JPS58137973A - Cross flow molith reactor with solid electrolyte sheet and method of producing same sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to lipped catalyst coated solid state electrolyte sheets and methods of making such sheets.

Chemical reactions that release large amounts of heat can be carried out in fuel cell reactors, where most of the energy change is converted to electricity rather than heat. This direct conversion of chemical energy to electrical energy is subject to the Carnot limit (Carnot
t 1llitatio11) and therefore very high thermodynamic efficiencies can be achieved.

Solid electrolyte fuel cells operating with Hl or CO as fuel are well known. Solid electrolyte electrochemical reactor 1
The advantage of these two is that they are electrodes! This allows operation at the typical 21°C temperature, which is catalytically advantageous and minimizes turbulence. For example, a doped zirconia cell with a Pt catalytic electrode can be used with faJv of electrical energy
It has been shown that ammonia can be used to convert ammonia to nitrogen oxide with the generation of I.
(S clones) was recently shown by Nas) et al.
IQJ-593, 1980 and U.S. Patent No. 4272
No. 336).

A major factor determining the commercial utility of solid electrolyte batteries is their power density.
). Although the use of thin solid electrolyte components as in the present invention can yield high current densities, typically 200 mA/am, fuel cell designs experimentally demonstrated to date have low electrolyte to reactor volume. These reactors were therefore characterized by a relatively low power density.

In the reactor of the present invention, a typical electrolyte surface to reactor ratio of 10C1 electrolyte 7101 reactor capacity is possible.

Also relevant to the present invention is US Pat. No. 3,854,186 which teaches mixing ceramic materials in particulate form with polymeric binders (eg polyethylene and plasticizers).

The blend is mixed to achieve homogeneity and then extruded to form a lipped sheet. The sheet pieces are layered in an alternating manner and sealed to each other to form a cross-flow monolith.
ith) to extract the plasticizer, and the monolith is then fired to remove the binder and sinter the ceramic material.

Monolithic (10n011thic) reactor heat exchangers are manufactured by Deonan and Wei (Cheslcal Re
actiOn E nQ-eneering, AC
8,5ysposiu-5eries No.

65.1978), in which a catalyst was deposited on a monolith and it was used to oxidize carbon-oxide.

It is also known to carry out chemical reactions in layered structures in which ceramic materials are solid electrolytes.

In particular, US Pat. No. 4,272,336 teaches that a layer of tubing can be coupled to a manifold.

The inner and outer surfaces of the tube are coated with an oxygen dissociation catalyst and a catalyst to promote ammonia oxidation, respectively. In operation, oxygen is decomposed by a catalyst to form oxygen ions that are transported through the solid electrolyte. At the surface of the oxidation catalyst, am ions react with ammonia to produce nitrogen oxide.

Electrolytic reactions produce electricity, which is dyed by electrical conductors. In one embodiment, gas is passed through the catalyst coated tube while allowing a second gas to flow past the tube in a direction perpendicular to the gas flow within the tube. other 1lIv
A (Figures 5 and 6 of U.S. Pat. No. 4,272,336)
is a series of parallel chambers between the plates.
ers) is a series of catalyst-coated plates. The chambers are divided into two groups, the chambers of the first group being arranged alternately between the books of the second group. A first gas (eg, l! element) is passed through the 1111 group of chambers, and at the same time a second gas (eg, ammonia) is passed vertically through the second group of chambers. Ammonia is oxidized to form element 11 oxide. DE 1928300 describes an oxidation system similar to that of US Pat. No. 4,272,336
The number is also advantageous.

Suitable sheets for use in the fuel cell reactor described herein are: 1) When melted, l! 2) homogeneously mixing a particulate inorganic filler capable of transporting ions, an olefinic polymer having about 150,000 to 5,000,000 molecular weights, and a plasticizer; 2) forming the mixture into a lipped sheet; 3) extracting the plasticizer; and 4) heating the sheet to decompose it and remove the organic aggregates and melt the inorganic filler particles. .

A sheet produced as described above is shown in FIG. The manufacture of such a sheet is further described in Example 1. Referring to FIG. 1, the sheet 4 is comprised of an inorganic, ceramic, oxygen ion transporting material, such as yttria-stabilized zirconia, and is arranged parallel to the rear (i.e. lipped) surface 5 of the sheet, essentially It consists of a rectangular member with a series of lips forming parallel channels 4a.

Although the lip shown is straight, the lip is a straight line (
linear). For example, they may have non-linear shapes such as curved or zigzag shapes insofar as they are spaced apart on the sheet forming approximately parallel channels through which gas can flow extending from one end of the sheet to the other. It can also take a nonlinear shape. The other front side of the seat has a smooth, lip-free surface.

The sheet 4 is essentially gas flow impermeable in the sense that gases and liquids do not pass through the sheet.

A suitably impermeable sheet is described in Example 1.

Referring to FIG. 2, the two sheets 4 and 6
and 6b are positioned on top of the other such that they form an angle of 90'' with respect to each other. If non-linear ribs are used, the angle formed by the adjacent sheets is Measured with respect to the angle formed by the orientation of parallel elongated channels in the two sheets: channel 4a is coated with a catalyst for the oxidation of the reactant (e.g. ammonia), whereas channel 6a is coated with a catalyst for the oxidation of the reactant (e.g. ammonia), whereas channel 6a is The reactor of Figure 4 can also be designed using sheets with as little as 30' angle of adjoining sheets. This can be achieved by adjusting the sheets to each other while shaping them to match. Alternatively, angles other than 90", e.g. 30°
It is to form a lip in the sheet at an angle of .

The sheets for preparing the layered structures of Figures 2.3 and 4 are made from starting materials consisting of inorganic fillers capable of transporting oxygen ions in the solid state. Furthermore, polyolefins and plasticizers are used. References made to polyolefins should generally be understood as referring to high molecular weight polyethylene. More specifically, polyolefins with very high I-I (e.g. at least 150,000) are good binders for ceramic powders and can absorb filler loads without embrittlement in the presence of plasticizers. can be tolerated. This is compared to conventional thermoplastics such as approximately 60,000
It is very similar to, for example, low molecular weight polyethylene with a molecular weight of 100,000 to 100,000. These low molecular weight polyethylenes produce brittle products at relatively low filler concentrations.

In preparing the initial mixture, the actual amounts of filler polymer and plastic can vary over a wide range. However, for purposes of processing the blend, it is essential that the blend be viscoelastic in the sense that it has melt elongation when melted. The blend must also have a viscosity low enough to undergo molding or extrusion, and following molding the strength must be sufficient to permit removal from the mold. Generally, the blend has a torque of 200 to 280 as measured on a Prabender plastograph with a roller head operating at about 50"p and 165°C.
0 meter duram, preferably 2000-2500 meter grams will satisfy the above parameters. In addition to the components listed above, other materials (eg, inorganic fillers or thickeners or catalyst support materials) can be used in the blend as long as they do not adversely affect the final ceramic structure. Useful blends range from 1.20 to 2
8% by volume, preferably 25%, of inorganic filler and 2. Ultra-high molecular weight linear polyethylene (preferably 20%) with a molecular weight greater than 2.150.000.
LIHMW-PE) 18-25% by volume, these materials meet ASTM D-4020-81
．． 3.47-62% by volume, preferably 54%, of a hydrocarbon oil plasticizer. Any oil from white mineral oil to Bunker C fuel oil can be used as a plasticizer. Additionally, up to 1% by volume of zinc stearate can be used in high concentrations as an internal lllllllll agent to promote dispersion of the filler in the polymer suspension. This is not a required additive; other similar materials can be used.

Solid electrolytes capable of transporting oxygen ions can be used in this case. In terms of square shape, the oxygen ion conductive solid electrolyte is Zr0z, ThO! and oxides containing tetravalent cations such as C60t and oxides containing divalent and trivalent cations, such as cao, S C1tO
3, YzOg.

A solid solution formed between LazO3, etc.

Their higher ionic conductivity is due to 0-1 site vacancy (0-
'''5ite vacanoles).1
Two 0-1 vacancies occur for each divalent or for each two trivalent cations substituted for a tetravalent ion in the lattice. Particularly advantageous is about 15 mol% Ca in zr Ot.
A solid solution containing O (calcia-stabilized zirconia) or about 1 to 10 mol% (preferably 3-7 mol%) of Y2O2 (ytria-stabilized zirconia) in z'0! These latter two solid electrolytes are characterized by high ionic conductivity, pure mion conductivity over a wide range of concentrations and oxygen pressures, and relatively low cost.

The materials are listed in Figure 1! Methods of forming such sheets are well known and include compression molding and extrusion. When the sheet is constructed by compression molding (at 165° C.), a thickness reduction ratio that is sufficient but as small as possible is used so as not to adversely affect the structural integrity of the sheet. In general, a thickness reduction ratio of: Q, 05 to 0.5 (7) is used. This ratio is defined in U.S. Pat. In calculating this ratio, the thickness reduction is measured only with respect to the surface of the sheet and does not include protrusions such as rips. Similar process parameters are used in extrusion. However, The extrusion concentration is generally 30-50 DEG C. to suitably reduce the viscosity.As can be seen by referring to FIGS. 1 and 2, the lip has a structure with uniform channel openings in both directions. Clearly the construction method can be used to provide non-uniform channels if desired.

After the sheet is formed, the plasticizer is extracted.

Extraction is accomplished with a solvent in which the plasticizer is soluble.

For example, when the plasticizer is a hydrocarbon oil, it can be extracted with organic WI media such as hexane, heptane, pentane and chlorinated solvents such as carbon tetrachloride, trichlorethylene and perchlorethylene. Other organic solvents such as petroleum ether and diethyl ether can also be used. If the plasticizer is a water-soluble compound, the plasticizer can be extracted with water. Suitable plasticizers can be soluble or insoluble in water. Typical water-insoluble plasticizers include organic esters such as sebacates, phthalates, stearates, adipates, and citrates; epoxy compounds such as epoxidized vegetable oils;
Phosphate esters such as tricresyl phosphate, S+M oils and fuel oils, petroleum crudes including hydrocarbon resins and pure compounds such as asphalt and eicosane; polyisobutylene, polybutadiene, polystyrene,
low molecular weight polymers such as atactic polypropylene, ethylene-propylene rubber, ethylene-vinyl acetate copolymers, polyethylene oxide, coumaron-indene resins and terpene resins, tall oil and linseed oil.

Examples of water-soluble plasticizers are ethylene glycol, polyethylene glycol, polypropylene glycol, glycerol and its ethers and esters: alkyl sulfates such as triethyl phosphate; polyvinyl alcohol: polyacrylic acid and polyvinylvinylidene.

After the plasticizer has been extracted, the units can be cut from large sheets. These units should be sized to suitably allow for shrinkage in subsequent process steps, which can range from about 10 to 50%. Preferably, the sheet is cut to its final shape at this point rather than after firing. This is because it reduces breakage problems caused by cutting the ceramic structure.

Firing the sheet is accomplished by heating it above the decomposition temperature of the thermoplastic so as to completely burn out the polyolefin. Of course, the degree of decomposition will vary with the choice of polyolefin.

^ Using linear polyethylene, the viscosity is at least 240
It is possible to initiate the decomposition using concentrations in the range of -260°C. At a concentration of about 240°C (when polyethylene is a polyolefin), the structure begins to turn black;
At about 700° C. the structure begins to turn white, indicating that a significant portion of the thermoplastic has been removed. As soon as the thermoplastic is removed, the filler begins to sinter,
That is, the particles begin to coalesce. To complete the sintering stage,
The temperature is increased sufficiently above the concentration required to remove the thermoplastic. When using yttoria-stabilized zirconia, for example, about 1300°C~! !
A concentration of 2000°C is recommended.

That is, within this 11 degree range, it is preferred to use the lowest concentration that results in sufficient sintering to produce a sheet that is impermeable to gaseous reactants. The concentration is held at the sintering point long enough to complete sintering, and then the structure is allowed to cool slowly to room temperature.

The mechanism by which a fluid (ie, gas) impermeable sheet is produced begins with the disintegration and removal of the integral binder.

If the residual carbonized residue of the binder is not removed, the carbonaceous material acts as an "Iceland" in the flowable sintered ceramic material. Such carbonaceous residues are visible and impart a grayish coloration to the ceramic sheet. Importantly, these "Icelands" also introduce porosity to the sheet and should therefore be removed as completely as possible. This can conveniently be achieved by operating the calcination under oxidizing conditions, at least for a portion of the calcination (Cornlno) (particle size smaller than 325 mesh, i.e. particles larger than about 30 microns). sil-coa zirconia (7ir-coa zlr) from
When using conla), the temperature should be 1400℃! ! 19
Sintering at 00° C. 1I11 [was applied but resulted in a porous sheet. In contrast, Zirker zirconia is sintered at 1500° C. to provide a fluid-impermeable sheet.

Zirker zirconia u had a particle size of 0.1 to 0.03 microns.

The final sheet structure has the same geometric appearance as the structure as previously cut, except that significant linear shrinkage has occurred. Shrinkage increases with the amount of thermoplastic and plasticizer used. During polyolefin removal and filler sintering, buckling should be reduced to 16/h. ni-)C restraint object (co
nstraints) are strained onto the sheet. Following calcination, an electrically conductive catalyst for oxygen dissociation or oxidation can be applied to the sheet by conventional means such as precipitation, base coating, or vapor deposition from the carrier composition.

Typical catalytic materials useful for decomposing 11 ions into elementary ions include platinum, platinum-rhodium alloys, gold, silver, and the like.

Typical catalysts suitable for promoting oxidation include platinum, platinum-
Includes rhodium alloys, platinum-rhodium-palladium alloys, and the like. A preferred catalyst for oxygen ion production and ammonia oxidation may comprise a platinum-rhodium alloy containing about 5% to 15111i% rhodium. Rhodium provides little catalytic activity in oxidizing ammonia, because this catalyst is effective in promoting the desired reaction and can withstand the reaction conditions encountered for long periods of time. However, it acts to stabilize platinum under the reaction conditions.

A wide variety of catalysts can be used for the oxidation reactions that occur in the 6a channel. In order to preserve reactor efficiency, a catalyst that is electrically conductive (in both channels 4a and 6a) should be deposited (at X) in an essentially uniform, continuous porous layer. A typical organic material sensitive to oxidation is Cl-Cs hydrocarbon, i.e. ethylene,
Light olefins (i.e. C I- C b ), methane and light olefins (i.e. CI-04), benzene and light aromatics, i.e. benzene or naphthalene, where the total number of carbon atoms in the alkyl substituent is from 1 to 6. Like Anoleki J
and includes substituted rings. Suitable catalysts and reaction conditions for oxidizing the above materials are well known in the art and include Pt%Ao, Pd, Rh, Fe, Go, N
i, V181, MO 1Ru, Rh, Sn,
Includes metals such as Sb and their alloys or oxides. For the various fuel materials to be oxidized, a preferred catalyst system is as follows: platinum (C.

/H! , for the oxidation of paraffins, olefins and aromatics): palladium (for ethylene and Go/H!); silver (for methanol, ethylene, propylene)
: bismuth and molybdenum (for propylene); iron (for ethylbenzene and Go, 'Hs); and nickel, cobalt and ruthenium (for GO/Ht
). Platinum is also very useful as a catalyst for the oxidation of ammonia and sulfur. For the above description of catalysts, the actual active form of the catalyst can be oxides and other forms, and therefore the designation of a particular metal catalyst is intended to encompass its art-recognized equivalents.

In describing a fuel cell reactor, the term "reactor" refers to a series of stacked sheets coated with various catalysts in which an oxidation reaction takes place.The term "fuel cell reactor" or "fuel cell reactor" shows a reactor equipped with electrical conductors for conducting the current generated during the oxidation reaction. The term “chemical reaction” refers to oxidation and l! Includes both prefecture-based armor. A catalyst is described as ``promoting'' a reaction when it increases the rate of the reaction, either directly or by increasing the activity of other catalytic materials.

A one-piece, integral fuel cell reactor can be constructed from sheets such as those described in FIGS. 1 and 2. Referring to FIGS. 2 to 5, the reactor 40 includes a first
It consists of a plurality of stacked, essentially planar, parallel sheets 4 and 6 consisting essentially of a fluid-impermeable solid electrolyte such as the electrolyte used to string the sheets of FIGS.

Each sheet has a plurality of parallel elongated channels 4a and 6a separated by lips 4b and 6b extending perpendicular to the longitudinal plane of the sheet. The sheets are also divided into two groups (4 and 6) based on channel function and alignment. The first group of channels 6a are essentially continuous-
The second group of channels 4a has electrically conductive oxygen dissociation catalysts arranged in an essentially continuous layer, whereas the second group of channels 4a has reaction promoting catalysts arranged in essentially continuous layers. In the reactor of FIGS. 4 and 5, channels 4a and 6a have a "roof" (not shown) formed by the rear of the adjacent sheet resting on lip 4b or 6b. For example, for channel 48, the roof is
is formed by the rear side of the adjacent sheet 6 in contact with. 68
For the channel, I! The root is formed by the rear side of the adjacent sheet 4 that contacts the lip 6b. Preferably, the roof for each channel is covered with an essentially continuous chamber of catalyst contained within the channel. After a series of reactors, if the catalyst is inserted into the probe and channel and the channel and lip surfaces are swabbed (SW-abbing)
), the cabinet parts can also be coated with catalyst by the same method and at the same time. Examples of suitable catalysts are given above. The first group of sheets 6 are connected to the second group of channels 4
30' to 90'' (preferably 90'') to a
arranged in an alternating manner between the channels 6a of the sheets in the first group and the sheets 4 of twelve groups forming an angle of . The reactor is also equipped with an electrical bran (described below) that transports the electricity produced during operation of the reactor. Reactor 40 is housed within a casing 42 made of a material that withstands the temperatures and gaseous materials used in fuel cell reactor operation. Suitable casing materials include, for example, steel,
Includes ceramics and various high temperature and chemically resistant materials.

The casing 42 is a plenum chamber.
rs) 44.46.48 and 50 and the corresponding ports 44a 146a 148a and 50a. Opposite sides of the reactor are 14, 12, 16 and 1, respectively.
5 (see Figure 3). The plenum chambers are not in direct fluid contact with each other, ie one plenum chamber into which gas enters can only be admitted into the second chamber after passing through the channels of the reactor.

4 and 5, port 44a and plenum chamber 4
4 is the reactant gas to be oxidized (e.g. ammonia)
and ports 48a are adapted to receive oxidized gas (oxidized 11) and pass it to purification and collection equipment (not shown).Boat 46a and The chamber 46 contains an oxidizing gas (
For example l! entrained in air or oxygen or a mixture thereof or an inert gas! *) is now accepted.
Boat 50a is adapted to send the emptied oxidizing gas to the atmosphere or to a purification and regeneration system (not shown).

Fuel cell reactors, particularly lipped sheet members, have been found to have a number of advantages. For example, the unique function of lips compared to lip-free sheet structures is to allow the various gases to be exposed to greatly increased amounts of the catalyst surface, thereby increasing reaction rates. Additionally, the catalyst coating the lip is electrically conductive and provides localized charge storage.
This contributes to efficiency by reducing build-up) and resulting power losses. The catalyst coating is also thermally conductive and is designed to provide improved control over the catalytic reaction by distributing heat.

Multiple lips also support adjacent sheets, thereby allowing these sheets to be relatively thin, eg, 100 microns to 1 millimeter thick. Suitably the sheet may have a thickness of 200-300 microns. Since the sheet is comprised of a solid electrolyte that transports oxygen ions, the reduced thickness of the sheet also reduces the distance that oxygen ions must travel prior to reaction to the surface of the catalyst on an adjacent sheet. This will contribute to the efficiency of the reaction, ie at a given concentration the reaction rate will be greater than if a thicker sheet without lips is used. It is also believed that the use of thin sheets reduces internal heating of the reactor. The supporting action of the lips also allows larger reactors to be constructed than would otherwise be possible with similar thicknesses of electrolyte material.

The reactor of the present invention has a relatively large electrolyte surface area, e.g.
Allows the WJ/reactor volume ratio to be obtained.

In operation, a chemical oxidation reaction is carried out in the reactor by passing an oxidizing gas (e.g. 11 into chamber 46 and then through channel 6a. At the same time, a reactant gas (e.g. ethylene or ammonia) is passed through chamber 44. and passed through channel 4a. 68
In the channel, the oxidizing gas contacts the oxygen dissociation catalyst and produces oxygen ions that migrate through the zirconia sheet. At the same time, it was consumed by oxygen reduction.

The electrons create an electrical current in the conductive catalyst layer and the reactant gas is oxidized to produce a product, such as ethylene oxide. The emptied oxidizing gas then passes through chamber 50 and is removed and the reactant gas (now product gas)
passes through chamber 48 and then to the necessary equipment for collection, concentration and/or purification (not shown). Suitable reaction concentrations and conditions for the oxidation of ammonia are described in US Pat. No. 4,272,336. Catalysts for other substances such as paraffin and ethylene are mentioned above. During the oxidation reaction, electricity is generated and collected by electrical leads as described below.

6) The reactor each comprises a sheet with channels 6a for the dissociation of oxygen and a sheet with channels 4a for the oxidation of the chemical feed material (for example ammonia). multiple units 21
It can be thought of as having the following. channel 4a
is the appropriate conductor 23 in the channel 6a of the adjacent unit.
can be electrically connected by. The conductors can be applied to the surfaces of the various units using a "hard" wiring system or a conductive material that is subsequently cured by well-known methods. Suitable platinum materials and methods of application and curing include application of a dispersion of silver in butyl acetate with a binder and subsequent drying at room temperature and e.g. Ink” (En-gelhard Platin
tlm “)nk”>A3788, which is 100
It can be dried at 0.degree. C. and calcined at 800.degree. C. for 4-6 hours. The wiring diagram is continuous through the battery, ie the units 21 are wired in series. However, this wiring method is disadvantageous in that the wires 23 are relatively long and the small dimensions of the channels (and conductor lengths) make it laborious and difficult to wire as a unit without creating multiple short circuits. A related practical problem arises. Therefore, if desired, another wiring system (as shown in FIG. 7) could be developed, according to which the two units 21 are wired in parallel by suitable conductors 25 and 27. The parallel wired units are then connected by suitable conductors 29. This diagram can be continued through the reactor. Wire the battery as shown in Figure 17.
The net result of (-inlcell) is that adjacent units wired together in parallel can be thought of as a single cell (-inlcell), and the cells themselves are each divided into four sheets (Figs. 4 and 5). (labeled M1, M2 in the figure) can be thought of as a series of small cells. Each sub-cell is preferably connected to each adjacent sub-cell by wiring in series. This is the type shown in FIG. As mentioned above, conductors 25, 27 and 29 can be hard wired or can be applied to the cell using a suitable conductive material as described above using conventional methods. Compared to the strictly series wiring type of FIG. 6, the parallel wiring diagram described above is advantageous in that the electrical conductors are shorter and the risk of shorting out the batteries is reduced. It will be understood that by 'Series' wiring is intended a type such as that shown in either FIG. 6 or FIG.

4 and 5, during the construction period the end channels are filled with non-conductive, thermosetting cement to form transverse strips 13, both on the surface 12 of the reactor and on the outer surface of the sheet 4. 15 (corresponding to the scoliosis of the rib) is coated with an electrically conductive material, such as the silver/butyl acetate composition described above. The outer surface 17 of the sheet 6 on the surface 14 is likewise coated with an electrically conductive material. The coating on surface 15 contacts between the electrically conductive catalysts deposited in channels 6a, thereby collecting current from adjacent sheets 4. M1
'' are all considered to form a single cell. A similar cell is formed by layers labeled M2, M3 and M4. Cell M5 is the second cell.
Incomplete (but still operable) due to the lack of sheet 4. Using the model shown in Figure 7,
The condolences 1fi1M1-M5 are wired in series by conductors 33, which can be hard wired or "painted" circuits as described above. Figures 14 and 5 are central cross sections of the reactor! 11 (midsectional vi
ew ), but electrical leads 33 were added to indicate the electrical connections between the layers present in the green of the reactor.

In due course, current is transported through the external conductor 35 to accomplish work. Consider the flow of electrical circuits! In fact, the sheet separating the upper and lower channels M1 from the upper channel M2 is short-circuited (Sho) because the two catalyst layers on its two sides are electrically connected through the outer connector 33.
rted). The same is true for the sheet separating the lower channel of M2 from the upper channel of M3. This wiring diagram does not interfere with the rest of the equipment (perrors ln(1) 9). If desired, the electrical current produced by the fuel cell reactor increases the reactor concentration required to carry out the dissociation and oxidation reactions. It can be partially used to generate heat for retention.

Rather than generating electrical power, the reactor can be connected to an external current source so that the rate of oxidation in the reactor is increased. That is, an external current can be used to speed up the flow of all ions through the solid electrolyte. Obviously, if an external Al source is used, the fuel cell cannot operate within the range of diffusion currents. That is, the current must not cause depletion of the solid electrolyte. The electric current must also not adversely affect the catalytic material used. When wiring a reactor in which an external power source is used, it is preferable to wire the sheets (or units as described above) in parallel to maximize the current applied to each sheet and 7' or unit. The reactor is H! It can also be used to dissociate (electrolyze) oxygen-containing compounds such as water or nitrogen oxides by connecting the reactor to an external power source with its positive electrode connected to a channel through which 0 or 0 or No is flowing. It will be understood by those skilled in the art.

Cross flow monolith reactor (crossJlow e+o
To construct the noli-thiCreator), the sheets are placed in an adjacent face-to-front butt relationship. That is, the ribs projecting from each sheet contact the back or unripped surface of each adjacent sheet. Catalytic II! A first group of sheets having channels supporting dissociated substances are also interleaved between the second group of sheets. The channels of the first group of sheets form a predetermined angle (eg, 30-90°) with the channels of the twelve groups. During the stacking period, a ceramic thermosetting adhesive is applied to each sheet, and after the desired number of sheets have been stacked, the resulting layered structure is heated (i.e., fired) to harden the cement and bond the sheets together. to form a ceramic article. Suitable cementing compositions include ceramic silica cements (e.g. Dylon Indus
D ylon C-3 cement); water glass and glaze (91aZθ); and when a sheet such as that shown in Figure 1 is used, an oxygen dissociation catalyst and a reaction accelerating catalyst are used. Alternate the layers before or after assembly of the reactor (altar-nat
e) be m. The catalyst is applied by coating the channels with the catalyst composition to form an essentially continuous coating. The catalyst composition is then preferably cured during a calcination step.

After firing, the fuel cell reactor is essentially complete except for the electrical leads shown in FIGS. 4-7.

Referring to FIGS. 4 and 5, the electrical communication target W11
Nos. 5 and 17 are applied by coating the appropriate surfaces with a conductive composition, such as a platinum or platinum as described above. The conductive coating is cured by heating to excessive density. For example, for platinum, the curing concentration is 800-8
Al at 50°C.

In the embodiment of the invention shown in FIGS. 4 and 5,
The hardened reactor is filled with the cementitious material in the end channels of the cell.
A strip 13 is also provided by filling it with a suitable non-conducting material such as 300 .reals. Strip 13 is optional, but adds to the strength of the battery, and provides a barrier to facilitate wiring and reduce the possibility of short circuits.

If necessary, the material used to form the strip is cured by heating. In some cases (preferably)
Strip 13 and conductive coatings 15 and 17 are cured during the first stage of cementing the layers.

Wires 33 can be either hard wires or painted conductors. If hard wiring is used (eg, wire, silver or platinum wiring), such wiring is conveniently placed on the reactor prior to curing of the conductive coatings 15 and 17. If coated circuits are used, these can be applied simultaneously as coatings 15 and 17.

The electrical leads shown in FIGS. 4 and 5 (including conductive coatings 15 and 17) are only one possible design for collecting current from the reactor. All hard wiring can be used if the channels are of sufficient size. Alternatively, conductive layers 15 and 17
For example, the wiring type shown in FIG. 6 can be arranged.

[11,59 granular polyethylene, 82,39 yttria-stabilized zirconia, i.e. about 12% by weight Y2O3
The composition was prepared by mixing zirconia containing 27.5 g of mineral oil. Zirconia is Z1
rcar products, Inc.

7 by (Florida, New York)
1rcar Fvl). This zirconia has a component that has a larger surface area than Silcor at 165℃.
Mixed in a commercially available shear type mixer heated to .

The composition is compressed at about 200 psi and 160°C to form a 0°5-1 thick sheet. Then set this sheet to 0
．． Contact with parallel miso-containing plates having an average depth of 3- and 1.251-. The grooves were tapered and were measured to be approximately 15% larger at the surface of the plate than at the bottom of the grooves. The distance between the centers of the miso was 3 pegs.

The sheet is compressed against the plate to a thickness of 0.25-1 to cause the plastic material to flow into the grooves. The sheet also had lips that matched the grooves in the plate, ie the lips were laid parallel with a length of 1.251- and a center-to-center distance of 3-. The lipped sheet is cooled in the press and removed.

Removal was facilitated by pre-applying a silicone mold release agent. The plasticizer was extracted by refluxing in methyl chloroform at a concentration of 79°C for approximately 60 minutes. The resulting sheet was porous and consisted essentially of polyethylene and mineral filler. The sheet was cut into squares with dimensions of 63 mm. The square is then placed between parallel contact plates covered with fluorocarbon and heated for 5 minutes above the melting point of polyethylene (i.e., above 110°C) to relax the plastic while preventing warping of the sheet, and placing the square between parallel contact plates covered with fluorocarbon. It was cooled while being restrained in between. Little shrinkage occurred, ie less than 10%. The quadrilateral was then placed on a flat alumina surface impregnated with a thin layer of yttria-stabilized zirconia that served as a IIWA inhibitor. quadrilateral shim
) and cover the plate to prevent excessive vertical movement but allow horizontal movement. The stabilized squares are then heated in a kiln to decompose and remove the polyethylene and sinter the inorganic filler particles. The temperature used for sintering was approximately 1450°C and held for at least 2 hours. During the heating period, the sheet underwent linear shrinkage of approximately 30% to 40%. the sheet is essentially non-porous to gas permeation as determined by fluid permeation;
That is, when a fluid such as ink is placed on one side of the sheet, it will not permeate to the other side as a result of capillary action.

In case of invisible hairline cracks, the ink will immediately appear on the other side.

Sheets were made according to the method of Example 1, except that shims of varying thickness were used in the heating step in a similar manner to the sheets. In Example 1, the shim 6 placed around the sheet to be heated is ceramic and has a constant thickness that is held constant during the heating period.

As the sheet is heated it will contract and as it attempts to buckle it will contact the cover plate thereby preventing excessive vertical movement.

However, as the sheet shrinks, it becomes thinner;
There is more space between the sheet and the cover plate constant, which allows for a little bit of buckling.

This possible buckling is caused by the addition of stirrups around sheet shims, each manufactured by fitting two small pieces of the same lipped sheet material, which are heated, with one lip fitted between the other. It is further reduced by The height of the shim is one sheet thicker than the covered sheet being covered, and as the heated sheet contracts in height, the shim also contracts and this lowers the height of the cover plate. did. The lipped sheet made by this method was even flatter than the sheet made by the method of Example 1.

111 Two lipped zirconia sheets made by the method of Example 2 were used to make a very simple test fuel cell. The sheet is made of platinum ink (Engelhar).
Br1 manufactured by d l industries
oht Platinum Ink, En
The catalyst was first coated on both sides by applying Oelhard A-3788) to the surface and then heating to 800°C. This process was repeated two more times to obtain an electrically conductive porous catalyst coating. Two catalyst coated lipped sheets are then placed, one in contact after the other.
It was cemented with two lipsticks. This assembly was sealed into a slot in the zirconia tube. It extended from the tube with a channel between the two sheets formed in pairs. The conductive catalyst coating the inner channel of the assembly, formed by the lip between the two sheets, was connected to one silver wire, while the two outer surface coatings were connected to two silver wires. . These two wires formed the terminals of the battery.

The unit was placed in an electric furnace at a concentration of approximately 800°C. Ammonia was fed to the feedstock and flowed out of the slot through a channel between the two sheets, while air was fed to the outside surface through a separate non-contacting stainless steel manifold.

The test cell initially delivered 0.056 watts, which demonstrated the operability of the system. Unfortunately, the voltage at a constant current decreased over time, and the structure cracked as it cooled.

[Brief explanation of the drawing]

FIG. 1 is a lipped sheet used in manufacturing the fuel cell reactor of FIG. FIG. 112 is an enlarged partial cross-sectional view from FIG. 4 showing two catalyst coated lipped sheets. Figure W%28 shows a sheet as in Figure 12 with a beam angle of 60''. Figure 3 is a plan view of the reactor of Figures 4 and 5. Figure 4 shows the electrical connections between the layers. Figure 5 is a cross-sectional view of the reactor of Figure 4 rotated 90'' including additional electrical connections; FIG. 11!6 shows a possible series wiring configuration for the reactor of FIG. 4. FIG. 17 shows a modified series wiring scheme for the reactor of FIG. 4. In the figure, 4...sheet, 4a...channel,
4b...Rip, 5...Rear surface of sheet, 6...Seat, 6a...Channel, 6b...Rip, 40.
...Reactor, 42...Casing, 44.46.48
．． 50...Full chamber, 44a, 46a, 48a,
50a... Corresponding boat, 13... Lateral strip, 15.17... Outer surface of sheet, 21... Unit, 23.25.27.29... Conductor, 33... Conductor It is. Patent Applicant: W. R. Brace & Law Company

Claims (1)

Claims: 1. A monolithic reactor adapted for use in a fuel cell comprising a plurality of elms of fluid-impermeable isoelectrolyte capable of transporting oxygen ions. comprising essentially planar parallel sheets, each sheet having a plurality of parallel elongated channels separated by lips, the sheets being divided into a first group and a second group, the sheets of the cough group being arranged in an alternating manner, said first group of channels forming an angle with said second group of channels;
the first group of channels has a catalytic saponyrolytic material disposed therein, and the second group of channels has a catalyst disposed therein for promoting the oxidation reaction. , the above reactor. 2. The reactor according to claim 1, wherein the solid electrolyte comprises yttria-pacified zirconia or calcia-stabilized zirconia. 3. The reactor according to claim 211, wherein the catalyst or catalytic material comprises platinum or a platinum-0-dium alloy. 4. an essentially planar fluid permeable ceramic sheet having first and second parallel surfaces on each side, the cough sheet having a plurality of essentially parallel surfaces formed on the first surface; having a load-bearing lip and extending therefrom generally vertically to a uniform constriction, the lips defining a plurality of channels for transporting gaseous substances when the cough sheets are stacked on top of each other; Consisting of a solid electrolyte capable of transporting oxygen ions, the channel is coated with an essentially continuous layer of electrically conductive material for catalyzing chemical reactions in the gaseous substances transported through the channel. The above sheet. 1114. The sheet of claim 1114, wherein the 511A solid electrolyte comprises yttria-stabilized zirconia or calcia-stabilized zirconia. 6. 6. The sheet according to claim 5, wherein the electrically conductive material is either an oxygen dissociation catalyst or an oxidation reaction promoting catalyst made of platinum or a platinum-rhodium alloy. 1. A method of repelling a sheet of fluid-impermeable solid electrolyte, comprising: a particulate inorganic filler capable of transporting oxygen ions in the sintered state;
,000 molecular weight and a plasticizer, forming the mixture into a sheet having a lip, extracting the plasticizer, and heating the sheet to form a cough organic material. A method comprising the steps of decomposing and removing a polymer, sintering the inorganic filler particles, and applying an oxygen dissociation catalyst or an oxidation reaction promoting catalyst to a cough sheet. 8. Cough filler/- coalescing/plasticizer blend 200-280 as measured in Prabender Plastograph
Claim 7 having a torque of 0 meter grams
The method described in section. 9. Claim 7, wherein the polymer is polyethylene
The method described in section. 10. The method of claim 7, wherein the filler/incorporate/plasticizer blend also includes an internal lubricant to facilitate dispersion of the filler in the polymer suspension. 11. The method according to claim 7, wherein the inorganic filler is yttria-stabilized zirconia or calcia-stabilized zirconia. 12. The method according to claim 7, wherein the catalyst comprises platinum or a platinum-rhodium alloy. 18. The method of claim 17, wherein the catalyst is applied by heating the cough catalyst to a concentration lower than that for heating the cough sheet to sinter the inorganic filler particles.