CN1861519A - Plasma catalyzing process of preparing hydrogen by ammonia decomposition - Google Patents
Plasma catalyzing process of preparing hydrogen by ammonia decomposition Download PDFInfo
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- CN1861519A CN1861519A CNA2006102005630A CN200610200563A CN1861519A CN 1861519 A CN1861519 A CN 1861519A CN A2006102005630 A CNA2006102005630 A CN A2006102005630A CN 200610200563 A CN200610200563 A CN 200610200563A CN 1861519 A CN1861519 A CN 1861519A
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
A plasma catalysis process for preparing H2 by decomposing ammonia at lower temp to obtain the H2-N2 mixture used for the proton exchange membrane type fuel battery of car features that the non-noble-metal carried catalyst, whose active component is chosen from Fe, Co, Ni, Cr, Mo, Mn, Cu and W, is loaded in the discharge region in a plasma catalytic reactor.
Description
Technical field
The invention belongs to plasma chemistry and Hydrogen Technology field, relate to a kind of ammonia that can make and decompose at a lower temperature, generation helps the Proton Exchange Membrane Fuel Cells automobile to be used, and does not contain the hydrogen of carbon monoxide and carbonic acid gas, the method for nitrogen mixed gas.
Background technology
The exhaustion day by day of fossil energy such as coal, oil and natural gas, and directly use these fossil energies to the severe contamination that environment causes, force people must improve constantly validity and the spatter property that uses the energy.The Application and Development of Hydrogen Energy is subjected to countries in the world attention more and more widely just under such background.
Utilize Proton Exchange Membrane Fuel Cells (PEMFC) Hydrogen Energy can be converted into electric energy.What take place in this conversion process is the cell reaction that hydrogen and oxygen generate water.Utilize the advantage of Hydrogen Energy to comprise by fuel cell: (1) hydrogen and oxygen are not direct burning when operation of fuel cells, but generate electricity by electrochemical appliance, therefore its energy conversion efficiency is not limited by carnot's working cycle, theoretical efficiency can reach 83%, actual efficiency can reach 50-60%, is 2-3 times of the actual efficiency of ordinary internal combustion engine; (2) discharge water during operation of fuel cells.Therefore, not only can save energy but also can accomplish zero pollution if use the fuel cell-driven automobile.
At present, Proton Exchange Membrane Fuel Cells (PEMFC) technology is ripe, and many in the world automobile factorys commercial city has been released the fuel cell sample car of oneself.But fuel cell car wants the formation industry, except will overcoming the inferior position on the cost, also will solve this key issue of hydrogen supply.
Because vehicle-mounted compression hydrogen energy density is little, and has potential safety hazard, so the fuel cell car vehicle-mounted hydrogen production is practicable technical scheme.According to raw material route difference, the fuel cell car vehicle-mounted hydrogen production method that has proposed so far can be summed up as hydrogen manufacturing of carbon back hydrogen source and the hydrogen manufacturing of non-carbon back hydrogen source.
The main means of carbon back hydrogen source vehicle-mounted hydrogen production are steam reformings.Though Sweet natural gas, conventional liq fuel (diesel oil, boat coal, gasoline) and alcohols (ethanol, methyl alcohol) all can be used for reformation hydrogen production in principle, but for the automobile fuel battery, the steam reformation temperature of Sweet natural gas too high (700-800 ℃), conventional liq fuel then sulphur content is relatively too high, wait to solve ultra-deep desulfurization technical problem [Chunshan Song, Catal.Today 77 (2002) 17-49.].Comparatively speaking, the steam reformation technology maturation of methyl alcohol, reforming temperature low (200-300 ℃) relatively is fit to PEMFC and uses.In addition, the production technology maturation of methyl alcohol itself, industrial scale is big, low price, convenient transportation.And the energy density of methyl alcohol is higher, H in the steam reformation product
2Content can reach 75% (V), need not propose the dense PEMFC generating that promptly can be used for.Therefore, the steam reforming of methyl alcohol is very attractive as a kind of vehicle-mounted hydrogen production approach.
But carbon back hydrogen sources such as methyl alcohol produce a large amount of CO inevitably in the steam reforming process
X(CO content can reach 10% to problem in the methanol reformed gas, CO
2Content is also higher than CO content) application has been constituted major obstacles.CO is to the maximum poisonous substance of PEMFC Pt electrode harm (strong absorption causes poisoning), and battery efficiency is descended rapidly.Therefore PEMFC requires the CO content in the reformed gas must not surpass 10ppm[T.V.Choudhary, et al., Catal.Today, 77 (2002) 65-78.].For this reason, the raw hydrogen that comes out from the steam reforming device is before entering PEMFC, usually to pass through high-temperature water gas conversion (350-550 ℃) successively and low temperature water gas conversion (200-300 ℃) is reduced to about 1%～1.5% (V) with CO, handle through the low temperature selective oxidation that again CO is reduced to below the 10ppm.This just makes that automobile-used steam reformation technology is very complicated, and potential faults increases, and is unfavorable for practical application [Toyokazu Tanabe, et al., Catal.Today 111 (2006) 153-157.].
Use the hydrogen manufacturing of non-carbon back hydrogen source can fundamentally break away from CO
X, the trouble brought of CO especially.At present, ammonia is by the consistent non-carbon back hydrogen source of having an optimistic view of.
Advantage with ammonia hydrogen manufacturing also comprises: NH
3Be a kind of large Chemicals.The purity of commercially available liquefied ammonia can reach 99.5%, and wherein impurity is water, and is harmless to fuel cell, does not need pre-treatment.NH
3Gas at room temperature pressure to reach 0.8MPa be that liquefiable and ignition range are narrower, security is better.NH
3Though itself be corrosive and irritating smell, its corrodibility is to solve easily, as for irritating smell, then can be used to leak prompting just.The complete cracking resultant of ammonia has only hydrogen and nitrogen, and wherein the volumetric concentration of hydrogen can reach 75% (nitrogen is harmless to fuel cell), need not concentrate just to be used for the Proton Exchange Membrane Fuel Cells generating.The energy density height of ammonia (the maximum specific energy of ammonia splitting gas is 5.59KWh/Kg, the maximum specific energy 3.8KWh/Kg of methanol steam reforming gas), green degree height (have only H in the ammonia splitting gas
2And N
2, can make fuel cell car become ' zero release ' automobile; But the fuel cell car that is restructured as hydrogen source with methanol steam will discharge CO
2) and light (the 1Kg H of fuel load
2Consumption 5.67Kg ammonia.But then will consume 5.17Kg methyl alcohol and 3.0Kg water to methanol steam reforming, the cracking of fuel load ratio ammonia exceeds 44%).
In order to study synthetic ammonia mechanism, the research report that decomposes about ammonia is in a large number arranged in the early stage document.But, be that the ammonia disaggregate approach of purpose is only just occurring in recent years with hydrogen manufacturing.
Except that the advantage of having set forth with the hydrogen manufacturing of ammonia raw material, also report [T.V.Choudhary, et al., Catal.Today, 77 (2002) 65-78. have been made in the research of adopting conventional catalysis process to decompose ammonia hydrogen manufacturing in the following discloses document; T.V.Choudhary, et al., Chem.Eng.J.93 (2003) 69-80.; Jamely D., et al., Chem.Rev.104 (2004) 4767-4790.; T.V.Choudhary, et al., Catal.Letter 72,3-4 (2001) 197-201.; A.S.Chellapa, et al., Appl.Catal.A:General, 227 (2002) 231-240.; S.F.Yin, et al., Appl.Catal.A:General 277 (2004) 1-9.; A.Mitsos, et al., Int.Eng.Chem.Res., 43 (2004) 74-84.; Li Li, energy technology 26,3 (2005) 102-105].
Following patent documentation also relates to ammonia hydrogen manufacturing:
Disclosed Catalysts and its preparation method in the Chinese invention patent (application number 03143112.7) with ammonia decomposition reaction preparation zero COx hydrogen.Its principal character is: catalyzer is made of 0.5-20% active ingredient, 0-20% auxiliary agent and 70-99% carrier.Wherein, the metal nitride that active ingredient is selected from precious metal and has precious metal character, preferred noble ruthenium (Ru), Noble Metal Rhodium (Rh) and molybdenum nitride (MoN); Carrier is a carbon nanotube; Auxiliary agent is selected from basic metal, alkaline-earth metal and rare earth compound.Carry out in conventional fixed-bed reactor with the hydrogen manufacturing of above-mentioned catalyst decomposes ammonia.Implementation result shows, need use under 470 ℃-550 ℃ high temperature with the catalyzer of the method preparation of this Patent publish.
Disclose low temperature modification ammonia in the Chinese invention patent (application number 03134691.X) and decomposed the Catalysts and its preparation method for preparing hydrogen.Its principal character is: catalyzer is made of 0.1-30% active ingredient, 0-20% auxiliary agent and 60-99% carrier.Wherein, the metal nitride that active ingredient is selected from transition metal and has precious metal character, preferred noble ruthenium (Ru), Noble Metal Rhodium (Rh), base metal nickel (Ni) and molybdenum nitride (MoN); Carrier is a nanocrystal metal oxide, preferred aluminum oxide (Al
2O
3), magnesium oxide (MgO), zirconium white (ZrO
2) and zinc oxide (ZnO); Auxiliary agent is selected from basic metal, alkaline-earth metal and rare earth compound.This patent proposes to replace carbon nanotube as support of the catalyst with nanocrystal metal oxide on its patent (application number 03143112.7) basis in early stage, and purpose is to reduce the catalyzer cost.Carry out in conventional fixed-bed reactor with the hydrogen manufacturing of above-mentioned catalyst decomposes ammonia.Implementation result shows, need use under 480 ℃-550 ℃ high temperature with the catalyzer of the method preparation of this Patent publish.
Disclosed a kind of high-activity ommonia decomposition catalyst in the Chinese invention patent (application number 98114265.6).It is characterized in that: catalyzer is made of active ingredient and carrier.Wherein, active ingredient is molybdenum and nickel, and carrier is aluminum oxide (Al
2O
3) or magnesium oxide (MgO).Its feature also is: catalyzer will carry out pre-nitriding treatment before use under whole temperature is 650 ℃-750 ℃ high temperature, make metal oxide be converted into metal nitride.The purposes of the catalyzer of this invention; one is the environmental protection aspect; in order to handle the remaining ammonia in coke(oven)gas, fuel gas, petroleum refinery's waste gas and the Nox reduction processing tail gas, another is in metallurgy, vents one's spleen as the protection gas of steel and non-ferrous metal heat treatment process with the branch of ammonia.Carry out in conventional fixed-bed reactor with above-mentioned catalyst decomposes ammonia.Implementation result shows, need use under the high temperature more than 600 ℃ with the catalyzer of the method preparation of this Patent publish.
A kind of Ni-based preparing hydrogen by ammonia decomposition nitrogen mixed gas Preparation of catalysts methods and applications have been disclosed in the Chinese invention patent (application number 02155943.0).It is characterized in that: catalyzer master active ingredient is nickel (Ni), and carrier is silicon oxide (SiO
2) or aluminum oxide (Al
2O
3), auxiliary agent is one or more in IA, IIA, IIIB, VIII or the rare earth element.The purposes of the catalyzer of this invention mainly is environmental protection, reducing gas and protection gas field.Catalyzer uses in conventional fixed bed, and temperature of reaction is 650 ℃.
Disclosed a kind of ruthenium base preparing hydrogen by ammonia decomposition nitrogen mixed gas Catalysts and its preparation method in the Chinese invention patent (application number 02155944.9).It is characterized in that: catalyzer master active ingredient is ruthenium (Ru), and carrier is silicon oxide (SiO
2), aluminum oxide (Al
2O
3), magnesium oxide (MgO), calcium oxide (CaO), titanium oxide (TiO
2) or gac; Auxiliary agent is one or more in IA, IIA, IIIA, IVA and the rare earth element.The purposes of the catalyzer of this invention mainly is environmental protection, reducing gas and protection gas field.Catalyzer uses in conventional fixed bed, and temperature of reaction is more than 500 ℃, and the use temperature more catalyst based than traditional nickel decreases.
Disclose ammonia in the Chinese invention patent (application number 200510031519.7) and decomposed high-efficient carrier nanometer catalyst of system zero COx hydrogen and preparation method thereof.It is characterized in that: catalyzer is made of 0.5-40% active ingredient, 0-30% auxiliary agent and 50-95% carrier.Wherein, active ingredient is selected from transition metal, preferred ruthenium (Ru), iron (Fe), rhodium (Rh) and nickel (Ni), and auxiliary agent is selected from rare earth compound, preferred lanthanum trioxide (La
2O
3), cerium oxide (CeO
2), Neodymium trioxide (Nd
2O
3), carrier is a solid super base, preferred Na/NaOH/ γ-Al
2O
3, K/KOH/ γ-Al
2O
3And Na/KOH/ZrO
2Catalyzer uses in conventional fixed bed, and temperature of reaction is more than 400 ℃.Implementation result shows, the active height of noble ruthenium (Ru) and rhodium (Rh) loaded catalyst, and base metal iron (Fe) and nickel (Ni) loaded catalyst is active low.
U.S. Pat P4544527 has disclosed a kind of reactor assembly with ammonia hydrogen manufacturing.The principal character of this reactor assembly is to use the hydrogen in the hydride beds selectivity absorption ammonia degradation production.And the ammonia decomposition method is not the content of this patent.
U.S. Pat P4704267 has disclosed a kind of technology with ammonia hydrogen manufacturing.The principal character of this technology is to use an adiabatic metal hydride cells to purify from the hydrogen in the product gas of ammonia resolving cell, and the employing of ammonia resolving cell is calandria type fixed bed reactor.
Disclosed among the International Patent Application WO 01/87770A1 with ammonia produce hydrogen from thermal decomposition process.The feature of this technology is, makes ammonia enter the reaction zone of reactor with oxygen-containing gas, and reaction zone is equipped with ammonia decomposition catalyzer.Unstripped gas with the catalyzer contact process in be decomposed into hydrogen and nitrogen, the heat absorption of this process; Meanwhile, make a part of hydrogen that generates in the heat release of reaction zone internal combustion, thereby remedy the heat that the ammonia decomposition course is absorbed.Wherein, at least contain a kind of metal in iron (Fe), cobalt (Co), nickel (Ni), cadmium (Cr), manganese (Mn), platinum (Pt), palladium (Pd), rhodium (Rh) and the ruthenium (Ru) in the ammonia decomposition catalyzer, the carrier of catalyzer is carbon and metal oxide, and the temperature of reaction of ammonia decomposition catalyzer is at least more than 500 ℃.
Disclosed a kind of ammonia cracker that is used to produce hydrogen in the U.S. Patent application (US 2003/0232224 A1).Its principal character is, the metal catalyst of alumina globule load is housed in the ammonia cracker, and the loaded metal activeconstituents is selected from nickel (Ni), ruthenium (Ru) and platinum (Pt), and service temperature is between 500-750 ℃.
A kind of apparatus and method have been disclosed among U.S. Patent application US 2004/0154223 A1 with ammonia hydrogen manufacturing.Its principal character is that reactor is divided into reaction chamber and combustion chamber, can carry out heat exchange between the two.The ammonia decomposition catalyst can be seated in the reaction chamber as fixed bed, also can be applied to the reaction chamber internal surface, forms catalyst film, and the activeconstituents of ammonia decomposition catalyzer is ruthenium Ru) or nickel (Ni).Combustioncatalysts is housed in the combustion chamber, and its activeconstituents is platinum (Pt).Hydrocarbon fuel is burnt under the combustioncatalysts effect, for the ammonia decomposition reaction provides heat.Ammonia decomposes and need carry out under 550 ℃-650 ℃.
Disclosed a kind of fuel cell car that has UV-light ammonia cracker among the Canadian Patent CA2403741.Its principal character is to carry out under the electromagnetic radiation that is reflected at the ultraviolet source generation of ammonia decomposition generation hydrogen.
U.S. Pat P7037484 B1 has disclosed the plasma reactor that a kind of cracking ammonia is produced hydrogen-rich gas.The inside of this plasma reactor is divided into two chambeies with the dielectric medium diaphragm, plasma body is produced by microwave generator, microwave generator is by launching electromagnetic energy in first chamber of sky alignment, electromagnetic energy is passed dielectric diaphragm and produce plasma discharge in second chamber, make the ammonia or other unstripped gas that inject second chamber decompose generation hydrogen, do not have catalyzer to get involved in this process.
Summary of the invention
The purpose of this invention is to provide a kind of ammonia that can make decomposes at a lower temperature, generation helps the Proton Exchange Membrane Fuel Cells automobile and uses, do not contain the hydrogen of carbon monoxide and carbonic acid gas, the method for nitrogen mixed gas, a kind of reactor that can realize aforesaid method is provided simultaneously.Preceding method is that the auxiliary activation with the katalysis of non-noble metal supported catalyzer and dielectric barrier discharge plasma combines and forms.
In traditional heterogeneous catalytic reaction method, use base metal, as iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), when loaded catalyst decomposes ammonia hydrogen manufacturing, because this type of activity of such catalysts is lower than noble metal carrier catalyst, therefore temperature of reaction generally all very high (as, greater than 500 ℃).Its major cause has two, and the one, the bond energy height of ammonia intramolecularly nitrogen-hydrogen bond, higher relatively with the needed activation energy of non-noble metal supported catalyzer fracture nitrogen-hydrogen bond; The 2nd, behind the nitrogen-hydrogen bond rupture in the amino molecule, nitrogen-atoms is adsorbed on catalyst surface, in occupation of the active centre of catalyst surface.The nitrogen-atoms reorganization desorption that has only the surface adsorption attitude is nitrogen molecule freely, and the active centre of catalyst surface could be recovered, and catalyzed reaction could be carried out continuously.But, recombinate desorption for this reactions steps activation energy of nitrogen molecule is very high freely at non-noble metal supported catalyst surface upper surface ADSORPTION STATE nitrogen-atoms, speed of response is very slow, becomes the rate determining step (step that speed is the slowest) of whole heterogeneous reaction process from the ammonia to hydrogen usually.
Can (temperature of high-energy electron reach 1 to utilize dielectric barrier discharge can produce high-energy electron in gas? 0 electron-volt).By bumping with the ammonia molecule, high-energy electron can be given the ammonia molecule with electrical energy transfer, thereby makes that amino molecule is excited under mild conditions, disassociation and ionization, produces the plasma body of ammonia.In the plasma body of ammonia, the nitrogen in the amino molecule-hydrogen bond quilt is activatable in various degree, and some are by the abundant activatory amino molecule of dielectric barrier discharge plasma even can decompose generation hydrogen and nitrogen under mild conditions voluntarily.In addition, when non-noble metal supported catalyst loading during in the dielectric barrier discharge district, the dielectric barrier discharge effect can also the deactivated catalyst surface, is the speed of this speed of reaction controlled step of nitrogen molecule freely thereby accelerate ADSORPTION STATE nitrogen-atoms reorganization desorption.Therefore, in the presence of dielectric barrier discharge, the ammonia degrading activity of non-noble metal supported catalyzer significantly improves, and temperature of reaction can reduce significantly.
Dielectric barrier discharge also has pyrogenic action when producing above-mentioned activation.This pyrogenic action can be used for catalyzer just and temperature of reaction is provided and provide heat to the ammonia scission reaction of absorbing heat, thereby makes generate energy coupling between dielectric barrier discharge and the catalyzer.Because the pyrogenic action of dielectric barrier discharge directly acts on catalyzer and reaction system, indirect heating unlike methanol self-heating recapitalization, so the coupling of the energy between dielectric barrier discharge and the catalyzer is more conducive to energy-conservation.
Technical scheme of the present invention is as follows:
The plasma-catalytic ammonia decomposition reaction carries out in a plasma catalytic reactor.Does described plasma catalytic reactor have that the residual protruding well-behaved shank of line Jiu＜stand tall and upright sticks up continuous and meandering meal deep blue from the ζ epiphysis stand tall and upright that outspoken meal deep blue is pure sticks up the flat fish hawk bow of tranquil anti-rampant rice huller Li a surname that continues and try to gain 1. Σ crickets visitor Chi and gather around the impossible pyrrole seal 7 of third constellations Ke Yun and return the row order purple ant of making a noise from ζ condyle any of several broadleaf plants pine crack food two M ü play food and consult the Dao Cuo porphin character used in proper names and in rendering some foreign names Guo, a state in the Zhou Dynasty fish hawk legendary ruler of great antiquity, the first of the Three August Ones from the ζ ilium? line) as the high-voltage discharging electrode of reactor, wire (line) stretches out and is connected with ac high voltage source from the reactor upper cover, passes through reactor end socket place and seals with insulating material.The ammonia inlet is established in the barrel upper end of reactor, and the lower cover of reactor is established hydrogen, nitrogen mixed gas outlet.Non-noble metal supported catalyzer is loaded on the region of discharge in the reactor, and beds supports with ceramic sieve plate.
The high-voltage discharging electrode of above-mentioned plasma catalytic reactor is made with surface cleaning, corrosion resistant metallic substance, first-selected stainless steel.The housing of reactor is made with alumina-ceramic, hard glass or silica glass, the block media of reactor shell double as two interpolars discharge simultaneously.The ac high voltage source that is used to discharge belongs to the commercial goods, is output voltage range 8? 0 kilovolt, the discharge frequency scope can satisfy requirement of the present invention in the high-voltage power supply of 50Hz-1MHz.
Have the precious metal of catalytic activity and non-noble metal supported catalyzer can both be used for the present invention any ammonia is decomposed.But the cost factor of considering, the preferred non-noble metal supported catalyzer of the present invention, wherein one or more elements in iron content (Fe), cobalt (Co), nickel (Ni), chromium (Cr), molybdenum (Mo), manganese (Mn), copper (Cu) and the tungsten (W) are as the activity of such catalysts composition.Activeconstituents shared weight percent in catalyzer is 0.5-40%.
The carrier that described non-noble metal supported catalyzer is suitable for comprises activated carbon, CNT (carbon nano-tube), aluminum oxide, silicon oxide, titanium oxide, magnesium oxide and silica-based zeolite molecular sieve.But the cost factor of considering, the preferred support of the catalyst of the present invention are gac, aluminum oxide, silicon-dioxide, titanium dioxide, magnesium oxide and silica-based zeolite molecular sieve.Above-mentioned carrier will be used the ordinary method moulding before using, to the carrier granule shape without limits, but the optimum range of the particulate equivalent diameter after the carrier moulding and the ratio of reactor inside diameter is 0.01-0.4, and first-selected scope is 0.05-0.2.The too little meeting of this ratio causes the gas flow resistance excessive.Otherwise this ratio is too big, then can cause reactant to produce channel in beds, contacts bad with catalyzer.
The said non-noble metal supported catalyzer of preparation can be finished by any Utility Engineers's currently known methods of being familiar with this area on above-mentioned carrier, such as using solution dipping method.
Effect of the present invention and benefit are: reduce the decomposition temperature of ammonia on the base metal supported catalyst, improve the use properties (cold start-up is fast) of fuel cell car.Simultaneously, the use of non-noble metal supported catalyzer helps reducing the cost of fuel cell car.
Description of drawings
Accompanying drawing be have the residual protruding well-behaved bright-coloured of line Jiu admire the first ancient piece of jade, round, flat and with a hole in its centre Bu Nuo a kind of thick silk of sculling stretch tight that have eaten one's fill Guang furan of Buddhist nunnery soul badger from ζ Gu loess hills so subcutaneous ulcer food flesh
Among the figure: 1, insulated enclosure material, 2, metal high-voltage discharging electrode, 3, non-noble metal supported catalyzer, 4, reactor shell (double as block media), 5, the heat-insulation and heat-preservation material, 6, wire ground electrode, 7, ceramic sieve plate, 8, splitting gas outlet, 9, grounding wire, 10, ammonia inlet, 11, high voltage power supply.
Embodiment
Be described in detail specific embodiments of the invention below in conjunction with technical scheme and accompanying drawing.
Concrete steps are as follows:
The first step will be according to pack into the region of discharge of reactor of the non-noble metal supported catalyzer of ordinary method preparation, and according to the common way of dielectric barrier discharge reactor is inserted high voltage power supply.
Second step, anhydrous liquid ammonia is drawn through reducing valve from storage tank, and, send into reactor from ammonia inlet 10 through under meter and mediation valve control, with the air in the ammonia metathesis reactor, discharged from splitting gas outlet 8 by metathetical gas.
The 3rd step, high voltage power supply 11 energisings, then by the voltage regulator on the high-voltage power supply, frequency regulator and transformer, ac high-voltage progressively is loaded on the metal high-voltage discharging electrode 2 of reactor, between the metal high-voltage discharging electrode 2 of reactor and metal earthing pole 6, in the presence of block media 4, produces said dielectric barrier discharge (being thread discharge).At this moment, the ammonia that enters reactor has just become plasma gas under the effect of dielectric barrier discharge, meanwhile can be observed temperature of reactor and rises.By the ammonia of plasma bodyization, a part resolves into hydrogen and nitrogen voluntarily, and a part further resolves into hydrogen and nitrogen under the katalysis of catalyzer 3.In this process, high voltage power supply is injected in the electric energy of reactor, and some finally is converted into chemical energy by the activating ammonia molecule, and another part has then become heat energy.In order to stop heat energy dissipation, the outside of reactor shell 4 adopts heat-insulation and heat-preservation material 5 fully adiabatic.Therefore the heat energy that dielectric barrier discharge produced, the ammonia decomposition reaction that a part is absorbed heat consumes, and the part product that is decomposed is taken reactor out of, and remainder makes the reactor heat temperature raising.Along with the rising of temperature of reactor, catalyst activity increases, and the ammonia rates of decomposing and transforming improves, and the caloric receptivity of ammonia decomposition reaction increases, and this makes the heat that is used for the reactor intensification reduce.After producing dielectric barrier discharge, in a single day the initial voltage of transformer sets (setting by the voltage regulator on the high-voltage power supply), and then the actual electric power of high-voltage power supply has just been determined.Under the certain situation of high-voltage power supply actual electric power, also be determined by the power of high-voltage power supply injecting reactor, ammonia rates of decomposing and transforming and temperature of reactor finally can tend towards stability.
In the 4th step, improve the electric power of high-voltage power supply, thereby improve the electric power of injecting reactor, so that obtain high ammonia rates of decomposing and transforming.Can increase the electric power of injecting reactor with the voltage regulator on the electrion power supply 11.After the electric power of injecting reactor improved, the electric energy that reactor obtains increased, so dielectric barrier discharge plasma strengthens the activation of ammonia, and temperature of reactor also increases, and impels the catalytic activity of catalyzer further to improve.Finally, ammonia transformation efficiency and temperature of reactor can be stabilized on the higher level again.
Embodiment 1
6 milliliters of base metal iron catalysts with the alumina supporter load (are expressed as Fe/Al
2O
3) fill in the region of discharge of line cartridge type dielectric barrier discharge plasma reactor, granules of catalyst is irregularly shaped, equivalent diameter is the 1-1.5 millimeter, wherein the activeconstituents charge capacity in elemental iron (Fe) is 10% (weight), all the other are alumina supporter, and the catalyzer equivalent diameter is 0.1-0.17 with the ratio of reactor inside diameter.Reactor shell 4 (block media) is made with hard glass, 1 millimeter of wall thickness, and 9 millimeters of internal diameters, 100 millimeters of region of discharge length, the outer heat-insulation and heat-preservation material 5 of housing adopts asbestos.The metal high-voltage discharging electrode 2 of reactor adopts the common stainless steel silks, 2 millimeters of diameters, and the insulated enclosure between itself and the reactor shell adopts alumina ceramic material.Wire ground electrode 6 is a copper mesh, and passive ceramic sieve plate 7 usefulness alumina-ceramic are made below the beds.Common way according to dielectric barrier discharge inserts high voltage power supply with reactor, then anhydrous liquid ammonia is drawn through reducing valve from storage tank, and through under meter and mediation valve control makes flow velocity reach 40 ml/min, send into reactor from ammonia inlet 10, air in the metathesis reactor is discharged from splitting gas outlet 8 by metathetical gas.Give high voltage power supply 11 energisings, then by the voltage regulator on the high-voltage power supply, frequency regulator and transformer, ac high-voltage progressively is loaded on the metal high-voltage discharging electrode 2 of reactor, between the metal high-voltage discharging electrode 2 of reactor and metal earthing pole 6, in the presence of block media 4, produces said dielectric barrier discharge (being thread discharge).Discharge parameter is set at: 19 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 27 watts, and actual discharge voltage is 11.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 333 ℃, and the ammonia rates of decomposing and transforming reaches 4%.
Repeat embodiment 1, but discharge parameter is set at: 23 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 35.19 watts, and actual discharge voltage is 12.33 kilovolts, and the temperature-stable of stable reaction post-reactor is at 363 ℃, and the ammonia rates of decomposing and transforming reaches 21%.
Repeat embodiment 1, but discharge parameter is set at: 27 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 41 watts, and actual discharge voltage is 12.1 kilovolts, and the temperature-stable of stable reaction post-reactor is at 371 ℃, and the ammonia rates of decomposing and transforming reaches 36%.
Repeat embodiment 1, but discharge parameter is set at: 30 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 43 watts, and actual discharge voltage is 11.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 375 ℃, and the ammonia rates of decomposing and transforming reaches 85%.
Repeat embodiment 1, but discharge parameter is set at: 34 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 46 watts, and actual discharge voltage is 10.7 kilovolts, and the temperature-stable of stable reaction post-reactor is at 388 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
The comparative example 1
Anhydrous liquid ammonia is drawn through reducing valve from storage tank, and through under meter and mediation valve control makes flow velocity reach 40 ml/min, send into the dielectric barrier discharge plasma reactor from ammonia inlet 10, the scantlings of the structure of this reactor is identical with embodiment 1 with material, but does not adorn any catalyzer in the reactor.With the air in the charging ammonia metathesis reactor, discharged from splitting gas outlet 8 by metathetical gas.Give high voltage power supply 11 energisings, then by the voltage regulator on the high-voltage power supply, frequency regulator and transformer, ac high-voltage progressively is loaded on the metal high-voltage discharging electrode 2 of reactor, between the metal high-voltage discharging electrode 2 of reactor and metal earthing pole 6, in the presence of block media 4, produces said dielectric barrier discharge (being thread discharge).Discharge parameter is set at: 38 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 11 watts, and actual discharge voltage is 9.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 381 ℃, and the ammonia rates of decomposing and transforming reaches 2%.
The comparative example 2
Repeat comparative example 1, but discharge parameter is set at: 41 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 25 watts, and actual discharge voltage is 10.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 409 ℃, and the ammonia rates of decomposing and transforming reaches 9%.
The comparative example 3
Repeat comparative example 1, but discharge parameter is set at: 44 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 30 watts, and actual discharge voltage is 11.1 kilovolts, and the temperature-stable of stable reaction post-reactor is at 466 ℃, and the ammonia rates of decomposing and transforming reaches 10%.
The comparative example 4
Repeat comparative example 1, but discharge parameter is set at: 48 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 41 watts, and actual discharge voltage is 11.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 472 ℃, and the ammonia rates of decomposing and transforming reaches 15%.
The comparative example 5
Repeat comparative example 1, but discharge parameter is set at: 51 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 48 watts, and actual discharge voltage is 12.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 504 ℃, and the ammonia rates of decomposing and transforming reaches 18%.
The comparative example 6
Repeat embodiment 1, but remove the external heat-insulation and heat-preservation material 5 of reactor enclosure, and reactor does not connect with high voltage power supply 11 and grounding wire 9, but reactor is inserted in the electrically heated tubular type stove of a routine, and the resistance wire by tube furnace is heated to be reactor provides temperature.That is to say, remove the dielectric barrier discharge function of reactor, make it be equal to traditional fixed-bed reactor fully.Then, when the temperature of given reactor was 375 ℃, the ammonia rates of decomposing and transforming was 1%.
The comparative example 7
Repeat comparative example 6, when still the temperature of given reactor was 400 ℃, then the ammonia rates of decomposing and transforming was 4%.
The comparative example 8
Repeat comparative example 6, when still the temperature of given reactor was 425 ℃, then the ammonia rates of decomposing and transforming was 11%.
The comparative example 9
Repeat comparative example 6, when still the temperature of given reactor was 450 ℃, then the ammonia rates of decomposing and transforming was 29%.
The comparative example 10
Repeat comparative example 6, when still the temperature of given reactor was 475 ℃, then the ammonia rates of decomposing and transforming was 65%.
The comparative example 11
Repeat comparative example 6, when still the temperature of given reactor was 500 ℃, then the ammonia rates of decomposing and transforming was 83%.
The comparative example 12
Repeat comparative example 6, when still the temperature of given reactor was 525 ℃, then the ammonia rates of decomposing and transforming was greater than 99%.
Repeat embodiment 1, but the feed rate of ammonia changes 100 ml/min into, and discharge parameter is set at: 30 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 45 watts, and actual discharge voltage is 11.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 370 ℃, ammonia rates of decomposing and transforming 52%.
Repeat embodiment 1, but the feed rate of ammonia changes 300 ml/min into, and discharge parameter is set at: 30 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 49 watts, and actual discharge voltage is 12.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 366 ℃, ammonia rates of decomposing and transforming 27%.
Embodiment 8
6 milliliters of base metal nickel catalyzators with the alumina supporter load (are expressed as Ni/Al
2O
3) fill in the region of discharge of line cartridge type dielectric barrier discharge plasma reactor, granules of catalyst is spherical, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in elemental nickel (Ni) is 10% (weight), all the other are alumina supporter, and the catalyzer equivalent diameter is 0.1 with the ratio of reactor inside diameter.Reactor shell 4 (block media) is made with hard glass, 1 millimeter of wall thickness, and 9 millimeters of internal diameters, 100 millimeters of region of discharge length, the outer heat-insulation and heat-preservation material 5 of housing adopts asbestos.The metal high-voltage discharging electrode 2 of reactor adopts the common stainless steel silks, 2 millimeters of diameters, and the insulated enclosure between itself and the reactor shell adopts alumina ceramic material.Wire ground electrode 6 is a copper mesh, and passive ceramic sieve plate 7 usefulness alumina-ceramic are made below the beds.Common way according to dielectric barrier discharge inserts high voltage power supply with reactor, then anhydrous liquid ammonia is drawn through reducing valve from storage tank, and through under meter and mediation valve control makes flow velocity reach 40 ml/min, send into reactor from ammonia inlet 10, air in the metathesis reactor is discharged from splitting gas outlet 8 by metathetical gas.Give high voltage power supply 11 energisings, then by the voltage regulator on the high-voltage power supply, frequency regulator and transformer, ac high-voltage progressively is loaded on the metal high-voltage discharging electrode 2 of reactor, between the metal high-voltage discharging electrode 2 of reactor and metal earthing pole 6, in the presence of block media 4, produces said dielectric barrier discharge (being thread discharge).Discharge parameter is set at: 45 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 62 watts, and actual discharge voltage is 11.7 kilovolts, and the temperature-stable of stable reaction post-reactor is at 367 ℃, and the ammonia rates of decomposing and transforming reaches 88%.
Embodiment 9
Repeat embodiment 8, but 6 milliliters of base metal cobalt catalyst with the alumina supporter load of repacking (are expressed as Co/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in element cobalt (Co) is 10% (weight), all the other are alumina supporter.Discharge parameter is set at: 45 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 57 watts, and actual discharge voltage is 11.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 374 ℃, and the ammonia rates of decomposing and transforming reaches 79%.
Repeat embodiment 8, but 6 milliliters of base metal molybdenum catalysts with the alumina supporter load of repacking (are expressed as Mo/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in molybdenum (Mo) is 10% (weight), all the other are alumina supporter.Discharge parameter is set at: 43 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 53 watts, and actual discharge voltage is 10.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 365 ℃, and the ammonia rates of decomposing and transforming reaches 95%.
Repeat embodiment 8, but 6 milliliters of base metal chrome catalysts with the alumina supporter load of repacking (are expressed as Cr/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in elemental chromium (Cr) is 10% (weight), all the other are alumina supporter.Discharge parameter is set at: 50 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 64 watts, and actual discharge voltage is 12.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 417 ℃, and the ammonia rates of decomposing and transforming reaches 96%.
Embodiment 12
Repeat embodiment 8, but 6 milliliters of base metal Mn catalysts with the alumina supporter load of repacking (are expressed as Mn/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in element manganese (Mn) is 10% (weight), all the other are alumina supporter.Discharge parameter is set at: 40 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 48 watts, and actual discharge voltage is 11.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 393 ℃, and the ammonia rates of decomposing and transforming reaches 71%.
Embodiment 13
Repeat embodiment 8, but 6 milliliters of base metal copper catalysts with the alumina supporter load of repacking (are expressed as Cu/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in elemental copper (Cu) is 10% (weight), all the other are alumina supporter.Discharge parameter is set at: 35 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 40 watts, and actual discharge voltage is 11.3 kilovolts, and the temperature-stable of stable reaction post-reactor is at 379 ℃, and the ammonia rates of decomposing and transforming reaches 33%.
Embodiment 14
Repeat embodiment 8, but 6 milliliters of iron nickel bimetal catalyzer with the alumina supporter load of repacking (are expressed as FeNi/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, wherein elemental iron nickel weight ratio Fe: Ni=5: 1, and be 24% (weight) in the activeconstituents charge capacity of elemental iron nickel gross weight, all the other are alumina supporter.Discharge parameter is set at: 35 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 47 watts, and actual discharge voltage is 10.9 kilovolts, and the temperature-stable of stable reaction post-reactor is at 394 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 15
Repeat embodiment 8, but contain iron (Fe), cobalt (Co), nickel (Ni), molybdenum (Mo) in 6 milliliters of alumina load non-precious metal catalysts that load in the reactor simultaneously, granules of catalyst is spherical in shape, 1 millimeter of diameter, Fe: Co: Ni wherein: the ratio of the weight content of Mo element is 1: 1: 1: 1, in the activeconstituents charge capacity of above-mentioned four kinds of element gross weight sums be
16% (weight), all the other are alumina supporter.Discharge parameter is set at: 34 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 45 watts, and actual discharge voltage is 10.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 372 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 16
Repeat embodiment 8, but contain chromium (Cr), manganese (Mn), copper (Cu), tungsten (W) in 6 milliliters of alumina load non-precious metal catalysts that load in the reactor simultaneously, granules of catalyst is spherical in shape, 1 millimeter of diameter, Cr: Mn wherein: the weight content ratio of Cu:W element is 0.5: 1: 1: 8, activeconstituents charge capacity in above-mentioned four kinds of element gross weight sums is 15% (weight), and all the other are alumina supporter.Discharge parameter is set at: 45 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 52 watts, and actual discharge voltage is 10.8 kilovolts, and the temperature-stable of stable reaction post-reactor is at 380 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 17
Repeat embodiment 8, but the iron catalyst of 6 milliliters of alumina loads of filling (is expressed as Fe/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in elemental iron (Fe) is 1% (weight), all the other are alumina supporter.Discharge parameter is set at: 30 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 40 watts, and actual discharge voltage is 12.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 405 ℃, and the ammonia rates of decomposing and transforming reaches 31%.
Embodiment 18
Repeat embodiment 8, but the iron catalyst of 6 milliliters of alumina loads of filling (is expressed as Fe/Al in the reactor
2O
3), granules of catalyst is spherical in shape, 1 millimeter of diameter, and wherein the activeconstituents charge capacity in elemental iron (Fe) is 40% (weight), all the other are alumina supporter.Discharge parameter is set at: 30 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 49 watts, and actual discharge voltage is 10.2 kilovolts, and the temperature-stable of stable reaction post-reactor is at 385 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 19
Repeat embodiment 8, but the iron catalyst (being expressed as Fe/MgO) of 6 milliliters of magnesium oxide loads of filling in the reactor, granules of catalyst is irregularly shaped, equivalent diameter 0.5-1.0 millimeter, the catalyzer equivalent diameter is 0.05-0.1 with the ratio of reactor inside diameter, wherein the activeconstituents charge capacity in elemental iron (Fe) is 10% (weight), and all the other are magnesium oxide carrier.Discharge parameter is set at: 40 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 38 watts, and actual discharge voltage is 11.0 kilovolts, and the temperature-stable of stable reaction post-reactor is at 370 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 20
Repeat embodiment 8, but the iron catalyst (being expressed as Fe/AC) of 6 milliliters of active carbon from coal loads of filling in the reactor, granules of catalyst is irregularly shaped, equivalent diameter 0.5-1.0 millimeter, the catalyzer equivalent diameter is 0.05-0.1 with the ratio of reactor inside diameter, wherein the activeconstituents charge capacity in elemental iron (Fe) is 10% (weight), and all the other are absorbent charcoal carrier.Discharge parameter is set at: 40 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 36 watts, and actual discharge voltage is 11.4 kilovolts, and the temperature-stable of stable reaction post-reactor is at 369 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 21
Repeat embodiment 8, but the iron catalyst (being expressed as Fe/TS-1) of 6 milliliters of silica-based titanium zeolite molecular sieves of filling load in the reactor, granules of catalyst is bar shaped, 1 millimeter of diameter, the catalyzer equivalent diameter is 0.1 with the ratio of reactor inside diameter, wherein the activeconstituents charge capacity in elemental iron (Fe) is 10% (weight), and all the other are silica-based titanium zeolite molecular sieve carrier (Si/Ti=50).Discharge parameter is set at: 37 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 33 watts, and actual discharge voltage is 10.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 394 ℃, and the ammonia rates of decomposing and transforming reaches 92%.
Embodiment 22
6 milliliters of base metal iron catalysts with the alumina supporter load (are expressed as Fe/Al
2O
3) fill in the region of discharge of line cartridge type dielectric barrier discharge plasma reactor, granules of catalyst is irregularly shaped, equivalent diameter is the 1-1.5 millimeter, wherein the activeconstituents charge capacity in elemental iron (Fe) is 10% (weight), all the other are alumina supporter, and the catalyzer equivalent diameter is 0.1-0.17 with the ratio of reactor inside diameter.Reactor shell 4 (block media) is made with silica glass, 1 millimeter of wall thickness, and 9 millimeters of internal diameters, 100 millimeters of region of discharge length, the outer heat-insulation and heat-preservation material 5 of housing adopts asbestos.The metal high-voltage discharging electrode 2 of reactor adopts the common stainless steel silks, 2 millimeters of diameters, and the insulated enclosure between itself and the reactor shell adopts alumina ceramic material.Wire ground electrode 6 is a copper mesh, and passive ceramic sieve plate 7 usefulness alumina-ceramic are made below the beds.Common way according to dielectric barrier discharge inserts high voltage power supply with reactor, then anhydrous liquid ammonia is drawn through reducing valve from storage tank, and through under meter and mediation valve control makes flow velocity reach 40 ml/min, send into reactor from ammonia inlet 10, air in the metathesis reactor is discharged from splitting gas outlet 8 by metathetical gas.Give high voltage power supply 11 energisings, then by the voltage regulator on the high-voltage power supply, frequency regulator and transformer, ac high-voltage progressively is loaded on the metal high-voltage discharging electrode 2 of reactor, between the metal high-voltage discharging electrode 2 of reactor and metal earthing pole 6, in the presence of block media 4, produces said dielectric barrier discharge (being thread discharge).Discharge parameter is set at: 37 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 50 watts, and actual discharge voltage is 10.6 kilovolts, and the temperature-stable of stable reaction post-reactor is at 390 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Embodiment 23
Repeat embodiment 22, but reactor reaction device housing 4 (block media) is made 2.5 millimeters of wall thickness with alumina-ceramic, 8 millimeters of internal diameters, the catalyzer equivalent diameter is 0.1-0.2 with the ratio of reactor inside diameter, 100 millimeters of region of discharge length, and loaded catalyst is 5 milliliters.Discharge parameter is set at: 35 volts of the initial voltages of transformer, discharge frequency 12 kilohertzs.Then high-voltage power supply power reaches 49 watts, and actual discharge voltage is 11.5 kilovolts, and the temperature-stable of stable reaction post-reactor is at 379 ℃, and the ammonia rates of decomposing and transforming is greater than 99%.
Claims (6)
1. the plasma catalyzing process of a preparing hydrogen by ammonia decomposition is characterized in that, ammonia decomposition reaction carries out in the plasma catalytic reactor of a dielectric barrier discharge and the coexistence of non-noble metal supported catalyzer.
2. the plasma catalyzing process of a kind of preparing hydrogen by ammonia decomposition according to claim 1, it is characterized in that, one or more elements in the described non-noble metal supported catalyzer in iron content, cobalt, nickel, chromium, molybdenum, manganese, copper and the tungsten are as the activity of such catalysts composition, and activeconstituents shared weight percent in catalyzer is 0.5-40%.
3. the plasma catalyzing process of a kind of preparing hydrogen by ammonia decomposition according to claim 1, it is characterized in that, the carrier of described non-noble metal supported catalyzer is preferably aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, silica-based zeolite molecular sieve or activated carbon, catalyst particle size is 0.01-0.4 with the ratio of reactor inside diameter, and preferable range is 0.05-0.2.
4. plasma catalytic reactor that is used for the plasma catalyzing process of preparing hydrogen by ammonia decomposition, the housing that it is characterized in that plasma catalytic reactor is cylindric, outside surface at cylinder shell twines paper tinsel, thin slice or the silk screen of the metallic conductor ground-electrode as reactor, is connected with ground wire; End socket is established at the housing two ends, centre hole by upper cover inserts the high-voltage discharging electrode of tinsel as reactor along axis in housing, this tinsel stretches out with ac high voltage source from upper cover and is connected, high-voltage discharging electrode passes through the upper cover place and seals with insulating material, the ammonia inlet is established in the reactor shell upper end, on the lower cover of reactor, establish hydrogen, nitrogen mixed gas outlet, non-noble metal supported catalyzer is loaded on the dielectric barrier discharge district in the reactor, and beds supports with ceramic sieve plate.
5. a kind of plasma catalytic reactor that is used for the plasma catalyzing process of preparing hydrogen by ammonia decomposition according to claim 4, the high-voltage discharging electrode that it is characterized in that described plasma catalytic reactor is made with corrosion resistant metallic substance, and preferred material is a stainless steel.
6. a kind of plasma catalytic reactor that is used for the plasma catalyzing process of preparing hydrogen by ammonia decomposition according to claim 4 is characterized in that the housing of described plasma catalytic reactor is made with alumina-ceramic, hard glass or silica glass.
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