, the liquid phase products in the reaction tube and the condensing tube are washed out, and ultraviolet visible spectrometer, gas chromatography-mass spectrometry and hydrogen nuclear magnetic analysis are carried out after the volume is fixed.
The device can realize the efficient selective oxidation of methane at normal temperature and normal pressure.
The implementation effect of the invention can be measured by methane conversion rate, selectivity and yield of oxygen-containing compounds such as methanol and the like.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
Example 1
(1) Liquid membrane reactor device and selection of reaction process conditions
The device takes a metal core coated by saturated NaCl solution in a thin-wall glass tube as a high-voltage electrode. CH 4、O2 and Ar gas flow rates were 18, 6 and 10mL/min, respectively, and the water pump flow rate was 50mL/min. The circulating water is constant at 5 ℃ outside the discharge zone. The device works in the atmospheric environment, and the grounding wire is placed in an external circulating water system. After 10 minutes of aeration, the plasma generator was turned on, the frequency was adjusted to 10 khz at the center frequency, the input voltage was adjusted to 45V, the current was 0.4A, the power was maintained at 18 watts, the reaction time was 1h, the power was turned off after the reaction was completed, and the liquid phase product was collected and analyzed.
(2) Reaction results
After the experiment is completed, various reaction products, such as gaseous products of carbon monoxide, carbon dioxide, low-carbon alkane and the like, and liquid products of methanol, formaldehyde, formic acid, methyl hydrogen peroxide and the like are detected. Finally, through calculation, 14.8 percent of methane conversion rate, 34 percent of methanol selectivity and 90 percent of oxygenate selectivity can be obtained, and finally, 5 percent of methanol yield and 13.3 percent of oxygenate yield are obtained.
Comparative example 1
(1) Liquid membrane reactor device and selection of reaction process conditions
The reactor apparatus and reaction process conditions of this comparative example were the same as in example 1, except that the water pump was turned off and the reactor was free of liquid film.
(2) Reaction results
After the experiment is completed, various reaction products, such as gaseous products of carbon monoxide, carbon dioxide, low-carbon alkane and the like, and liquid products of methanol, formaldehyde, formic acid, methyl hydrogen peroxide and the like are detected. Finally, through calculation, 14.5 percent of methane conversion rate, 22.6 percent of methanol selectivity and 84 percent of oxygenate selectivity can be obtained, and finally, 3.3 percent of methanol yield and 12.2 percent of oxygenate yield are obtained.
From the analysis of the results of comparative example 1 and example 1 described above, it can be concluded that the presence of a liquid film can increase the selectivity of oxygenates, particularly methanol.
Comparative example 2
(1) Liquid membrane reactor device and selection of reaction process conditions
The reactor apparatus and reaction process conditions of this comparative example were the same as in example 1, except that the flow rate of argon was 0 mL/min.
(2) Reaction results
After the experiment is completed, various reaction products, such as gaseous products of carbon monoxide, carbon dioxide, low-carbon alkane and the like, and liquid products of methanol, formaldehyde, formic acid, methyl hydrogen peroxide and the like are detected. Finally, through calculation, 7.3 percent of methane conversion rate, 36.3 percent of methanol selectivity and 88 percent of oxygenate selectivity can be obtained, and finally, 2.6 percent of methanol yield and 6.4 percent of oxygenate yield are obtained.
From the analysis of the results of comparative example 2 and example 1 described above, it can be concluded that the co-feed of Ar gas can significantly increase the conversion of methane.
Example 2
The device takes a metal core coated by saturated NaCl solution in a thin-wall glass tube as a high-voltage electrode, the gas flow rates of CH 4、O2 are respectively 12 mL/min and 6mL/min, and the water pump flow rate is 50mL/min. The circulating water is constant at 5 ℃ outside the discharge zone. The device works in the atmospheric environment, and the grounding wire is placed in an external circulating water system. After 10 minutes of aeration, the plasma generator was turned on, the frequency was adjusted to 10 khz at the center frequency, the input voltage was adjusted to 45V, the current was 0.7A, the power was maintained at 31.5 watts, the reaction time was 1h, the power was turned off after the reaction was completed, and the liquid phase product was collected and analyzed.
(2) Reaction results
After the experiment is completed, various reaction products, such as gaseous products of carbon monoxide, carbon dioxide, low-carbon alkane and the like, and liquid products of methanol, formaldehyde, formic acid, methyl hydrogen peroxide and the like are detected. Finally, through calculation, 21 percent of methane conversion rate, 33 percent of methanol selectivity and 72 percent of oxygenate selectivity can be obtained, and finally, 7 percent of methanol yield and 15 percent of oxygenate yield are obtained.
From the analysis of the results of comparative example 2 and example 2 described above, it can be concluded that lowering the alkoxide ratio, lowering the gas flow rate, and increasing the input power favors an increase in methane conversion, but slightly reduces oxygenate selectivity.
Example 3
The device takes a metal core coated by saturated NaCl solution in a thin-wall glass tube as a high-voltage electrode. CH 4、O2 and Ar gas flow rates were 18, 6 and 10mL/min, respectively, and the water pump flow rate was 50mL/min. The circulating water is constant at 5 ℃ outside the discharge zone. The device works in the atmospheric environment, and the grounding wire is placed in an external circulating water system. After 10 minutes of aeration, the plasma generator was turned on, the frequency was adjusted to 10 khz at the center frequency, the input power was adjusted to 18 watts, the reaction time was 2 hours, the power was turned off after the reaction was completed, and the liquid phase product was collected and analyzed.
(2) Reaction results
After the experiment is completed, various reaction products, such as gaseous products of carbon monoxide, carbon dioxide, low-carbon alkane and the like, and liquid products of methanol, formaldehyde, formic acid, methyl hydrogen peroxide and the like are detected. Finally, through calculation, 42% methane conversion rate, 43% methanol selectivity and 75.5% oxygenate selectivity can be obtained, and finally, 18% methanol yield and 32% oxygenate yield are obtained.
Other embodiments of the application will be apparent to those skilled in the art from consideration of the specification and practice of the application disclosed herein. This application is intended to cover any variations, uses, or adaptations of the application following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the application pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It is to be understood that the invention is not limited to the precise arrangements and instrumentalities shown in the drawings, which have been described above, and that various modifications and changes may be effected without departing from the scope thereof. The scope of the invention is limited only by the appended claims.
Claims (9)
1. The utility model provides a low temperature plasma dielectric barrier discharge liquid membrane reactor, its characterized in that includes central high-voltage electrode (2), reducing glass pipe (3), liquid film water inlet ware gathers tetrafluoro cutting ferrule (4), gas-liquid outlet gathers tetrafluoro cutting ferrule (5), central high-voltage electrode (2) cross in proper order and pass liquid film water inlet ware gathers tetrafluoro cutting ferrule (4), reducing glass pipe (3) and gas-liquid outlet gathers tetrafluoro cutting ferrule (5) center, the diameter in the middle of reducing glass pipe (3) is lighter than both ends, for discharge interval (1), the glass pipe inner wall of discharge interval (1) has stable flowing liquid film.
2. The low-temperature plasma dielectric barrier discharge liquid film reactor according to claim 1, wherein the high-voltage electrode (2) is one of a thin-wall glass tube filled with NaCl solution, a metal rod with a glass shell and a glass tube filled with metal powder at the center; wherein the wall thickness of the thin-wall glass tube is 0.05-1mm.
3. A low temperature plasma dielectric barrier discharge liquid film reactor according to claim 1, wherein,
The liquid film water inlet device polytetrafluoroethylene cutting sleeve (4) comprises an interface module (6), a water storage module (11) and a first cutting sleeve module which are sequentially connected from top to bottom;
A threaded interface (7) for fixing a high-voltage electrode is arranged in the middle of the interface module, one side of the interface module is provided with a gas sample inlet (8), and the other side of the interface module is provided with a water inlet (9);
A water delivery channel (10) is arranged in the water storage module (11), a gas filtering ring (13) is arranged at the bottom end of the water delivery channel (10), and the top end of the water delivery channel (10) is communicated with the water inlet (9);
The first cutting sleeve module comprises a first connecting part (14), a second connecting part (16) and a first sealing gasket (17), wherein the sealing gasket (17) is arranged between the first connecting part (14) and the second connecting part (16), and an inclined-plane crack (15) is formed between the inner wall of the first connecting part (14) and the outer wall of the water storage module (11);
The gas filtering ring (13) is communicated with the inclined surface crack (15);
the lower end of the first cutting sleeve module is connected with the reducing glass tube (3);
the central high-voltage electrode (2) is arranged in the polytetrafluoroethylene clamping sleeve (4) of the liquid film water inlet device, a gap is reserved in the polytetrafluoroethylene clamping sleeve, and the gap is used for enabling gas to enter the inside of the reducing glass tube (3) along a vertical gap parallel to the high-voltage electrode;
the first connecting part (14) is connected with the water storage module (11) through an annular steel ring and is sealed by adopting a sealing gasket.
4. A low temperature plasma dielectric barrier discharge liquid film reactor according to claim 3, characterized in that the threaded interface (7) of the stationary high voltage electrode is sealed by a polytetrafluoroethylene sealing ring and a hollow peak plastic bolt.
5. The low-temperature plasma dielectric barrier discharge liquid film reactor according to claim 1, wherein the reducing glass tube (3) is of an integrated structure and comprises two end tube areas, a middle tube area and a peripheral glass tubule (20), the diameters of the two end tube areas are larger than those of the middle tube area, the peripheral glass tubule (20) is positioned on the outer wall of the reducing glass tube (3), and water inlets/outlets (21) are formed on two sides of the middle tube area.
6. A low temperature plasma dielectric barrier discharge liquid film reactor according to claim 1, characterized in that the gas-liquid outlet polytetrafluoro-ferrule (5) comprises a second ferrule, a fifth connection (25);
The second clamping sleeve comprises a third connecting part (22), a second sealing gasket (23) and a fourth connecting part (24);
The second sealing gasket (23) is arranged between the third connecting part (22) and the fourth connecting part (24);
The fourth connecting part (24) and the fifth connecting part (25) are connected together by adopting an annular steel ring and are sealed by a sealing gasket;
One side of the fifth connecting part (25) is provided with an outlet (27), the center of the bottom end of the fifth connecting part is provided with a threaded interface (26),
The threaded interface (26) is sealed by a polytetrafluoroethylene sealing ring and a hollow peak plastic bolt;
The upper end of the fifth connecting part (25) is conical.
7. A low temperature plasma dielectric barrier discharge liquid film reactor according to claim 1, wherein,
The diameter of the high-voltage electrode (2) is 1-4mm;
The diameter-variable glass tube (3) has the outer diameter of the two end tube areas (18) of 8-20mm, the wall thickness of 0.5-2mm and the length of 5-30cm; the outer diameter of the middle pipe area (19) is 5-15mm, the wall thickness is 0.5-2mm, and the length is 1-10cm; the outer diameter of the peripheral glass tubule (20) is 8-25mm, the wall thickness is 0.5-2mm, and the length is 1-10cm;
The length of the diameter-reduced part of the reducing glass tube (3) is 0.5-4cm, and the joint is smooth.
8. Use of a low temperature plasma dielectric barrier discharge liquid film reactor as claimed in claims 1-6, wherein the reactor is applied in the reaction of methane and oxygen gas mixture to produce oxygen-containing compound, the flow rate of water introduced into the water inlet (9) is 10-100mL/min, and the inflow mode can be single-pass inflow or circulating inflow.
9. The use according to claim 8, characterized by the steps of:
(1) The temperature of the circulating water solution in the peripheral glass tubule (20) is controlled to be kept at a fixed value through an external circulating water system, and the range is 0-90 ℃;
(2) The total flow and the mole ratio of methane and oxygen and the flow of inert gases such as argon added are controlled by adopting a flow controller, and the mixture is mixed by a mixing air chamber and then is introduced into a low-temperature plasma dielectric barrier discharge liquid film reactor device through a gas sample inlet (8);
(3) Starting a plasma generator, regulating a transformer, and gradually loading alternating-current high voltage on the plasma generator until uniform discharge occurs; the voltage is finely adjusted to adjust the input power, and the discharge frequency is matched to ensure the mildness and uniformity of discharge; the reaction products are carried by the unreacted mixed gas and enter a collector; collecting liquid phase products through a condensing tube; wherein the discharge power ranges from 5 to 25 watts and the discharge frequency ranges from 1 to 100 kilohertz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410251360.2A CN118079615A (en) | 2024-03-06 | 2024-03-06 | Low-temperature plasma dielectric barrier discharge liquid film reactor and application thereof in methane selective oxidation reaction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410251360.2A CN118079615A (en) | 2024-03-06 | 2024-03-06 | Low-temperature plasma dielectric barrier discharge liquid film reactor and application thereof in methane selective oxidation reaction |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118079615A true CN118079615A (en) | 2024-05-28 |
Family
ID=91145156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410251360.2A Pending CN118079615A (en) | 2024-03-06 | 2024-03-06 | Low-temperature plasma dielectric barrier discharge liquid film reactor and application thereof in methane selective oxidation reaction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118079615A (en) |
-
2024
- 2024-03-06 CN CN202410251360.2A patent/CN118079615A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pou et al. | CO2 reduction using non-thermal plasma generated with photovoltaic energy in a fluidized reactor | |
| CN109663555B (en) | System and method for synergistically converting greenhouse gas and biochar by pulsating jet plasma | |
| Du et al. | Plasma reforming of bio-ethanol for hydrogen rich gas production | |
| CN109911850B (en) | Methane reforming device and methane reforming method | |
| CN112624893B (en) | Catalytic coupling method of light alkane | |
| CN110394127B (en) | Fluidized bed methane dry reforming reaction device and method with plasma in-situ coupled ultraviolet light | |
| Kado et al. | Low temperature reforming of methane to synthesis gas with direct current pulse discharge method | |
| Li et al. | The function of porous working electrodes for hydrogen production from water splitting in non-thermal plasma reactor | |
| WO2010041113A1 (en) | Process for the direct oxidation of methane to methanol by means of non-thermal plasma in a reactor with the gliding arc in tornado (gat) technology | |
| CN118079615A (en) | Low-temperature plasma dielectric barrier discharge liquid film reactor and application thereof in methane selective oxidation reaction | |
| CN104725271B (en) | One methane and ammonia plasmas synthesizing amino acetonitrile and the method for N, N-Cyanamide, dimethyl- | |
| ZHANG et al. | Conversion of methane by steam reforming using dielectric-barrier discharge | |
| Lin et al. | Reforming of CH 4 and CO 2 by combination of alternating current-driven nonthermal arc plasma and catalyst | |
| CN107011120B (en) | Method for high-selectivity synthesis of ethanol by resource treatment of carbon dioxide and water | |
| CN110127623A (en) | The method of plasma decomposing hydrogen sulfide | |
| KR20240042518A (en) | Apparatus, system and method for producing hydrogen peroxide, hydrocarbon(s) and syngas | |
| CN209815681U (en) | Methane reforming device | |
| Wang et al. | Hydrocracking of n-hexadecane via liquid or gaseous water assisted pulsed spark discharge in liquid | |
| CN110885285B (en) | Method for synthesizing natural anisic aldehyde | |
| Wang et al. | Hydrogen production from methanol through dielectric barrier discharge | |
| CN116726830A (en) | Low-temperature plasma dielectric barrier discharge reactor device and application of methane selective oxidation reaction thereof | |
| Meiyazhagan et al. | Feasible production of hydrogen from methanol reforming through single stage DC microplasma reactor | |
| Yu et al. | Conversion from dimethyl ether to dimethoxymethane and dimethoxyethane using dielectric-barrier discharge plasma | |
| CN114874804B (en) | Renewable electric power driven multitube circulating water electrode plasma conversion device and method | |
| CN113105306B (en) | Device and method for synthesizing organic matters by using plasma electric field to assist methanol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |