GB2498741A - Improved fuel cell electrolyte regenerator and separator - Google Patents
Improved fuel cell electrolyte regenerator and separator Download PDFInfo
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- GB2498741A GB2498741A GB1201246.4A GB201201246A GB2498741A GB 2498741 A GB2498741 A GB 2498741A GB 201201246 A GB201201246 A GB 201201246A GB 2498741 A GB2498741 A GB 2498741A
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- 239000000446 fuel Substances 0.000 title claims abstract description 54
- 239000003792 electrolyte Substances 0.000 title claims description 16
- 239000007788 liquid Substances 0.000 claims abstract description 124
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000012530 fluid Substances 0.000 claims abstract description 23
- 239000011244 liquid electrolyte Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims description 33
- 239000012071 phase Substances 0.000 claims description 22
- 239000007791 liquid phase Substances 0.000 claims description 8
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- 239000007789 gas Substances 0.000 description 59
- 210000004027 cell Anatomy 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000005484 gravity Effects 0.000 description 8
- 238000012546 transfer Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
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- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000005518 polymer electrolyte Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 235000011449 Rosa Nutrition 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
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- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
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- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- QFMZQPDHXULLKC-UHFFFAOYSA-N 1,2-bis(diphenylphosphino)ethane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCP(C=1C=CC=CC=1)C1=CC=CC=C1 QFMZQPDHXULLKC-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000237858 Gastropoda Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
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- 239000003570 air Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
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- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B04—CENTRIFUGAL APPARATUS OR MACHINES FOR CARRYING-OUT PHYSICAL OR CHEMICAL PROCESSES
- B04C—APPARATUS USING FREE VORTEX FLOW, e.g. CYCLONES
- B04C1/00—Apparatus in which the main direction of flow follows a flat spiral ; so-called flat cyclones or vortex chambers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention concerns a separator (100, 200) for a liquid electrolyte regenerator of a fuel cell system. A helical fluid channel (100, 200, 300) formed on a helix (150) is arranged to conduct liquid and gas of a gas-liquid mixture and separate the liquid from the gas-liquid mixture. Preferably the helical channel (100, 200) is an enclosed channel or pipe (210) along which the gas-liquid mixture is constrained to travel, and the overall diameter (Dhelix) of the helical channel is close to twice the pipe diameter (Dpipe) of the helical channel along at least a portion of the helical channel. The helical channel can form part of a bulk gas-liquid separator, or a gas-liquid contactor and separator, or a condensing heat exchanger.
Description
IMPROVED FUEL CELL ELECTROLYTE REGENERATOR AND
SEPARATOR
The present invention relates to an indirect or redox fuel cefl system, and in particular to a liquid electrolyte regenerator and separator for such an (ndftect or redox fu& cefl system.
Fu& ceHs have apphcations in stationary, backup and combined heat and power (CF-F) contexts, as weU as in fuel cefls for the automotive industry and in micro fuel cefls for electronic and portable electronic devices.
io Fuel cefis are devices that produce electrical energy using the chemical properties of a fuel (often hydrogen) and oxygen to directly create electrical current. They are technicaHy similar to a battery although, unlike a battery, they do not store energy but produce electrical energy from an external fuel source as required.
iS Fuel cells were initially demonstrated in 1839, by Sir William Grove, however, a truly workable fuel cell was not demonstrated until 1959. After use in NASAS5 space programme, interest in fuel cells decreased until the 1990s when they were considered as a replacement for combustion engines because of their potential to be a more efficient and clean way to create power. Fuel Cells now find use in a range of applications such as transport, stationary power and even laptop computers.
In its simplest form, a fuel cell is an electrochemical energy conversion device that converts fuel and oxidant into reaction product(s), producing electrical energy and heat energy in the process. When hydrogen is used as fuel and air or oxygen as oxidant, the products of the reaclion are water and heat. The hydrogen and air/oxygen gases are fed respectively into catalysing, diffusionS type anode and cathode electrodes separated by a solid or liquid electrolyte which carries electricaUy charged particles between the two electrodes.
In an indirect or redox fuel cell, the oxidant (and/or fuel in some cases) is not reacted directly at the electrode but instead reacts with the reduced form (oxidized form for fuel) of a redox couple to oxidise it, and this oxidised species is fed to the cathode.
There are a number of types of fuel ceU which are normally distinguished by io the electrolyte they contain. The bestknown types are alkaline, molten carbonate, phosphoric acid, solid oxide and Proton Exchange Membranes (PEM). PEM membranes include Polymer Electrolyte Membranes. Direct methanol and regenerative fuel ceHs are the subject of extensive research.
Fuel cells utilising alkali electrolyte have an inherent disadvantage in that the Is electrolyte dissolves CO2 and therefore needs to be replaced periodically.
Polymer electrolyte or PEM-type cells with proton<onducting solid cell membranes are acidic and avoid this problem.
PEM fuel cells are used in automobiles. Most fuel cells used in vehicles produce less than 1.16 volts of electricity which is not enough to power a vehicle. Therefore, multiple cells are assembled into a fuel cefl stack. The potential power generated by a fuel cell stack depends on the surface area of the membrane in each cell and the total number of the individual fuel cells that comprise the stack.
A PEM fuel cell comprises a polymer electrolyte membrane (PEM) sandwiched between an anode and a cathode. Anode and cathode flow plates are attached to the anode and cathode respectively via respective backing layers. The anode flow plate acts to distribute hydrogen across the anode. The cathode flow plate 110 distrIbutes oxygen/air across the cathode and channels water as a by-product away from the cathode and provides heat as another by-product. An electrical current flows between the cathode and anode flow plates.
The anode typically comprises platinum particles uniformly supported on carbon particles. The platinum acts as a catalyst by increasing the rate of the oxidation process. Th. anode is porous so that the hydrogen fuel can pass through it. Similarly, the cathode too typically comprises platinum particles uniformly supported on carbon particles. The platinum of the cathode acts as a catalyst by increasing the rate of the reduction process. The cathode is is porous so that oxygen can pass through it.
A problem exists In that it has proved difficult in practice to attain power outputs from such PEM-type fuel ceils approaching the theoretical maximum level, due to the relatively poor electrocatalysls of the oxygen reduction reaction. A further problem Is that expensive noble metal electrocatalysts such as platinum are often used, causing a significant cost impact.
A recently-developed technology addresses these problems and promises to make PEM fuel cells competitive with conventlonai electricity generators, such as diesel generators, by replacing the fixed platinum catalysts on the cathode with a liquid regenerating catalyst system.
Such a liquid regenerating catalyst system is described in international published patent appflcation W02010128333, the contents of which are incorporated herein by reference.
In a known liquid regenerafing catalyst system, liquid electrolyte (cathioyte) is s continuously pumped through the fuel cell, by a pump into a regenerator and then back to the fuel cell. Air is forced by a blower into the regenerator at an input port and air (depleted of oxygen), water vapour and heat are output from the regenerator at an output port. As well as providing gasUquid contacting, the regenerator also includes a gasliquid separator which aHows the regenerator to remove air/oxygen from the cathotyte and return the catholyte, substantiafly free of air/oxygen, to the stack.
This liquid electrolyte regenerating technology reduces platinum content by up to 80% and simplifies the overall fuel cell system. As a consequence the technology not only radically reduces cost, ii also improves durability and is robustness of the system. This technology overcomes the three major limitations associated with conventional PEM fuel cell operation, namely catalyst loading, catalyst agglomeration and heat management. Additionally, a peak performance power density of nearly 900 mW/cm2 has been achieved.
which is a substantial improvement over a previously announced peak power record of around 600 mW/cm2.
A known redox reaction occurs within a fuel cell of the liquid regenerating catalyst systems described above. The composition of a redox mediator couple and/or a redox catalyst of the redox reaction has been described in international patent applications having publication numbers WO/2007/1 10663, WO/2009/040577, WO/2008/009993, WO/2009/093080, 4.
WO/2009/093082, WO/2008/009992 and WO/2009f093081, the contents of which are incorporated herein by reference.
In order to regenerate the liquid electrolyte (catholyte) in the liquid regenerating catalyst system, it is necessary to create a large gas-Uquid interfacial area to enable the reaction together of sufficient electrons, protons and oxygen molecules to form the oxidized catholyte and the water by-product. This can be achieved by the creation of gas bubbles in the quid stream or liquid droplets in a gas stream (both these methods being known generally as gas-liquid contacting). The total surface area of the gas bubbles o is maintained for sufficient time to achieve sufficient mass transfer, after which separation of the gas and liquid streams is performed as rapidly as possible with minimal energy input. This separation is done prior to the input of the liquid electrolyte into the fuel cefl so as to provide good operation of the fuel cell.
Therefore, a bubble generator for a liquid electrolyte fuel cell system is arranged to input liquid electrolyte and gas, to generate gas bubbles in the liquid electrolyte and to output the liquid and gas in bubble form.
Preferably most of the electrolyte liquid output from the cathode region is converted into a foam form by the formation of bubbles within it, The bubbles greatly speed the re-oxidation of the electrolyte liquid during the regeneration process, prior to the electrolyte being input once again to the PEM fuel cell.
The fuel cefl uses cathode electrolyte (catholyte) in liquid form, and best performance of the fuel cell is obtained when the electrolyte at the cathode is free of gas. However, as explained above, the electrolyte output from the
C
regenerator Is mixed with air and then contains a significant proportion of gas and Is preferably In a bubbled or foamed form.
Cycionic separation is a known method of separating fine particles from a gaseous (or liquid) stream without the use of filters, through vortex separation.
s The combination of centrifugal effects and gravity are used to separate mixtures of solids and gas, and/or solids and liquid, and/or liquid and gas.
international patent application W02009006672 descilbes a gas-liquid separator used in the petroleum industry, in which an input mixture of fluids flows downward in an outer pipe along a spiral guide vane such that a gas and a liquid are separated centrifugally.
In cyclonic separation, a high speed rotating (gas) flow Is established within a cylindrical or conical container called a cyclone. Air flows In a helical pattern, beginning at the top (wide end) of the cyclone and ending at the bottom (narrow) end before exiting the cyclone upwards in a straight stream through is the centre of the cyclone and out of the top. Larger (denser) particles In the rotating stream have too much inertia to follow the tight curve of the stream, and strike the outside wall, then falling to the bottom of the cyclone where they can be removed. in a conical cyclone, as the rotating flow moves towards the narrow end of the cyclone, the rotational radius of the stream Is reduced, thus separating smaller and smaller particles. Such conIcal cyclones find applIcation In sawmills, vacuum cleaners, and in the separation of gas and liquid in a gas-liquid mixture.
However, tests with conical cyclones have shown poor performance when attempting to separate gas-liquid foams when the gas-liquid ratio is approximately 4:1, as is required in the liquid electrolyte regeneration system for best performance of the regenerator. High values of g (acceleration) are required to break down such hams, requiring a large amount of energy to accelerate the two phase mixture, giving rise to large operational cost due to parasitic power loss. Also ve,y high carry-over of liquid into the gas stream and carry-under of gas into the liquid have been observed as a result of Inadequate downward momentum of the liquid stream. These problems can be partly reduced by utilising a Gas Liquid Cylindrical Cyclone (GLCC).
A known gas liquid cylindrical cyclone was developed by Chevron and the UnIversity of Tulsa for the purpose of separation of oil and gas (e.g. Rosa, E, The cyclone gas-liquid separator: operation and mechanistic modelling, Journal of Petroleum Science and Engineering 32, 87-101(2001)). In one design a gas-liquid mixture enters a cyclone at an Input port, gas exits at an upper output port and the liquid Is extracted tangentially from the cyclone at a lower output port thereby Increasing the diameter of the gas vortex and Improving separation.
A problem arises with such a cyclone separator the time (residence time') during which the liquid is under high g conditions Is limited. This is partly because the fluid velocity Is slowed by wall drag and by separation of the gas.
However, the predominant mechanism for limited residence time Is the effect of gravity dragging the fluid out of the cylindrical section of the cyclone. These two mechanisms for fluid slowing result in a downward motion, instead of radially outward motion (as desired). To some extent this can be offset by increasing the tangential inlet velocity but doing this requires extra pumping energy which adds increased pressure drop which in turn costs more (both energetically and financially).
It Is an object of the invention to provide an improved fuel cell electrolyte regenerator that addresses the above-described problems and limitations and, in particular, to provide a regenerator that Is capable of separating gas and liquid contained in a gas-liquid mixture as rapidly as possible with minimal energy input. This is particularly desirable in the case of a gas-liquid mixture where a large gas-to-liquid ratio is employed (for example, ten times as much air as liquid, which results in a "dry foam"). Such a case conventionally requires a more energy or time Intensive separation process due to the domination of surface tension effects on coalescence.
In attempting to address the above problems and limitations, It has been found that better performance can be obtained by inducing spiral flow of the two phase gas-liquid mixture and additionally constraining the flow of the is mixture within an enclosed helical channel (i.e. a pipe rather than an open cylinder). By doing this, a high gravitational separating force (represented by effective acceleration g) can be sustained for a longer time interval, achieving more effective bubble collapse and therefore faster separation of gas and liquid.
This technique is particularly effective in breaking down a gas-liquid mixture in the form of foam (comprising bubbles), said foam containing liquid (electrolyte) and air/oxygen. However, It should be understood that the technique is also capable of providing improved separation of gas and liquid of a gas-liquid mixture when the gas-liquid mixture comprises little or no foam -8:-or bubbles, or indeed a two phase mixture of immiscible liquids which display a difference in density (i.e. liquid-liquid separation).
According to an aspect of the Invention, therefore, there is provided a separator for a liquid electrolyte regenerator of a fuel cell system, the separator comprising a helical channel In the form of a fluid channel fomied on a helix and arranged to conduct a gas-liquid mixture and separate liquid from the gas-liquid mixture.
Further aspects of the InventIon will now be described In the following detailed description of preferred embodiments of the invention which are illustrated, by io way of example only, in FIGs. I to 5 of the accompanyIng drawings, in which: FIG. 1 Is a simplified view of a helix of a helical channel for use in a liquid catalyst fuel cell. FIG. Ia is a side view of the helix and FIG. lb is a perspective view of the helix.
FIG. 2 is a part-transparent perspective view of a helical separator comprising a helical channel.
FIG. 3a Is a perspective view of a helical air-plate heat exchanger for use as a condenser.
FIG. 3b Is a part cut-away view of an end portion of the heat exchanger shown in FIG. 3a.
FIG. 4a is a perspective view of a tapered helical channel.
FIG.4bisaperspectiveviewofaventandcorestructurearrangedtobe placed In the centre of the tapered helical channel of FIG. 4a.
FIG. 5 is an internal perspective view of a tapered helical channel internal apparatus.
The helical channel of the invention will now be described.
FIG. I Is a simplified view of a helIx 150 of a helical channel 100 for use In a liquid catalyst fuel cell to separate liquid and gas of a gas-liquid mixture. FIG. Ia is a side view of the helix 150 and FIG. lb Is a perspective view of the helix 150.
The helix 150 has a helical axIs 102 (z), a helical pitch 104 (PHSS) and a dlarneter 106. Gas-liquId mixture is input to the channel at an Input end 108 to of the helical channel and is constrained to travel along the helical channel In the direction of the helix 150 towards an output end 110 of the helIcal channel 100.
It Is worth noting that the Image of the helix 150 shown in the figure represents the centre line of the helical channel and the dimension of PH needs to take Into account the thickness of a wall of the helical channel between adjacent helical flights In a longitudinal direction (parallel to the helical axIs 102). That is, PH&Ix should be rneasured from the top of one flight of the helical channel to the top of the adjacent flight above it. or from the bottom of one flight of the helical channel to the bottom of the adjacent flight below It. This can be more easily understood by refening briefly to FIG. 2 which will be described further below.
Clearly the helical channel has a hdraullc diameter I.e. a cross-sectional channel width or channel diameter (Dp) at any one point along the helical channel as shown In FIG. 2. For example, If the channel is defined by a circular section pipe, the channel diameter is the diameter of the pipe (Dpi.) whereas a square section pipe would have a channel diameter Dp that is equivalent to the square sections hydraulIc diameter.
Through the use of computational fluid dynamics, results have been obtained which indicate an optimal value of a dimensionless diameter ratio parameter (A), this parameter being a ratio between the overall transverse-axial diameter or helical diameter (D) of the helical channel and the hydraulic diameter (Dp) of a cross-section of the helical channel at any one point on the channel (A = DH6xI Dppe).
io The optimal value of A resulted in a maximal modified Dean number (Dm) for a chosen set of operational parameters, as will be explained below.
The Dean number (On) is a measure of secondary flow (inertial to centrifugal forces) and Dm takes into account appropriate helical geometrical factors.
By way of explanation, maximal separation should in theory occur at is maximum Dm by virtue of the difference In the densities of each phase.
Modified Dean Number Is given by: Dm=Re1/(KD./2) where Curvature of the helix is gIven by: K(DHSJ2)/E(DKSJ2)A2+(PHINJ21T)A2] where PH is defined as the vertical distance from the bottom of the previous flight to the bottom of the next flight (i.e. Dp,, + thickness of the helical flight), and Reynolds number (Re) for two phase flow given by Re=(pmpx Vm Dpipe)Jpinix -it-, where P,,ix (viscosity of the gas-liquid mixture) and p,,u (density of the gas-liquid mixture) are given by Pmix 416a5+(14)PL)q and S Pmix=EPGs4(l4)Puq respectively, where £ is the gas volume fraction, p is the density of the gas-liquid mixture, V is the velocity of gas-liquid mixture, Mmix Is the viscosity of the gas-liquid mixture, and p, Mug, p and pug are the viscosity and density of the gas and liquid, respectively. The gas volume fraction c is given to by: £ t QGaJ(Qas+Quq) where Oc and Qug are the flow rates of the gas and liquid respectively.
In turbulent flow, centrifugal forces are dominated by inertial forces and thus secondary effects are reduced. This accounts for the delayed development of turbulent flow In helical pipes (Mends!, S.N. & Des, S.K, Gas-Liquid Flow through Helical Coils In Vertical Orientation, Industrial & Engineering Chemlst,y Research 4Z 3487-3494, 2003).
Initial modelling studies have been conducted by the inventors, in which Ppj,c was fixed as 1.3 times greater than the channel or pipe diameter p1*3*p It should be noted that manufacturing constraints (i.e. thickness of pipe wall)) limited this ratio. The free variables were thus flow rate and diameter ratio A. Flow rates for the liquid and gas were constrained to practical operational -12 -values. That is to say, liquid flow rate (Qu) was chosen to be between 3 and Litres per minute (L/min) and gas flow rate (Q0) was chosen to be between 12 and 120 Litres per minute (L/min). The diameter ratio A was varied from 0 to 1000 with Dm as an output. The results of this study suggested an optimal value of A occurs when a dimensionless pitch parameter (H) approaches unity, where H = PHex / (2T1RHex), where: RHsiDkeIij2 That is, the results suggested an optimal value of A occurs when the heHcal ic pitch PHepx is equal to it times the overafl helical diameter DHdI, i.e. Optimum PH0; = TTDH1t This results in maximum modified Dean number being obtained.
Experiments were performed in which the variation of modified Dean number Dm was noted for different values of the dimensionless pitch parameter, H. It was found that Dm is maximum when H approaches unity, as suggested above. This corresponds to an optimal value of diameter ratio A of 1/n, which is physicafly impossible.
From these results, values of Dm were calculated for different values of A. The optimum value of A provides a maximum value of Dm. Optimising A for maximal Dm (in addition to optimising the dimensionless pitch parameter, H) provides a fully defined system.
As can be seen from the above, a consequence of the mathematical relations governing flow in a helical geometry means that the greatest Dm will occur in a pipe of given diameter when the helical diameter is smaller than the pipe 13 -diameter (optimum A is 1/Ti). However, clearly, such a theorefical optimum value for A is physically impossible, since the overall helical diameter DHejg cannot be less than twice the pipe diameter Dpipe (see for example HG. 2 described below). This means that A is constrained to be greater than or s equal to two. In practice, A must be greater than two because of non-zero wafl thickness of the hehcal channeL Therefore the best physicaHy-realisable value of A is slightly greater than two, that is, as close to two as possible, to achieve maximum value of Dm.
Preferably therefore, according to a preferred embodiment, DHe and at io any one point are arranged such that the overall helical channel diameter DH is as close to 2*Dpp as physicafly achievable.
FIG. 2 is a part-transparent perspective view of a helical separator comprising a helical channel that has been used successfully to separate electrolyte liquid and gas (air) at full scale flows. The resulting pressure drop in this configuration is less than 12.5% of the pressure drop that occurs in a known GLCC design of similar size, thus performing bulk separation of the liquid and gas.
After bulk separation is performed by the apparatus of FIG. 2, some mist droplets are seen in the air flow in the output region. Also, it is known that the air exiting the separator is saturated with vapour phase liquid.
Even though the separator of FIG. 2 is effective at separating gas and liquid, a relatively large proportion of liquid becomes trapped in its vapour phase even upon separation of the gas and liquid phases. This is due to the operating conditions of the FlowCathTM system, i.e. the operating conditions of gas liquid contacting and the relatively high temperature at which this gas-liquid contacting operation is carded out. This represents a potential application of this technology for a heat transfer application (see FIGs. 3a, 3b, discussed below).
s Separation of vapour phase liquid from gas can be performed by known air-air heat exchanger technology. However, although air-air heat exchangers are relatively efficient at the industrial scale, they do not condense enough liquid from the vapour phase to control concentration in at least one known I kW net steady state system with the Ssting size and power constraints of the FlowCathN System. This limitation represents a problem to solve.
Two methods of achieving better vapour phase removal of liquid are: (a) increasing surface area of the heat exchanger; and (b) increasing cold air flow through the heat exchanger. However these methods are non-optimum because of large packaging volume and large parasitic load, respectively. A is problem therefore still exists.
In attempting to address the above problems and limitations, it has been found that a second spiral separator (of the same dimensions of the first) can be very effective in removing any entrained liquid phase droplets, giving exceptionally good separation of electrolyte and also some preliminary condensation of water.
Additionally, in a preferred envisaged configuration of a helical separator, a cold-air stream and a hot-air stream (water rich in the vapour phase) are segregated by a metal (e.g. steel) enclosure in a helical flow path.
A first helical chann& (e.g. the helical channel 200 of FIG. 2) separates the liquid and gas of the gasHquid mixture to produce (a) bulk liquid that is still in the Hquid phase, (b) a gas phase saturated with vapour phase liquid and (c) a liquid phase that is entrained in the gas phase in the form of mist. A second s helical channel (e.g. the helical channel 302 of FIG.3a or 302 of AG. 3b discussed b&ow) then separates the saturated gas phase and liquid phase droplets into gas and liquid phase liquid.
Secondary flow within the curved geometry of a helical channel increases heat transfer coefficients, the effect of which is greater for laminar flow. The ic flow regime for the current FlowCathTM system (and those in the near future) will be laminar for an air-plate condenser. It has been found that confining a plate or fin of a heat exchanger within, or as part of, an enclosed helical channel serves to enhance separation of vapour phase liquid and gas as a result of the (approximately two-fold) increase in heat transfer coefficient.
This allows the surface area of a condenser to be halved whilst still affecting the same amount of separation.
It follows that an aspect of the invention is providing a separator for a liquid electrolyte regenerator of a fuel cell system comprising a helical channel in the form of a pipe formed on a helix and arranged to conduct a gas-liquid mixture and separate liquid from the gas-liquid mixture, wherein the helical channel of the separator is an enclosed channe along which the gas-liquid mixture is constrained to travel. The helical channel can be used as a heat exchanger (for example, an air-air plate condenser or counter current shell and tube exchanger for denser fluids) for conducting a fluid to be cooled. Such a heat exchanger is particularly useful for conducting and cooling fluid in vapour phase so as to perform condensing of the fluid.
FIG. 3a is a perspective view of a proposed configuration of a new helical air-plate heat exchanger 300 employing this principle for use as a condenser.
S The heat exchanger 300 comprises six enclosed helical channels 302, 304 306, 306, 310, 312 (five channels for the cooling air and the remaining channel to be used for the hot, vapour rich air.) FIG. 3b is a part cut-away view of an end portion of the heat exchanger 300 shown in FIG. 3a, Helical channels 302, 304, etc. can be seen more dearly.
Between adjacent (cold-air) helical channels, a gap 320 exists, in which fluid such as hot, vapour rich air can move past the outer surface 310, 312 of each helical channel. As can be seen, the helical channels in this embodiment are in the form of hollow fins. In this case the helical channel' comprises plural hollow fins. The hollow construction allows separate supply of cooling fluid is (e.g. air) which will flow over the outer surface of the helical channel but will not mix with the gas-liquid mixture within the helical channel.
A currently employed, off-the-shelf air-air plate condenser has approximately 0.6m2 total surface area (UK Heat Exchangerstm). By contrast, the heat exchanger shown in FIG.s 3a and 3b has a total cold surface area of 0.431m2, made possible by the two-fold increase in heat transfer coefficient, which allows a significant reduction in overall size of a condenser used in a given PEM fuel cell system.
Further improvement of the heat exchanger may be achieved by increasing the surface area of the fins or cooling surfaces of the helical channel of the I7-heat exchanger, by providing nonsmooth cooUng surfaces, for example by means of corrugation and/or dimpling of the cooling surfaces (FIG. 3b, 310, 312), without any need for increased packaging volume.
A further improvement in separation may be achieved by arranging the fins or s cooling surfaces so that they comprise a surface comprising a low surface energy material (for example PTFE). A highly hydrophobic material can induce coalescence by harnessing the de-wetting force to force plateau borders apart, thereby becoming energeticaUy favourable to form a single bubble, rather than two bubbles separated by a plateau border.
to According to an embodiment, there is provided a combination of the heflces shown respectively in FIGs. 2 and 3 with the exception that the closed section shown in FIG. 3b is left open. In this embodiment, the gasiiquid mixture enters the helix as described above for FIG. 2. However, the fluid passage houses several "fins" with flights running parallel to the main helix flight.
These fins, the wall of the helix tube and the main helix flights would be coated with a low surface energy material. The diameter of the fins would be slightly less than the main helix diameter to allow the development of helical flow as described above for the embodiment shown in FIG. 2.
The above-described low surface energy fins would not affect the overaH fluid flow within the helix greatly, although there would be additional pressure drop per unit length due to an increased internal surface area/friction effect.
However, it is likely that there would not be an overall increase in pressure drop as these low surface energy fins would increase the rate at which gas-liquid separation is effected and therefore would require a shorter overall length of helix. This embodiment allows the overall size of the device to be reduced whilst maintaining effective separation.
FIG. 4a is a perspective view of the fluid passage of a tapered helical channel 400 having a greater helical diameter at the inlet and a smaller helical diameter at the exit. The gas-liquid mixture enters at the Inlet. The separated gas then exits gradually through gas vents in an Inner core of the helix (FIG.
4b) with a minimal amount of air exiting through the fluid exit, thus approaching pipe flow and moving away from free surface flow. The venting of air paitway down a helix has been proposed by Rosa et al (Rosa, E, Journal of Petroleum Science and Engineering 32, 87-101, 2001,and OAPI patent application publication no. OAI 1321(A)). However, Rosa discloses an arrangement having a constant helix diameter unlike the embodiments described above and shown in FIGs. 4 and 5 whIch have a graduated helical diameter and a graduated pipe diameter.
is The embodiment shown in FIGs. 4a and 4b provides an improvement over the design shown In FIG. 2. Using a pipe that decreases in diameter as the fluid travels downward towards the outlet will result In an increase in velocity according to the continuity equation. Concomitantly, the effective gravity force acting on the gas-liquid mixture will increase.
Even in the case of a high gas to liquid ratio the difference In densities is very large such that the contribution of the gas to the momentum of the gas-liquid mixture is minor. Thus, even when complete separation is achieved, the fluid maintains the majority of the momentum It had when entering the helix as a gas-liquid mixture. The decrease in pipe diameter as the fluid travels towards the outlet is such that the liquid will increase in velocity. As a result of the increase In fluid velocity and the decrease in radius of rotation the effective gravity acting on the gas-liquid mixture Increases dramatically compared to a constant-section helical separator.
For example, using the same flow rate and composition of gas-liquid mixture the effective gravity imposed on the constant section (FIG. 2)is lOg (i.e. 10 times gravity, that Is, 98.1 mIs2), whereas the effective gravity Imposed on the tapered helix shown in FIG. 3a and FIG. 3b starts at lOg and reaches a much higher maximum of 21g.
FIG. 5 is an internal perspective view of an internal apparatus 500 that may be io used to define the tapered helical channel 400 shown In FIG. 4a. The internal apparatus 500 has a spiral vane 501 and an inner wall 502, attached to the vane 501, which may have one or more gas vents 503 in It, allowing gas to exit vertically or part-vertically so as to prevent re-entrainment upon fluid exit This configuration serves to abrogate pulsating flows which can be caused by is "slugs" of liquid-rich material forming in the channel. It also serves to reduce the overall size of the channel, to move away from free surface flow and, most Importantly, to increase separation efficiency. The helical channel 400 (FiG.
4a) comprises an outer wall (not shown) adjacent to and surrounding the spiral vane 501 of the apparatus 500.
The gas vents 503 may comprise a microporous membrane 503, which may form all or part of the inner wall 502 of the hellcat channel 400, allowIng gas to escape early and preventing liquid escape due to the hydrophobic nature of the membrane. The gas vents 503 are arranged to inhIbit the passing of lIquid through them due at least in part to their small dIameter. -20.
The helical channel 400 (FIG. 4a) may comprise a porous bubble generating &ement 504 (not shown in FIG. 4a) incorporated in the outer wall of the hehcal channel 400. The positioning of the porous bubble generating element 504 utflises the already existing differential density between gas and liquid in addition to the imposed cenLrifugal gravity as a result of the helical flow path in the heflcal channel 400 to ensure rapid movement of gas from outer wall to inner waH 502. This arrangement allows the greatest mass transfer rate (which corresponds to reaction rate in this system) between the gas and liquid as a result of the greatest driving force for mass transfer and reaction (high concentration of reactants).
Additionally, this arrangement allows an overall very high gasliquid ratio to be achieved which would not be possible by using a single air injection point.
The porous bubblegenerating element 504 may be used to concurrently perform ga&liquid contacting, whilst the turn (flight) of the helix after the porous element can be used for separation. The porous element 504 is shown in FIG. 5 as plural openings or vents, but could equally be a microporous membrane. The porous element 504 allows the helical channel to operate both as a separator and as a regenerator. It should be understood that the gas vent 503 and porous element 504 can be used with a helical channel having a helical diameter that is not tapered or graduated, i.e. is constant.
The use of the porous &ement or aperture(s) may enable more volumetric efficient helix geometry because of the dual function of gasliquid contacting and gasliquid separation.
Helical flow devices are widely used in heat transfer apphcations. However, helical flow has not been used in a liquid catalyst fuel cell system. Such liquid catalyst fuel cell systems have not included any capability for the destruction of foams or separation of droplet streams having high gas-liquid ratio. The use s of a microporous membrane to vent air/gas from a helical channel to achieve separation of a gas-liquid mixture is novel.
--
Claims (1)
- <claim-text>CLAIMS1. A separator for a liquid electrolyte regenerator of a fuel cell system, the separator comprising a helical channel in the form of a fluid channel formed on a helix and arranged to conduct a gas-liquid mixture and separate liquid from the gas-liquid mixture.</claim-text> <claim-text>2. The separator of claim I wherein the overall helical diameter (Dp,) of the helical channel is close to twice the hydraulic diameter (D,,w) of the helical channel along at least a portion of the helical channel.</claim-text> <claim-text>3. The separator of claim I or 2, comprising a porous element, located at an exterior wail region of the helical channel, through which gas can pass.</claim-text> <claim-text>4. The separator of any preceding claim, comprising a porous element located at an interior wail region of the helical channel, through which gas can pass.</claim-text> <claim-text>5. The separator of any preceding claim, comprising a further helical channel formed on a smaller-diameter helix and In fluid communication with the helical channel, the further helical channel being arranged to conduct liquid and gas of a portion of the gas-liquid mixture that passes from the helical channel to the further helical channel and to separate liquid from the portion of the gas-liquid mixture.</claim-text> <claim-text>6. The separator of claim 5, wherein at least one of the helical channel and the further helical channel has a surface comprisIng a low surface energy material.</claim-text> <claim-text>7. The separator of claim 5 or 6, whereIn the further helical channel comprises heat conductive material and is surrounded by the helical channel, the further helical channel being for conducting a fluid colder than said gas-liquid mixture, 8. The separator of any preceding claim, wherein the helical channel comprises a non-smooth outer surface.9. The separator of any preceding claim, wherein the helical channel comprises plural channels brined on respective plural heiices substantially parallel to each other.10. The separator of claim 9, wherein the plural helices have separate longitudinal axes.11. The separator of any preceding claim, wherein the overall helical diameter and the hydraulic diameter of the helical channel are graduated along the helical channel between an inlet having larger overall helical diameter and larger hydraulic diameter and an outlet having smaller overall helical diameter and smaller hydraulic diameter.12. The separator of any preceding claim, comprising a gas vent between the heflcal chann& and an inner core surrounded by the hecal channel, aflowing separated gas to pass through the gas vent between the heflcal chann& and the inner core.13. The separator of claim 12, wherein the gas vent comprises a hydrophobic material having pores or micro-pores for inhibiting passage a Uquid through the pores and aflowing passage of gas through the pores.14. The separator of any preceding claim, wherein the heUcal channel comprises a first heUcal channel for separating liquid from the gas-Uquid mixture to produce bulk Uquid-phase Uquid and gas, and a second helical channel, coupled to the first helical channel, for separating vapour-phase Uquid and entrained liquid phase Hquid from the gas.15. The separator of any preceding claim, wherein the gas-liquid mixture comprises liquid in the vapour phase.16. The separator of any preceding claim, wherein the separator comprises a bulk separator for performing separation of a gas-liquid mixture comprising Uquid in liquid-phase, a demister for performing separation of a gas-liquid mixture comprising liquid in both liquid-phase and vapour-phase, and a condenser comprising an air-air plate heat exchanger for performing separation of a gas-liquid mixture comprising liquid in vapour-phase, wherein at east one of the bu'k separator, the demister and the condenser has a helical channeL 17. A separator and regenerator apparatus, comprising the separator of any one of claims I to 16 and a regenerator arranged to input liquid &ectrolyte and gas to generate gas bubbles in the Uquid electrolyte and output the hquid and gas in bubble form.18. Use of a fuel cefl system comprising the separator of any one of claims I to 16 or the separator and regenerator apparaLus of claim 17, for the combined generation of heat and power.19. Use of a fuel cefl system comprising the separator of any one of claims I to 16 or the separator and regenerator apparatus of claim 17 to provide motive power to a vehicle.20. Use of a fuel cefl system comprising the separator of any one of claims I to 16 or the separator and regenerator apparatus of claim 17 to generate power in an electronic component.21. A separator substantiafly as described herein and as illustrated in one or more of the accompanying drawings.22. A separator and regenerator apparatus substantiafly as described herein and as illustrated in one or more of the accompanying drawings. -2623. A helical heat exchanger substantially as described herein and as illustrated in one or more of the accompanying drawings.</claim-text>
Priority Applications (14)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1201246.4A GB2498741B (en) | 2012-01-25 | 2012-01-25 | Improved fuel cell electrolyte regenerator and separator |
| JP2014553803A JP2015511872A (en) | 2012-01-25 | 2013-01-25 | Improved fuel cell electrolyte regenerator and separator |
| PCT/GB2013/050173 WO2013110950A1 (en) | 2012-01-25 | 2013-01-25 | Improved fuel cell electrolyte regenerator and separator |
| EP13704220.6A EP2806959A1 (en) | 2012-01-25 | 2013-01-25 | Improved fuel cell electrolyte regenerator and separator |
| PCT/GB2013/050174 WO2013110951A1 (en) | 2012-01-25 | 2013-01-25 | Separator |
| BR112014018155A BR112014018155A8 (en) | 2012-01-25 | 2013-01-25 | SEPARATOR, SEPARATOR UNIT, METHOD FOR SEPARATING THE GASEOUS AND LIQUID PHASES OF A FOAM, FUEL OR HYDROLYTIC CELL, BIOCHEMICAL FERMENTATION UNIT OR FOAM FLOTATION UNIT, USES OF A SEPARATOR, DEVICE AND FOAM SYSTEM FUEL CELL, FOAM REDUCTION AND GAS/LIQUID SEPARATION EQUIPMENT, AND FUEL CELL SYSTEM |
| EP13702098.8A EP2806960A1 (en) | 2012-01-25 | 2013-01-25 | Separator |
| KR1020147023590A KR102129891B1 (en) | 2012-01-25 | 2013-01-25 | Separator |
| US14/374,874 US20150037695A1 (en) | 2012-01-25 | 2013-01-25 | Fuel cell electrolyte regenerator and separator |
| CN201380006781.9A CN104203362B (en) | 2012-01-25 | 2013-01-25 | Separator |
| JP2014553804A JP2015511873A (en) | 2012-01-25 | 2013-01-25 | Separator |
| US14/374,884 US20150031124A1 (en) | 2012-01-25 | 2013-01-25 | Separator |
| EP16190007.1A EP3138617B1 (en) | 2012-01-25 | 2013-01-25 | Separator |
| JP2016186876A JP6310982B2 (en) | 2012-01-25 | 2016-09-26 | system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1201246.4A GB2498741B (en) | 2012-01-25 | 2012-01-25 | Improved fuel cell electrolyte regenerator and separator |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB201201246D0 GB201201246D0 (en) | 2012-03-07 |
| GB2498741A true GB2498741A (en) | 2013-07-31 |
| GB2498741B GB2498741B (en) | 2015-04-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1201246.4A Expired - Fee Related GB2498741B (en) | 2012-01-25 | 2012-01-25 | Improved fuel cell electrolyte regenerator and separator |
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| GB (1) | GB2498741B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700876A (en) * | 2013-12-11 | 2014-04-02 | 西安交通大学 | Helical-like connector flat plate solid oxide fuel cell stack |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10305070B2 (en) | 2015-07-14 | 2019-05-28 | Johnson Controls Technology Company | Textured lead-acid battery housing |
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|---|---|---|---|---|
| SU1519734A1 (en) * | 1987-06-18 | 1989-11-07 | Научно-производственное объединение "Полимерсинтез" | Mass-exchange apparatus |
| OA11321A (en) * | 1997-08-26 | 2003-10-27 | Petroleo Brasileiro Sa | Improved helical separator. |
| WO2009006672A1 (en) * | 2007-07-12 | 2009-01-15 | Commonwealth Scientific And Industrial Research Organisation | Fluid-fluid separator |
| JP2011104501A (en) * | 2009-11-16 | 2011-06-02 | Mingasu:Kk | Gas separation apparatus and gas separation method |
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- 2012-01-25 GB GB1201246.4A patent/GB2498741B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SU1519734A1 (en) * | 1987-06-18 | 1989-11-07 | Научно-производственное объединение "Полимерсинтез" | Mass-exchange apparatus |
| OA11321A (en) * | 1997-08-26 | 2003-10-27 | Petroleo Brasileiro Sa | Improved helical separator. |
| WO2009006672A1 (en) * | 2007-07-12 | 2009-01-15 | Commonwealth Scientific And Industrial Research Organisation | Fluid-fluid separator |
| JP2011104501A (en) * | 2009-11-16 | 2011-06-02 | Mingasu:Kk | Gas separation apparatus and gas separation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103700876A (en) * | 2013-12-11 | 2014-04-02 | 西安交通大学 | Helical-like connector flat plate solid oxide fuel cell stack |
| CN103700876B (en) * | 2013-12-11 | 2016-12-07 | 西安交通大学 | One kind helical form connector flat-plate solid-oxide fuel battery stack |
Also Published As
| Publication number | Publication date |
|---|---|
| GB201201246D0 (en) | 2012-03-07 |
| GB2498741B (en) | 2015-04-01 |
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