Permeable laminated composite unit for physico-chemical processing
United States Patent Aguinet et al.  
 PERMEABLE LAMINATED COMPOSITE UNIT FOR PHYSICO-CHEMICAL PROCESSING Inventors: Gerard Aguinet, Meudon; Jean Manoury, Ville DAvray; Edouard Martin, Saint Cloud, all of France Assignee: Societe Anonyme Products Chimiques Ugine Kyhlman, Paris, France Filed: Oct. 9, 1973 Appl. No.: 404,154  
 Related US. Application Data Continuation-impart of Ser. No. 175,588, Aug. 27, 1971.  
 Foreign Application Priority Data Sept. 4, 1970 France 70.32304 US. Cl. 267/112, 23/288 R Int. Cl BOlj 9/04 Field of Search 267/110, 112; 23/288 R,  
 [56] References Cited UNITED STATES PATENTS 1,734,696 9/1930 Bernstein 263/112 2,156,422 5/1939 Border 23/288 R 2,988,137 6/1961 Richardson 267/110 3,077,149 2/1963 Eckel 267/112 3,790,350 2/1974 Haensel 23/288 F Primary ExaminerJames R. Marbert Attorney, Agent, or Firm1-1ammond &amp; Littell [57] ABSTRACT Use is made, in order to support a sheet of a material active in a chemical or physical process operated at widely varying temperatures, process contemplated for example a catalytic gauze made of a precious metal in the case of the catalytic oxidation of ammonia, of an articulated cloth consisting of helixes of wire made of a refractory metal alloy, said helixes being assembled in a parallel direction with respect to one another through screwing of the adjacent helixes with one another, said cloth being stretched, with an extension of approximately 2% in length in all directions, in a frame of appropriate shape.  
 3 Claims, 3 Drawing Figures PERMEABLE LAMINATED COMPOSITE UNIT FOR PHYSICO-CHEMICAL PROCESSING PRIOR APPLICATION This application is a continuation-in-part of our copending, commonly assigned U.S. patent application Ser. No. 175,588 filed Aug. 27, 1971.  
  The invention relates to permeable, laminated, composite units for chemical or physical processing at temperatures varying within wide ranges. Permeable, laminated composite units as used herein refers to assemblies comprising a latticed or similar support on which is applied a sheet of a material which is chemically or physically active in the process contemplated.  
  Characteristic examples of such assemblies include, in the first place, those comprising precious metal gauzes, used for the catalysis of certain chemical reactions, particularly in the gas phase, carried on a latticed support, said support providing the assembly with a mechanical strength which the gauze by itself does not offer. The following description will deal practically exclusively with such assemblies. However, the invention must not be considered as being limited to this specific type of unit for it also applies to assemblies consisting of a support and, for example, a sheet of filtering material or material acting in any other manner in a physical or chemical processing operation on fluids which may possibly contain solids as more or less fine suspensions.  
  The constitution of the catalytic assemblies of the type contemplated above, and, in particular, of those to be used for the catalytic oxidation of ammonia,  
 . whether or not under pressure, raises problems which are difficult to solve because of the large temperature differences to which they are subjected, thus giving rise to heavy stresses.  
  Indeed, precious metal gauzes used as catalysts are very fine and very fragile mechanically. They must therefore be maintained very flat and be supported at numerous points. Up to now, this was accomplished by superposing a relatively coarse support and a distribution gauze fastened to said support on which was attached the precious metal catalytic gauze. The support and distribution gauze must, however, be made of expensive, noble refractory alloys. Suggestions have indeed been made to use as the main support or as intermediate parts, non metallic refractory materials which are less expensive, but these materials have a low resistance to thermal shock.  
  Furthermore, parts made of refractory alloys comprising the main support are necessarily large and, as a result, because of temperature differences, undergo permanent deformations which often appear rapidly, thus making it necessary to frequently replace the support.  
  Taking into account the fact that catalytic gauzes are generally placed horizontally and in a flat position in cylindrical reactors, the simplest embodiment of a support for said gauzes would consist in stretching, in a crown, a network of refractory wires. But dimensional variations of the various parts of the support assembly must be compensated for if stresses which are very harmfull to the mechanical qualities of the catalytic gauzes are to be avoided. It would then be desirable that the network absorb these variations while remaining in the elastic range during the various phases comprising idle time ignition, normal operation and shutting off of the installation.  
  If, in a more concrete fashion, in the case contemplated above relating to the catalytic oxidation of ammonia, a cicular crown is used made of a metal alloy with a thermal expansion coefficient of the order of 18 X 10 within which is directly attached a wire network and if it is desired that this network remain stretched in the elastic range during the various operating phases ignition (crown at C, network at 900C) normal operation (crown at 400C, network at 900C) extinction (crown at 350C, network at 50C) idle phase (crown at 20C, network at 20C) the alloy of which the wire is formed must have an elastic resistance and thermal expansion coefficient a which at least will satisfy precise conditions resulting from considerations developed hereinafter.  
  1. If the installation is considered at the end of the ignition period (crown at 150C and network at 900C), the diametrical wires have undergone an expansion of:  
 The crown has undergone a diametrical expansion of:  
 2. During normal operation (crown at 400C, network at 900C) the diametrical wires have the same,  
 natural expansion as above, but the crown has undergone an additional diametrical expansion of:  
 I =13 x 10-&#34; x 400 150) If in phase 1 above, the diametrical wires were stretched, at the beginning of the elastic range, and if it is required that in phase 2, they do not go beyond the end of the elastic range, the latter must extend over:  
 and an expansion of the crown of:  
 corresponding, with respect to phase 1, to an elongation of the diametrical wires of:  
 which gives a 1.65 X  
  However, there is no industrial refractory alloy in existence which has such an expansion coefficient.  
  Furthermore, in order for the assembly to have a normal industrial service life, the alloy must have good creep strength, i.e., it must not undergo, for example, an elongation greater than 1% in 10,000 hours.  
  It has been explained that some of the above mentioned condition do not exist. It will then be all the more possible to combine them together in a same alloy. Mathematically, an alloy with a Youngs modulus of5,000 would make it possible to meet all the required conditions if its creep strength would be sufficient, but such a modulus implies, by itself, a substantial drop in strength in the elastic range.  
  The main object of the invention is to provide a permeable, laminated, composite unit which meets the required conditions of elongation and contraction without being rapidly destroyed or damaged in operation.  
  This object is achieved by using, for constituting the support for the active material, such as a precious metal catalytic gauze, an articulated cloth comprising helixes consisting of wires made of a refractory metal alloy, assembled in a parallel direction with respect to one another through screwing of the adjacent helixes with one another, said cloth being stretched, with an extension of approximately 2% in length in all directions, in a frame of appropriate shape.  
  The frame may comprise a crown which is circular in the case contemplated above for the support of a catalytic gauze or rectangular if, for example, it is required to support a filtering sheet, or of any form adapted to the apparatus in which the assembly under consideration is used. It comprises advantageously several independent segments to which is connected the articulated cloth, said segments being themselves connected to an external continuous frame by tensile means.  
  The helixes forming the articulated cloth have a low pseudo-Youngs modulus, although the Youngs modulus of the wires forming said helixes has a high value and it is thus possible to meet the required conditions in order to provide, at a definitely lower price than before, a support, which, while remaining in the elastic range, can undergo a very substantial elongation, in all directions, this support, in its application to the oxidation of ammonia, absorbing strains due to the thermal expansion of the assembly and of the parts of the catalytic oven, including its own expansions, the  
 cloth remaining continuously stretched without any appreciable bending during the ignition, normal operating, extinction and idle periods.  
  Furthermore, the resting points of the catalytic gauzes on such a support are very numerous and pinpointed, which decreases, to an appreciable extent, turbulences of gas streams and increases the useful surface area of the catalyst, which are two very important advantages enhancing the chemical conversion yield of NH to NO.  
  The same advantages are found, with the required changes being made, in the application of this support to the other units contemplated, such as filtering units and, in general, in the uses of the units according to the invention in processes where the temperatures go from room temperature not only to high values, as indicated above, but also to very low values.  
  The appended drawings show, by way of examples, various embodiments of the support in a unit according to the invention. In said drawings:  
  FIG. 1 is a diagrammatic plan view of a fragment of articulated cloth;  
 FIG. 2 is a similar view of another embodiment of such a cloth;  
  FIG. 3 is a partial view, in vertical cross-section, of a unit according to the invention applied to the catalytic oxidation of ammonia.  
  As shown in FIGS. 1 and 2, the support used in the unit according to the invention is formed of an articulated cloth consisting of wires rolled into helixes 1, 1a, each helix being engaged with its two neighbours by mutual screwing Such cloths are known per se in their application to the manufacture of metal bed frames.  
  Each helix may comprise only one wire, as shown at 1 in FIG. 1, or several wires, for example two wires as shown at 10 in FIG. 2, the second solution providing greater elasticity for the same given total wire crosssection.  
  In the embodiment of the laminated unit such as shown in FIG. 3, a sheet of articulated cloth 2, which for example is circular, is welded by its edges on segments of crown 3 which are made integral with an external continuous crown 4 through anchors 5, screwed into segments 3 in a parallel direction with the bisectric of the latter and passing through corresponding holes 6 provided in the external crown 4, the free end of these anchors being threaded at 7 so as to receive a nut 8 which serves to give cloth 2 the required prestress. A catalytic gauze 9, made of precious metal, whose edges are maintained by segments 3 through pinching with arc-shaped plates 10 screwed onto said segments, rests on articulated cloth 2, in contact with the tops of each of the turns of the helixes comprising the latter, and therefore on resting points which are extremely nu merous and close to one another.  
  It can be imagined that any other mode of attachment of cloth 2 on segments 3 could be adopted, for example, pinching as in the case of catalytic gauze 9, hooking onto hooks or points, etc.  
  The materials comprising the assembly are chosen as a function of the operating temperature and chemical conditions of the chamber in the catalytic oven or other processing equipment. Thus, in the oxidation of ammonia to nitric oxide, a refractory alloy Fluginox N 45 was used for the preparation of wires having a diameter of 0.75mm, this alloy showing very good creep strength.  
 The chemical composition of the refractory alloy Fluginox N 45 is as follows: 0.12% carbon, 1.5% silicon, l% manganese, 18 to 21% chromium, 15 to 21% cobalt, 1.8 to 3.0% titanium, 0.7 to 1.8% aluminum, 0.l% copper, g 2% iron, and the balance up to 100% of nickel. Said wires were formed in pairs of helical coils having a diameter of mm with a mm pitch. The double coils were screwed into one another so as to constitute the cloth. The pressure in the catalytic chamber has no bearing on the behavior of the cloth, and it may have any value. Such a cloth can withstand, in the cold, 21 prestress substantially greater than 2%, its expansion coefficient being 18 X 10 and its YOUNGs modulus close to 10, which is of course much lower than the value of 5,000 which is the upper limit required according to the calculation presented hereinabove.  
 In the same way, a refractory alloy lnconel X 750 was to 1.2% niobium (with a low content of tantalum), 0.01% sulfur, and nickel (with a low content of cobalt).  
 We claim:  
  1. In a process for gaseous chemical or physical processes operated over a wide range of temperatures employing a fragile sheet of material chemically or physically active in the process, the improvement comprising a lattice support formed of an articulated cloth consisting of helixes of wire made of a refractory metal a1- loy, said helixes being assembled parallel to each other by screwing the adjacent helixes with one another, said cloth being stretched in an appropriately shaped frame with an extension of about 2% in length in all directions.  
  2. The process of claim 1 wherein said frame is formed of a plurality of independent segments to which is connected the articulated cloth, said segments being themselves connected to an external continuous frame through tensile means.  
  3. The process of claim 1, wherein said metal alloy does not undergo elongation greater than 1% in 10,000  
 hours.  
  UNITED STATES PATENT OFFICE Page 1 of 3 I CERTIFICATE OF CORRECTION 4 Patent NO- I Dated l, I  
 Inventofls) GERARD AGUTNET, JEAN MANOURY and EDOUARD MARTIN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
  Patent Col. Line UNDER ASSIGNEE:  
 &#34;Societe Anonyme Products Chimiques Ugine Kyhlman, Paris, France&#34; should be -Societe Anonyme Produits Chimiques Ugine Kuhlmann, Paris, France-- 2 I 25 &#34;All =0: (9002Q)&#34;,shouldbe &#34;416 =oz (9o0-20)-- 2 30 &#34;A21 18 X 10 X (150-20)&#34; should be UNITED STATES PATENT OFFICE we 2 of 3 CERTIFICATE OF CORRECTION April 1, 1975 Patent No. 3, 7 ,6 4; D d  
 Inventor) GERARD AGUINET, JEAN MANOURY and EDOUARD MARTIN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
  Patent Col. Line 2 4o 1 &#34;A31 18 X X 100450)&#34; should be 2 50 &#34;A31 18 X 10 X 250 8 0.  
 should be ----A3 18 X 10&#39; X 250 0. 5%  
 2 65 I I &#34;Aul&#39;w (900-)&#34; should be -AH@ =Ol. (goo-50)&#34;- T &#39;3 1 &#34;A51 18 X 10&#34; (350-150) should be v UNITED STATES PATENT OFFICE Page 5 at 3 CERTIFICATE OF CORRECTION 7; I I 55&#39; n &#34;1 &#39;7&#39;- Patent No. Dated Eprll 1, i9,  
 lnventofls) GBJIRD AGUIZ&#39;EET, JEN? MAHGURY AND EDOUARD MARTIN It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:  
  Patent CO1 Tine A61 M1 A51 should be l l l -=A6r A R A52 &#34;100 on A61&#34; should be 20,000 1 3 18 ---100 on a A60 after &#34;support&#34; insert Claim 6 l --for said sheet of material-- Signed and sealed this 151: day of July 1975.  
 (SEAL) Attest&#39;:  
  1 C. MARSHALL DANN EUTI-I C T-E-I OI Commissioner of Patents attesting Officer and Trademarks