CN101462694A - Miniaturized methanol self-heating reforming hydrogen making integrated apparatus and hydrogen production method - Google Patents
Miniaturized methanol self-heating reforming hydrogen making integrated apparatus and hydrogen production method Download PDFInfo
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- CN101462694A CN101462694A CNA200710159028XA CN200710159028A CN101462694A CN 101462694 A CN101462694 A CN 101462694A CN A200710159028X A CNA200710159028X A CN A200710159028XA CN 200710159028 A CN200710159028 A CN 200710159028A CN 101462694 A CN101462694 A CN 101462694A
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Abstract
The invention relates to a miniaturized hydrogen production integrated device through methanol autothermal reforming and a hydrogen production method. The hydrogen source technology is characterized by integrating main reaction units such as the methanol autothermal reforming and CO selective oxidation (PROX), and only using two stages of the CO selective oxidation without the prior CO water-gas conversion unit; and the hydrogen source integrated system comprises a group of methanol autothermal reforming/heat exchange modules, a group of catalytic combustion/vapourization modules, and two groups of CO selective oxidation/heat exchange modules, wherein the four groups of modules all adopt a welding integration method of an integral catalytic reactor and a microchannel heat exchanger. The device and the method can obtain 1 kW class reformed gas (dry gas) of which CO concentration is less than 30 ppm and H2 concentration is more than 53 percent. The invention is particularly suitable for fuel cell hydrogen source systems in the range of between 100W and 100kW.
Description
Technical field
The present invention relates to methanol self-heating reforming hydrogen manufacturing, the methanol self-heating reforming hydrogen making integrated apparatus of a kind of microminiaturization specifically and hydrogen production process, it is for a kind ofly need not to adopt the CO hydrosphere transformation, only using the microminiaturized hydrogen producing technology of methanol self-heating recapitalization and the integrated system of two-stage CO selective oxidation.H in the dry gas of reformed gas after selective oxidation
2Concentration greater than 53%, CO concentration is less than 30ppm.The present invention is particularly suitable for the fuel cell hydrogen source in 100W-100kW scope, belongs to hydrogen energy source chemical industry and equipment miniaturization technologies field.
Background technology
Fuel cell is the optimal candidate power supply of following electromobile and distributing-supplying-energy system with its effciency of energy transfer height, advantages of environment protection.Fuel cell technology must have suitable fuel, and Proton Exchange Membrane Fuel Cells (PEMFC) is fuel with hydrogen.At present, the on-the-spot hydrogen manufacturing of methyl alcohol is the most real PEMFC hydrogen source.The nineties in 20th century, the PEMFC technology has obtained high speed development, progressively enters the commercialization stage, but hydrogen source technology remains one of bottleneck technology of fuel cell practicability.Compare with sophisticated large-scale industry hydrogen producing technology, no matter move or the dispersive fixed power source, the basic prerequisite of hydrogen source technology practicability is that the hydrogen source system must realize microminiaturization.
Microminiaturized basis is the chemical process reinforcement, relates generally to effective catalyst development, novel reactor and little design of heat exchanger, system capacity step optimization utilization etc. for the hydrogen from methyl alcohol process.
The hydrogen through reforming oxidized methyl alcohol reactive system is usually by oxidation and reformation of methanol reaction, steam conversion, CO selective oxidation, burning/four big subsystems such as vaporization.CO is higher than 3% in the most oxidation and reformation of methanol gas, therefore must CO be removed to through the steam conversion to be lower than 1.5%, through the CO selective oxidation it is removed to be lower than 50ppm again.But the CO steam transformation catalyst that is suitable at present in the small-sized on-the-spot hydrogen generating system is still immature, and this reaction process is subjected to thermodynamic(al)equilibrium control and speed of reaction low, thus the last 1/3 that causes the transform subsystem volume to account for the full response system.
Miniature chemical industry technology is a new research field of rising early 1990s, it study emphatically the space-time characteristic yardstick in hundreds of microns and hundreds of milliseconds micromodule equipment and the feature and the rule of the chemical process in the system.Because yardstick fine, specific surface area increases, surface action strengthens, and flows simultaneously, the end effect of heat transfer and mass transfer is obvious especially, thereby causes transmission effect that tangible enhancing is arranged, and improves the 2-3 order of magnitude than conventional yardstick.Using miniature chemical industry technology can increase substantially the efficient of corresponding system and reduce its volume and weight.The height integrated technology of microchannel reaction system and heat exchange system is the major technique in little chemical system, strengthen the basic and applied research of this respect, to provide the important theory directive function for the microminiaturization that realizes the fuel cell hydrogen source system, thereby quicken the practicalization of fuel cell hydrogen source system.
The hydrogen from methyl alcohol fuel cell hydrogen source is because technology maturation is easy to industrialization most.It is with the PEMFC battery system, as tunnel, bombproof, island, civilian dispersion power station, also is to accelerate PEMFC to move towards key in application.
Existing miniature hydrogen source integrated system, most Sweet natural gases that adopt are made raw material, comprise gas by partial oxidation of natural, CO high temperature and low temperature hydrosphere transformation, CO selective oxidation three parts composition (WO 01/79112A1 in the system; F.Cipiti, et al., J.Power Sources, 2006,157,914-920; S.G.Goebel, et al., Int.J.Hydrog.Energy, 2005,30,953-962; J.Mathiak, et al., J.Power Sources, 2004,131,112-119).Pan etc. (Int.J.Hydrog.Energy, 2006,31,447-454) disclosed integrated system comprises plate-fin heat reformer (PFR) and level Four CO selective oxidation reactor, PFR and plate fin type heat exchanger are used for the steam reformation of methanol to produce hydrogen reaction in one.(USP.835354, B2) described integrated reactor is with CH to United States Patent (USP)
4The ATR reactor place oxidation unit (WGO) inner chamber of the tail gas of discharging by fuel cell, between the inside and outside wall of WGO device around water pipe, the portfire tail gas preheating water pipe that ignites forms along the heat pipe of ATR reactor wall heat of reaction is provided, there are simultaneously many heat pipes to derive the ATR heat again, multistage CO water gas shift reactor and CO selective oxidation reactor are arranged in the WGO chamber simultaneously, all have converter plant to make the gas spiral formula pass through beds.(J.Power Sources, 2006,160,505-509 such as Wang Lai Yoon; 2006,161,1208-1216; 2006,163,119-124) hydrogen making integrated apparatus that supplies 1kW and 2kW fuel cell to use hydrogen source is successively disclosed.Utilize combustion of natural gas as the thermal source preheating evaporator, Sweet natural gas after the desulfurization and H
2O enters that vaporizer is vaporized and preheating is laggard goes into the aqueous vapor reforming reactor, again through high low temperature CO hydrosphere transformation and two-stage CO selective oxidation reaction.Because the gas water steam reformation is a strong endothermic reaction, the system after heat exchange is difficult to keep the required heat of gas water steam reforming, must be constantly from external complement heat energy.
Summary of the invention
One of the technical problem to be solved in the present invention is that oxidation and reformation of methanol and CO selective oxidation are the integrated system of one, reaches the self-circulation that need not outside heat supply; Another technical problem that solves is the CO hydrosphere transformation part in the omission system, only needs two-stage CO selective oxidation just can satisfy fuel cell and uses.
The purpose of this invention is to provide little methanol self-heating reforming hydrogen manufacturing of a kind of compact construction, external form volume and CO selective oxidation in the hydrogen source integrated system of the multikilowatt used in proton exchange membrane fuel cell of one.
To achieve these goals, the present invention adopts technical scheme to be:
A kind of methanol self-heating reforming hydrogen making integrated apparatus of microminiaturization comprises a methanol self-heating recapitalization reactor Rr, combustion reactor Rc and two CO selective oxidation reactor Rp1 and Rp2;
(1) methanol self-heating recapitalization reactor Rr and the integrated reformer unit module of micro-channel heat exchanger Hr (or claiming little interchanger) that realizes the reformed gas heat exchange, contained member of this module and annexation thereof are as follows:
1. be filled with integrally-built methanol self-heating recapitalization catalyzer in the methanol self-heating recapitalization reactor Rr;
2. interchanger Hr is connected on the reforming reactor Rr by flange F1; The side seal board of interchanger Hr is provided with hot-fluid (high temperature reformed gas) inlet E1, it docks with pneumatic outlet E2 on the reforming reactor Rr, the sidewall of interchanger Hr is provided with hot-fluid (high temperature reformed gas after the heat exchange) outlet E10, hot-fluid outlet E10 is through threeway T3 and turn to reversing valve V1 to be connected with atmosphere, and another outlet of threeway T3 is connected via outer pipeline P1 and hot-fluid on the interchanger H1 that the is arranged at reactor Rp1 front end E9 that enters the mouth;
The cold fluid of interchanger Hr (the low temperature reformer feed of having vaporized) inlet E14 is connected with P8 with branch line P7 respectively through threeway T4 by outer pipeline P4;
3. be provided with cold fluid (high temperature reformer feed after the heat exchange) channel outlet E3 at interchanger Hr, outlet E3 passes flanged plate F1 and is connected with the gas distributor D1 that is arranged at reforming reactor Rr inlet region R1; Be provided with spark coil between the micropore of gas distributor D1 and reforming catalyst front end face, spark coil connects external power;
(2) combustion reactor Rc and the integrated fuel element module of little interchanger Hc that realizes combustion heat exchange are used for the vaporization of reformer feed; Contained member of this module and annexation thereof are as follows:
1. combustion reactor Rc, in adorn integrally-built combustioncatalysts
2. R2 place, burner Rc inlet region be provided with gas distributor D2, the external T-shape interface component T1 of gas distributor D2, fuel enter gas distributor D2 after member converges thus;
3. combustion reactor Rc is connected with little interchanger Hc by flange F2; Little interchanger Hc is provided with hot-fluid (high-temp combustion tail gas) inlet E4, it docks with burner outlet E5, the hot-fluid outlet emptying of little interchanger Hc, the cold fluid of little interchanger Hc (being reformer feed) inlet E6 is connected with the outlet E7 of a micro-channel heat exchanger H3 by outer pipeline P2, and the cold fluid outlet E8 of little interchanger Hc is divided into two-way P5 and P6 by outer pipeline P3 through threeway T2 and is connected to a cold fluid on the interchanger H1 sidewall cold fluid on E12 and the interchanger H2 sidewall E18 that enters the mouth that enters the mouth respectively;
The selective oxidation unit module that (3) two CO selective oxidation reactor Rp1 and Rp2 and three little interchanger H1, H2, H3 connect integrated, contained member of this module and annexation thereof are as follows:
1. two CO selective oxidation reactor Rp1, Rp2 inside all are filled with integrally-built Rh base CO selective oxidation catalyzer;
2. micro-channel heat exchanger H1 is affixed with reactor Rp1 by a flanged plate F3 (being that flanged plate is provided with some uniform gas micropores) who has the micropore sparger; The hot-fluid of interchanger H1 inlet E9 is connected with the outlet E10 of interchanger Hr by outer pipeline P1, is provided with perforate E21 in the enter the mouth side of E9 of hot-fluid, and perforate E21 is connected with the airline P10 of first step CO selective oxidation; Hot-fluid outlet E11 is connected with the space interlayer that is arranged at the flanged plate F3 front end that has the micropore sparger, and the space band height is 3～5mm; Cold fluid inlet E12 is connected with interchanger Hc cold fluid outlet E8 through threeway T2 by branch line P5; Cold fluid outlet E13 is connected through the cold medium inlet E14 of threeway T4 and interchanger Hr by branch line P7;
3. micro-channel heat exchanger H2 one side seal board outward flange is welded on reactor Rp1 housing bottom, reactor Rp1 outlet promptly is the hot-fluid inlet E15 of interchanger, side at hot-fluid inlet E15 is provided with perforate E16, and perforate E16 is connected with the airline P9 of second stage CO selective oxidation; Exchanger heat fluid outlet E17 side seal board periphery and a flanged plate F4 integrally welded (being that flanged plate is provided with some uniform gas micropores) who has the micropore sparger, and make the space interlayer that leaves 3～5mm between hot-fluid outlet E17 and distribution hole; Cold fluid inlet E18 is connected with combustion heat-exchange device Hc cold fluid outlet E8 through threeway T2 by branch line P6; Cold fluid outlet E19 is connected with reforming heat exchanger Hr cold fluid inlet E14 through threeway T4 by branch line P8;
4. micro-channel heat exchanger H3 one side seal board outward flange is welded on reactor Rp2 housing bottom, and reactor outlet promptly is that the hot-fluid inlet E20 hot-fluid outlet E23 of interchanger links to each other with extraneous hydrogen feeding pipe road through a switch-valve V2; Corresponding use when switch-valve V2 starts in system with V1, hot-fluid outlet E23 place promptly obtains the rich hydrogen wet basis product gas (moisture) of lower concentration, the cold fluid inlet E22 of interchanger H3 is as the initial inlet of reformation mixing raw material, extraneous air and methanol aqueous solution enter system thus, and cold fluid outlet E7 is connected with combustion heat-exchange device Hc cold fluid inlet E6 by outer pipeline P2.
Described reforming reactor, combustion reactor and CO selective oxidation reactor are the catalyticreactor of one-piece construction formula, can the side's of being body or right cylinder surface structure.
This hydrogen source integrated system does not contain the pilot process unit of CO hydrosphere transformation; CO selective oxidation reactor adopts the two-stage series connection combination; But described reforming reactor, combustion reactor and selective oxidation reactor volume fuel cell output rating situation design by the standard of 150～350ml/kW, and its inner body catalyst volume designs by 40～70% of reactor volume; Interchanger is stainless steel or aluminium is the micro-channel heat exchanger of material, each interchanger is cross layered by 20～40 microchannel plates, seal with the vacuum diffusion welding connection technology, every microchannel thickness of slab is 0.3～1.0mm, generally between 0.2～1.0mm, the reactor size on interchanger size and the corresponding module adapts the passage hydraulic diameter; The necessary stainless steel tube connecting pipeline of fluid flow P1～P10 for reducing the pipeline resistance to flow, adopts Φ 6 stainless steel tubes;
Start the spark coil of reforming reaction, in the middle of reformation sparger micropore and reforming catalyst, this spark coil is a resistance wire, and its electric current input is by a low-voltage transformer control, the about 5～10V of input voltage, the about 40～100W of power input;
Be provided with the gas micrometering valve V5 that is used to distribute two-stage CO selective oxidation amount of oxygen at the airline P9 of second stage CO selective oxidation.
Adopt the hydrogen production process of the methanol self-heating reforming hydrogen making integrated apparatus of described microminiaturization:
(1) hydrogen manufacturing operation: the multicomponent of packing in reforming reactor non-precious metal catalyst (Pat.No.CN 1760115), mol ratio is O
2/ H
2O/CH
3The reformer feed of OH=0.19～0.23:1.2:1 through little interchanger H3, Hc, H1, H2, Hr heat exchange and vaporization, sprays into the reformation catalytic bed by reformer front end gas distributor (D1) successively; Under the of short duration ignition condition of lighter for ignition, start the reformation catalyzed reaction, produce the high temperature hydrogen-rich reformed gas;
(2) CO cleaning section: CO selective oxidation catalyzer adopts Rh/K/ γ-Al
2O
3(Pat.No.CN 1508233A), the CO volumetric concentration that contains that is produced by the hydrogen manufacturing operation is about 0.9～1.3% high temperature reformed gas and goes into to select oxidation module front end interchanger H1 by reforming heat exchanger Hr is laggard, and purify air ingress and first section and to converge, enter the Rp1 reaction zone by the micro-pore plate type sparger on the flange F3, flow into little interchanger H2 successively again and converge through the orifice plate sparger and enter the Rp2 reaction zone with two sections air, obtain the hydrogen rich gas (wet basis) of extremely low concentration CO at last via little interchanger H3 heat exchange, further the condensation dehydration obtains the butt hydrogen-rich gas, here the total oxygen demand of two sections air is 1.0～1.5 times of CO total amount in the reformed gas, and first section partition ratio with second section is 2:1～5:1;
(3) burning/vaporization process: combustioncatalysts adopts 0.5 ‰ Pt/ γ-Al
2O
3, be fuel with pure methyl alcohol or reformation tail gas or hydrogen, air is an oxygenant, the oxygen amount feeds than 0.5-0.7:1 by excessive slightly mole metering when being fuel with hydrogen, if be that fuel compares charging by the 1.7-2.5:1 molar weight with methyl alcohol; Liquid or geseous fuel and Air mixing material enter the combustioncatalysts bed by T-shape member T1, natural starting catalyst combustion reaction under the room temperature, the hot-fluid that produces directly enters the Hc interchanger on the integration module, the cold raw material of reforming is vaporized on interchanger Hc, and combustion tail gas is discharged after heat exchange.
Described hydrogen production process is when ignition trigger, and system outlet is closed, and V2 ends, and reformate gas stream does not enter selective oxidation/heat exchange module, but places the emptying position earlier, and V1 is open-minded, and reformate gas stream just switches in the system when treating that reforming reaction is stablized.
Described CO selective oxidation section air distributes the two-way flow by a mass flow controller control total amount by the aciculiform micrometering valve that is positioned on the low resistance pipeline P9.
Hydrogen source of the present invention has following domestic and international leading technology advantage:
1, used a kind of base metal reforming catalyst of multicomponent, this catalyzer oxidation and reformation of methanol transformation efficiency 100%, the reformed gas hydrogen concentration reaches 60%, and CO concentration is lower than 1.4%, and by 1000 hours stability tests.
2, used the precious metal Rh of a kind of highly selective, low temperature high activity, high stability catalyst based, this catalyzer in the time of 140～180 ℃ the CO transformation efficiency greater than 98%, and to H
2The methanation and the selection rate of deep oxidation almost nil.
3, because of CO concentration in the reformed gas is lower than 1.4%, thereby hydrogen source of the present invention does not have the subprocess of CO hydrosphere transformation.
4, because of using the CO selective oxidation catalyzer of independent development, the CO transformation efficiency is greater than 98%, and CO concentration is lower than 1.4% in the reformed gas, so hydrogen source of the present invention adopts two-stage CO purification process.
5, used micro-channel heat exchanger equipment with high heat-transfer performance.
6, monolith honeycomb reactor and the integrated mode of connection of micro-channel heat exchanger height, and be modular construction, for convenience detach and installation.
7, Zui You system integration scheme and hydrogen producing technology scheme truly realize the cascade utilization of energy.
8, the use of simple annex is simplified and is easy to and controls.
Description of drawings
Fig. 1 is reforming catalyst stability test in 1000 hours in the hydrogen source system; O
2/ CH
3OH=0.3, H
2O/CH
3OH=1.2 (molar ratio), GHSV=3850h
-1, control temperatureT=280 ℃;
Fig. 2 is that the hydrogen source integrated system starts totally 90 hours life experiment results 10 times; O
2/ CH
3OH=0.224, O
2/ CO=1.18～1.50;
Fig. 3 is methanol self-heating recapitalization and CO selective oxidation integrated system wiring layout.
Fig. 4 is methanol self-heating recapitalization and CO selective oxidation integrated system schema.
Embodiment
Below in conjunction with accompanying drawing enforcement of the present invention is described in detail.
The present invention proposes a kind of integrated system and is applicable to the hydrogen producing technology scheme of this system.This system comprises one group of reformation/heat exchange, one group of fuel combustion/vaporization, two groups of four modular structure unit that CO selective oxidation/heat exchange is integrated, and four modular structure unit are whole catalyticreactor and are connected with the integrated mode of micro-channel heat exchanger.The hydrogen producing technology scheme that is applicable to this system comprises the hydrogen through reforming oxidized methyl alcohol process, the CO two step selective oxidation processes in the reformed gas, the process of carrying out the step heat exchange in fuel combustion/vaporescence and the reformer feed interchanger in each process unit.
1, integrated system.A kind of unitary microminiaturized hydrogen source such as methanol self-heating recapitalization, CO selective oxidation and burning/vaporization system that is integrated with comprises the following modules structure:
(1), methanol self-heating recapitalization reactor Rr and the integrated reformer unit module of little interchanger Hr that realizes the reformed gas heat exchange, contained member of this module and annexation thereof are as follows:
1. methanol self-heating recapitalization reactor Rr, in adorn integrally-built methanol self-heating recapitalization catalyzer.
2. one is connected micro-channel heat exchanger Hr on the reforming reactor by flange F1, hot-fluid on interchanger Hr one side seal board (high temperature reformed gas) inlet E1 butt joint reformer outlet E2, hot-fluid (high temperature reformed gas after the heat exchange) outlet E10 turns to reversing valve V1 or is connected to interchanger H1 hot-fluid inlet E9 by outer pipeline P1 through threeway member T3; The cold fluid of interchanger Hr (the low temperature reformer feed of having vaporized) inlet E14 is connected with P8 with branch line P7 through threeway member T4 by outer pipeline P4.
3. a gas distributor D1 who is connected interchanger Hr cold fluid (the high temperature reformer feed after the heat exchange) channel outlet E3 passes the inlet region R1 that flanged plate F1 is arranged on reformer.
4. spark coil that is arranged on R1 middle part, reformer inlet region, spark coil is between sparger micropore and reforming catalyst front end face.
(2), combustion reactor Rc and one realizes that the integrated fuel element module of little interchanger Hc of combustion heat exchange is used for the preheating and the vaporization of methanol recapitalization raw material, contained member of this module and annexation thereof are as follows:
1. combustion reactor Rc, in adorn integrally-built combustioncatalysts.
2. gas distributor D2 who is arranged on R2 place, burner Rc inlet region, an external T-shape interface component T1, fuel enters gas distributor D2 after this member converges.
3. one is connected micro-channel heat exchanger Hc on the combustion reactor, the hot-fluid of interchanger (high-temp combustion tail gas) inlet E4 butt joint burner outlet E5, hot-fluid outlet emptying by flange F2; Cold fluid (being reformer feed) inlet E6 is connected with interchanger H3 outlet E7 by outer pipeline P2, and cold fluid exports E8 and is divided into two-way P5 and P6 is connected to interchanger H1 and interchanger H2 by outer pipeline P3 through threeway member T2.
(3), two CO selective oxidation reactor Rp1, Rp2 and three little interchanger H1, H2, H3 connect the selective oxidation unit module integrated, contained member of this module and annexation thereof are as follows:
1. two CO selective oxidation reactor Rp1, Rp2, in adorn integrally-built Rh base CO selective oxidation catalyzer.
2. micro-channel heat exchanger H1 is welded on the flanged plate F3 that has the micropore sparger, exchanger heat fluid intake E9 is connected with the outlet E10 of interchanger Hr by outer pipeline P1, connect the airline P10 of first step selective oxidation at the interchanger radial edges one side hole E21 of vertical this inlet, hot-fluid outlet E11 and have the space interlayer that leaves 3～5mm between the flanged plate F3 of micropore sparger; Cold fluid inlet E12 is connected with interchanger Hc cold fluid outlet E8 through threeway member T2 by branch line P5; Cold fluid outlet E13 is connected through the cold medium inlet E14 of threeway member T4 and interchanger Hr by branch line P7.
3. flanged plate F3, F4 are provided with some uniform gas micropores.
4. micro-channel heat exchanger H2 one side seal board outward flange is welded on reactor Rp1 housing bottom, reactor outlet promptly is the hot-fluid inlet E15 of interchanger, the airline P9 that connects two sections selective oxidations at the interchanger radial edges one side hole E16 of vertical this inlet, exchanger heat fluid outlet E17 side seal board periphery is integrally welded with the flanged plate F4 that has the micropore sparger, and makes the space interlayer that leaves 3～5mm between outlet and distribution hole; Cold fluid inlet E18 is connected with combustion heat-exchange device Hc cold fluid outlet E8 through threeway member T2 by branch line P6; Cold fluid outlet E19 is connected with reforming heat exchanger Hr cold fluid inlet E14 through threeway member T4 by branch line P8.
5. micro-channel heat exchanger H3 one side seal board outward flange is welded on reactor Rp2 housing bottom, reactor outlet promptly is the hot-fluid inlet E20 of interchanger, hot-fluid outlet E23 connects a switch-valve V2, corresponding use when switch-valve V2 starts in system with V1, hot-fluid outlet E23 place promptly obtains the rich hydrogen wet basis product gas (moisture) of lower concentration, the cold fluid inlet E22 of interchanger H3 is as the initial inlet of reformation mixing raw material, air and methanol aqueous solution enter system thus, and cold fluid outlet E7 is connected with combustion heat-exchange device Hc cold fluid inlet E6 by outer pipeline P2.
By the miniature hydrogen source system that above member is formed, wherein said reforming reactor, combustion reactor and CO selective oxidation reactor are integrally-built catalyticreactor, can the side's of being body or right cylinder surface structure.But reactor volume fuel cell output rating is by 150～350ml/kW design, and its inner body catalyst volume designs by 40～70% of reactor volume.
Described whole interchanger is the stainless steel micro-channel heat exchanger, relates to cryogenic material heat exchange and also can adopt the little interchanger of aluminum.Each interchanger is cross layered by 20～40 microchannel plate bundles, the chemical etching method technology of preparing is adopted in the microchannel, seal with the vacuum diffusion welding connection technology, every microchannel thickness of slab is 0.3～1.0mm, the passage hydraulic diameter is about 0.2～1.0mm, interchanger size adapts to the reactor size on the corresponding module, simultaneously in order to make system architecture compacter, and integrated little interchanger on reformer, burner, oxidation reactor respectively; An inlet mouth of little interchanger can be used as the outlet of reactor, and a side seal board of little interchanger is as a structural plane of reactor in other words, and the shrouding periphery is provided with flange hole ligation device and interchanger.
Be the miniature hydrogen source system that adapts to that kW level fuel cell of the present invention uses, the concrete enforcement of the operating parameters of reactor and little interchanger shown as table 1.
System of the present invention also comprises some indispensable annexes: the gas distributor that 1. is arranged on each reactor front end except above-mentioned reactor and little interchanger; 2. start the spark coil of reforming reaction, in the middle of reformation sparger micropore and reforming catalyst, this spark coil is a resistance wire, and its electric current input is by a low-voltage transformer control, the about 5～10V of input voltage, the about 40～100W of power input; 3. the necessary stainless steel tube connecting pipeline of fluid flow P1～P10 for reducing the pipeline resistance to flow, adopts Φ 6 stainless steel tubes; 4. be used to control the valve member V1 and the V2 of reformate gas stream flow direction when starting, be located between reformation module and the cleaning module respectively and system general export place; 5. be used to distribute the gas micrometering valve V5 of two sections CO selective oxidation amount of oxygen, be located on the air branch road of second stage selective oxidation.
2, the process for making hydrogen of the microminiaturization of a kind of integrated methanol self-heating recapitalization and CO selective oxidation comprises the following steps:
(1), hydrogen manufacturing operation: the reformer feed that is pre-mixed is successively through little interchanger H3, Hc, H1, H2, Hr heat exchange and vaporization, D1 sprays into the reformation catalytic bed by reformer front end gas distributor, under the of short duration ignition condition of lighter for ignition, start the reformation catalyzed reaction, produce the high temperature hydrogen-rich reformed gas.
(2), CO cleaning section: after containing the CO volumetric concentration and being about 0.9～1.3% hydrogen-rich reformed gas and exchanging the part heat by reforming heat exchanger Hr, enter the front end interchanger H1 of two sections selective oxidation modules, and purify air in ingress and the first step and to converge, enter the Rp1 reaction zone by the micro-pore plate type sparger on the flange F3, flow into H2 successively again and converge through the orifice plate sparger and enter the Rp2 reaction zone with second stage air, obtaining CO concentration via the H3 heat exchange at last is the hydrogen rich gas (wet basis) of ppm level, and further the condensation dehydration obtains butt hydrogen-rich gas (dry gas).
(3), burning/vaporization process: fuel and air enter the micropore sparger by ' T ' type member T1, then enter the combustioncatalysts bed, this catalyzer can start catalyst combustion reaction under room temperature, the hot-fluid that produces directly enters the Hc interchanger on the integration module, reformer feed is vaporized on interchanger Hc, and combustion tail gas is discharged after heat exchange.
Hydrogen producing technology scheme proposed by the invention, the proportioning of the mixing raw material of wherein reforming is: oxygen/methyl alcohol is 0.19～0.23:1.2:1 (mol ratio); The required total amount of oxygen of CO selective oxidation is 1.0～1.5 times of CO total amount in the reformed gas, and amount of oxygen is 2:1～5:1 in the first step and partial partition ratio; Burner fuel can be pure methyl alcohol, also can be reformation tail gas or hydrogen, the requisite oxygen amount when being fuel with hydrogen by excessive slightly metering ratio 0.5-0.7:1, as being that fuel compares charging by the 1.7-2.5:1 molar weight with methyl alcohol.
The methanol recapitalization reaction is the CO that steam reforming or oxidation and reformation all can produce different concns.The CO concentration that produces when reforming reaction is greater than 2%, the fuel processor system just needs the aqueous vapor change reaction (WGS) of CO that CO concentration is reduced to below 1.5%, and then through CO selective oxidation (PROX) reaction purification hydrogen-rich reformed gas, otherwise only depend on H in the PROX process reformed gas
2With mass consumption, or reduce H because of dilution effect
2Therefore concentration increase the complicacy that the WGS unit will cause the hydrogen source system again.One of gordian technique of this invention is the exploitation of reforming catalyst and cleaning catalyst, and at first CO concentration is lower than 1.4% in the ATR reaction reformed gas, and secondly the CO transformation efficiency is higher than 95% in the PROX process, thus can direct integrated ATR and PROX process.Hydrogen producing technology scheme proposed by the invention, the one-piece construction catalyzer adopts the catalyzer of independent development development, and wherein integrally-built methanol self-heating recapitalization catalyzer adopts Ce-Zr/Zn-Cr/ γ-Al
2O
3(Pat.No.CN 1760115), CO selective oxidation catalyzer adopts Rh/K/ γ-Al
2O
3(Pat.No.CN1508233A), combustioncatalysts adopts 0.5 ‰ Pt/ γ-Al
2O
3
The present invention also proposes at the integrated system intermodule two airflow-reversing valve V1 and V2 that use when supplying system to start to be set, and is located between reformation module and the cleaning module respectively and system general export place.The reason of arranging reversing valve is: in the methanol self-heating recapitalization reaction start-up course, because of system self thermal equilibrium needs a steady time, unreacted like this reformer feed can enter into CO selective oxidation catalytic bed with reformed gas, catalyzer in this bed is that Rh is catalyst based, and CO and CO very easily take place
2Methanation reaction, because of CO
2Concentration is up to 20%, CO
2Methanation reaction is emitted big calorimetric, causes the selective oxidation catalyst deactivation.For avoiding this phenomenon to take place, during ignition trigger with port closing (V2 by), the reformation hot gas flow selective oxidation catalytic bed of directly not flowing through, but by the direct emptying of reversing valve V1, reformate gas stream just switches in the system when treating that reforming reaction is stablized, and promptly V1 ends, and V2 is open-minded.
The present invention is for simplifying the external control number of devices, and only adopt two sections CO selective oxidation processes, thereby the two-step purification air establishes mass flow controller control output total amount, establishes the aciculiform micrometering valve on the second stage that is positioned at low resistance point purifies air inlet ductwork, with distribution two-way flow size.
The present invention has adopted the multicomponent non-precious metal catalyst that a kind of hydrogen through reforming oxidized methyl alcohol with one-piece construction formula of good catalytic activity and highly selective, good thermostability uses, and (Pat.No.CN 1760115, methanol conversion is near 100%, so this process has been exempted CO steam varitron process CO concentration＜1.4% in the reformed gas) and CO selective oxidation catalyzer.Little heat transfer technology has been adopted in this invention simultaneously, this not only improves the integrated level of hydrogen source system and the capability of fast response of system, promote the practicalization of PEMFC on-board hydrogen source system, also will improve the integrated level and the utilization efficiency of energy of ground hydrogen generating system simultaneously.
The present invention adopts the technological line of oxidation and reformation of methanol reaction (formula (1)), leads not as good as methanol steam reforming reaction (formula (2)) although it produces H2.But can on a kind of catalyzer, realize the heat balance of the thermo-negative reaction process that the thermopositive reaction of methyl alcohol partial oxidation and methanol steam are reformed and energizing quantity outside need not reaches self-heating recapitalization.But so the quick startup of realization response system and the demand of variable load.
CH
3OH+βO
2+(1-2β)H
2O→(3-2β)H
2+CO
2 (1)
CH
3OH+H
2O→3H
2+CO
2 (2)
Fig. 3 is the unitary miniature hydrogen source of integrated methanol self-heating recapitalization, CO selective oxidation, burning/vaporization etc. a provided by the invention system wiring layout.Dotted line is four modules (M1～4) of system of the present invention among the figure, the M1 module is integrated oxidation and reformation of methanol monolith honeycomb reactor and cuboid micro-channel heat exchanger, the fire coil of setting up an office in the inlet region of reforming reactor, and on the spark coil opposite that is outlet side establish the thermocouple hole, to detect reformation catalytic bed temperature, check point is located at 2～5mm place, reforming catalyst front end face inboard.The M2 module is integrated catalytic burning integral type reactor and cuboid micro-channel heat exchanger, the retention point fire coil interface only in the inlet region of combustion reactor, establishing the measurement thermocouple in combustioncatalysts front end face inboard equally, is not to be connected on the interchanger but directly to be connected with a three-way piece T1 with the fuel distribution device that is not both of M1 module maximum.M3 and M4 module purify part for the CO selective oxidation, two modules all are welded to form by a monolith honeycomb reactor and a micro-channel heat exchanger, connect by flange, the temperature detecting point of monolith honeycomb reactor is located at 2～5mm position, catalyst center front end inboard, the thermocouple perforate is on reactor top radially, the radial edges perforate E16 of integrated micro-channel heat exchanger H2 feeds two sections oxygen that oxidizing reaction is required on module M3, is bearing heat exchanging process between low temperature purification reformed gas and reformation mixing raw material as the end heat exchanger of system at micro-channel heat exchanger integrated on the module M4.And establish an independently interchanger on the top of M3 module, this interchanger has three and greatly system has been moved critical effect, the one, further reduce the reformed gas temperature, the 2nd, make the reformed gas and the air thorough mixing that enter first step cleaner, the 3rd, the board-like sparger of flange hole that is integrated on this interchanger makes first step cleaning catalyst effectively utilize (evidence suggests that first step decontamination effect improving plays a decisive role to system), thereby can not think simply that this interchanger and reforming heat exchanger can be merged into an interchanger, also are related to the thermal capacity problem of interchanger here.Two nodes in addition that operation plays an important role to system among the figure merit attention, the one, on the connecting pipeline between separate exchangers H1 and reforming heat exchanger, this pipeline is provided with a bypass delivery valve, another is the access tube at interchanger H2 air intlet E16 place, know that by fluid flow principals the static pressure at E16 place is lower than the static pressure at interchanger H1 air intlet E21 place, thereby the distribution variable valve of air is located on the access tube at E16 place.
Technical process (seeing accompanying drawing 4) according to integrated system of the present invention is further described the application.
Fig. 4 is the annexation and the process flow sheet of system of the present invention.The reformation mixing raw material earlier enters combustion heat-exchange device Hc after end heat exchanger H3 heat exchange, be divided into two fluid streams then and merge after H1 and H2 heat exchange and enter reforming heat exchanger Hr, enters autothermal reforming reaction device Rr reaction generation high temperature reformed gas at last.High temperature reformed gas enters the front end interchanger H1 of two sections selective oxidation modules after by integrated reforming heat exchanger Hr on it, and purify air ingress and first section and to converge, enter CO selective oxidation beds Rp1 by the orifice plate sparger on the flange, enter little interchanger H2 more successively and converge and enter Rp2 with two sections air, after little interchanger H3 heat exchange gets the hydrogen rich gas of lesser temps, further the condensation dehydration obtains butt hydrogen-rich gas (dry gas).Pure methyl alcohol of fuel on the burning/interchanger module and air enter the micropore sparger by ' T ' type inlet, enter into the combustioncatalysts bed then and begin reaction, and the hot-fluid of generation directly enters integrated little interchanger Hc on it, emptying after the heat exchange.
Fuel methanol (GHSV=1200～1700h
-1) by valve V4 and air ' 3 ' (O
2/ CH
3OH mol ratio 1.5～2.0) feed catalytic combustion reactor Rc under the room temperature, when the bed temperature of combustioncatalysts is begun to rise by room temperature, show the burner natural starting, the hot gas flow after the burning enters combustion heat-exchange device gasifying reforming raw material.When purifying the reaction generation, the methyl alcohol gas hourly space velocity in the burner can be reduced and be low to moderate 400～650h
-1
Open reformation lighter for ignition N1 (18V, 4A) power supply feeds system with the reformer feed methanol aqueous solution with air ' 4 ' simultaneously, and both amounts can be controlled at 5～10ml/min (liq.) and 5～8L/min (gas) respectively during igniting, the methyl alcohol gas hourly space velocity is lower when promptly lighting a fire, about 800～1500h
-1, open reversing valve V1 and shut-off valve V2, the reformation hot gas flow that makes ignition process is by the direct emptying of valve V1.When reforming temperature reaches more than 300 ℃, close lighter for ignition, regulate reformed oxygen quantity rapidly, keep reforming temperature after moving 5～10 minutes under 480～550 ℃, strengthen reformer feed inlet amount and air capacity, adjust suitable oxygen-methanol ratio (0.3 → 0.2) from high to low gradually.Reformer methyl alcohol gas hourly space velocity during steady state is 2300～4000h
-1, the reformation core temperature is 480～520 ℃, H in the system outlet dry gas
2～60%, main by product CO is 1.0～1.3vol%.
When the reformation catalyzed reaction was stablized, valve V2 opened, and reversing valve V1 closes, and behind high temperature reformed gas process reforming heat exchanger Hr, the separate exchangers H1, entered clean unit.Regulate needle valve V5 and distribute two sections purify air (1) and (2), control total O
2/ CO mol ratio is kept Rp1 and Rp2 inner catalyst temperature between 160～220 ℃ between 1.0～1.5.
Example is to realize in the miniature hydrogen source system that uses according to the 1kW fuel cell.Each unit volume of system and processing parameter such as following table:
Each reactor, little interchanger, catalyzer and processing parameter in the miniature hydrogen source of the subordinate list 1 1kW system
Reformed gas is formed (vol%): H
259～60%, 1.0% ≦ CO ≦ 1.3%, experimental result is illustrated by subordinate list 2 on the integrated system.
The above; only be the embodiment among the present invention; but protection scope of the present invention is not limited thereto; anyly be familiar with the people of this technology in the disclosed technical scope of the present invention; can understand conversion or the replacement expected; all should be encompassed in of the present invention comprising within the scope, therefore, protection scope of the present invention should be as the criterion with the protection domain of claims.
Claims (10)
1, a kind of methanol self-heating reforming hydrogen making integrated apparatus of microminiaturization comprises a methanol self-heating recapitalization reactor (Rr), a combustion reactor (Rc) and two CO selective oxidation reactors (Rp1 and Rp2), it is characterized in that:
(1) a methanol self-heating recapitalization reactor (Rr) and an integrated reformer unit module of micro-channel heat exchanger (Hr) that realizes the reformed gas heat exchange, contained member of this module and annexation thereof are as follows:
1. be filled with integrally-built methanol self-heating recapitalization catalyzer in the methanol self-heating recapitalization reactor (Rr);
2. interchanger (Hr) is connected on the reforming reactor (Rr) by flange (F1); One side seal board of interchanger (Hr) is provided with hot-fluid inlet (E1), it docks with pneumatic outlet (E2) on the reforming reactor (Rr), the sidewall of interchanger (Hr) is provided with hot-fluid outlet (E10), hot-fluid outlet (E10) turns to reversing valve (V1) to communicate with atmosphere through threeway (T3) a tunnel, another outlet of threeway (T3) by outer pipeline (P1) and hot-fluid on the interchanger (H1) that is arranged at reactor (Rp1) front end enter the mouth (E9) be connected;
The cold fluid of interchanger (Hr) is gone into (E14) and is connected with (P8) with branch line (P7) respectively through threeway (T4) by outer pipeline (P4);
3. be provided with cold fluid pass outlet (E3) at interchanger (Hr),, and place reforming reactor (Rr) inlet region (R1) at outlet (E3) cover welded tube formula gas distributor (D1); Be provided with spark coil between the micropore of gas distributor (D1) and reforming catalyst front end face, spark coil connects external power;
(2) combustion reactor (Rc) and an integrated fuel element module of little interchanger (Hc) that realizes combustion heat exchange are used for the vaporization of reformer feed; Contained member of this module and annexation thereof are as follows:
1. combustion reactor (Rc), in adorn integrally-built combustioncatalysts;
2. locate to be provided with a gas distributor (D2) in burner (Rc) inlet region (R2), the external T-shape mouthpiece (T1) of gas distributor (D2), fuel enters gas distributor (D2) after member converges thus;
3. combustion reactor (Rc) is connected with little interchanger (Hc) by flange (F2); Little interchanger (Hc) is provided with hot-fluid inlet (E4), it docks with burner outlet (E5), the hot-fluid outlet emptying of little interchanger (Hc), the cold fluid of little interchanger (Hc) inlet (E6) is connected with the outlet (E7) of micro-channel heat exchanger (H3) by outer pipeline (P2), the cold fluid outlet (E8) of little interchanger (Hc) by outer pipeline (P3) through threeway (T2) be divided into two-way (P5) and (P6) be connected to respectively that cold fluid on interchanger (H1) sidewall enters the mouth (E12) and interchanger (H2) sidewall on cold fluid enter the mouth (E18);
The selective oxidation unit module that (3) two CO selective oxidation reactors (Rp1 and Rp2) and three little interchanger (H1, H2, H3) are connected integrated, contained member of this module and annexation thereof are as follows:
1. integrally-built Rh base CO selective oxidation catalyzer is all loaded in two CO selective oxidation reactors (Rp1, Rp2) inside;
2. micro-channel heat exchanger (H1) is affixed with reactor (Rp1) by a flanged plate (F3) that has the micropore sparger; The hot-fluid inlet (E9) of interchanger (H1) is connected with the outlet (E10) of interchanger (Hr) by outer pipeline (P1), side at hot-fluid inlet (E9) is provided with perforate (E21), and perforate (E21) is connected with the airline (P10) of first step CO selective oxidation; Hot-fluid outlet (E11) communicates with the space interlayer that is arranged at flanged plate (F3) front end that has the micropore sparger, and the space band height is 3～5mm; Cold fluid inlet (E12) is connected with interchanger (Hc) cold fluid outlet (E8) through threeway (T2) by branch line (P5); Cold fluid outlet (E13) is connected with the cold medium inlet of interchanger (Hr) (E14) through threeway (T4) by branch line (P7);
3. micro-channel heat exchanger (H2) side seal board outward flange is welded on reactor (Rp1) housing bottom, reactor (Rp1) outlet promptly is the hot-fluid inlet (E15) of interchanger, side at hot-fluid inlet (E15) is provided with perforate (E16), and perforate (E16) is connected with the airline (P9) of second stage CO selective oxidation; Exchanger heat fluid outlet (E17) side seal board periphery is integrally welded with a flanged plate (F4) that has the micropore sparger, and makes the space interlayer that leaves 3～5mm between hot-fluid outlet (E17) and distribution hole; Cold fluid inlet (E18) is connected with combustion heat-exchange device (Hc) cold fluid outlet (E8) through threeway (T2) by branch line (P6); Cold fluid outlet (E19) is connected with reforming heat exchanger (Hr) cold fluid inlet (E14) through threeway (T4) by branch line (P8);
4. micro-channel heat exchanger (H3) side seal board outward flange is welded on reactor (Rp2) housing bottom, and reactor outlet promptly is that the hot-fluid of interchanger is gone into (E20), and hot-fluid outlet (E23) links to each other with extraneous hydrogen feeding pipe road through a switch-valve (V2); The cold fluid inlet (E22) of interchanger (H3) is as the initial inlet of reformation mixing raw material, and reformation air and methanol aqueous solution enter system thus, and cold fluid outlet (E7) is connected with combustion heat-exchange device (Hc) cold fluid inlet (E6) by outer pipeline (P2).
2. integrating device according to claim 1, it is characterized in that: described reforming reactor, combustion reactor and CO selective oxidation reactor are the catalyticreactor of one-piece construction formula, can the side's of being body or right cylinder surface structure.
3. integrating device according to claim 1, it is characterized in that: but described reforming reactor, combustion reactor and selective oxidation reactor volume fuel cell output rating situation design by the standard of 150～350ml/kW, and its inner body catalyst volume designs by 40～70% of reactor volume.
4. integrating device according to claim 1, it is characterized in that: described interchanger is stainless steel or aluminium is the micro-channel heat exchanger of material, each interchanger is cross layered by 20～40 microchannel plates, seal with the vacuum diffusion welding connection technology, every microchannel thickness of slab is 0.3～1.0mm, generally between 0.2～1.0mm, the reactor size on interchanger size and the corresponding module adapts the passage hydraulic diameter.
5. integrating device according to claim 1, it is characterized in that: the spark coil of described startup reforming reaction, in the middle of reformation sparger micropore and reforming catalyst, this spark coil is a resistance wire, its electric current input is by a low-voltage transformer control, about 5～the 10V of input voltage, the about 40～100W of power input.
6. integrating device according to claim 1, it is characterized in that: the necessary stainless steel tube connecting pipeline of described fluid flow P1～P10 is to reduce the pipeline resistance to flow, adopts Φ 6 stainless steel tubes;
7. integrating device according to claim 1, it is characterized in that: the airline (P9) in second stage CO selective oxidation is provided with the gas micrometering valve V5 that is used to distribute two-stage CO selective oxidation amount of oxygen.
8, a kind of hydrogen production process that adopts the methanol self-heating reforming hydrogen making integrated apparatus of the described microminiaturization of claim 1 is characterized in that:
(1) hydrogen manufacturing operation: the multicomponent of packing in reforming reactor non-precious metal catalyst, mol ratio are O
2/ H
2O/CH
3The reformer feed of OH=0.19～0.23: 1.2: 1 through little interchanger H3, Hc, H1, H2, Hr heat exchange and vaporization, sprays into the reformation catalytic bed by reformer front end gas distributor (D1) successively; Under the of short duration ignition condition of lighter for ignition, start the reformation catalyzed reaction, produce the high temperature hydrogen-rich reformed gas;
(2) CO cleaning section: CO selective oxidation catalyzer adopts Rh/K/ γ-Al
2O
3The CO volumetric concentration that contains that is produced by the hydrogen manufacturing operation is about 0.9～1.3% high temperature reformed gas and goes into to select oxidation module front end interchanger (H1) by reforming heat exchanger (Hr) is laggard, and purify air ingress and first section and to converge, enter (Rp1) reaction zone by the micro-pore plate type sparger on the flange (F3), flow into little interchanger (H2) successively again and converge through the orifice plate sparger and enter (Rp2) reaction zone with two sections air, obtain the hydrogen rich gas of extremely low concentration CO at last via little interchanger (H3) heat exchange, further the condensation dehydration obtains the butt hydrogen-rich gas, here the total oxygen demand of two sections air is 1.0～1.5 times of CO total amount in the reformed gas, and first section partition ratio with second section is 2:1～5:1;
(3) burning/vaporization process: combustioncatalysts adopts 0.5 ‰ Pt/ γ-Al
2O
3, be fuel with pure methyl alcohol or reformation tail gas or hydrogen, air is an oxygenant, the oxygen amount feeds than 0.5-0.7:1 by excessive slightly mole metering when being fuel with hydrogen, if be that fuel compares charging by the 1.7-2.5:1 molar weight with methyl alcohol; Liquid or geseous fuel and Air mixing material enter the combustioncatalysts bed by T-shape member (T1), natural starting catalyst combustion reaction under the room temperature, the hot-fluid that produces directly enters the Hc interchanger on the integration module, the cold raw material of reforming is vaporized on interchanger Hc, and combustion tail gas is discharged after heat exchange.
9. the hydrogen production process of microminiaturized according to claim 1 methanol self-heating reforming hydrogen making integrated apparatus, it is characterized in that: described hydrogen production process is when ignition trigger, system outlet is closed, V2 ends, reformate gas stream does not enter selective oxidation/heat exchange module, but place the emptying position earlier, and V1 is open-minded, and reformate gas stream just switches in the system when treating that reforming reaction is stablized.
10. the hydrogen production process of microminiaturized according to claim 1 methanol self-heating reforming hydrogen making integrated apparatus, it is characterized in that: described CO selective oxidation section air distributes the two-way flow by a mass flow controller control total amount by the aciculiform micrometering valve that is positioned on the low resistance pipeline (P9).
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