DE102008024674A1 - Exhaust gas-fuel reformer-fuel cells combination for stop-start cycles in motor vehicles, comprises reformer-reactor, shift reactor, turbine wheel of radially acting fresh-air loader, auxiliary heating tube, and thermal insulator - Google Patents

Abstract

The exhaust gas-fuel reformer-fuel cells combination comprises a reformer-reactor (3), a shift reactor, a turbine wheel of a radially acting fresh-air loader, whose radial turbine blades are raised with the turbine wheel outwardly and/or inwardly on a common rotor, inserted into a combustion engine-exhaust gas or in reformer reactor and/or shift reactor-remaining gas stream, an auxiliary heating tube inserted by loading fuel or air for heating the combustion engine of the exhaust gas (1) before the reformer reactor and fuel cell combination, and a thermal insulator. The exhaust gas-fuel reformer-fuel cells combination comprises a reformer-reactor (3), a shift reactor, a turbine wheel of a radially acting fresh-air loader, whose radial turbine blades are raised with the turbine wheel outwardly and/or inwardly on a common rotor, inserted into a combustion engine-exhaust gas or in reformer reactor and/or shift reactor-remaining gas stream, an auxiliary heating tube inserted by loading fuel or air for heating the combustion engine of the exhaust gas (1) before the reformer reactor and fuel cell combination, and a thermal insulator provided around the reformer reactor, fuel cell (10) and the shift reactor. The thermal energy contained in the exhaust gas is used for heating the reactor (RR) of the reformer and the fuel cell (BZ) at respective operating temperatures. A pre-heated hydrocarbon-containing fuel gas is added as buffer gas and transport gas to the exhaust gas and endothermally reacts to hydrogen (H 2), carbon monoxide (CO) and carbon dioxide (CO 2) with the water steam H 2Og contained or additionally added in the exhaust gas under the use of the thermal energy delivered in the exhaust gas and recycled by the fuel cell and the remaining chemical energy of the exhaust gas. The reaction gas such as H 2, CO and CO 2is supplied directly or only H 2to the fuel cell of cathodic or anodic atmospheric oxygen over a hydrogen separator. The cylindrical entire-fuel cell is composed of segmented solid oxide individual-fuel cells, which consist of an internal carrier layer, a cathode layer, an electrolyte layer and an anode layer, where all the layers are sintered with one another in series. The solid oxide individual-fuel cells are individually arranged in pairs or triples part shells on cylinder, which are densely sintered to two separated biconcentric helix windings. The interior of the exhaust gas fuel tube of the reactor is equipped with deviating sections (33) and is opened to the cathodic inner helix winding over a radial slit opening, where the cathodic inner helix winding is formed together as reactor. The other anodic helix winding of the cylinder front side is densely sintered with an air supply pipe. The cathodic helix winding ends in a sintered pipe for the reception of the heated fuel remaining gases, which is fed back into the interior of the reactor tube over an exhaust gas inlet orifice, which is formed as jet pump. The anodic helix winding ends in a residual air of delivery pipe, which is sintered to gas-tight ceramic layer of the fuel cell. The center curvature of the cylinders part shells and the thicknesses of the fuel cell layers and the carrier layer are selected, so that the expansions of the layers with different temperatures compensate themselves over their lengths. The individual fuel cell is again segmented part shell webs in cylinder. The webs are separated by a peripheral joint, in which the layer converges the electrolyte or the electrolyte is replaced by a thin gas-tight ceramic insulating layer with expansion coefficient. The individual fuel cells overlap or interlock the part shells at the joints, are gas-tightly sintered with an insulated ceramic web with expansion coefficient and are connected in series by a nickel flag. The fuel cell with integrated reactor consists of rectangular surfaces superimposed on each other in the form of a double-helix made of two polygon-coils, in whose center the reactor internal tube and the air supply pipe are enclosed. The elongated fuel cell rectangular surfaces are subdivided into narrower single fuel cell segment with expansion joints. The reformer gas is supplied to the shift reactor after the reformer reactor for completely converting the carbon monoxide by additionally admixing evaporated and preheated water steam to carbon dioxide under further production of hydrogen. The hydrogen developed in the reformer and shift reactors is separated from the reformer gas and the shift gas by a hydrogen permeable separating device and then supplied over a conveying pump of the fuel cell. Only the shift reactor contains the hydrogen separating device and the separated hydrogen gas of the solid oxide fuel cell head is supplied to the combustion gas or cathodically supplied as combustion gas to a medium-temperature additional-fuel cell. The hydrogen separating device consists of coiled tubes, which is made of porous ceramic and are vaporized with a palladium-silver layer on an internal wall. The coil is arranged in an inner chamber of the shift reactor and/or the reformer-reactor. For converting the remaining portions of carbon monoxide, hydrogen and if necessary sulfur oxide and nitrous oxide in the remaining gas of the fuel cell to carbon dioxide, water and innoxious sulfur and nitrogen compounds, a catalyst in a pipe of a heat exchanger (19) is introduced on a porous ceramic carrier in an inner area of the reformer reactor or in an exhaust discharge. An independent claim is included for a device for an exhaust gas-fuel reformer-fuel cells combination.

Description

• – durch Nutzung des heißen Abgases zum Aufheizen des RR als auch der BZ,
• – durch Nutzung der hohen VM Abgas Wärme sowohl des Verbrennungsmotors als auch der recycleten Wärmeeneergie der BZ, insbesondere einer Festoxid-BZ, einer Solid Oxide Fuel Cell (SOFC),
• – durch Nutzung der restlichen, verwertbaren chemischen Energie des VM Abgases und unter Zugabe von zusätzlichem Kraftstoff zur Erzeugung des BZ Brenngases, und
• – durch Nutzung des Abgases als Träger- und Puffergas

The object of the invention is to significantly increase the total, mechanical and electrical, degree of utilization of a motor vehicle (motor vehicle) with a compact, heat energy-coupled combination of internal combustion engine (VM) reformer reactor (RR) fuel cell (BZ) and thereby the consumption of fuel to lower. This task is solved

• By using the hot exhaust gas to heat the RR and the fuel cell,
• By using the high VM exhaust gas heat of both the internal combustion engine and the recycled heat energy of the BZ, in particular a solid oxide BZ, a solid oxide fuel cell (SOFC),
• - By using the remaining, usable chemical energy of the VM exhaust gas and with the addition of additional fuel for the production of BZ fuel gas, and
• - By using the exhaust gas as carrier and buffer gas

It high-temperature SOFC configurations will continue to be presented the fast, multiple heating / cooling cycles, essential for the mobile use in motor vehicles, enable, by compensation for the expansion of the components of the individual BZ's.

description

During the operation of the RR there is a loss of heat energy W _endo by the endothermic reactions of the added fuel consisting mainly of gaseous hydrocarbons C _n H _m with the contained in the VM exhaust, hot water H ₂ Og according to the schematic equation to carbon mon-CO, - dioxide CO ₂ and hydrogen H ₂ : W _endo + C _n H _m + (2c + b) H ₂ Og → c CO ₂ + b CO + a H ₂ , (1) with n = b + c, b >> c, a = (2c + b + m / 2), all sizes in mol, and
W _endo = (206.3 + (n-1) 141.2 + (n-2) 9.4) mol × kJ / mol = 1100 kJ for n = 7.

Competing processes, such as B, W ' _endo + C _n H _m + n CO ₂ > 2n CO + m / 2 H ₂ , do not change the amount of charge Q generated in the BZ for the same amount of converted fuel gas, see Eq. 2 for the SOFC.

The energy loss W _endo is compensated by the heat energy W _{abg of} the VM exhaust gas and by the recycled BZ residual gas, which is heated by the exothermic reactions in the BZ-2 and so the RR and the BZ at an operating temperature of 800 to 950 ° C. is held.

The recoverable reaction products (b + b ') CO + a H ₂ , with b = 1.2 mol CO residual of the VM exhaust gas for 1 mol of gasoline with an average stoichiometric composition of C ₇ H ₁₆ , see below, the SOFC directly on the cathode side added as fuel gas and with the anode-side added atmospheric oxygen, according to the Eq. 3 and 4, see below, converted into a theoretical charge Q in C (Coulomb) Q = 2 (n + m / 2 + b ') e ^- . (2)

The SOFC has the great advantage that it can use CO and H ₂ equivalent as fuel gas. As can be seen from the Eq. 2 for Q, the shares b and c of CO and CO ₂ do not go into Q, so the production ratio b / c also does not matter.

For RR temperatures t> 900 ° C is b / c> 10.

at uncatalyzed exhaust gas z. As a natural gas or LPG or gasoline operated Otto Motors is the carbon monoxide (CO) content at about 2% by volume, which did not completely burn off an effective 19% share Corresponds to carbon.

The high exhaust heat energy W _Abg , z. As an Otto engine, is about 40% of the fuel supplied calorific value.

For 100 g of gasoline, corresponding to 1 mol with the average stoichiometric composition C ₇ H ₁₆ (average calorific value H = 4200 kJ), ie for n = 7, m = 16 and b '= 1.2, the theoretically maximum electrical energy output of the SOFC is obtained from the exothermic reactions that take place in the BZ CO + O ^- > CO ₂ + 2e ^- + (-283,2 kJ), (3) H ₂ + O ^- → H ₂ O + 2e ^- + (-242 kJ) (4) So the charge Q according to Eq. 2 too
Q = 2 (16,2) A e ^- = 3,13 10 ⁶ C with A = Avogadro constant = 6,0222 10 ²³ and
the electron charge e ^- = 1.602 10 ^-16 C.

At an open circuit voltage of U = 1 V, the electrical energy is W _el = QU = 3125 kJ which corresponds to an efficiency of BZ of μ = 0.58.

At a BZ voltage of U = 0.8 V under load becomes W _el = QU 2500 kJ. (5)

This corresponds to an effective performance of P _el = W _el / 3600 s = 0.69 kW for 1 mol = 100 g of gasoline. (6)

The total heat energy W from the above reactions according to Eq. 3 and 4 without dissipated W _el would result with n = 7 and m = 16 and b '= 1.2, in each case in mol to
W = (8.2 × 283.2 + 8 × 242) kJ = 4258 kJ. From this, the above value for W _el = 2500 kJ is subtracted in order to obtain the excess residual heat of the BZ W _BZ = 1758 kJ.

These is by repatriation of the BZ residual gases, directly or via a heat exchanger, fed back to the RR.

With the same fuel consumption of the VM and the RR of 100 g each, the heat-coupled combination RR + BZ results in a heat energy surplus of W = W _BZ - W _endo = 658 kJ, with the value W _endo = 1100 kJ calculated above. Thus, the excess heat of the BZ residual gas more than offsets the loss due to the endothermic reactions in the RR, thus maintaining the operating temperature of RR and BZ.

Assuming the same fuel consumption of VM and the RR + BZ combination of 15 mol of gasoline, corresponding to 1.5 kg or about 2 l,
results from Eq. 6 an electric power of the combination RR + BZ
P _el = 10.4 kW.

With a calorific value of 42000 kJ / kg for gasoline and a mean efficiency of the VM of μ = 0.275, W _VM = 17330 kJ and thus
P = W _{VM VM} / 3600 s = 4.8 kW,
So a mean total power of the combination RR + BZ of P _ges = 15.2 kW = 20.7 HP.

In order to can also have a heavier car with a medium speed from 100 km / h to 130 km / h. Of course, the VM is for a clear higher Peak performance designed.

The electrical power is in this example in partial load operation by a factor of 2.15 higher as that of the VM.

Of the Overall efficiency of VM + BZ increases by about a factor 1.5.

The heated to about 900 ° C exhaust / buffer gas fraction consists for 100 g of gasoline from 44 moles of N ₂ , 8 moles of water vapor H ₂ O, 5.8 mol CO ₂ and 1.2 mol CO.

• 2. einer Einsparung von 44% an Kraftstoff, unter Einrechnung des verwertbaren CO Anteils im Abgas,
• 3. einer erhöhten Produktionsrate des Brenngases CO und H₂, da in der Gasphase das Abgas als Puffergas die Produktion durch Dreikörperstoß Prozesse fördert, ohne Kontakt mit einem Feststoff Katalysator. Das Abgas/Puffergas wirkt wie eine Druckerhöhung.
• 3. Für das Puffer- plus Kraftstoffgas kann der BZ-Kathodenraum als Reformer Reaktor Raum genutzt werden, wodurch sich die Masse des aufzuheizenden und auf Betriebstemperatur zu haltenden Volumens deutlich reduziert.

The exhaust-fed combination RR + BZ has the decisive advantages over an autonomously fed and heated with O ₂ combustion RR, because:

• 2. a saving of 44% in fuel, including the recoverable CO content in the exhaust gas,
• 3. An increased production rate of the fuel gas CO and H ₂ , since in the gas phase, the exhaust gas as a buffer gas promotes the production by three-body impact processes, without contact with a solid catalyst. The exhaust gas / buffer gas acts as an increase in pressure.
• 3. For the buffer plus fuel gas, the BZ cathode space can be used as a reformer reactor space, which significantly reduces the mass to be heated and maintained at operating temperature volume.

Since only the sum of the fuel gas produced by the RR amount CO + H ₂ enters into the energy balance of SOFC and these in the operating temperature ranges of RR from 450 to 950 ° C (the BZ from 800 to 950 ° C, more recently 650 to 950 ° C possible) is largely independent of the respective temperature, the combination RR + SOFC is very flexible. This allows for very low-temperature standby operation of the RR to even bridge a longer standstill of the VM, as well as full load operation for acceleration operations.

The Regulation becomes very easy. Supplying the RR with fuel gas is advantageously proportional to that of the internal combustion engine regulated to the maximum power of the BZ and above it constant held, or even slightly eased because of the increased CO supply in the exhaust, see above.

The Combination VM + RR + BZ is designed to give optimum efficiency operating at part load; So in the mileage moderately common Operating state in which other hybrid systems no or only one show little effect.

• – Eine weitgehende Ausnutzung der Wärmeenergie des VM Abgases und des BZ Restgases.
• – Eine kompakte, ggf. integrierte Bauweise des RR und der BZ zur Aufrechterhaltung der Betriebstemperatur in weiten Bereichen des Betriebes vom Stand-by Modus bis zum Vollast Betrieb.
• – Ein Vorheizen des Kraftstoffes und des Wasserdampfes für den RR als auch der Luft für die BZ
• – Eine gute thermische Wärme- und Strahlungsisolation des RR und der BZ.

Important prerequisites for a successful implementation of this combination are:

• - An extensive utilization of the heat energy of the VM exhaust gas and the BZ residual gas.
• - A compact, possibly integrated design of the RR and the BZ to maintain the operating temperature in wide areas of operation from standby mode to full load operation.
• - Preheating the fuel and water vapor for the RR and the air for the BZ
• - A good thermal heat and radiation isolation of the RR and the BZ.

Due to the very good thermal insulation of compact combination RR + BZ + shift reactor (SR) with, z. As high-temperature fiberboards of SiO ₂ and Al ₂ O ₃ , longer life of the car, advantageously, in a standby mode, can be bridged and the resulting electrical energy to charge the larger sized z. B. a Li-ion battery can be used.

To the additional Continuous use of this combination as auxiliary power unit (APU), see below.

• 1. den Anlasser bei entsprechend großer Auslegung der Batterie, vorteilhafter weise eine Li-Ionen Batterie, da durch Anrollen mit den Elektromotoren gestartet werden kann.
• 2. den Generator, da die BZ die Wiederaufladung der Batterie übernimmt.
• 3. auf den CO(NOx, SO₂)-Kathalysator, bei entsprechender Abstimmung der Kombination RR + SR + BZ.

It can be dispensed with the combination VM + RR + BZ on:

• 1. the starter with a correspondingly large design of the battery, advantageously a Li-ion battery, since it can be started by rolling with the electric motors.
• 2. the generator, as the BZ takes over the recharging of the battery.
• 3. on the CO (NOx, SO ₂ ) -Kathalysator, with appropriate coordination of the combination RR + SR + BZ.

These Savings can in the RR (SR), the BZ and the electric motors are invested.

The latter can be used during braking of the vehicle, as in a normal part hybrid motor vehicle, as generators during deceleration processes for the production of electrical energy. The most cost-effective for the task set small-volume, "downsized", supercharged Otto engines in natural gas or LPG or gasoline operation can be used because of consistently high in all modes exhaust gas temperature and high percent exhaust heat W _Abg .

at a suitably sized battery can be protected in emissions Downtown areas then longer Time driven only with the electric drive and only at low Charge state of the battery of the internal combustion engine are switched on.

The disadvantage of the SOFC, the high working temperature, does not apply to this VM exhaust gas fed RR-BZ combinations, since the heating of the RR and the BZ by the heat energy W _exhaust occurs, and the RR is supplied with fuel only after heating. Furthermore, the handling of the solid electrolyte in the SOFC is less problematic compared to a liquid electrolyte.

To solve the expansion problems in the rapid heating / cooling of the SOFC, see 3c , c ', c''and f.

at Diesel engines has a slightly different starting situation.

In front idle and in under-load operation, the diesel engine with vigorous Pleasure surplus up operated at a factor of 10 to avoid sooting.

This leads to low exhaust gas temperatures of about 250 to 350 ° C in diesel engines and thus also to a lower efficiency of the VM and the downstream RR. When using an RR + SOFC combination, the operating mode in diesel vehicles can and must be changed in the above mentioned ranges:
Significantly lower excess air - increasing the efficiency of the diesel engine - and the use of a post-combustion stage, see 5b to burn with the oxygen remaining in the exhaust gas, the residual fuel and the generated soot particles, for heating the exhaust gas to the desired working temperature of about 900 ° C, at which the subsequent RR, optionally with the additional addition of preheated water vapor is optimally operated. This afterburner replaces and eliminates the exhaust gas soot filter in diesel vehicles.

Investments in the compact versions of reformer reactors and fuel cells, particularly the SOFC, announced here, should pay off at average mileage, especially if they are manufactured as standard in a larger series. A use as a noiseless electric power supply for heating and especially for cooling of vehicles or trucks (refrigerated) transporter is also very inexpensive. In normal operation, the normal exhaust gas is omitted here and is provided by a planned regulated air combustion of fuel, see 5b , and ensures an additional addition of water vapor H ₂ O g.

Integrating an exhaust gas turbocharger for the internal combustion engine, possibly with a branch also for the anode-side, flow-increasing loading of the BZ with fresh air, is provided in front of and behind the RR + BZ combination, wherein the drive of the turbocharger is separated from the air transport, please refer 5a ,

For the fuel gas feed of a medium temperature BZ with liquid electrolyte is separated from the RR H ₂ and possibly an SR by a H ₂ permeable wall H ₂ , here advantageously as the inner coating of a tube system made of porous ceramic with a vapor-deposited Pd Ag layer of about 25 μ thickness.

Since these fuel cells, z. B. operated at about 600 to 700 C carbonate melt BZ, Molten Carbonates Fuel Cell (MCFC) or operated at about 200 ° C BZ with phosphoric acid electrolyte, a "Phosphoric Acid Fuel Cell" (PAFC) only H ₂ and no CO gas can handle and very sensitive In the case of sulfur impurities, the two stages are designed with one RR and SR stage and both are equipped with H ₂ separation.

The first stage is a high temperature reformer, as provided for the SOFC, and the second stage is a medium temperature shift reactor (SR), advantageously using catalysts, e.g. B. from nickel and iron oxide, the non-reformed CO content with H ₂ O according to the reaction equation CO + H ₂ O → CO ₂ + H ₂ (7) is completely converted into CO ₂ with further production of hydrogen H ₂ .

The hydrogen H ₂ generated in the SR can also be used to feed a second mean temperature BZ, see 3d , Such a combination RR + SOFC with a downstream combination SR + PAFC or SR + MCFC allows optimal use of the heat content of the exhaust gas and the SOFC, while the downstream combination can be made significantly smaller in performance.

State of the art

So far, reformer and shift reactors with autonomous firing were used for the upstream production of a fuel gas, eg. As H ₂ and CO, for fuel cells.

• – Zur Vorheizung sowohl der Reformer Reaktoren als auch der Brennstoffzellen.
• – Als Wärmeenergie Quelle für die endothermen Reaktionen des eingesetzten Kraftstoffes mit dem Abgas für die Oxidation mit Wasserdampf H₂Og.
• – Der Überschuss an CO₂ des Abgases wird zur Verschiebung des im Reformer erzeugten CO/CO₂ Gemisches in Richtung zu mehr CO Gehalt verwendet.
• – Das Abgas wird als Träger- und Puffergas verwendet für die in der Brennstoffzelle zu verwertenden, reagierenden Verbindungen, in der Hauptsache H₂ und ggf. CO und dem Restgehalt des Abgases an CO als Brenngas.

In this application, the exhaust gas is mainly used advantageously by motor vehicles in many ways:

• - For preheating both the reformer reactors and the fuel cells.
• - As a thermal energy source for the endothermic reactions of the fuel used with the exhaust gas for the oxidation with water vapor H ₂ Og.
• - The excess CO _{2 of} the exhaust gas is used to shift the CO / CO ₂ mixture generated in the reformer towards more CO content.
• - The exhaust gas is used as a carrier and buffer gas for the reacting compounds to be utilized in the fuel cell, mainly H ₂ and possibly CO and the residual content of the exhaust gas to CO as fuel gas.

at appropriate interpretation of the RR and a downstream shift Reactor optionally with catalyst (s) and in series or series fuel cells can advantageously on a catalyst for exhaust gas purification be waived.

In particular, in SOFC cells, in addition to hydrogen H ₂ equivalent carbon monoxide CO as reaction gases at the same rate of 2 e ^- convert per molecule into electrical energy, is not the mutually changing proportion of H ₂ to CO generated in the reformer, but only their total amount in the final won electrical energy of the BZ.

Consequently depends on that electrical yield at same fuel inserts in the working limits (400 or 600 to 950 ° C) of the reformer as well as the SOFC not strongly dependent on their temperatures.

With The combination VM-RR-SOFC can under optimal conditions a increase the efficiency can be achieved by a factor of 1.55, see above.

A SOFC configuration is presented, which allows fast, multiple heating / cooling cycles.

characters

The pictures 1 to 5 illustrate the key parts of the combination VM, exhaust-fed RR, SR and BZ, as well as an exhaust-driven fresh air turbocharger and an auxiliary heating of the exhaust gas.

The RR + SR arrangements and their working temperatures will be optimal adapted to the fuel cells to be used.

The solid oxide BZ, SOFC, is operated at (600) 800-950 ° C with H ₂ + CO as fuel gas and atmospheric oxygen, the carbonate melt BZ, Molten Carbonate Fuell Cell (MCFC) at 600-700 ° C with H ₂ and recycled CO ₂ and atmospheric oxygen, the phosphoric acid BZ, Phosphoric Acid Fuell Cell (PAFC), at 200-250 ° C with H ₂ and atmospheric oxygen.

In 1 and 2 schematically two different arrangements, in particular for a SOFC and a MCFC are shown in FIG 3 and 4 each a compact configuration in two versions with an expansion compensated SOFC.

These Figures each represent a configuration of RR, SR and BZ. diverse Combinations, in particular the replacement of individual components are possible. Likewise different gaseous, liquid as well as solid fuels (in normal conditions) as preheated Fuel gases for the RR and SR and thus the used BZ.

1a : Longitudinal section through a combustion engine with exhaust gas 1 heated reformer reactor RR 3 with fuel gas 2g Supply and heating by the BZ 10 Residual gas by means of a Wärmetau exchanger 19 ,

1b : Longitudinal section through a RR 3 '' with catalyst filling 9 and returning the BZ residual gas through a supply line 26 ' with jet pump 21 ,

1c : Schematic longitudinal section through a high-temperature solid oxide BZ 10 with cathode-side fuel gas (a H ₂ + b CO) supply from the RR 3 with anode-side preheated air supply.

2a and b: longitudinal sections through an RR 3 ' with preheated fuel gas 2g and water vapor 22g Feed and a shift reactor 23 with catalyst 18 Filling, both with a helical hydrogen H ₂ separator 6 consisting of porous ceramic tubes 6 ' with a Pd-Ag inner wall coating 7 ,

2c : Longitudinal section through a phosphoric acid BZ 10 '' with cathodes - 5 sided H ₂ and anodes - 4 sided preheated air supply.

3a and c: longitudinal and cross section through a high temperature solid oxide BZ 10 , their single cells 51 the shape of cylinder half shells 50 have arranged in a bi-concentric helix helical structure with an integrated RR 13 with fuel gas 2g pipe 25 and a preheated air supply pipe 29 , as well as a thermo insulating jacket 45 , With

3c ' and c '': detail enlargement of the overlap 56 two single BZ cells 51 in cross-section and in plan view with a ceramic insulating sheet 48 and a nickel connection banner 46 ' , as well as an interruption / constriction 63 the cylinder subshells in single segments 51 ' . 52 '' ,

3b : Shift reactor 23 as in 2 B with H ₂ separator 6 and preheated steam 22g Feeder, as well as a fuel tank 56 and a water tank 57 ,

3d : Longitudinal section through a medium temperature phosphoric acid BZ 10 '' supplied with H ₂ from the SR 23 ,

3e : Longitudinal section through the middle part of one in the BZ 10 integrated RR 13 ' with a coaxial heat exchanger 19 to recycle the heated BZ 10 Residual gas.

3f Cross section through the middle part of a BZ 10 ' with integrated RR 13 ' in the form of a double helix of meandering rectangle surfaces 50 ' ,

4a and b: longitudinal and cross section through a high temperature solid oxide BZ 10 ' consisting of tubular, single-sided single BZ elements 40 arranged in four rows with preheated air supply through inner tubes 44 around the centrally located, rectangular heat exchanger 19 pipe 27 in the upstream RR 13 ' ,

4c : Detailed view of the tubular single BZ 51 consisting of porous ceramic sheath 47 with cathode layer 15 , the solid electrolyte 17 and the anode layer 14 connected via nickel buffer 48 and nickel flags 46 ,

5a : Exhaust 1 driven turbocharger 60 with a separate turbine 58 and a radial fan 54 ,

5b : Additional heating 61 for diesel engines.

figure description

1a and b are schematic longitudinal section with exhaust gas 1 fed reformer reactors RR 3 and 3 '' shown in which a preheated, gaseous fuel 2g from hydrocarbons CmHn via a supply line 25 is added.

The exhaust 1 is possible close to the cylinders of the gasoline or diesel engine, so on the exhaust manifold 16 decreased.

The gaseous energy source 2g is through a heat exchanger 19 z. B. over the air outlet 31 (N2 + (O2)) of the fuel cell BZ 10 heated and liquid fuel 2f , such as As gasoline or diesel fuels possibly additionally by a heat exchanger ( 19 '' ) above the exhaust pipe 36 (not shown) evaporated.

The fuel gas 2g responds in the RR 3 with the components contained in the exhaust gas CO ₂ , (CO), and H ₂ O according to the schematic Eq. 1 to a H ₂ + (b + b ') CO, where H ₂ and CO are the fuel gas for the high-temperature fuel cell SOFC 10 are, and a and b, b 'factors in mol, see above.

In the RR 3 are on the outer wall and on the heat exchanger 19 Pipe alternately hollow cylinder shaped deflecting webs 33 arranged to extend the reaction time. Possibly. These can be covered with a catalyst.

The reactions according to Eq. 1 can be in the cathode compartment of the BZ 10 so that this is an essential part of the RR 3 becomes.

If necessary can be via a valve 12 and a supply line 24 additional, in a heat exchanger 19 '' Waser preheated steam H ₂ Og at the input of RR 3 ( 3 '' ) the exhaust gas 1 and the fuel 2g Trains will give.

In 1c is schematically the longitudinal section of a high temperature BZ 10 , a SOFC, with cathode 5 and anode 4 and the solid oxide electrolyte 17 shown in between. Anodenseits becomes the BZ 10 Air supplied in a heat exchanger 19 '' above the exhaust pipe 36 the BZ 10 was preheated.

This fuel gas, a H ₂ + (b + b ') CO, with the carrier gas from N ₂ , CO ₂ and possibly residual H ₂ O steam in the cathode compartment of the SOFC 10 admitted. This fuel gas reacts with the (a + b + b ') O ^- ions, which on the anode arise by taking up two electrons from the atmospheric oxygen and diffuse through the solid oxide electrolyte, and on the cathode side according to Eq. 3 and 4 react to produce a H ₂ O + (b + b ') CO ₂ and the amount of charge Q = 2 (a + b + b') e ^- which is delivered to the anode via the connected load.

In 1a is the heated exhaust gas of SOFC, consisting of carrier gas, see above, and a H ₂ O + (b + b ') CO in a recycle line 26 and the heat exchanger 19 back through the reform reactor 3 and keeps it at a constant reaction temperature of about 600 to 950 ° C, see below.

In 1b becomes the residual gas of the BZ 10 through the pipe 26 in the constriction 38 the exhaust gas supply line 16 led, as a jet pump 21 is trained, and so sucked back through the RR 3 '' led, with a porous catalyst 9 , z. As Ni and Fe oxide, is filled. A narrowing 39 in the exhaust pipe 36 at the end of the RR 3 '' accumulates the gas flow and directs the main flow through the BZ 10 ,

Right behind the exit narrowing 39 is a check valve plunger 35 used, which has a spring and a magnetic coil 37 is opened and closed in the partial cycle of the VM. The opening and closing frequency of the coil 37 may be about 1/4 to 1/64 of the revolution frequency of the VM in a four-stroke VM. The opening and closing intervals are based on maximum charge Q in the BZ 10 optimized.

In the heat exchanger 19 can in the RR 3 Area a catalyst 28 for the rest CO and SO _x also in the exhaust pipe 36 be used, which converts the unreacted remainder CO and the traces SO _x and NO _x in CO ₂ and harmless sulfide and nitrogen compounds before the exhaust gas 11 the exhaust pipe 36 is supplied.

In 2a and b is a longitudinal section of a high-temperature reformer 3 ' and a medium temperature shift reactor 23 shown. The former is directly to the exhaust manifold 16 Flanged and is through a supply line 25 with fuel gas 2g charged, which has a heat exchanger 19 the between the two reactors 3 ' and 23 is used, is preheated. Possibly. can also have a heat exchanger 19 ''' vaporized and preheated H ₂ Og via a supply line 24 be added.

In the reformer 3 ' Run at temperatures above 600 ° C, the reactions to the Eq. 1 off. The CO fraction not converted into CO ₂ reacts in the downstream shift reactor 23 with the additionally added H ₂ Og at temperatures of 400 to 600 ° C according to Eq. 7 with further production of H ₂ using a Ni and Fe oxide catalyst 18 ,

In both reactors 3 ' and 23 are over the entire inner cross section Wendel snakes of an H ₂ separator 6 arranged, made of porous ceramic tubes 6 ' exist, which are on the inner wall with a palladium-silver layer, only about 25 microns thick, are occupied.

The separated in this way H ₂ gas is via a feed pump 34 aspirated and cathode side of a PAFC medium temperature Brenstoffzelle 10 '' fed.

The one from the reaction, Eq. 4 in the cathode compartment of the BZ 10 '' formed H ₂ O vapor is condensed and re-evaporated the SR 23 and possibly the RR 3 ' over the supply line 24 and through a valve 12 ' controlled supplied. Anodenseits becomes the BZ 10 '' Supplied to atmospheric oxygen, in a heat exchanger 19 '' around the exhaust pipe 36 of the two reactors 3 ' and 23 was preheated.

In 3a to c are the longitudinal and the cross section shown by a compact, cylindrical high-temperature fuel cell 10 with a solid oxide electrolyte, a SOFC, with an integrated RR 13 , a configuration that is suitable for use in a motor vehicle.

It consists of 2.5-3 turns of a bi-concentric double helix of a porous carrier coat 47 . 47 ' out, z. As zirconium oxide (ZrO ₂ ), the cylinder shells 50 by sintering at the overlapping, possibly toothed joints 56 are firmly joined, see 3c ' ,

On these cylinders partial shells 50 are on the opposite sides of the double helix 16 individual fuel cells 51 Sintered configurations, consisting of: one directly on the carrier coat 47 . 47 ' sintered cathode layer 15 from z. B. lanthanum manganate (LaMnO ₃ ), an electrolyte layer of z. B. a ceramic mixture of yttrium oxide (Y ₂ O ₃₎ and ZrO ₂ and an anode layer of z. B. a nickel-ZrO ₂ metal-ceramic compound. The cathodes layers 15 ste In the helix, windings are opposite, through which the H ₂ + CO fuel gas is passed and the anode layers 14 stand in the air leading Helix turn opposite.

The 16 cells 51 the BZ 10 are on opposite sides of the cylinder shells 50 by Ni flags 46 ' connected in series with a cathode 5 and an anode 4 connection to the outer cells, see 3c ' , and c ''.

The mean curvature of the cylinder subshells BZ cells 51 is chosen so that the different dimensions of the carrier shell 47 . 47 ' and the three layers of the cathode - 15, the electrolyte - 17 and the anode - 14 layers are largely compensated.

Along the cylinder length are the BZ cells 51 again in narrower individual segments 51 ' . 51 '' divided by dividing into the cylinder subshells along the perimeter expansion joints 63 are arranged, in which either the electrolyte layer 17 tapered or this through a thin, gas-tight Keranik insulating sheet 64 replaced with the appropriate coefficient of expansion.

The BZ cells 51 are gas-tight and electrically connected and series connected, as in the circled detail magnification, 3c ' , drawn.

The two carrier coats 47 and 47 ' are (possibly toothed) at the joints 56 sintered and with a longitudinal insulating track 48 made of gas-tight ceramic with matching expansion coefficient and with a Ni (metal-ceramic) flag 46 ' between the cathodes - 15 and the anodes - 14 layer of adjacent cells 51 connected.

The inner turn of the double helix in the form of a RR 13 ' pipe 27 consists of dense, z. B. Al ₂ O ₃ ceramic, with narrowed one - 38 and outlet pipe 39 ,

In the tube 27 are semicircular Umlenksstege 33 ' introduced to prolong the reaction time, before the constriction 38 added fuel gas 2g with the VM exhaust 1 from the exhaust manifold pipe 16 and optionally additionally added H ₂ O steam 22g ,

The inner tube 27 is with a radial opening slot 32 provided by the RR 13 in the cathode-side Helixwindung the BZ 10 continues.

In the second helix winding of the BZ 10 is narrowed by an outlet over the outlet 39 in the cylinder sidewall 30 the BZ 10 suspended pipe 29 preheated air initiated.

The outlet of the air-guiding helix winding is a slotted Al ₂ O ₃ tube 31 to these and the gas-tight cylinder jacket 20 the BZ 10 tightly sintered.

A heat exchanger 19 '' over the pipe 31 heats the air supply of the BZ 10 ,

On the approx. 180 ° opposite side of the Bz 10 is a second Al ₂ O ₃ tube 26 with the fuel gas leading helix turn and the BZ shell 20 sintered.

This pipe 26 flows into the Einlaßverengung 38 the BZ 10 , which by the exothermic reactions in the BZ 10 heated residual fuel gas through a jet pump 21 Opening sucked and the RR 13 is fed again.

Both discharge pipes 26 and 31 are at the other end by a spherical cap 54 closed, as well as the air supply 29 ,

The RR is loaded 13 before the inlet narrowing 38 over the flanged exhaust pipe 16 with the VM exhaust 1 , the other fuel gas 2g over the supply line 25 and optionally additionally preheated water vapor 22g over the supply line 24 is supplied.

In the RR 13 run the endothermic reaction, Eq. 1 for the production of the fuel gas a H2 + b CO.

Behind the outlet narrowing 39 over which the heat exchanger 19 ' for the fuel gas 2g sits, is a shift reactor 23 with catalyst insert 18 and H ₂ separator pipes 6 ' , as in 2 B described, flanged.

This SR 23 is run at temperatures below 500 ° C and by adding further preheated H ₂ Og the remaining CO + H ₂ O in CO ₂ + H ₂ according to Eq. 7 converted.

The resulting H ₂ gas is pumped 34 or a jet pump 21 from the H ₂ separator tubes 6 indicating the volume of SR 23 pull through like a spiral, see 2 B , in the fuel gas supply line 25 to the RR 13 pumped or sucked.

Behind the outlet narrowing 39 again a check valve 35 with magnetic coils - 37 Control be incorporated to the residence time of the fuel gas in the RR 13 and in the BZ 10 to extend. The volume of the RR 13 , the SR 23 and the BZ act as a buffer, so that the increase in pressure due to the pulsation of the residual gas flow is not so great as to seriously chill the VM.

In 3d is a mean temperature BZ 10 '' , z. As a PAFC, shown schematically in longitudinal section, see also 2c , in which in the SR 23 separated H ₂ gas anode is added.

This combination RR 13 + BZ 10 , SOFC, + SR 23 + BZ 10 '' , PAFC, uses the heat content of the VM exhaust gas and the BZ 10 Restgases and their usable chemical energy optimally. The PAFC cell can according to the H ₂ from the attack SR 23 be designed with lower power than the SOFC.

Both end faces of the BZ cell 10 made of closed porous ceramic, z. B. Al ₂ O ₃ are by means of introduced grooves with the helix turns and the feed 29 and the drain pipes and 26 and 31 tightly sintered.

The 16 segmented single fuel cells 51 have the dimensions of, z. B. a cylinder half-shell circumference width b = 20 cm, length L = 29 cm electrical power of P = 750 W and a voltage U = 0.8 V under load. This results in the output voltage of the entire cell to 12.8 V and a possible total power of 12 kW, in external dimensions of the cell 10 with diameter = 20 cm and length L = 30 cm.

As fuel gas 2g for the RR 13 can be used car or natural gas or vaporized gasoline, diesel, biodiesel or other low-cost, low-sulfur liquid fuel.

Even at room temperature, under normal conditions, solid fuels such. B. naphthalene, C ₁₀ H ₈ , which is obtained in the coal fractionation up to about 11% proportion, can be used, or other (solid) CnH _m compounds which boil at temperatures up to about 400 ° C.

Of the Melting point of naphthalene is 80 ° C and the boiling point is at 210 ° C.

The two tanks 56 and 57 for the fuels or for the H ₂ O can preheat behind a thermal insulation (not shown) to the SR 13 be grouped.

Evaporation and preheating of fuels 2g takes place in a heat exchanger 19 ' around the outlet narrowing 39 between the RR 13 and the SR 23 ,

Two other versions of the RR 13 ' . 13 '' + BZ 10 . 10 ' , SOFC, combination are in 3e and f shown as a section in the longitudinal or cross section, wherein the RR 13 ' . 13 '' also in the BZ 10 . 10 ' is integrated. In 3e becomes the residual gas pipe 26 in the heat exchanger 19 extended and through the interior of the RR 13 ' returned to reheating. In the RR 13 ' are deflectors 33 ' made of ceramic and optionally coated with a Ni and / or Fe oxide layer on the heat exchanger 19 Inner tube and the reformer outer tube attached. The further construction with feeder 26 and exhaust pipe 36 is like in 3a and c described. Here is the SR 23 This is omitted in the heat exchanger 19 Pipe, still inside the RR 13 ' a catalyst 28 for CO and SO _x , as in 1b used.

In 3f is a section of the middle part of a BZ in cross section 10 ' with integrated RR consisting of juxtaposed rectangle surfaces 50 ' which meanders around the RR inner tube 27 and the air supply pipe 29 ' arranged in a double helix and
with these and with each other again at the joints 56 and the connection corners 56 ' , as in 3c drawn, connected.

This elongated BZ 10 ' Rectangle surfaces 50 ' can turn into narrower single BZ segments 51 ' . 51 '' with expansion joints ( 63 ) be divided between, see 3c '' ,

The Double Helix can also consist of two spirals of polygons, being the polygon number to the outside can increase.

In 4a and b is a longitudinal and a cross section through another integrated combination RR 13 '' -SOFC high-temperature fuel cell 10 '' shown in another, deployable in a car configuration.

This BZ 10 '' is built from here 32 single, arranged in a rectangle, closed at one end tubes 40 at the open end in a common base plate 43 are densely sintered. These tubes 40 again consist of a porous carrier coat 47 from CrO ₂ , see 4c Extensive magnification on which a closed cathode layer 15 and an anode layer 14 , as in 3c ' described, is applied. In a recess 42 the anodes 14 and the electrolyte layer 17 sits a nickel plug 48 , which establishes the electrical connection to the neighboring cells.

The individual BZ tubes 40 are here z. B. in each 2 × 5 pairs each outside the broad sides of the also rectangular heat exchanger 19 Pipe arranged projecting, as well as 2 × 3 pairs in the space, and are aligned with the closed end against the flow of the fuel gas.

The heat exchanger 19 Tube does not reach to the sintered base plate 43 for the Reacti onsgas to the central heat exchanger 19 in the RR 3 can flow back, the catalyst again 28 for the rest contains H ₂ and CO and before the RR 3 laterally to the exhaust pipe ( 36 ) (not shown).

In the middle of each of the 32 BZ tubes 40 ranges ever an air supply pipe 44 which are tight in a distribution system 29 ' are admitted by the preheated air from a heat exchanger 19 '' , please refer 2 B , is supplied to the anode side.

The residual air N ₂ plus unused oxygen (O ₂ ) flows out of the open tubes 40 Ends in a closed collection room 49 as well as the case 20 ' the entire fuel cell 10 '' tight with the base plate 43 connected is.

The 32 Single fuel cells 40 are two each in series and the 16 pairs then connected in series, so that they come with an output voltage under load of 0.8 V to 12.8 V, which is slightly higher than the normal car battery voltage.

The electrical connections are made with nickel tapes 46 between the Ni plugs 48 the cathode 15 and the nickel plus ZrO ₂ anode layer 14 produced.

At a mean diameter of d = 5 cm of the tubes 40 and a length of the electrolyte layer 17 of about L = 20 cm results in a usable area of 400 cm ² .

This can be per tube B tube 40 generate an electrical power of 400W. So they come 32 roar 40 to 12.8 kW.

In 5a is an exhaust turbocharger 60 shown in longitudinal section, made of a turbine wheel 58 which is either through the exhaust stream 1 the VM engine or the exhaust 11 the reformer 3 . 3 ' . 3 '' . 13 . 13 ' or the shift reactor 23 is driven. Possibly. may still have a small amount of fuel before that 2'g through a supply line 25 be injected. The turbine wheel 58 is inside a ball-bearing runner 59 attached, on the outside of the impellers 54 the fresh air turbine are used, with a radial outlet 57 and an air intake close to the axle 56 , The main part of the compressed air is diverted to charge the VM and a smaller part for forced feeding of the anode space of the BZ with atmospheric oxygen.

In 5b is an additional heating 61 the exhaust gas of z. B. Diesel engines shown in longitudinal section, in the preheated fuel 2'g is added, and optionally via a valve 12 the additional atmospheric oxygen required for combustion.

Claims (11)

Exhaust-fed reformer fuel cell combination, characterized in that 1. the exhaust gas ( 1 ) contained heat energy W _Abg for heating a reformer reactor RR ( 3 . 3 ' . 3 '' . 13 . 13 ' ) and a fuel cell BZ ( 10 . 10 ' . 10 '' ) is used to the respective operating temperatures, and 2. the exhaust gas ( 1 ), as a buffer gas and transport gas, a preheated hydrocarbon containing fuel gas ( 2g ) is added, which with the contained or additionally added in the exhaust water H ₂ Og ( 22g ) endothermic reacts to H ₂ , CO and CO ₂ using the delivered in the exhaust and the BZ ( 10 . 10 ' . 10 '' ) recycled heat energy and the residual chemical energy of the exhaust gas ( 1 ), and 3. the reaction gas H ₂ , CO and CO ₂ directly or only H ₂ via an H ₂ separator ( 6 ) a fuel cell ( 10 . 10 ' . 10 '' ) is supplied on the cathode side and on the anode side atmospheric oxygen. Exhaust-fed reformer fuel cell combination according to claim 1, characterized in that 1. the cylinder-shaped overall BZ ( 10 ) from many segmented solid oxide single BZ ( 51 ) is composed, the z. B. from an inner carrier coat ( 47 . 47 ' ) of porous ceramic, a cathode layer ( 15 ) made of lanthanum manganate, an electrolyte layer ( 17 ) From a ceramic mixture of z. B. yttrium and zirconium oxide and an anode layer ( 14 ) consist of a nickel-zirconium oxide metal-ceramic compound, all sintered together in this order, 2. these individual BZs ( 51 ) are arranged individually, in pairs or drippings on cylinder subshells, which are tightly sintered to two separate, bi-concentric helix turns, and 3. the inner, exhaust gas ( 1 ) fed tube-shaped RR ( 13 . 13 ' ) with deflecting webs ( 33 ) and via a radial slot opening ( 32 ) is open to the cathode-side inner helix turn, which together as RR ( 13 ) are formed, and 4. the other anode-side helix winding from the cylinder end face ( 30 ) with an air supply pipe ( 29 ) is densely sintered, and 5. the cathode-side Helixwindung in a sintered tube ( 26 ) for receiving the heated BZ- ( 13 ) Residual gas ending in the inner RR- ( 13 ) Pipe is recirculated via an exhaust gas inlet constriction ( 38 ), which serves as a jet pump ( 21 ), and 6. the anode-side helix winding in a residual air discharge pipe ( 31 ), which also with this and the gas-tight ceramic shell ( 20 ) of the BZ ( 10 ) is sintered. Exhaust gas fed reformer fuel cells Combination according to claim 2, characterized in that 1. the average curvature of the cylinder shells ( 50 ) and the thicknesses of the BZ 10 Layers ( 14 . 15 . 17 ) and the carrier coat ( 47 . 47 ' ) are selected so that the different temperature expansions of the layers largely compensate over their lengths, and 2. the individual BZ ( 51 ) again in cylinder part shells webs ( 51 ' . 51 '' segmented by circumferential joints ( 63 ) in which either the electrolyte ( 17 ) Layer constricted or this through a thin, gas-tight ceramic insulating layer ( 64 ) is replaced with a suitable coefficient of expansion, and 3. the individual BZ ( 51 ) Partial shells ( 50 ) at the joints ( 56 ) overlapping or toothed and with an insulating sheet ( 48 ) are gas-tight sintered from a ceramic with a suitable coefficient of expansion, and the individual BZ ( 50 ) by a Ni (metal-ceramic) flag ( 46 ' ) are electrically connected in series. Exhaust-fed reformer fuel cell combination according to claims 2 and 3, characterized in that 1. the BZ ( 10 '' ) with integrated RR ( 13 '' ) consists of juxtaposed rectangle surfaces ( 50 ' ) in the form of a double helix consisting of two polygons, in the middle of which the RR ( 13 '' ) Inner tube ( 27 ) and the air supply pipe ( 29 ' ) and 2. these oblong BZs 10 ' Rectangle surfaces 50 ' again in narrower single BZ segment 51 ' . 51 '' with expansion joints ( 63 ) are divided between them, and 3. the number of polygons can increase towards the outside. Exhaust-fed reformer-fuel cell combination according to at least one of claims 1 to 3, characterized in that 1. the reformer gas downstream of the reformer reactor ( 3 ' . 13 ) a shift reactor ( 23 ) is fed to the fullest possible conversion of CO with additional addition of vaporized and preheated H ₂ Og to CO ₂ with further production of H ₂ , and 2. which in both the reformer ( 13 ) as well as the shift reactor ( 23 ) hydrogen H _{2 is} separated by an H ₂ permeable separator device from the reformer and shift gas and then via a feed pump ( 34 ) of the fuel cell ( 10 ) or only the SR ( 23 ) the H ₂ separation device ( 6 ) and the separated H ₂ gas of the SOFC main BZ ( 13 ) in addition to the fuel gas, or 5. a mean temperature secondary BZ ( 10 '' ) is supplied as fuel gas on the cathode side, and 6. the H ₂ separator device ( 6 ) of coiled, porous ceramic tubes ( 6 ' ), which are vapor-deposited on the inner wall with a Pd-Ag layer, and the helix uniformly in the interior of the SR ( 23 ) or the RR ( 13 ) is arranged. Exhaust-fed reformer fuel cell combination according to at least one of claims 1 to 5, characterized in that in the heat exchanger ( 19 ) Tube a catalyst ( 28 ) on a porous ceramic carrier inside the RR ( 3 ' . 13 ' ) or in the exhaust derivative 36 is introduced, for converting the residual proportions of CO, H ₂ and optionally SO _x and NO _x in the residual gas of the BZ ( 3 . 3 ' . 3 '' . 13 . 13 ' ) to CO ₂ , H ₂ O and harmless S and N compounds. Exhaust-fed reformer fuel cell combination according to at least one of claims 1 to 6, characterized in that 1. in the VM exhaust gas ( 1 ) or in the RR ( 10 ) or SR- ( 13 ) Residual gas flow ( 11 ) a turbine wheel ( 58 ) of a radially acting fresh air charger ( 60 ) whose radial turbine blades ( 54 ) with the turbine wheel ( 58 ) outside or inside on a common runner ( 59 ), and 2. an additional heating tube ( 61 ) by fuel ( 2'g ) and air charge for heating the VM exhaust gas before the RR + BZ combination is used. Device for an exhaust gas fed reformer fuel cell combination consisting of 1. an internal combustion engine (VM) and 2. one through the VM exhaust ( 1 ) Heat-boosted reformer reactor RR ( 3 . 3 ' . 3 '' . 13 . 13 ' ) in the exhaust gas ( 1 ) or additionally added water vapor H ₂ Og ( 22 ) with one in a supply line ( 25 ) supplied hydrocarbon-containing fuel gas ( 2g ) reacts in endothermic reactions to H ₂ , CO and CO ₂ , and 3. a fuel cell BZ ( 10 . 10 ' . 10 '' ), in which the cathode side, the reaction gas or the still reacting gas directly or only the hydrogen H ₂ via a H ₂ separator ( 6 ) and anode-side preheated air oxygen, and 4. a heat exchanger 19 , for the return of the BZ ( 10 . 10 ' ) Waste heat in the RR ( 3 . 13 ' ), and heat exchangers ( 19 ' . 19 '' ) over the exhaust pipes ( 26 . 26 ' . 31 . 31 ' . 39 ) for evaporation and heating of the RR fuel 2g , of the additional H ₂ Og ( 22 ) or the anode-side air stream, and 5. an additional shift reactor SR ( 23 . 23 ' ) for the conversion of CO to CO ₂ with additionally added H ₂ Og ( 22 ) under H ₂ production. Exhaust-fed reformer fuel cell combination according to claim 3, characterized in that 1. a check valve ( 35 ) at the exit of the RR ( 3 ' . 3 '' . 13 ) or the SR ( 23 ) the outflow of the fuel and the recycled residual gas of the BZ ( 10 . 10 '' ) interrupts at a clock rate and in open / close intervals which the charge-producing reactions in the BZ ( 10 . 10 '' ), and 2. the check valve ( 35 ) by an electromagnetic coil ( 37 ) is pressed. Exhaust-fed reformer fuel cell combination according to at least one of claims 1 to 4, characterized in that 1. these are provided with a thermal insulation ( 45 ) around the RR ( 3 . 3 ' . 3 '' . 13 . 13 ' ), the BZ ( 10 . 10 ' . 10 '' ) as well as the shift reactor SR ( 23 ) and 2. thus a longer standstill of the VM engine with reduced fuel ( 2g ) And the corresponding air supply can be bridged into a stand-by mode., And 3. the inside or a part of the interior of the RR (FIG. 3 '' . 13 . 13 ' ) and the SR ( 23 ) with a catalyst ( 9 . 18 ) on a porous ceramic carrier or on the deflection webs ( 33 . 33 ' ), which accelerates the reactions in the desired products by surface contacts. Exhaust-fed reformer fuel cell combination according to at least one of claims 1 to 9, characterized in that the fuel gas ( 2g ) to load the RR ( 3 . 3 ' . 3 '' . 13 . 13 ' ) consists of car or natural gas, or evaporated gasoline or diesel fuels, or evaporated bio-diesel oils, or evaporated, solid hydrocarbons under normal conditions, such as. B. naphthalene.