Title of Invention

REACTOR WITH A HEAT EXCHANGER AREA COMPRISING AN INSERT.

Abstract

The invention relates to a reactor at least comprising, connected wiyh each other in fluid-conducting fashion:a reaction area, whereby the reaction area comprises at least one solid state catalyst;a coolable heat exchanger area, whereby the heat exchanger area comprises at least one housing, whereby the housing accommodates at least partially an insert, whereby the insert comprises a plurality of elements, a process for oxidation of a hydrocarbon using the reactor, an oxidised hydrocarbon product obtainable by this process, chemical products, such as threads, sheets, formed bodies and the like based on this oxidised hydrocarbon product as well as the use of this oxidised hydrocarbon product in chemical products of this type.

Full Text

PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Reactor with a heat exchanger area comprising an insert The invention relates to a reactor, to a process for oxidation of a hydrocarbon using the reactor, to an oxidised hydrocarbon product obtainable by this process, to chemical products such as threads, sheets, formed bodies and the like based on this oxidised hydrocarbon product as well as to the use of this oxidised hydrocarbon product in chemical products of these types. A number of heterogeneous gas phase reactions are known from the prior art, in particular gas phase oxidations in which the desired reaction product is obtained from reactants in one, two or more steps. With gas phase reactions, in particular with gas phase reactions carried out in one step, it can often be observed that the product gas leaving the reaction area is brought into contact with a fluid medium in a so-called quench device. In the section between the reaction unit and the quench unit further undesired reactions can occur which lead to an increase in impurities and thus, generally, to a reduced yield and increased complexity of purification. The reactions occurring in this section are particularly caused by too high temperatures of the product gas leaving the reaction area. It is thus conceivable to provide, between reaction area and quench unit, a heat exchanger area in which the product gas leaving the reaction area can be cooled. For reasons of economy, it is preferred to carry out the above-mentioned two- or multistep reactions as far as possible without time-consuming work-up of the in-termediate products of the individual reactions. When carrying out a reaction of this type, it must, however, be ensured that the products obtained in the individual -1 - PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR reaction steps are conducted to the next reaction step in as unchanged a form as possible. An example for a multistep reaction of this type is the synthesis of acrylic acid, which commonly occurs by a heterogeneously catalysed gas phase oxidation process of propylene with oxygen, at a catalyst situated in a solid aggre-gate state, at temperatures between 200 and 450°C. In a first step, propylene is converted with oxygen to acrolein at a temperature within the range from 300 to 450°C. The acrolein obtained from this reaction area is then oxidised to acrylic acid in a further reaction area in the presence of oxygen. The risk exists, however, that the acrolein obtained in the first reaction area spontaneously combusts, or that acrolein further reacts to water and carbon. With both of these undesired reac-tions, carbon-based deposits can occur which disturb the operation of the reactor. In addition, the de-sublimation of high-boiling side-products such as maleic acid anhydride (MSA), phthalic acid anhydride (PHTA) can lead to formation of de-posits. In order to prevent this, the acrolein-comprising gas mixture from the first reaction area is cooled in a coolable heat exchanger area. In order to avoid as far as possible the undesired further reactions of the acrolein, the cooling to less than 280°C must occur as quickly as possible. It is further possible that a coolable heat exchanger area, followed by a quench device, follows the last reaction area of the two- or multistep reactions in the same way as after the reaction area of the one-step reaction. In order to optimise the function of heat exchanger areas for use on an industrial scale, various filling materials present as individual elements, such as balls, rings, fragments, wire, threads, ribbons and the like, in particular raschig rings, are rec-ommended as flow obstacles in the heat exchanger area and disclosed for the im-provement of the heat transfer. These filling materials are, however, disadvantageous, since, on the one hand, they lead to significant loss of pressure and, furthermore, a rapid deposition of -2- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR combustion residues, inter alia - referred to as coking in the following, is ob-served in industrial scale operation. With many filling materials, this coking in-creases disadvantageously when actually an increased conducting away of heat is desired. Because of the coking of the filling materials in the heat exchanger area and of the heat exchanger area as such, the operation of the reactor must often be interrupted for cleaning purposes. This is undesired, because the reactor must generally be shut down, which is time-consuming, and after the pause, during which the clean-ing occurs, started up again, which is also time-consuming. The significant down times arising therefrom are commercially very disadvantageous. In general, the invention has the object of lessening or even overcoming the dis-advantages arising from the prior art. In particular, an object according to the invention is to reduce the coking of heat exchanger areas and/or of filling materials provided in these heat exchanger areas. A further object according to the invention is to reduce down times of reactors. In addition, an object according to the invention is to achieve, in addition to a re-duced tendency to coking of heat exchanger areas and/or of the filling materials used therein, as high as possible a heat removal of these heat exchanger areas. Additionally, an object according to the invention is to reduce the formation of undesired side-products and side-reactions for gas phase reactions, in order to increase the yield. -3- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR According to another object according to the invention, the cleaning of the heat exchanger area and/or of the filling materials located in the heat exchanger area should be made easier. Furthermore, an object according to the invention is to provide gas phase reaction products of high purity and high yield, in order to reduce the purification effort after the reaction. An object according to the invention is also to reduce the formation of the depos-its of reaction side-products, such as MSA or PTHA in the synthesis of acrylic acid. In addition, an object according to the invention is to achieve a good heat transfer with little coking with a small amount of material. The objects according to the invention are presently solved by the invention de-scribed herein, in particular by the main and sub-claims, whereby the sub-claims represent preferred embodiments of the invention. Accordingly, the invention relates to a reactor, at least comprising, connected with each other in fluid-conducting fashion: a reaction area, wherein the reaction area comprises at least one solid state catalyst; a coolable heat exchanger area, wherein the heat exchanger area comprises at least one housing, wherein the housing comprises at least partially an insert, wherein the insert comprises a plurality of elements. -4- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR As reactors according to the invention, all reactors which are used in gas phase reactions, in particular in heterogeneous gas phase reactions and which are known to the skilled person are considered. These are usually stainless steel reactors, or black steel ("Schwarzstahl") such as pipe bundle reactors, plate reactors and the like. By "fluid-conducting" it is understood according to the invention that at least gases can be transported, as is possible through, for example, pipes. The reaction area, preferably temperature-controllable, comprises at least one solid state catalyst. This can be, on the one hand, a powder catalyst, which is pre-sent as full contact as pellets, on a carrier or not on a carrier. According to another embodiment, the walls of the reaction area can also be coated with solid state cata-lyst. The spatial design of the reaction area has no restrictions, it depends upon the respective mode of reaction. Thus, the reaction area can be present, on the one hand, in pipe-like form or in the form of plates arranged parallel to each other. "Thermoplates" represent a particular form of the plates present parallel to each other. These are plates which are connected with each other in sections and, in this way, provide a cushion-like hollow space structure. Reactors of this type are de-scribed in such detail in DE 101 08 380 A1 for catalyst-coated thermoplates and in DE 100 19 381 Al for thermoplates provided with powder catalyst, that refer-ence is made to this disclosure as part of the present text. Another group of reactors comprises, as a reaction area between two walls, slit-like designed reaction areas. Reactors of this type, also known as "slit-reactors", are described, for example in WO 02/18042 Al, whereby reference is also made to this disclosure as part of this text. The coolable heat exchanger area following the reaction area comprises at least one housing, which preferably directly follows the reaction area. Housings of this type can comprise all forms known to the skilled person and suitable for the pur- -5- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR pose of heat exchange. Among this plurality of forms, on the one hand pipe forms and on the other hand two housings comprising plates and running substantially parallel to each other are preferred. The pipe-like housings are preferably used in reactors whose heat reaction area comprises pipes. Particularly preferably, the catalyst-comprising pipes of the reaction area are extended, preferably maintain-ing the same diameter, and the catalyst is replaced in the thus-extended pipe by one or more inserts. For the case that the construction comprising walls running substantially parallel to each other is preferred, this housing, comparable with the reaction area, can comprise similar to the there-defined thermoplates or slit-reactors, whereby these do not comprise catalyst, but, rather, one or more inserts. It is further preferred that the inner space of the housing, in particular the area of the inner space of the housing which receives the insert, is formed as far as possible free of bends or angles and preferably as straight as possible. In this way, the insert can be re-moved most easily from the housing. According to a preferred embodiment the insert comprises at least one of the fol-lowing properties, preferably all, determined according to the test methods de-scribed herein: (A) a heat pressure quotient Al at an empty pipe speed v of 0.485 m/s of greater than 1.11, preferably greater than 10 and particularly prefera-bly at least 50 as well as yet more preferably at least 70 W/m2/K/(mbar/m); (B) a heat pressure quotient A2 at an empty pipe speed v of 0.728 m/s of greater than 1.53, preferably greater than 2, yet more preferably -6- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR greater than 12 and particularly preferably at least 60 as well as yet more preferably at least 90 W/m2/K/(mbar/rn); (C) a heat pressure quotient A3 at an empty pipe speed v of 0.970 m/s of greater than 1.81, preferably greater than 3.33, yet more preferably greater than 14 and particularly preferably at least 70 as well as yet more preferably at least 110 W/m2/K/(mbar/m). Each of the individual properties A, B or C represents in itself a preferred em-bodiment according to the invention. Further preferred embodiments according to the invention arise from property combinations according to the following combi-nations of letters: AB, AC, BC, AC or ABC. In an embodiment of the invention it can be preferred that the thermal compression quotient A, B and/or C have a maximum and are therefore less than 1000, preferably less than 500, preferably less than 350 and more preferably less than 200 and yet more preferably less than 150 W/mVK/(mbar/m). This can be true for the individual heat pressure compo-nents but also for the property combinations which arise from the following com-binations of letters: AB, AC, BC, AC or ABC. It is further possible that the indi-vidual heat pressure quotients are present in ranges formed by the above lower limits and maxima. In an embodiment, the invention relates to a reactor at least comprising, connected with each other in fluid-conducting fashion: - a reaction area, wherein the reaction area comprises at least one solid state catalyst; - a coolable heat exchanger area, -7- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR wherein the heat exchanger area comprises at least one housing, wherein the housing accommodates at least partially an insert, wherein the insert comprises at least one of the following, preferably all properties (A) to (C), determined according to the test methods described herein. The heat pressure quotient A is formed by division of the heat transfer coefficient k and the pressure loss Ap based on the sample length. Mostly, A does not reach more than 800 W/m2/K/(mbar/m). According to another embodiment of this invention, the insert comprises a degree of perforation of at least 30, preferably at least 60 and particularly preferably at least 80. Moreover, an insert with a degree of perforation within the range from 90 to 99 is preferred. The degree of perforation is determined by a litering out ("Auslitern"). In addition, it is preferred according to the invention that, in contrast to the indi-vidually present raschig rings, a part of the plurality of elements of a given insert is formed contiguous, preferably in one piece, yet more preferably from one and the same material. It is further preferred that at least one part of the elements is formed from a mate-rial which is at least partially thread-like. Here, 2 to 30, preferably 2 to 15 and particularly preferably 2 to 10 elements/cm insert lengths of the plurality of ele-ments are formed contiguous, preferably in one piece, from the at least partially thread-like materials. -8- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR As thread-like materials, in principal all materials known to the skilled person are considered, whose length is substantially larger, preferably at least ten-fold, pref-erably at least a hundred-fold and particularly preferably at least a thousand-fold longer than the diameter of this material. As materials for the thread-like materi-als, metals, metal alloys, plastics, in particular high-temperature resistant plastics such as carbon threads or polyfluorinated plastics (Teflon®) as well as ceramic materials, in particular basalt wools are considered. When selecting suitable mate-rials for using for the elements or the thread-like material, the skilled person se-lects individual materials or material combinations according to whether these materials enable, on the one hand, a sufficient solidity of the insert, a sufficient resistance to chemicals and a satisfactory producibility of the inserts. It is further preferred according to an embodiment according to the invention that at least a part of the plurality of the elements are arranged around a core. It is hereby preferred that at least a part of the plurality of the elements is accommo-dated by this core. As a core, a longitudinal element is considered. Preferably, the core is formed from at least two longitudinal elements. The at least two longitudi-nal elements can be connected with each other via a loop-like area, preferably in one piece. The longitudinal elements can also be formed from the materials of the thread-like material. Generally, the skilled person selects the material for the core according to the same criteria that apply to the thread-like material. It is additionally preferred that the elements are accommodated by the core in such a way that the elements pass through the core. This can be achieved according to a preferred embodiment according to the invention in that at least two of the longi-tudinal elements are twined around each other to form one or more windings. The thus-obtained windings accommodate at least one of the elements. It has here -9- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR proven particularly advantageous that within the range from 1 to 20, preferably from 4 to 15 and particularly preferably from 6 to 10 elements are accommodated in one of these windings, whereby in this case, the winding has a rotation of the longitudinal element of 360°. It is additionally preferred that the windings are designed such that the elements are clamped by these windings in such a way that the elements are held in a given position which cannot be changed by the action of the gravity of the standing insert. It is furthermore preferred according to the invention that the elements are accommodated by a core which, compared to its diameter, is clearly longer than the average of the diameter, preferably by at least 10 times, particularly preferably by at least 100 times and yet more preferably by at least 500 times. A core designed in such a way has a longitudinal axis around which, according to another embodiment of the present invention, the elements are arranged wound, preferably helically. It is here preferred that respectively 2 to 20, preferably from 4 to 15 and particularly preferably from 6 to 10 elements form a section of this helix which describes a complete circular arc. A complete circular arc of the helix is present if a line formed, starting from the central axis of the core up to the point of the element at the fiirthest distance from this central axis matches the same line of another, following element. In another form of the insert, element groups are disposed in annular arrangement around a core. Annuli of this type comprise from 2 to 20, preferably from 4 to 15 and particularly preferably from 6 to 10 elements. It is further preferred according to the invention that at least one part, preferably the entire plurality of the elements are made from wire. It is likewise preferred that the core is also made from wire. Metal wires are particularly preferred. Considered as suitable metals for these metal wires are steel alloys, preferably stainless steel, brass alloys and platinum alloys, whereby spring steel is particularly preferred. -10- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR It is further preferred according to the invention that the insert at an inner space cross-section of the housing fills this inner space cross-section. This is, for example, the case if, with a pipe-like housing the circle as inner space cross-section is filled by the arrangement of the elements in which an imaginary circle formed by looking at the elements covers the circle formed by the pipe-like interior section to at least 80% of the area formed by both circles. With an angular internal space, the area of an angular inner space cross-section arising therefrom would cover to at least 60, preferably to at least 80%, the outlined area formed by the elements by looking at the insert. It is further preferred that the housing comprises a cylindrical inner space. This is particularly advantageous if the insert accommodated by this inner space is likewise in cylindrical form. In this context it is particularly preferred that the cylindrical inner space and the insert of cylindrical form are alike or that the insert of cylindrical form in its circular radius in unmounted state is a little larger, preferably by 1 to 30, preferably from 2 to 20 and particularly preferably from 5 to 10% of that of the cylindrical inner space. It is here preferred that the circular radius differences decrease with increasing stiffness of the material. This measure contributes to the force-fit of the insert in the housing. This has the advantages that the pliable and thus flexible insert can be pressed, depending on the dimensions of the housing, at the inner walls thereof. This provides purchase for the insert itself within the housing and further enables the removal of impurities adhering to the inner walls of the housing, in particular carbon-comprising deposits such as carbon particulate matter, when taking out the insert. -11 - PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR In this context it is particularly preferred that the housing comprises an inner wall which is contacted by at least a part of the plurality of elements. This contacting can be in such a form that the elements are at least slightly moved away from the positions in the contact-free state outside the housing. In this way, the elements press the insert at the inner wall of the housing and thus lead to the insert not being able to slip of its own accord within the housing. In the present invention, the elements used can be all suitable elements known to the skilled person for the purpose of the present invention, in particular for the improvement of the heat transfer, the gas mixing and the reduction of carbon-based particulates. It is here preferred that the elements comprise sheet or loop forms, or that elements with sheet form are combined with elements with loop form. It has windinged out to be particularly preferable that the elements are formed as loops. An insert according to the invention comprises within the range from 1 to 10, preferably from 1 to 6 and particularly preferably 1 to 4 elements/cm. Inserts which comprise a self-carrying skeletal-like structure, which in turn comprises at least two longitudinal elements which form a substantially centrally arranged core, in which these longitudinal elements are wound around each other, whereby this core comprises a plurality of loops which are held in the openings formed by the windings, whereby a plurality of the individual loops starting from the core extend helically over the longitudinal core, have further particularly proved themselves according to the invention. Inserts of this type are, for example, disclosed in GB-patent 1 570 530, whereby this reference forms parts of this disclosure. Further preferred inserts according to the invention as well as processes for their production are disclosed in GB 2 097 910 A. This reference also -12- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR forms part of this disclosure. Furthermore, particularly preferred inserts according to the invention are commercially obtainable from the company Cal Gavin Ltd., England, under the trade name HiTRAN®. In the context of carrying out two- and multistep reactions, it is preferred according to the invention that at least one further reaction area follows the heat exchanger area. For the case that these multistep reactions are different synthesis steps, it is preferred that the catalyst in the reaction area and a further catalyst in the further reaction area are different. The selection of the catalyst in the reaction area and the selection of the further catalyst in the further reaction area depend upon the reactions which should be carried out in the reaction areas. The invention also relates to a reactor, wherein the insert according to the invention, preferably coming out of the heat exchanger area, at least partially extends into the reaction area. In this context it is preferred that the part of the insert which extends into the reaction area comprises a catalyst. The catalyst can, on the hand, be present as coating on at least one of the elements. In addition, at least one of the elements can be formed from a catalyst material. Thus, in reactions catalysed by platinum, elements made from platinum wire can be used. Further, the elements can also carry or hold solid state catalyst particles because of their spatial design. In addition, the insert can better distribute the reactant gas and the reaction gases in the reaction area; in this case, the insert must not be coated with catalyst. It is sufficient if the reaction area and/or the housing is coated or lined with catalyst. -13- PCT/EP2005/001116 July 13,2006 Stockhausen GmbH DG81547PC HZ/HR The invention further relates to a reactor with a reaction area comprising an insert according to the invention, whereby this insert comprises a catalyst. The housing details and forms of the catalyst are also valid for this variant. Furthermore, the invention relates to a process for oxidation of a hydrocarbon, wherein the hydrocarbon as a gas is converted in a reactor according to the invention into an oxidised hydrocarbon product. As hydrocarbon used for oxidation, preferably an unsaturated hydrocarbon is considered. In this case it is particularly preferably propane. Acrolein or acrylic acid should be mentioned as preferred oxidised hydrocarbon products according to the invention. Acrolein is obtained in a first step in a reactor with a first reaction unit and acrylic acid from the thus-obtained acrolein in a further reaction unit. In connection with suitable catalysts, common reactors, reaction conditions and purification methods for the production of acrolein and acrylic acid, reference is made to "Stets Geforscht", Vol. 2, Chemieforschung im Degussa-Forschungszentrum Wolfgang 1988, pages 108-126, chapter "Acrolein und Deri-vate" D. Arntz und Ewald Noll, whereby reference is made to this content as part of this disclosure. In addition, the invention relates to threads, sheets, formed bodies, food or feed additives, pharmaceuticals, cosmetics, foams, superabsorbers, paper additives, leather additives or textile additives comprising or based upon an oxidised hydrocarbon product according to the invention, preferably acrylic acid. The invention further relates to the use of an oxidised hydrocarbon product, preferably acrylic acid, in or for threads, sheets, formed bodies, food or feed additives, -14- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Pharmaceuticals, cosmetics, foams, superabsorbers, paper additives, leather additives or textile additives. In connection with superabsorbers, their production, composition, properties and use, reference is made to "Modern superabsorbent polymer technology", Fredrick L. Buchholz, Andrew T. Graham, Viley-VCH, 1998. The invention is more closely illustrated in the following by non-limiting figures. Fig. 1 shows the schematic representation of an insert according to the invention, Fig. 2 shows the schematic representation of a housing according to the invention with an insert according to the invention, Fig. 3 shows the view of a housing according to the invention which comprises an insert according to the invention, Fig. 4 shows a schematic representation of a part of a reactor according to the invention, Fig. 5 shows a schematic representation of another embodiment of a housing according to the invention, -15- PCT/EP2005/001116 July 13,2006 Stockhausen GmbH DG81547PC HZ/HR Fig. 6 shows a schematic representation of a further embodiment of a housing according to the invention, Fig. 7 shows a schematic representation of another embodiment of a housing according to the invention, Fig. 8 shows a schematic representation of a housing according to the invention arranged in a reactor, Fig. 9 shows a diagram-like representation of a reactor according to the invention with quench, purification and polymerisation unit attached thereto, Fig. 10 shows a sketch for the construction of the measurement device for selection of inserts suitable according to the invention, Fig. 11 shows a schematic representation of another embodiment of a housing in cross-section. Figure 1 represents the preferred embodiment of an insert 6 according to the invention as cutaway. This comprises a core 9, which is formed from two longitudinal elements 10 made from metal wire and wound around each other. Through the twisting of the longitudinal elements 10, windings 11, which accommodate the elements 7 in recesses 17, form in the core. Because the element 7 is formed from a thread-like material 8, in the present case likewise a metal wire, the elements 7 are held by means of the windings 11 in the core 9. The windings 11 and the guide of the thread-like material 8 are designed such that the elements 7 are braced in -16- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR the form of loops by the central longitudinal axis 16 formed by the core 9. An element area 18 is formed, in respect of element 7, in its largest area extension. An element axis 19 cuts element area 18 at its longest extension, seen from longitudinal axis 16. Between the longitudinal axis 16 and element axis 19 lies an angle P which is preferably within the range from 45 to 135°, preferably within the range from 75 to 115° and particularly preferably within the range from 85 to 95°. The closer the angle P is to 90°, the better the inserts can be moved in both directions within a pipe without jamming. Furthermore, the ability to move without jamming increases with a design of element 7 which is as round, arc-shaped or with as few edges as possible towards the pipe inner wall. The elements 7 are, because of the accommodation of one or more elements 7 in the recesses 17 of the windings 11, through the turning of the longitudinal elements 10 counter to each other, like a spiral staircase around the core 9 to form an element-helix. The "density" as number of elements per given length of the insert 6 and the degree of perforation can, on the one hand, be increased by the accommodation of more elements 7 in the respective windings 11 or by stronger turning counter to each other of the longitudinal elements 10 which form the core 9 or by a combination of each these measures. Through the design described for this embodiment of the insert 6, it is achieved that a plurality of elements 7 are connected to a unit and an insert 6 with a self-carrying stiffness is obtained, which withstands sufficiently the flow ratios in a housing 5. In addition, it is advantageous for the movement of inserts 6 if a loop is formed at at least one end. Preferably, this loop is formed from the longitudinal elements 10. In figure 2, an embodiment of a housing 5 is depicted which comprises an insert 6 described in figure 1. The inner space 13 formed by the inner wall 14 of a housing 5 is filled by the insert 6 such that by connecting areas of the element 7 with the inner wall 14 the insert 6 is fit by force-fit into the inner space 13 of the housing 5. By means of this measure, on the one hand, the slipping of the insert 6 within -17- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR the housing 5 is made more difficult and on the other hand, upon taking the insert 6 out of the housing 5, deposits 20 such as carbon particulate matter adhering to the inner wall 14 are at least partially removed. For heat removal, the housing 5 comprises optional cooling elements 21 at its outer wall 22. The construction depicted in figure 2 can likewise be in a reactor which comprises an insert comprising a catalyst. Figure 3 shows a section through a housing 5 comprising an insert 6. The housing comprises an inner space 13 with an inner space diameter ID. Abutting the inner wall 14 of the housing 5 two loop-like elements 7 and 7'are formed which are held by two longitudinal elements 10 of the core 9 arranged centrally in the inner space 13. The elements 7 and 7'are formed from metal wire as thread-like material, whereby the thread-like material 8 runs held in place by the two longitudinal elements. The two elements 7 and 7' respectively comprise an element area 18 and 18', indicated with shading, which are divided in the middle in the same way by element axis 19 and 19' starting from the central longitudinal axis. The two element axes 19 and 19' form an angle a, which is preferably within the range from 5 to 180, preferably within the range from 10 to 130 and particularly preferably from 30 to 100°. The area at which the elements 7 after mounting in the housing 5 about the inner wall 14 of the housing 5 abut comprises an abut diameter AD. It is preferred that the ID is greater than the AD. Furthermore, the AD is preferably 10 to 90, preferably 20 to 70% of the ID and yet more preferably lies within a range of 25 to 50% of the ID. -18- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Figure 4 depicts a cutaway of a reactor 1 with a reaction area 2 and a heat exchanger area 3. The reactor 1 comprises a reactor plate 23 with a plurality of holes 24, through which a reactant gas 25 is conducted to the solid state catalyst 3 which can be present as catalyst pellets or also as layer catalyst. At catalyst 3 a chemical reaction occurs, whereby a hot product gas 26 is introduced into a housing 5, which it leaves as cooled product gas 27. This cooling is favoured by an insert 6 being built into housing 5, through which the hot product gas flows and at which the hot products gas is swirled. The heat given up to the housing 5 in this way is conducted away via an optional cooling element 21 applied at the outer wall 22 of the housing 5 by passing a cooling agent flow 28. In figure 5, a housing 5 is depicted in which the inner space 13 comprises a lens-like inner space cross-section 12. Furthermore, the inner space 13 is designed such that two plates arranged parallel to each other designed as sheets are connected along lines running parallel to each other substantially in a straight line and without interruption by means of weld seams 30 as connecting area, whereby the weld seams 30 are preferably not interrupted. The insert accommodated by the inner space 13 of such a housing 15 likewise comprises a lens-like cross section. In figure 6 another embodiment of a housing 5 according to the invention is represented. Here, two plates 29 designed as sheets, arranged substantially parallel to each other are welded to each other at various connection points 31 which are preferably arranged offset to each other. The inner space 13 comprises an inner space cross-section 12 formed between two connection points 31 in lens-like form. The areas lying between the connection points 31 and forming the inner space 13 of the housing 5 are formed cushion-like. This thus-formed inner space 13 can accommodate an insert 6. -19- PCT/EP2005/001116 My 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Figure 7 is a particular embodiment of the housing 5 depicted in figure 6 and differs from this in that instead of the connecting points 31, longitudinally formed connecting areas 32 for connecting the two plates 29 are arranged with interruptions along an imaginary line. Thus a pipe-like inner space 13 with a lens-like i inner space cross-sectionis obtained respectively between two connection areas 32, which can accommodate an insert 6. The housing 5 depicted in figure 8 likewise comprises a plurality of plates 29 arranged substantially parallel to each other, which are held at holding areas 33 and spaced to each other via a holding wall 34 such that an inner space 13 arises which comprises an inner space cross-section 12 which is sufficient to accommodate the inserts 6. So that the inserts 6 are arranged fixed in inner space 13, the plates 29 comprise convexities 35 which approach the cross-section form of the insert 6, partially via curves. In figure 9, a reactor 1 is represented, in which, via a reactant gas feed 37 reactant gas is introduced, which is first conducted for reaction to one of a plurality of reaction areas with solid state catalyst which are not shown but, are, however, identically designed, and the reaction product arising therefrom is conducted to a heat exchanger area 4 with a housing 5 which comprises an insert 6. The product gas cooled in the heat exchanger area 4 is converted in a further reaction area 15, which comprises a further catalyst 42, into a further product, which is likewise conducted in gaseous form to a further heat exchanger area 36, likewise equipped with a housing 5 which comprises an insert 6. The product gas, optionally cooled in the further heat exchanger area 36, is conducted via product gas exit 38 to a quench device 39. As quench device 39, devices are particularly preferred in which the product gas is brought into contact with a fluid such as water or solvent or solvents boiling above 100°C. The fluid phase comprising the product obtained -20- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR in the quench device 39 is conducted for further working up to a purification area 40. As purification area 40, distillation, crystallisation devices in themselves or in combination of distillation and crystallisation devices are considered. For the case that the thus-obtained purified product, for example acrylic acid, should be subjected to a further processing, in particular to a polymerisation, for example for the production of a superabsorber, the purified product obtained in the purification area 40 is conducted to a polymerisation area 41. The polymerisation area 41 can be in a spatial connection with the purification area 40, with the purification area 40 and the quench device 39 or with the purification area 40, the quench device 39 and the reactor 1. A spatial connection of this type is then in particular given if the arrangement occurs at a production plant. In figure 11, a combination of two housings 5 formed as thermoplates is shown, which comprise insert 6 and/or catalyst 3 in their interstices 59 which are limited by holding walls 34 and function as actual housing 5. The interstices 59 are formed in the form of well cracks and either hot product gas 26 with cooling with cooling agent 28, or, in the case of a reaction, with reactant gas 25, can flow through them. Furthermore, two or more inserts 6 can be brought together by an insert connection 60 to insert modules 61, which facilitates the handling of larger numbers of inserts. -21- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Test methods It should generally be noted with the test method for the selection of suitable inserts according to the invention that the shape of the cross-section of the cladding pipe 43 corresponds to the form of the cross-section of the insert and is not bigger than that of the housing for which the insert is provided. This is particularly the case for inserts with spring elements. For example, with a cylindrical element, a cladding pipe 43 with a round cross-section should be selected. If the cross-section of the insert is lens-like, the test method should be carried out in a cladding pipe 43 with likewise lens-like cross-section. As shown in figure 10, the measuring device consists of vertical cladding pipe 43 which is formed from a simple carbon steel (heat conduction capacity approximately 50 W/mK) with a wall thickness of 2mm. The cladding pipe 43 has an entry section and a heating area 53 following thereupon, which is wound with an electrical heating band 44. The windings of the heating band 44 lie directly upon the pipe outer wall 45 of the cladding pipe 43, so that a good heat transfer is ensured. The heating band 44 is provided with energy by means of an electrical capacity control, whereby the heating area 53 of the cladding pipe 43 is provided with a wall temperature. The heating band 44 consists of a continuous metal gauze band which is wound evenly with a winding distance of 30 mm in heating area 53 on cladding pipe 43. The heating band 44 has a nominal output of 60 W at an input supply voltage of 27 Volt. Beneath heating area 53, the cladding pipe 43 extends by a further 100 mm without a heating band winding 44. The heating area 53 comprises a sample chamber 57 for accommodation of a sample 48 with a probe length PL. The length of the heating area 53 and PL are the same. The entry section has four times the length of PL. At the ends of the cladding pipe 43 lying opposite the heating area 53 of the cladding pipe 43, this is closed by a stopper- -22- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR like seal. In order to prevent heat loss by convection and/or radiation, the windings of the heating band 44 in the heating area 53 are protected by a 150 mm thick insulation of mineral wool. At the upper end of the cladding pipe 43, a pressure measurement lance 47 is introduced vertically, held by the stopper-like seal 50. By means of the pressure measurement lance 47, the cladding pipe 43 can be provided with a gas flow. By means of the arrangement of manometer 54 in flow direction 51 via a baffle 49 and manometer 54', the pressure loss of the gas conducted through the cladding pipe 43 and/or to the sample can be determined. The gas temperature before the sample 48 (Tjn) is determined by Ni 100 thermometers (TI 101), whose measurement tip is located centrally 3 mm above the sample 48, the thermometer being mounted centrally in the pipe cross-section of the cladding pipe 43. The gas temperature after sample 48 (Tout) is determined by means of Ni 100 thermometers (TI 102), whose measurement tip is situated centrally 3 mm below the sample 48, the thermometer being mounted centrally in the pipe cross-section of the cladding pipe 43. With the Ni 100 thermometers (TI 103) the temperature (Twan) at the pipe outer wall 45 in the section of the heating area 53 is determined. DETERMINATION OF PRESSURE LOSS In order to determine the pressure loss Ap the pressures PG1 and PG2 are determined by manometers 54 and 54'. Ap can be calculated by means of the mathematical relationship shown in formula I. -23- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Formula I HEAT TRANSFER COEFFICIENT The heat transfer coefficient k results in the mathematical relationship of formulae II and III, whereby Q is the heat conduction, I the current of the electrical heating of the heating area 53, moas the mass flow of the air, APjpe and ATin the logarithmic temperature difference according to Dubbel, Taschenbuch fur den Maschinenbau, 19th edition, Springer Verlag Berlin 1997. Formula II Formula III -24- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR METHOD a. Sample Preparation The samples 48 given in the following table were inserted into the sample chamber 57 at room temperature. b. Pressure loss measurement At manometer 54, a pressure of 300 mbar was applied via a suspended ball flow meter 58. The pressure measurement lance 47 was placed on the cladding pipe 43 and sealed with stopper 50 and PG2 was measured at manometer 54'. c. Heat transfer coefficient measurement The empty pipe speeds v given in the following table were adjusted by means of valve 56. Energy is supplied via heating area 53 and transferred in the form of heat to the gas (air) which is flowing past. The amount of energy is selected such that after reaching a stationary state Tout is 90°C. Tjn and Twan are than measured. -25- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR d. Coking The suitability of the different inserts was determined by means of the frequency of cleaning work necessary for the individual inserts because of residues arising from coking. These results are likewise provided in the following table. For this purpose, the down time with raschig rings is set to 1, in order to obtain the "rela-tive down time". -26- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Tables Part I. Sample characterisation Material Degree o1 perforation Pressure Loss ,Ap" at ar empty pipe speed ,y 0.970 m/s Heat transfer coefficient [W/m2/K] ,,k" a1 various empty pipe speeds ,,v" [m/s] [-] [%] [mbar/m] 0.485 m/s 0.728 m/s 0.970 m/s a 57.0 7.2 8 11 13 b 94.1 0.5 5 6 7 c 93.3 1.5 1 3 5 Sample A 98.4 0.05 5 6 6 Sample B 97.7 0.07 6 9 11 Sample C 96.5 0.09 6 8 10 Sample D 4.9 0.1 10 12 Pressure Loss ,Ap" at an empty pipe Degree of speed ,,v"Heat transfer coefficient [W/m2/K] ,,k" at Material perforation 0.970 m/s various empty pipe speeds ,,v" [m/s] H [%] [mbar/m] 0.485 m/s 10.728 m/s 10.970 m/s a 57.0 72 8 11 13 b 94.1 03 5 6 7 c 93.3 1.5 1 3 5 Sample A 984 0.05 5 6 6 Sample B 97.7 0.07 6 9 fl Sample C 96.5 0.09 6 8 10 Sample D 949 0.1 7 10 12 a raschig rings fill b wire mesh 28 mm circular diameter, 1 m length (Company Anselm GmbH & Co. KG) c wire mesh 28 mm circular diameter and partially flat wire, 1 m length (Company Anselm GmbH & Co. KG) The ,,sample A to D" wire inserts with loops with 1 m length (Company Cal Gavin Ltd, GB) Part II. Down time and thermal compression quotient Material Relative Time Down Heat pressure quotient ,A" [W/m2/K/(mbar/m) at various empty pipe speeds ,,v" [m/s] [-] [-] 0.485 m/s 0.728 m/s 0.970 m/s a 1 1.1 1.5 1.8 b 0.6 1.0 12.0 14.0 c 0.5 0.7 2.0 3.3 Sample A 3 100.0 120.0 120.0 Sample B 2.8 85.7 128.6 157.1 Sample C 2.3 66.7 88.9 111.1 Sample D 2.1 70.0 100.0 120.0 Relative Down Heat pressure quotient ,A" [W/m2/K/(mbar/m)] Material Time at various empty pipe speeds ,,v" [m/s] [-j [-] 0.485 m/s 10.728 m/s 10.970 m/s a f fl L5 L8 b 0^6 L0 12X) 140 c 0.5 0.7 2.0 3.3 Sample A 3 100.0 120.0 120.0 Sample B 2.8 85.7 128.6 157.1 Sample C 23 66.7 88.9 111.1 Sample D 2.1 70.0 100.0 120.0 -27- PCT/EP2005/001116 July 13,2006 Stockhausen GmbH DG81547PC HZ/HR The inserts according to "sample A to D" have the best relative down times with very low pressure losses compared to the other samples. -28- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR List of reference numerals 1 reactor 2 reaction area 3 solid state catalyst 4 heat exchanger area 5 housing 6 insert 7 element 8 thread-like material 9 core 10 longitudinal element 11 winding 12 inner space cross-section 13 inner space 14 inner wall 15 further reaction area 16 central longitudinal axis 17 recess 18 element area 19 element axis 20 deposit -29- PCT/EP2005/001116 july 13> 2006 Stockhausen GmbH DG81547PC HZ/HR 21 cooling element 22 outer wall 23 reactor plate 24 hole 25 reactant gas 26 hot product gas 27 cooled product gas 28 cooling agent 29 plates 30 weld seam 31 connection point 32 connection area 33 holding area 34 holding wall 35 convexity 36 further heat exchanger area 37 reactant gas feed 38 product gas exit 39 quench device 40 purification area 41 polymerisation area 42 further catalyst -30- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR 43 cladding pipe 44 heating band 45 pipe outer wall 46 insulation 47 pressure measurement lance 48 sample 49 baffle 50 seal 51 flow direction 52 entry section 53 heating area 54 manometer 55 gas supply 56 valve 57 sample chamber 58 suspended bowl flowmeter 59 interstice 60 insert connection 61 insert module -31- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR 3. Reactor (1) at least comprising, connected with each other in fluid-conducting fashion, a reaction area (2), wherein the reaction area (2) comprises at least one solid state catalyst (3); a coolable heat exchanger area (4) wherein the heat exchanger area (4) comprises at least one housing (5), wherein the housing (5) accommodates at least partially an insert (6), wherein the insert (6) comprises at least one of the following properties determined according to the test methods described herein: (D) a heat pressure quotient Al at an empty pipe speed v of 0.485 m/s of greater than 1.11 W/m2/K/(mbar/m); (E) a heat pressure quotient A2 at an empty pipe speed v of 0.728 m/s of greater than 1.53 W/m2/K/(mbar/m); (F) a heat pressure quotient A3 at an empty pipe speed v of 0.970 m/s of greater than 1.81 W/m2/K/(mbar/m). -33- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR Claims 1. Reactor (1) at least comprising, connected with each other in fluid-conducting fashion, a reaction area (2), wherein the reaction area (2) comprises at least one solid state catalyst (3); a coolable heat exchanger area (4) wherein the heat exchanger area (4) comprises at least one housing (5), wherein the housing (5) accommodates at least partially an insert (6), wherein the insert (6) comprises a plurality of elements (7). 2. Reactor (1) according to claim 1, wherein the insert (6) comprises at least one of the following properties determined according to the test methods described herein: (A) a heat pressure quotient Al at an empty pipe speed v of 0.485 m/s of greater than 1.11 W/m2/K/(mbar/m); (B) a heat pressure quotient A2 at an empty pipe speed v of 0.728 m/s of greater than 1.53 W/m2/K/(mbar/m); (C) a heat pressure quotient A3 at an empty pipe speed v of 0.970 m/s of greater than 1.81 W/m2/K/(mbar/m). -32- PCT/EP2005/001116 July 13,2006 Stockhausen GmbH DG81547PC HZ/HR 4. Reactor (1) according to claim 3, wherein the insert (6) comprises a plural- ity of elements. 5. Reactor (1) according to any one of the preceding claims, wherein the in- sert (6) has a degree of perforation of at least 30. 6. Reactor (1) according to any one of the preceding claims, wherein the ele- ments (7) are formed from an at least partially thread-like material (8). 7. Reactor (1) according to claim 6, wherein at least two of the plurality of elements (7) are formed in one piece from the at least partially thread-like material (8). 8. Reactor (1) according to any one of the preceding claims, wherein at least a part of the plurality of elements (7) are arranged around a core (9). 9. Reactor (1) according to claim 8, wherein at least a part of the plurality of elements (7) are accommodated by the core (9). 10. Reactor (1) according to claim 8 or claim 9, wherein the core (9) is formed from at least two longitudinal elements (10). 11. Reactor (1) according to claim 10, wherein the at least two longitudinal elements (10) are twined around each other to form one or more windings (11). -34- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR 12. Reactor (1) according to claim 11, wherein at least one of the elements (7) is accommodated in the winding (11). 13. Reactor (1) according to any one of the preceding claims, wherein the plu- rality of elements (7) comprises wire. 14. Reactor (1) according to any one of claims 8 to 13, wherein the core (9) comprises wire. 15. Reactor (1) according to claim 13 or claim 14, whereby the wire is a metal wire. 16. Reactor (1) according to any one of the preceding claims, wherein the in- sert (6) at an inner space cross-section (12) of the housing (5) fills this in- ner space cross-section (12). 17. Reactor (1) according to any one of the preceding claims, wherein the housing (5) comprises a cylindrical inner space (13). 18. Reactor (1) according to any one of the preceding claims, wherein the in- sert (6) has a cylindrical form. -35- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR 19. Reactor (1) according to any one of the preceding claims, wherein the housing (5) comprises an inner wall (14) which is contacted by a part of the plurality of elements (7). 20. Reactor (1) according to any one of the preceding claims, wherein at least a part of the plurality of elements (7) are loops. 21. Reactor (1) according to any one of the preceding claims, wherein at least one further reaction area (15) is connected to the heat exchanger area (4). 22. Reactor (1) according to claim 21, wherein the solid state catalyst (3) in the reaction area (2) and a further catalyst (16) in the further reaction area (15) are different. 23. Reactor (1) according to any one of the preceding claims, wherein the in- sert (6) at least partially extends into the reaction area (2). 24. Reactor (1) according to claim 23, wherein the part of the insert (6) which extends into the reaction area (2) comprises a catalyst. 25. Reactor (1) with a reaction area (2) comprising an insert (6) as defined in any one of claims 2 to 15, 18 or 20, wherein this insert (6) comprises a catalyst. -36- PCT/EP2005/001116 July 13, 2006 Stockhausen GmbH DG81547PC HZ/HR 26. Process for oxidation of a hydrocarbon, wherein the hydrocarbon as a gas in converted in a reactor according to any one of the preceding claims into an oxidised hydrocarbon product. 27. Process according to claim 26, wherein the hydrocarbon is unsaturated. 28. Process according to claim 27, wherein the hydrocarbon is propene. 29. Process according to any one of claims 26 to 28, wherein the oxidised hy- drocarbon product is acrolein or acrylic acid. 30. Threads, sheets, formed bodies, food or feed additives, Pharmaceuticals, cosmetics, foams, superabsorbers, paper additives, leather additives or tex- tile additives, comprising or based upon an oxidised hydrocarbon product according to any one of claims 26 to 29. 31. Use of an oxidised hydrocarbon product according to any one of claims 26 to 29 in or for threads, sheets, formed bodies, food or feed additives, phar- maceuticals, cosmetics, foams, superabsorbers, paper additives, leather ad- ditives or textile additives. -37-

Documents:

02223-kolnp-2006 abstract.pdf

02223-kolnp-2006 claims.pdf

02223-kolnp-2006 correspondence others.pdf

02223-kolnp-2006 description (complete).pdf

02223-kolnp-2006 drawings.pdf

02223-kolnp-2006 form-1.pdf

02223-kolnp-2006 form-2.pdf

02223-kolnp-2006 form-3.pdf

02223-kolnp-2006 form-5.pdf

02223-kolnp-2006 international publication.pdf

02223-kolnp-2006 international search report.pdf

02223-kolnp-2006 pct others.pdf

02223-kolnp-2006 priority document.pdf

02223-kolnp-2006-correspondence others-1.1.pdf

02223-kolnp-2006-correspondence-1.2.pdf

02223-kolnp-2006-form-18.pdf

02223-kolnp-2006-form-26.pdf

02223-kolnp-2006-international search authority report-1.1.pdf

02223-kolnp-2006-priority document-1.1.pdf

2223-KOLNP-2006-(07-08-2013)-CORRESPONDENCE.pdf

2223-KOLNP-2006-(07-08-2013)-FORM-6.pdf

2223-KOLNP-2006-(07-08-2013)-OTHERS.pdf

2223-KOLNP-2006-(07-08-2013)-PA.pdf

2223-KOLNP-2006-(26-09-2012)-CORRESPONDENCE.pdf

2223-KOLNP-2006-ABSTRACT-1.1.pdf

2223-KOLNP-2006-AMANDED CLAIMS.pdf

2223-KOLNP-2006-AMANDED PAGES OF SPECIFICATION.pdf

2223-KOLNP-2006-CORRESPONDENCE.pdf

2223-KOLNP-2006-DESCRIPTION (COMPLETE)-1.1.pdf

2223-KOLNP-2006-DRAWINGS-1.1.pdf

2223-KOLNP-2006-EXAMINATION REPORT REPLY RECIEVED.pdf

2223-KOLNP-2006-FORM 1-1.1.pdf

2223-KOLNP-2006-FORM 2-1.1.pdf

2223-KOLNP-2006-FORM 3-1.1.pdf

2223-KOLNP-2006-OTHERS.pdf

2223-KOLNP-2006-PETITION UNDER RULE 137-1.1.pdf

2223-KOLNP-2006-PETITION UNDER RULE 137.pdf

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