CN102602885A - Method for manufacturing hydrogen in reforming way by catalyst loaded at heat conducting material through utilizing heat of tail gas of heat engine - Google Patents
Method for manufacturing hydrogen in reforming way by catalyst loaded at heat conducting material through utilizing heat of tail gas of heat engine Download PDFInfo
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- CN102602885A CN102602885A CN2012100623075A CN201210062307A CN102602885A CN 102602885 A CN102602885 A CN 102602885A CN 2012100623075 A CN2012100623075 A CN 2012100623075A CN 201210062307 A CN201210062307 A CN 201210062307A CN 102602885 A CN102602885 A CN 102602885A
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Abstract
The invention provides a method for manufacturing hydrogen in a reforming way by utilizing the heat of the tail gas of a heat engine through catalyzing methanol vapor via using a catalyst loaded on a heat conducting material. The technology comprises the following contents that: (1) a methanol vapor reforming catalyst with high activity is prepared at the surface of a heat conducting material by using a method of electrophoretic deposition, and a light and small catalyzing heat exchanger is also assembled by the methanol vapor reforming catalyst and a stainless steel pipe with small diameter; and (2) the mixture of methanol and water is reformed into hydrogen-rich reformed gas by utilizing the heat of the tail gas of a heat engine in the catalyzing heat exchanger, and the reformed gas is also used as the auxiliary fuel of an internal combustion engine.
Description
Technical field
The present invention relates to utilize tail gas of heat engine heat decomposition methyl alcohol and water mixture to prepare the method for hydrogen.Especially the oxide compound that relates to metals such as the Cu that is used in the thermally conductive material area load, Zn, Ce, Zr, Al is a catalyzer, and high-level efficiency is decomposed the heat that the first alcohol and water absorbs tail gas of heat engine simultaneously, prepares the preparation method of hydrogen and dioxide gas.This method can high-level efficiency be utilized the tail gas of heat engine heat, and less to the resistance of exhaust emissions, does not influence hot machine gas flow, utilizes hot machine used heat with less vapour lock.The hydrogen that produces can be utilized as efficient auxiliary fuel by hot machine.
Background technology
Comprise oil engine, steam turbine and gas turbine etc. at hot machine, for the various vehicles and power generation assembly provide power.The heat power efficiency of hot machine is not high: steamer the earliest has only 4-8%; Oil engine comprises that gasoline and oil motor are 25-45%; Power plant's steam turbine about 40%; Gas turbine and steam turbine association system efficient also only have an appointment 60% the most efficiently.The acting circulation of hot machine is limit by carnot's working cycle, and the temperature, pressure and the deflated temperature, pressure difference of acting gas have determined its efficient.The tail gas that hot machine is discharged has been taken away considerable heat and kinetic energy.With the aircraft engine is example, and the heat that mover discharge combustion gas is taken away accounts for the 55-75% (Lian Xiaochun, Wu Hu, aircraft engine principle, P21, first version in 2005) of overall thermal efficiency.Utilize deflated kinetic energy, oil motor and petrol motor have used exhaust turbine pressuring technology to raise the efficiency the minimizing oil consumption now widely.To the heat energy utilization of tail gas, the CN93224414.9 report produces high-temperature steam through heat exchange and gets into the method that mover is raised the efficiency.The CN201110026467 report utilizes exhaust heat-energy with thermoelectric conductor through the method for thermo-electric generation.
Steam reformation of methanol to produce hydrogen is the ripening process that widespread use is gone up in industry.Reactional equation is following: CH
3OH+H
2O → CO
2+ 3H
2, every mole of gaseous methanol of standard state and water are converted into 3 mol of hydrogen and 1 mole of carbon dioxide 49.4 kilojoules of need absorbing heat.If first alcohol and water liquid feeding adds the vaporization heat of water and methyl alcohol, every mole of liquid methanol and water are converted into 3 mol of hydrogen and 1 mole of carbon dioxide 131 kilojoules of need absorbing heat.Methanol steam reforming reacts usually at 250-300 ℃, 1-5MPa, H
20 and CH
3The 0H mol ratio is to carry out under the condition of 1.0-5.0, and the CO by-products content is lower than 5% usually.Reformate gas can get the hydrogen product of different size through scavenging process such as transformation absorption.Catalyst for steam reformation of methanol to produce hydrogen work-ing life can be above 4 years.Reaction unit is usually with fused salt or the abundant heat supply of Electric heating.
Every mole, of methanol combustion heat is 726.55 kilojoules, and the combustion heat of three moles hydrogen is 857.4 kilojoules, differs 131 kilojoules approximately, just in time is that liquid methanol and water are converted into hydrogen institute heat requirement.Through above-mentioned conversion, fuel combustion heat has improved 18%.The exhaust temperature of tail gas of heat engine all surpasses 400 ℃ usually, and the temperature of methanol conversion only needs 300 ℃, the vaporization temperature of first alcohol and water lower (vaporization temperature of water also has only 250 ℃ during 4MP).Obviously the heat of tail gas of heat engine can utilize with the thermo-negative reaction of first alcohol and water reformation hydrogen production, is stored in and obtains in the hydrogen recycling thereby heat energy is converted into chemical energy.Reclaim tail gas heat quantity and can will significantly promote hot machine heat power efficiency.Power-saving technology, 23 (3): 198 (2005) reports reclaim tail gas heat quantity with used heat reforming methanol and turbine compound mode, and complicated huge of high top pressure operation and device are suitable for naval vessel locomotive and stationary power generation.Adopt heating medium such as fused salt and huge reaction unit different with industrial hydrogen production; Car combustion engine tail gas requires the ground discharging of quick low resistance; The catalyticreactor that invests on the tail gas discharging pipe can not be too big, and this just requires to adopt the low high efficiency catalyticreactor of vapour lock.The present invention adopts the shell-and-tube reactor of low vapour lock and invests the surperficial high activated catalyst layer of Stainless Steel Fibre and realizes this goal.
It is the reaction of a strong heat absorption that methanol steam is reformed, and heat must pass to the active catalytic center just can make reaction carry out smoothly.The Cu active site normally is carried on the oxide compounds such as ZnO.These oxide compound thermal conductivity are very poor, need active ingredient and hot gas flow to contact effectively heat and mass fast.Appl. Catal. A, 259:83 (2004) report since powdered catalyst contacted catalytic activity with air-flow high more a lot of than the beaded catalyst of 5-10mm size.But powdered catalyst easy blocking air-flow also is blown away.The present invention is immobilized surperficial in the thermally conductive material Stainless Steel Fibre with catalyst powder, and heat can fully pass to catalytic center, and catalyzer is heated evenly active high, does not also stop up air-flow simultaneously.High catalytic activity makes the reacting replacing heat device can do lessly.
The oil engine of burning hydrogen has had a lot of researchs.If with the fuel mixture air inlet of petrol motor formula, because hydrogen density is little, the combustion heat value of gas mixture is lower than the calorific value of gasoline-air mixture, and rating of engine will obviously descend, and easy tempering of hydrogen and burning in advance.If adopt the cylinder injection fuel under high pressure, then rating of engine is not fallen and tail gas extremely cleans, and does not also have the tempered problem.Hydrogen receives extensive attention as auxiliary fuel.Research shows that if the diesel locomotive of gas-firing adds the hydrogen more than 5% in Sweet natural gas, then the content of oxynitride will reduce greatly in the exhaust emissions.Hydrogen can make oil inflame more abundant as the auxiliary fuel of other fuel oil, and tail gas becomes and more cleans.Hydrogen can be used as the igniter fuel of other fuel owing to inflammable.Spray hydrogen and in high temperature compressed gas, can directly burn, thereby light other fuel oil, therefore spray the sparking plug that the hydrogen mouth can replace oil engine.The pressure that the geseous fuel spray combustion is had relatively high expectations could spray into enough fuel gas in the short period of time.If methyl alcohol steam reformer has elevated pressures, then further to be compressed to the required kinetic energy of spraying pressure just little for reformed gas.But high pressure reaction assembly is expensive heavy usually.The pipe of small dia just can anti-very high pressure with thin tube wall.The stainless steel tube wall thickness 0.5mm normal temperature ability 15MPa pressure of the Φ 3mm external diameter used of gc for example, 400 ℃ of also ability 5MPa.And the heat exchanging pipe of small dia has bigger heat interchanging area.The present invention adopts the elongated tail gas heat exchanging pipe reactor drum of small dia, uses stainless steel tubule bundle to be heat exchanging pipe, and the reaction unit of the working pressure of 3MPa can be done lightly cheaply.
Summary of the invention
The objective of the invention is to utilize high-level efficiency and light little tail gas heat exchange and catalyst reaction device, absorb the heat energy in the tail gas of engine exhaust, the first alcohol and water is converted into the reformed gas of hydrogen and carbonic acid gas.The combustion heat value of reformed gas promotes 18% than methanol feedstock.Hydrogen-rich reformed gas can make other automotive fuel burning more abundant as auxiliary fuel, and tail gas more cleans.
The present invention adopts following technical scheme to achieve the above object:
With a kind of oxide compound active precursor that contains metals such as Cu, Zn, Ce, Zr, Al with the method for electrophoretic deposition (EPD) attached to the Stainless Steel Fibre surface.The Stainless Steel Fibre of supported catalyst inserted by a lot of stainless steel tubules form between the stainless steel tubule of tubular heat exchange.Interchanger is heated to 300 ℃, and the oxide compound that adheres to from interchanger sidewall feeding hydrogen reducing Stainless Steel Fibre then gets high reactivity Cu catalyzer.After reduction is accomplished with the catalysis interchanger be connected to can be vehicle-mounted tail gas heat exchange and methyl alcohol steam reformer.Methyl alcohol and the pressurization of the water mixed liquid body and function pump hot gas heat exchange through coming out after coil pipe and the reformation then.Methyl alcohol after the heating and water mixed liquid body get into catalysis interchanger low-temperature end by sidewall, and the tail gas of heat engine heating that receives to flow through in the stainless steel tubule is vaporized, and heat absorption is reformed and generated hydrogen and carbonic acid gas on the active Cu catalyzer of heat conducting fiber load then.Reformed gas is come out from catalysis interchanger temperature end sidewall opening, with low-temp methanol that passes through in the coil pipe and water mixed liquid body heat exchange cooling.Return the catalysis interchanger to the methyl alcohol and the water sepn of carrying secretly through the gas-liquid separation layer.Reformed gas after the gas-liquid separation mainly contains greater than the hydrogen of 70 vol.% with greater than carbonic acid gas and a small amount of carbon monoxide of 20 vol.%.Device is operated at 3MP, and reformed gas is through gas-holder and further directly be used as auxiliary fuel spray combustion in cylinder of internal-combustion engine after the pressurization.Exhaust gases of internal combustion engines is got in the tubulation pipe that the stainless steel tubule forms by catalysis interchanger one end, and the heat exchange cooling is then discharged by the tubulation the other end.
Specify technical scheme of the present invention at present:
The preparation of the first step catalysis interchanger
The oxide compound active precursor superfine powder of metals such as a kind of Cu of containing, Zn, Ce, Zr, Al is suspended in the Virahol, and polyetherimide (PEI) is as sticker.The stainless fiber beam connection electrodes of heat-conductivity conducting is immersed in the solution, is counter electrode with the stainless steel substrates, at 100V voltage that the oxide compound electrophoretic deposition is surperficial in Stainless Steel Fibre.The deposition for some time after, at the Stainless Steel Fibre surface deposition oxide skin of tens micron thick.Post-depositional fibrous bundle is placed on 500 ℃ of retort furnace roastings.Stainless steel tubule bundle is welded between two end plates,, connects elongated withstand voltage interchanger of formation then with sleeve pipe in the interbank heat conducting fiber that has deposited oxide skin of inserting.Interchanger is heated to 300 ℃, feeds the surperficial oxide compound of 20vol.% hydrogen/nitrogen stream reduction heat conducting fiber from the interchanger sidewall then and get high reactivity Cu catalyzer.After reduction is accomplished catalysis interchanger sealed attachment is arrived tail gas heat exchange methyl alcohol steam reformer.
The second step tail gas heat exchange and the operation of methyl alcohol steam reformation hydrogen production
Catalysis interchanger one end is connected to internal combustion engine air vent, and the tail gas after the heat exchange is discharged from the other end.Methyl alcohol and water mixed solution (methyl alcohol: water=1:1 (mol)) are imported with the high pressure plunger pump pressurization by storage tank.Methyl alcohol and the water mixed solution coil heat exchanger of flowing through earlier, the thermal reforming gas heat exchange of coming out with the catalysis interchanger.Methyl alcohol after the heating and water mixed liquid flow in the sidewall of catalysis interchanger low-temperature end.In the catalysis interchanger; The exhaust gases of internal combustion engines that receives to flow through in the stainless steel tube bank heats; Methyl alcohol and water mixed solution are vaporizated into HP steam earlier, then on the lip-deep active Cu catalyst layer of Stainless Steel Fibre heat absorption to be restructured as hydrogen and carbonic acid gas be the reformed gas of leading.Reformed gas keeps 3MPa.Reformed gas is come out from the sidewall opening of catalysis interchanger temperature end, gets into coil heat exchanger.After low-temp methanol that flows through in the coil pipe and water mixed solution heat exchange cooling, reformed gas is carried out gas-liquid separation through a metallic fibrous layer.The first alcohol and water liquid of carrying secretly flows back to the catalysis interchanger.Reformed gas after the gas-liquid separation is for greater than the hydrogen of 70Vol.% with greater than carbonic acid gas and a small amount of carbon monoxide of 20Vol.%.Reformed gas is through getting into withstand voltage storage tank behind the flow sensor.Storage tank keeps the air pressure of 3MPa.Reformed gas in the storage tank further is pressurized to spraying pressure through oil engine, through solenoid control injecting time and emitted dose, and direct injection cylinder of internal-combustion engine aid burning.The methanol aqueous solution amount that rampump pumps into is controlled by the reformate gas stream quantity sensor, and the logistics quality of coming in and going out keeps equating to make the catalysis interchanger that the situation of liquid flooding or dry combustion method does not take place.During internal combustion engine start, with tail gas the catalysis interchanger is heated up earlier.The methanol aqueous solution that catalysis interchanger temperature end pumps into after being warmed up to more than 300 ℃ again carries out tail gas heat exchange and the operation of methyl alcohol steam reformation hydrogen production.
With prior art, the present invention has following remarkable advantage:
Utilize the method for tail gas of heat engine heat to compare with other, the methyl alcohol steam reforming is converted into chemical energy with heat energy, and it is low to install simple cost, and the hydrogen that is obtained is fine oil engine auxiliary fuel.The present invention's employing is carried on the lip-deep catalyst layer of thermally conductive material and comes the reaction of catalysis methanol steam reforming, and catalyst layer has only tens microns thin heat conduction well to be heated fully.Catalyzer is high more a lot of than conventional particles catalyzer to the catalytic efficiency (of methyl alcohol steam reforming thermo-negative reaction.Therefore catalytic unit can do less be beneficial to vehicle-mounted.The present invention adopts the tail gas heat exchanging pipe reactor drum of small dia, uses thin stainless steel tube to be heat exchanging pipe, and the working pressure of 3MPa, reaction unit are lightly cheap.
Embodiment
Be carried on the reforming catalyst preparation of thermally conductive material: the oxide compound active precursor superfine powder of metals such as a kind of Cu of containing, Zn, Ce, Zr, Al is suspended in (100g/L) in the Virahol, and polyetherimide (PEI) is (1g/L) as sticker.12 microns thin stainless fiber beam connection electrodes is immersed in the solution, is counter electrode with the stainless steel substrates, and flow circulation is stirred oxide compound is not precipitated, 100V voltage with the oxide compound electrophoretic deposition in the stainless steel tube bank.Deposit after 10 minutes, the fibrous bundle that has deposited 30 to 40 micron thick oxide compounds is placed on 500 ℃ of retort furnace roastings 2 hours.Obtain being carried on the active catalyst oxide compound of thermally conductive material.
Embodiment 1: the active testing of thermally conductive material supported catalyst.The Stainless Steel Fibre catalyzer 6 gram catalyzer of load oxide compound are contained in the crystal reaction tube.With the 20vol.% hydrogen/nitrogen stream 300 ℃ of reductase 12s 0 minute.Water vapor and methyl alcohol carry out catalyzed reaction with the charging of 1.2:1 mol ratio at 300 ℃.Water vapor and methanol feeding amount are 60 Grams Per Hours when following, and methyl alcohol can transform fully, and carbon monoxide content is lower than 1 vol.%.The hydrogen incidence reaches 207 milliliters of every gram catalyzer PMs.
The comparative example: the identical cylindrical commodity beaded catalyst that the thick 3mm of 3mm is long 6 grams are contained in crystal reaction tube.With the 20vol.% hydrogen/nitrogen stream 300 ℃ of reductase 12s 0 minute.Water vapor and methyl alcohol carry out catalyzed reaction with the charging of 1.2:1 mol ratio at 300 ℃.Water vapor and methanol feeding amount are 20 Grams Per Hours when following, and methyl alcohol could transform fully.The hydrogen incidence has only 69 milliliters of every gram catalyzer PMs.
Embodiment 2: the assembling and the test of tail gas heat exchange methyl alcohol steam reforming catalysis interchanger: with long 800mm, Φ 76mm external diameter, wall thickness are that the stainless steel tube of 4mm is an outer cover of heat exchanger.Stainless steel tube with 150 Φ 3mm external diameter 0.5mm wall thickness is a heat exchanging pipe.Insert Stainless Steel Fibre catalyzer 600 grams of load oxide compound between tubulation.Heat exchanging pipe connects the graphite flake sealing then with the end plate welding with the outer cover of heat exchanger flange.Respectively there is a side pipe at the heat exchanger shell two ends.Interchanger is heated to 300 ℃ carries out voltage-withstand test earlier, feed the 20vol.% hydrogen/nitrogen stream 300 ℃ of reductase 12s 0 minute from the side pipe normal pressure then with nitrogen heat exchanging device.After the cooling side pipe is connected to a coil heat exchanger.A side pipe is the reformed gas outlet.After the heat exchange of reformed gas process coil pipe, after the gas-liquid separation of the cotton layer of a steel fiber, emit through a Pressure-stabilizing pressure reducing valve and under meter again.Another side pipe is the methanol solution import, links with the outlet of the coil pipe of coil heat exchanger.Methanol aqueous solution injects with a plunger metering pump pressurization, is introduced into the coil pipe of coil heat exchanger, gets into the reaction of catalysis interchanger then.
Test operation carries out in simulation exhaust gases of internal combustion engines condition.1.6 liters of four-stroke internal combustion engine of discharge capacity free air delivery when 2500 change per minute is 1000 liters of per minutes.The airflow of 1000 liters of per minutes is fed a burner, and the feeding geseous fuel is lighted back control fuel quantity is controlled at about 450 ℃ exhaust temperature.Hot gas flow is flowed into from catalysis interchanger one end, flow out from the interchanger the other end through the stainless steel tubulation, catalysis interchanger hot junction is warmed up to more than 300 ℃ very soon.Squeeze into methanol aqueous solution (first alcohol and water mol ratio is 1:1) with plunger metering pump to the heat exchange reformer then.The reformer internal pressure is raised to 3MPa gradually, and stable back reformate gas stream flows out through reducing valve.Reformed gas is with the gas chromatographic analysis of joining TCD.When the methanol aqueous solution amount of pumping into was 80 grams per minutes, the reformed gas air output reached 143 Liter Per Minutes, and wherein hydrogen content is about 74 vol.%, and carbon monoxide is about 1 vol.%.The conversion of hydrogen air output reaches about 9.5 gram/minute.9.5 the combustion heat value of gram hydrogen approximates the combustion heat of 24 gram methane greatly.General 2 liter capacity gasfueled vehicles are about 50 gram/minute in the fuel consumption of 70-80Km/h, so tail gas heat exchange catalytic reforming unit approximately can satisfy the about half of fuel supply of general-utility car.
Claims (7)
1. method of utilizing tail gas of heat engine heat reformation hydrogen production at the thermally conductive material catalyst supported on surface; It is characterized in that comprising following technology contents: (1) utilizes electrophoretic deposition technique; At thermally conductive material surface deposition oxide catalyst thin layer; And being assembled into catalysis interchanger (2) in the catalysis interchanger, methanol aqueous solution and tail gas of heat engine heat exchange absorb the heat vaporization and to be restructured as hydrogen be after main reformed gas (3) is pressurizeed reformed gas with carbonic acid gas absorbing heat on the catalyzer; Spray the entering cylinder of internal-combustion engine as auxiliary fuel, hydrogen-rich reformed gas can be improved combustion in IC engine makes the tail gas cleaning.
2. method according to claim 1; It is characterized in that normally Stainless Steel Fibre of the described thermally conductive material of technology contents (1); Oxide catalyst is generally the superfine powder of the oxide compound of metals such as containing Cu, Zn, Ce, Zr, Al, and its catalytic efficiency (is more much higher than the catalytic efficiency (of traditional beaded catalyst.
3. method according to claim 1 is characterized in that the described catalysis interchanger of technology contents (1) adopts stainless steel tube with small diameter, with thin tube wall higher compressive strength is arranged also, so interchanger can be done gently for a short time and heat interchanging area is big.
4. method according to claim 1, it is characterized in that the described heat of technology contents (2) from the chemical energy that hot machine especially exhaust gases of internal combustion engines is carried out direct heat exchange and tail gas heat quantity is converted into reformed gas to improve the heat power efficiency of oil engine.
5. method according to claim 1 is characterized in that the described reformed gas component of technology contents (2) is for greater than the hydrogen of 70 vol.% and the carbon monoxide that is usually less than 1 vol.% greater than carbonic acid gas and the content of 20 vol.%.
6. method according to claim 1 is characterized in that the described heat exchange temperature of technology contents (2) is 150-400 ℃, and reformed gas pressure remains on 0.1-4MPa.
7. method according to claim 1 is characterized in that the described reformed gas of technology contents (3) can provide the 10-70% of the total fuel combustion calorific value of oil engine, is generally 40-50%; Hydrogen-rich gas is spurted into cylinder of internal-combustion engine ability pilot fuel and is made fuel combustion more complete, and exhaust emissions more cleans.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316703A (en) * | 2019-06-20 | 2019-10-11 | 浙江工业大学 | A kind of self-heating preparing hydrogen by reforming methanol reaction system |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
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| JPH04108601A (en) * | 1990-08-30 | 1992-04-09 | Takuma Sogo Kenkyusho:Kk | Methanol reforming method utilizing waste heat and waste heat recovery-type methanol reformer |
| CN1130594A (en) * | 1995-03-07 | 1996-09-11 | 中国科学院山西煤炭化学研究所 | Industrial productive method for producing hydrogen by catalytic reforming methanol |
| EP1312413A2 (en) * | 2001-11-20 | 2003-05-21 | Mitsubishi Gas Chemical Company, Inc. | Process for producing hydrogen-containing gas |
| CN1654120A (en) * | 2004-02-10 | 2005-08-17 | 中国科学院大连化学物理研究所 | Catalyst used for methanol oxidation oxidizing and reforming hydrogen production and preparation method thereof |
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2012
- 2012-03-12 CN CN2012100623075A patent/CN102602885A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04108601A (en) * | 1990-08-30 | 1992-04-09 | Takuma Sogo Kenkyusho:Kk | Methanol reforming method utilizing waste heat and waste heat recovery-type methanol reformer |
| CN1130594A (en) * | 1995-03-07 | 1996-09-11 | 中国科学院山西煤炭化学研究所 | Industrial productive method for producing hydrogen by catalytic reforming methanol |
| EP1312413A2 (en) * | 2001-11-20 | 2003-05-21 | Mitsubishi Gas Chemical Company, Inc. | Process for producing hydrogen-containing gas |
| CN1654120A (en) * | 2004-02-10 | 2005-08-17 | 中国科学院大连化学物理研究所 | Catalyst used for methanol oxidation oxidizing and reforming hydrogen production and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110316703A (en) * | 2019-06-20 | 2019-10-11 | 浙江工业大学 | A kind of self-heating preparing hydrogen by reforming methanol reaction system |
| CN110316703B (en) * | 2019-06-20 | 2023-11-24 | 浙江工业大学 | Self-heating methanol reforming hydrogen production reaction system |
| CN113336555A (en) * | 2021-06-24 | 2021-09-03 | 浙江大学 | Photocuring type 3D printing manufacturing method of integral SiC-based microreactor |
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Application publication date: 20120725 |