CN1180976C - A microwave-excited methane conversion hydrogen production process - Google Patents
A microwave-excited methane conversion hydrogen production process Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 190
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 118
- 239000001257 hydrogen Substances 0.000 title claims abstract description 65
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000004519 manufacturing process Methods 0.000 title description 13
- 239000007789 gas Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 16
- 239000010937 tungsten Substances 0.000 claims abstract description 16
- 238000005336 cracking Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 11
- 230000005672 electromagnetic field Effects 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000005284 excitation Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910039444 MoC Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 abstract description 8
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 19
- 239000012495 reaction gas Substances 0.000 description 11
- 230000005855 radiation Effects 0.000 description 10
- 239000000376 reactant Substances 0.000 description 10
- 238000006356 dehydrogenation reaction Methods 0.000 description 9
- -1 gac Chemical compound 0.000 description 9
- 239000013078 crystal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000003921 oil Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
一种微波激励甲烷转化制氢的工艺，是使甲烷以1-10秒停留时间通过反应区，反应区内放置有电磁场作用下易放电的物质，然后使用连续或脉冲微波对反应区进行辐射，电磁场作用下易放电的物质在微波作用下放电引发等离子体，从而裂解甲烷制取氢，其特征在于，反应区内含甲烷气体压力为1-3个标准大气压，在常温下并且微波的频率应大于0.3GHz，输入功率最小为5W；所述易放电的物质为铂、钨、铁、镍铜及它们的合金或混合物。该工艺的特点是甲烷转化率高，反应过程容易控制，安全性高，工艺简单，产物氢不含一氧化碳，应用范围广，反应可在常压或常压以上进行，能够大规模工业化生产。A process for converting methane to hydrogen by microwave excitation, which is to make methane pass through the reaction zone with a residence time of 1-10 seconds, and place substances that are easy to discharge under the action of an electromagnetic field in the reaction zone, and then use continuous or pulsed microwaves to irradiate the reaction zone. Under the action of electromagnetic field, the material that is easy to discharge is discharged under the action of microwave to generate plasma, thereby cracking methane to produce hydrogen. It is characterized in that the pressure of methane gas in the reaction zone is 1-3 standard atmospheric pressure. At normal temperature and the frequency of microwave should be Greater than 0.3GHz, the minimum input power is 5W; the easily dischargeable substances are platinum, tungsten, iron, nickel copper and their alloys or mixtures. The process is characterized by high methane conversion rate, easy control of the reaction process, high safety, simple process, product hydrogen does not contain carbon monoxide, wide application range, reaction can be carried out at or above normal pressure, and can be industrialized on a large scale.
Description
Technical field
The present invention relates to the methane conversion hydrogen producing technology, microwave excitation methane conversion process for making hydrogen is provided especially.
Background technology
Hydrogen is important chemical goods and materials and energy and material.Especially under the environment requirement of preserving our planet, hydrogen gets most of the attention as the fuel that cleans most.The main energy sources material of our times is a fossil oil, and the burning of fossil oil will produce a large amount of carbonic acid gas, and obnoxious flavoures such as carbon monoxide, the Greenhouse effect of the earth just use closely related with a large amount of burnings of fossil oil.And the product of hydrogen burning has only water, and is nuisanceless pollution-free.But natural hydrogen resource seldom, and it mainly obtains by decomposing other hydrogen-containing compound.Methane is the major ingredient of Sweet natural gas, and the reserves of Sweet natural gas are very abundant on the earth, and the exploration result shows that the total resources of Sweet natural gas is also more than the summation of coal and oil.Methane is elementary composition by carbon and two kinds of hydrogen, and its cracking can produce hydrogen.Therefore preparing hydrogen from resourceful methane has better industrial application prospect.Existing approach from methane hydrogen manufacturing mainly contains to sow:
1, partial oxidation of methane hydrogen.The principal feature of this technological process has: methane conversion height, the selectivity height of hydrogen, reaction velocity height.But this reaction process is at high temperature carried out, and needs the oxygen feeding of high density, the reaction process complexity, and the reaction process security is lower, and hydrogen, carbon monoxide concentration that this process produces are higher, has certain limitation on using.[Production of synthesis gas，Catal.Today 18(1993)305-324]
2, the hydrogen manufacturing of methane steam reforming.The principal feature of this technological process is: the methane conversion height, and the selectivity height of hydrogen, reaction process is safer.But this reaction process needs high temperature and a large amount of water vapor, reaction process energy consumption height, and complex process, carbon monoxide concentration height in the product hydrogen, range of application is restricted.[Production of synthesis gas，Catal.Today18(1993)305-324]
3, the principal feature of this technological process of arc process cracking methane hydrogen manufacturing is: the methane conversion height, and technology is simple, and product hydrogen does not contain carbon monoxide, applied range.But reaction process is wayward, and energy consumption is too high, can only be used for the flourishing area of water power.[producing acetylene and derivative thereof from coal and Sweet natural gas, Chemical Industry Press (1992)]
4, under the microwave exposure there be the principal feature of this technological process of methane hydrogen manufacturing: the methane conversion height, and reaction process is controlled easily, and is safe, and product hydrogen does not contain carbon monoxide, applied range.But this reaction needed is carried out under negative pressure, is unfavorable for large-scale industrial production, thereby is in the research.[U.S. Pat 4574038, Decomposition ofhydrocarbons in a microwave discharge, J.Phys.Chem., Volume73, number 6,6 (1969)]
Summary of the invention
In order to overcome the problems referred to above, the technology that the purpose of this invention is to provide the hydrogen manufacturing of a kind of microwave excitation methane conversion, it is that the gas that contains finite concentration methane under the certain pressure passes through reaction zone with certain flow rate, be placed with the object that easily discharges under the electromagnetic field effect in the reaction zone, use then continuously or pulse microwave carries out radiation to reaction zone, the material that electromagnetic field effect easily discharges is down transferred the electroinitiation plasma body at microwave action, thereby cracking methane is produced hydrogen.The characteristics of this process are the methane conversion height, and reaction process is controlled easily, and are safe, and technology is simple, and product hydrogen does not contain carbon monoxide, applied range, and reaction can be carried out at normal pressure or more than the normal pressure, can large-scale industrial production.
Specifically, the technology of a kind of microwave excitation methane conversion provided by the invention hydrogen manufacturing, be to make methane-containing gas pass through reaction zone, be placed with the rhoptry of making by the material that under electromagnetic field effect, easily discharges in the reaction zone, use microwave that reaction zone is carried out radiation then, the material that electromagnetic field effect easily discharges is down transferred the electroinitiation plasma body at microwave action, thereby cracking methane is produced hydrogen, it is characterized in that, methane-containing gas pressure is 1-3 standard atmospheric pressure in the reaction zone, frequency at 15-35 ℃ normal temperature and microwave should be greater than 0.3GHz, and the power input minimum is initiation reaction under the 5W, and to make methane-containing gas be 1-10 second in the reaction zone residence time.
In above-mentioned the present invention, the material that the electromagnetic field effect of placing in the reaction zone easily discharges down can be platinum, tungsten, iron, nickel, copper and their alloy or mixture, and best optional tungsten is as discharging substance.
In addition, in above-mentioned the present invention, the material that the electromagnetic field effect of placing in the reaction zone easily discharges down also can be graphite, gac, silicon carbide, wolfram varbide, molybdenum carbide and composition thereof, and is preferably graphite.
In addition, in above-mentioned the present invention, concentration of methane gas is the 1%-100% volumn concentration, is applicable to a large amount of methane-containing gas kinds, as catalytic cracked dry gas, and Sweet natural gas, coal-seam gas etc.And preferably concentration of methane gas is chosen as 50%-100%.
In above-mentioned the present invention, methane-containing gas is 1-10 second in the reaction zone residence time, and the residence time, long more methane conversion was high more, and density of hydrogen is high more in the tail gas.But surpass 10 seconds when the residence time, methane conversion is almost 100%, and density of hydrogen also is difficult to improve again in the tail gas, and overstand influences the productive rate of product, is unfavorable for suitability for industrialized production.Therefore, the residence time preferably is no more than 10 seconds.
In addition, in above-mentioned the present invention, the microwave that acts on reaction zone can be continuously or pulsed, is applicable to most of existing microwave devices.As long as and its microwave frequency can reach 0.3GHz, power input surpasses 5W just can carry out conversion of methane.But, act on usually reaction zone continuously or the frequency of pulse microwave be 0.915,2.45,5.80 or 22.0GHz, power input is more than the 100W, and improves power input and help methane conversion Cheng Qing.Concrete power input can be set according to real reaction requirement and condition.
In addition, in above-mentioned the present invention, the duty that acts on the pulse microwave of reaction zone can be 0.1-1, and pulse-repetition can be 1-10Hz.
In the present invention, the primary product of methane conversion is hydrogen and carbon, by-product a little acetylene, ethene.
Compare the present invention with known technology and have following distinguishing feature:
1. reactant gases is at normal temperature (15-35 ℃) and normal pressure or can be initiated more than the normal pressure and react, and the activation temperature of methane need be higher than 1200 ℃ under the catalyst-free condition, and plasma-converted methane needs condition of negative pressure under the normal temperature at normal pressure usually.High temperature and negative pressure are the two big difficulties of methane activation process on industrialization road.The present invention is by placing the easily object of discharge in reaction zone, under continuous or pulse microwave effect, cause this process of discharge plasma and realize methane conversion, methane can be initiated at normal temperatures to react, can guarantee to be reflected at normal pressure again or be higher than stable carrying out under the normal pressure, this will help the process of industrialization of Sweet natural gas comprehensive utilization undoubtedly.
2. among the present invention, the conversion process of methane need not to use catalyzer, has avoided many difficulties that often run in catalyzed reaction, and this has simplified technical process undoubtedly greatly, has reduced the conversion cost of methane, more helps the further application of this process.
3. among the present invention, tail gas hydrogen concentration height does not contain carbon monoxide in the product hydrogen, and range of application is very extensive, is particularly useful for the proton membrane fuel battery field to carbon monoxide poisoning.
4. among the present invention, use microwave as energy derive, clean and safe, and also the response of microwave energy supplying system is rapidly, and production process is controlled easily, and is safe.
Embodiment
State the present invention below by embodiment is auspicious:
Embodiment 1. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters metal bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the reaction gas that will contain methane 100% feeds reaction tubes, reactant gases residence time in microwave resonator is 5 seconds, reaction gas pressure is 1 standard atmospheric pressure, apply the continuous microwave radiation, power 100W, frequency 2450MHz regulates short-circuit plunger, makes microwave reflection power reach minimum, the metal bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.The results are shown in table 1:
Table 1 different metal discharging substance is to the influence of reaction result
| Discharging substance | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| Tungsten | 96.1 | 10.0 | 1.0 | 0 | 89.0 | 91.1 |
| Platinum | 95.8 | 11.1 | 1.2 | 0 | 88.7 | 90.2 |
| Iron-nickel alloy | 96.5 | 9.5 | 0.8 | 0 | 89.7 | 92.2 |
Embodiment 2. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters carbon or carbide rod vertically place on the reaction tubes axis and are positioned at microwave resonator central authorities, the reaction gas that will contain methane 100% feeds reaction tubes, reactant gases residence time in microwave resonator is 5 seconds, reaction gas pressure is 1 standard atmospheric pressure, apply the continuous microwave radiation, power 100W, frequency 2450MHz regulates short-circuit plunger, makes microwave reflection power reach minimum, carbon or carbide rod tip produce discharge with this understanding and cause plasma body, thereby the methane cracking produces hydrogen.The results are shown in table 2:
Different carbon of table 2 or carbide discharging substance are to the influence of reaction result
| Discharging substance | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| Silicon carbide | 96.0 | 11.1 | 1.2 | 0 | 87.8 | 89.1 |
| Graphite | 96.1 | 10.8 | 1.1 | 0 | 88.1 | 90.2 |
Embodiment 3. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters tungsten bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the gas of different methane concentrations is fed reaction tubes, the diluent gas of reaction gas is an argon gas, reactant gases residence time in microwave resonator is 5 seconds, reaction gas pressure is 1 standard atmospheric pressure, apply the continuous microwave radiation, power 100W, frequency 2450MHz, regulate short-circuit plunger, make microwave reflection power reach minimum, the tungsten bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.The results are shown in table 3.By table 3 result as can be known, improve methane concentration and make density of hydrogen increase in the product.And it is little for selectivity of product influence beyond the dehydrogenation.
The different methane concentrations of table 3 are to the influence of reaction result
| Methane concentration/mol% | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| 1 | 99.3 | 10.3 | 1.5 | 0 | 88.2 | 0.9 |
| 50 | 99.0 | 10.1 | 1.1 | 0 | 88.8 | 49.1 |
| 100 | 96.1 | 10.0 | 1.0 | 0 | 89.0 | 91.1 |
Embodiment 4. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters tungsten bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the reactant gases that will contain methane 100% feeds reaction tubes, reactant gases residence time in microwave resonator is 5 seconds, apply the continuous microwave radiation, power 100W, frequency 2450MHz, regulate short-circuit plunger, make microwave reflection power reach minimum, the tungsten bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.Reaction gas pressure not simultaneously, different reaction results are listed in table 4.By table 4 result as can be known, the processing method of methane conversion hydrogen manufacturing of the present invention can or add at normal pressure to depress and carries out.Help large-scale industrialization production like this.
Table 4 differential responses pressure is to the influence of reaction result
| Pressure/atm | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| 1 | 96.1 | 10.0 | 1.0 | 0 | 89.0 | 91.1 |
| 2 | 97.2 | 9.0 | 0.8 | 0 | 90.2 | 92.2 |
| 3 | 98.0 | 8.0 | 0.7 | 0 | 91.3 | 93.2 |
Embodiment 5. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters tungsten bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the gas that will contain methane 100% feeds reaction tubes, reaction gas pressure is 1 standard atmospheric pressure, apply the continuous microwave radiation, power 100W, frequency 2450MHz, regulate short-circuit plunger, make microwave reflection power reach minimum, the tungsten bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.The reaction result difference the results are shown in table 5 to reactant gases not simultaneously the residence time in microwave resonator.By table 5 result as can be known, methane is long more in the reaction zone residence time, and the concentration of hydrogen is high more in the product.
The different residence time of table 5 are to the influence of reaction result
| The residence time/second | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| 1 | 84.0 | 77.5 | 2.1 | 0.4 | 20.0 | 81.8 |
| 5 | 96.1 | 10.0 | 1.0 | 0 | 89.0 | 91.1 |
| 10 | 99.0 | 2.7 | 0.3 | 0 | 97.0 | 97.2 |
Embodiment 6. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters tungsten bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the gas that will contain methane 100% feeds reaction tubes, reactant gases residence time in microwave resonator is 5 seconds, reaction gas pressure is 1 standard atmospheric pressure, apply the continuous microwave radiation, frequency 2450MHz, regulate short-circuit plunger, make microwave reflection power reach minimum, the tungsten bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.Microwave input power not simultaneously, the reaction result difference the results are shown in table 6.As shown in Table 6, the microwave power raising being helped methane conversion is hydrogen.
The different microwave input power of table 6 are to the influence of reaction result
| Microwave power/W | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| 5 | 15.0 | 76.0 | 2.2 | 0 | 21.8 | 11.0 |
| 5 | 70.8 | 35.2 | 1.8 | 0 | 63.0 | 80.9 |
| 100 | 96.1 | 10.0 | 1.0 | 0 | 89.0 | 91.0 |
| 500 | 98.0 | 8.0 | 0.6 | 0 | 91.4 | 93.2 |
Embodiment 7. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters tungsten bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the gas that will contain methane 100% feeds reaction tubes, reactant gases residence time in microwave resonator is 5 seconds, reaction gas pressure is 1 standard atmospheric pressure, apply pulsed microwave radiation, dutycycle is 0.1, power 100W, frequency 2450MHz, regulate short-circuit plunger, make microwave reflection power reach minimum, the tungsten bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.The microwave pulse frequency not simultaneously, the reaction result difference the results are shown in table 7.As shown in Table 7, improve pulse-repetition, help improving density of hydrogen.
The different microwave pulse frequencies of table 7 are to the influence of reaction result
| Pulse-repetition/Hz | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| 1 | 66.0 | 53.2 | 2.7 | 0 | 44.1 | 78.2 |
| 5 | 80.0 | 35.0 | 2.1 | 0 | 62.9 | 85.0 |
| 10 | 85.2 | 28.0 | 1.8 | 0 | 70.2 | 87.6 |
Embodiment 8. is that 25 millimeters crystal reaction tube places microwave resonator with internal diameter, with one section diameter is 3 millimeters, long 10 millimeters tungsten bar vertically places on the reaction tubes axis and is positioned at microwave resonator central authorities, the gas that will contain methane 100% feeds reaction tubes, reactant gases residence time in microwave resonator is 5 seconds, reaction gas pressure is 1 standard atmospheric pressure, apply pulsed microwave radiation, pulse-repetition 5Hz, power 100W, frequency 2450MHz, regulate short-circuit plunger, make microwave reflection power reach minimum, the tungsten bar tip produces discharge with this understanding and causes plasma body, thereby the methane cracking produces hydrogen.The pulse microwave dutycycle not simultaneously, the reaction result difference the results are shown in table 8.As shown in Table 8, improve the pulse microwave dutycycle and help methane conversion, and can improve the selectivity of hydrogen.
The different microwave pulse dutycycles of table 8 are to the influence of reaction result
| Dutycycle | Methane conversion/% | Selectivity of product/% beyond the dehydrogenation | Density of hydrogen/mol% | |||
| Acetylene | Ethene | Ethane | Carbon | |||
| 0.1 | 70.0 | 51.0 | 2.5 | 0 | 46.5 | 80.2 |
| 0.5 | 80.0 | 35.0 | 2.1 | 0 | 62.9 | 85.0 |
| 1 | 90.6 | 22.0 | 1.5 | 0 | 76.5 | 89.8 |
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| CN103011076B (en) * | 2011-11-03 | 2014-07-16 | 吉林大学 | Vehicle-mounted microwave low-temperature plasma reformer system for online hydrogen production |
| CN106185806B (en) * | 2016-07-01 | 2018-07-31 | 中国科学院电工研究所 | A kind of device and method using plasma-converted methane |
| CN110201617A (en) * | 2019-07-03 | 2019-09-06 | 西安交通大学 | A kind of high energy reaction starting method |
| CN111411001B (en) * | 2020-04-20 | 2020-12-29 | 广东石油化工学院 | A kind of promoting device for methane conversion and its promoting method |
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| CN116768156A (en) * | 2022-03-08 | 2023-09-19 | 深圳市弘玮微波技术有限公司 | A method for hydrogen production by methane cracking and reforming |
| CN115259983B (en) * | 2022-08-22 | 2023-11-10 | 大连理工大学 | A method for producing ethylene through oxygen-free coupling of methane |
| CN116253288B (en) * | 2023-01-17 | 2024-10-08 | 中国林业科学研究院林产化学工业研究所 | A method for producing hydrogen by cracking methane using variable frequency microwave catalysis |
| CN119838535B (en) * | 2025-03-20 | 2025-07-22 | 山东大学 | A green power microwave discharge plasma methane cracking hydrogen and carbon cogeneration system and method |
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