JPWO2020030598A5 - - Google Patents

Description

The invention consists of at least one device jacket part carrying a predetermined pressure and at least one modular framework system arranged inside the device jacket part ( shell) and made of a ceramic fiber composite material. The present invention relates to a modular modular lining device comprising refractory bricks in addition to a modular framework system , and a method of using this device for high temperature reactors, in particular electrically heated high temperature reactors.

Highly endothermic reactions are used in the value creation chain in the chemical industry, for example in the cracking of mineral oil fractions, in the reforming of natural gas or naphtha, in the dehydrogenation of propane, in the dehydroaromatization of methane to benzene, or in the pyrolysis of hydrocarbons. Occurs frequently at the beginning of. To achieve industrial and economic benefits, temperatures of 500°C to 1700°C are required. The main reason for this is the thermodynamic limit of equilibrium transformation.

Endothermic reactions for the preparation of basic products in the chemical industry require effective insulation of the reactor from the environment due to the high temperatures. Moreover, some reactions require a pressure-tight reaction zone, and therefore the reaction chamber must be hermetically sealed from the environment up to the designated inlets and outlets. Furthermore, some of the endothermic reactions mentioned above are performed under reducing conditions. Moreover, endothermic reactions require efficient schemes for heat supply. In the case of direct electrical heating, the reactor interior, eg the bed, must additionally be electrically insulated from the lateral reactor shell.

DE 8714113U1 describes a modular pressure vessel, the jacket part of which carries a given pressure consists of flat metal rings superimposed on each other, which can be held together at will by vertically arranged tension elements. is maintained. The container base and/or lid can optionally be formed from closely adjacent individual rib elements extending star-shaped from the container wall toward the axis. It is stated that there may be a ceramic flat insulating layer on the inner container wall, and that this insulating layer may furthermore be protected by a thin metal layer called the "vest". A disadvantage of this prior art is that the ceramic insulating layer is fixedly connected to the jacket part, which carries a predetermined pressure . Furthermore, the metal vest separating the ceramic layer from the reaction volume is electrically conductive and has less thermal stability than the ceramic lining. As a result, this solution is not applicable to reactors with electrically heatable packings. Furthermore, it is not disclosed how the unit consisting of the jacket part, the ceramic insulation layer and the metal vest, which carries a given pressure, compensates for thermal expansion.

US 2,982,622 discloses the concept of electrical heating of endothermic reactions. This involves passing conductive particles as a fluidized bed through a reaction chamber.

Electrodes are used to induce electrical current through the particle bed, and the electrodes thus function as resistance heaters, providing direct heating to the reaction chamber. The counterflow of gas and particle streams provides efficient heat integration within the device, with the hot region located in the center of the reaction chamber, while the top and bottom edges of the reactor remain cool. . This principle can be applied to many important endothermic reactions of industrial relevance. The PCT application with application number PCT/EP2019/051466 discloses a heatable pack-type device for implementing electrical heating and for performing endothermic reactions, in which vertically arranged electrodes are connected to conductive solids. Arranged within the packing and with the electrode connected through the entire upper or lower dome of the reactor, the current-conducting connecting element has a large contact area with the electrode.

Reactors for high temperature reactions typically have a lining to protect the metal jacket , which carries the given pressure of the reactor, from the effects of high temperatures, to reduce heat losses, and/or to protect the metal jacket from electrical power. used for. These linings must withstand , in part, very high temperatures and pressures, chemical corrosion attacks, particle erosion, and thermal cycling stresses. Thermal cycling stresses can be caused by, for example, batch mode of operation or the introduction of low temperature process materials.

The requirements for refractory linings for chemical high temperature reactions are therefore diverse , some of them contradictory. Firstly, high thermal insulation capacity and low apparent density/high porosity are required, and secondly, good processability as well as sufficient mechanical strength are required. Furthermore, high thermal stability is required under various atmospheres.

Reactor concepts that do not require thermal lining, such as the Rouge pressure gasifier, have a double-walled pressure jacket ( shell ) with forced cooling by water. The advantages of this concept are simple construction, low reactor mass, and low thermal stress on the reactor jacket . However, the disadvantage of this concept is that the structure and control technology are complex, and there is no guarantee that the cooling system will stop ( fail-safe operation ) . Furthermore, this concept is not suitable for directly electrically heated reactors where electrical current must be passed through the bed. In this case, a short circuit occurs between the bed and the device jacket (pressure rated reactor shell ) carrying the given pressure .

Typically, firebrick is used for the lining. Naturally, these calcined refractories have an open porosity ranging from 13% to 20% by volume, for example. Process substances such as slags, melts or gases can penetrate these open pores and destroy the bricks by chemical reactions and/or completely change the thermodynamic properties of the structure. Cyclic chemical attacks and cyclic thermal and thermodynamic stresses lead to accelerated wear and damage, such as the delamination of large pieces that may have a thickness of several millimeters. Therefore, the service life is limited, and when a certain degree of wear is reached, the respective lining must be replaced, which is accompanied by high inconvenience and costs.

A further disadvantage of these porous materials is that (thermal) convection can exist within the brick at relatively high reaction pressures of about 10 bar and above, which increases the transfer of heat to the tube wall and thus reduces the thermal insulation. May degrade performance.

Firebrick materials disclosed in the prior art include Al ₂ O ₃ (corundum), phosphate-bound Al ₂ O ₃ , cement-bound Al ₂ O ₃ , chromium corundum Al ₂ O ₃ -Cr ₂ O ₃ (“ Aurex 75" and "Aurex 90", Radex-BCF), MgO-Cr ₂ O ₃ , Cr ₂ O ₃ , Al ₂ O ₃ -Cr ₂ O ₃ -ZrO ₂ ("Dichrome 60"), Cr ₂ O ₃ -ZrO ₂ (“Dichrome 90”), AlPO ₄ , CrPO ₄ (“Aurex 95P”) [Gehre, P.; (2013)]. Corrosions-und thermoschock bestaendige Feuerfest materialien fuer Flugströmvergasungsanlagen auf Al ₂ O ₃ -Basis-Werkstoff [Corrosion-resistant and thermal shock-resistant refractory materials for entrained flow gasification plants based on Al ₂ O ₃ - Materials development and corrosion research] Thesis , Technische Universitaet Bergakademie Freiberg, Chapter 2.3.1]. Known as refractory materials are silicon carbide and carbon, preferably in the form of graphite. A refractory brick material disclosed as having specific thermal shock resistance is 6% by weight ZrO ₂ -Cr ₂ O ₃ -Al ₂ O ₃ .

Further, DE 102015202277 and WO 89/5285 disclose a brick material made of foamed ceramic as a refractory brick material. The disadvantage of the construction of linings consisting only of firebrick is that they must be supported to absorb horizontal forces, for example floor loads. Furthermore, linings made only of firebrick are prone to cracking due to thermal expansion of the structure. Without support, the bricks can become detached from the lining. As a result, the lining becomes structurally weak and can collapse and/or lose its insulating effect, causing damage to the shell of the device.

The search for thermally stable support structures is also known in the field of processes for heat treatment of components. WO 2011/18516 and WO 2004/11562 disclose planar modular product supports consisting of bridge-like fiber ceramics, for example carbon fiber reinforced carbon composites, as framework elements. A disadvantage of these supports is that they are only loosely supported on the support substrate. Without solid anchorage, it is not possible to absorb horizontal forces, such as those resulting from floor loads. Furthermore, the product support member does not function as a thermally or electrically insulating layer.

US 8,211,524 discloses an anchor structure consisting of a ceramic fiber composite material connecting a metal substrate to a ceramic insulating layer. The ceramic fiber composite structure projects onto the metal layer and the ceramic layer and is joined thereto in a form-fitting manner. The disadvantage of this anchor structure is that it is strongly bonded to both the ceramic and metal layers. This connection cannot be separated without destroying the structure.

Linings are currently used commercially in, for example, blast furnace processes, partial oxidation of hydrocarbons to synthesis gas, metallurgy (carbide processes), etc. For example, blast furnaces have suitable materials for each zone: (i) the furnace top with refractory bricks containing 39-42% by mass Al ₂ O ₃ (conventional product) or newer materials super refractory bricks; (ii) Shaft with refractory brick containing 39-42% by weight Al ₂ O ₃ (conventional product) or newer materials corundum, SiC-Si ₃ N ₄ , (iii) 62% by weight Al ₂ O ₃ , mullite (iv) 42-62% by mass of Al ₂ O ₃ , mullite, carbon (conventional) or newer materials SiC, chromium; Bosch, with refractory bricks containing corundum, (v) hearths containing 42-62% by weight of Al ₂ O ₃ , mullite, carbon (conventional) or carbon/graphite, a newer material with ultra-fine pores; It is lined with.

The prior art discloses various implementations of fittings for linings ("Feuerfestbau" [refractory construction] from Deutsche Gesellschaft Feuerfest-und Schornsteinbau e.V. [German Association of Refractories and Chimney Construction]): In industrial equipment, refractory materials are typically connected to supporting structures, such as steel structures, by anchors. The anchor can be made of ceramic or metal material. Ceramic anchors are always joined to steel structures by metal holding elements. The retaining (anchor) brick must be of the same quality as the material on the hot side (inside). The choice of type and material depends on the structure of the components and the requirements arising from thermal and corrosive stresses. It is also described that walls are constructed using refractory bricks and fixed to metal walls with specific steel anchors at specific intervals. To secure the brick structure and control thermal expansion, it is necessary to arrange metal consoles of heat-resistant steel that support the bricks at specific intervals. The bricks are approximately the same size as conventional bricks and are held together with mortar in the customary manner. It is also stated that all bricks are fixed to the pipe wall to be protected with plate-like fittings. For example, all the plates are supported and held in the wall direction by pins welded to the pipe wall on one side , and are joined to the pipe wall by SiC mortar on the other side . Alternatively, all plates are suspended on plate fixing pins that project obliquely upward from the pipe wall. Also disclosed is an insulating lining for an industrial oven with a refractory block and a steel anchor, in which the steel anchor engages a groove in the block at its tip and the block is circumferentially secured by a hardened refractory composition. A circumferential groove is formed in the depth of each brick so that it is secured in a form-fitting manner.

All linings described in the prior art are supported on a reactor jacket part, usually a metal wall, which carries a certain pressure . The choice of using a wall that bears a certain pressure as a support for the lining has advantages in the simple construction of this construction unit.

The weak point of the lining lies in the connection between the metal anchor and the anchor brick. As a result of the different coefficients of expansion of the materials, combined with temperature differences and mechanical stress, these connections can become separated. As a result, the lining can lose its hold over large areas. Therefore, the blocks may fall off the lining. The resulting gap can eventually lead to damage. For example, the insulation between the reaction zone and the reactor wall carrying the given pressure is weakened, so that the reactor wall carrying the given pressure overheats. It is also possible for particles, for example from the floor of the reaction zone, to get into the gaps and cause an electrical short between the bed and the reactor wall carrying a given pressure .

A frequently encountered problem in lining systems is that, for example, the lining and the reactor wall , which carries a given pressure , have different coefficients of thermal expansion and are also heated at different rates, so if the temperature changes too rapidly, the lining This means that it is easily damaged. The freedom of movement of the individual bricks is limited by the fixtures, so if there is a sudden temperature change, the unstressed deformation or movement of the bricks will be inhibited and the bricks will break or the fixtures will fail. Damage may occur. This can occur even with a single occurrence of a sharp local change in temperature, for example as a result of a fault .

Compensation for differences in thermal expansion is achieved in the prior art by the use of expansion joints between the bricks of the lining. A weakness of these expansion joints is the formation of gaps in the structure of the lining into which particles and gases can enter from the reaction zone. This can create undefined and undesirable bypass flow. To avoid this problem during start-up, it is necessary to choose a very slow heating rate, usually less than 3 K/min. The resulting long start-up times can significantly impair the effective capacity of the high temperature reactor.

Mechanical connection of the lining to a wall that carries a given pressure limits the ease of assembly, accessibility, and repair of the device. For example, it is not possible to lift the reactor jacket from the reactor base. Moreover, damaged individual bricks can only be repaired or replaced by complete removal of the lining.

In summary, with the linings disclosed in the prior art, the following requirements remain open:
The electrical insulation of the lining is not sufficiently ensured.

Active cooling of the reactor jacket is dangerous from a safety point of view (fail-safe operation, contamination of reactor contents, undesired side reactions).

Fluctuations in temperature and/or pressure can destroy the lining and cause subsequent damage to the reactor structure.

Due to the large mass of the lining, handling of the reactor is difficult.

For example, assembly and disassembly after failure is difficult and complicated.

Startup and shutdown characteristics, such as cooling in the event of a fault, are slow and sluggish.

As a result, for high-temperature pressure reactions, due to the good thermal insulation properties and low gas permeability of the lining in the high temperature range, as well as the mechanical and electrochemical separation between the lining and the jacket part carrying the given pressure. There is a lack of solutions.

DE8714113U1 US2,982,622 PCT/EP2019/051466 DE102015202277 WO89/5285 WO2011/18516 WO2004/11562 US8,211,524 US8,211,524

Corrosions-und thermoschock bestaendige Feuerfest materialien fuer Flugströmvergasungsanlagen auf Al2O3-Basis-Werkstoffentw [Corrosion-resistant and thermal shock-resistant refractory materials for entrained flow gasification plants based on Al2O3 - Materials development and corrosion research] Thesis, Technische Universitaet Bergakademie Freiber g, Chapter 2.3.1] Deutsche Gesellschaft Feuerfest-und Schornsteinbau e. V. "Feuerfestbau" [Refractory Structures] from [German Association of Refractories and Chimney Construction]

The basic objective was therefore to disclose a modular, self-supporting device which acts as electrical and/or thermal insulation and is mechanically separated from the reactor jacket section which carries a given pressure. Ta. A further objective was to disclose a modular self-supporting framework for high temperature reaction linings in order to achieve mechanical separation of the lining from the reactor jacket . A further aim was to disclose a lining that allows simple electrical isolation for the device between the reaction zone in the reactor and the reactor jacket part (pressure rated reactor shell ) carrying a given pressure. . A further aim was to disclose a lining that withstands reaction pressures of up to 60 bar and at the same time reliably retains its thermal insulation effect. A further aim was to disclose a lining that exhibits a long service life due to increased chemical corrosion resistance, increased thermal cycling stability and increased resistance to delamination of the material.

Surprisingly , it consists of at least one device jacket part carrying a predetermined pressure and at least one modular framework system arranged inside the device jacket part , said modular framework system comprising: A device system has been shown that is comprised of two different bridge types , wherein the plurality of lateral bridges form at least one prism or cylinder, and the plurality of lateral bridges form at least one prism or cylinder. Projecting into the interior of the cylinder, said transverse bridge and said lateral bridge are pluggable into each other and/or connectable with the aid of one or more connecting elements, said bridge The material is characterized in that it includes a ceramic fiber composite material.

Further disclosed is a self-supporting framework system comprising a ceramic fiber composite material having refractory bricks comprising a foamed ceramic material, wherein the bricks are provided by a modular framework system of the present invention. Supported.

A description of the internally arranged modular framework system is as follows:
Preferably, the transverse bridge forms a regular polygonal prism with a polygonal base or a homogeneous cylinder with a circular base.

Preferably, the cutout takes the form of a slot or a hole, advantageously having the shape of the hole as described in DIN 24041, for example a slotted hole, preferably an angular slotted hole, or a rounded corner. It takes the form of a long hole.

The connecting elements used may advantageously be form-fit connections and/or adhesive connections between the transverse bridge and the lateral bridges , such as mating plug connections and adhesive connections, preferably mortise and tenon connections. It is a seam, tongue and groove or dovetail joint.

A " framework " according to the invention preferably comprises vertical bridges (vertikale Stege: German) which are connected crosswise to each other and are able to accept ( absorb ) possible lateral forces of the lining in their planes. understood to mean. The framework can advantageously divide the lining into segments that can delimit radially and circumferentially .

"Freestanding" in the present invention is understood to mean a framework that does not require any support, in particular any lateral support by walls, even at pressures up to 60 MPa. Within the framework , stresses of approximately 0.5 MPa can dominate due to flow losses and what are called possible bed silo forces.

"Apparatus jacket part carrying a given pressure or reactor jacket part carrying a given pressure " is understood to mean the boundary part of the container which withstands the pressure difference between the interior of the container and the environment. The reactor jacket , which carries a given pressure , essentially comprises three parts: the lower end of the vessel, the upper end and the side walls.

"Lining" is understood to mean a protection consisting of a sheet, brick or molding that can be adhered by mortar or cement, which includes an air-tight or barrier intermediate layer and further includes applied layers and Ceramic interiors are understood to be sufficiently resistant to thermal, mechanical and chemical influences (DIN 28060 and DIN 28071). Since 1986, the German word Ausmauerung [brick-lining] has been replaced by Auskleidung [lining] (DIN 28071).

"Segment" is understood to mean a modular unit of the circumferential framework . The transverse bridges define the separation of segments in the radial direction . The lateral bridges define the position of the segment in the circumferential direction, and gaps between circumferentially adjacent lateral bridges , or separating bridges inserted into these gaps, bound the segment in the circumferential direction ( (See Figures 2 to 4).

"Box" means, seen in the radial direction, two adjacent parallel or concentric elliptical arc -shaped , preferably parallel or concentric circular curve-shaped transverse bridges , corresponding lateral bridges and, optionally, the gap between the circumferentially adjacent said lateral bridges or advantageously the area surrounded by said separating bridges inserted into this gap. (See Figures 2 to 4).

The words "front side" or "front side" are understood to mean the area directed toward the interior of the reactor. The words "rear side", "outside" or "back side" are understood to mean the area directed towards the outer circumference of the reactor. The words "top", "bottom" and "side" are understood to refer to an upright reactor. The words "lower", "center" and "upper" are used in a geodetic sense.

"Ceramic fiber composites" are understood to mean fiber-reinforced ceramics, in particular oxide ceramics, such as, for example, M. Schmuecker, “Fiber-reinforced oxide ceramic materials”, Materialwissenschaften und Werkstofftechnik, 2007, 38, No. 9, pages 698-704. Ceramic fiber composites include a fibrous framework , a woven fabric, a nonwoven scrim, a ceramic fiber knit and/or braid, and a filler matrix of sintered ceramic powder.

The fiber composite material is therefore a matrix of ceramic particles in which ceramic fibers, in particular continuous fibers with a fiber length greater than 50 mm, are embedded in the form of a winding or as a fabric. characterized. These are called fiber reinforced ceramics, composite ceramics, or fiber ceramics. The matrix and the fibers may in principle consist of any known ceramic material, carbon also being treated as a ceramic material in this connection.

"Oxidized fiber composite ceramic or oxidized fiber composite material" is understood to mean a matrix of oxidized ceramic particles comprising ceramic, oxidized fibers and/or non-oxidized fibers.

Preferred oxides of the fiber and/or matrix include Be, Mg, Ca, Sr, Ba, rare earth, Th, U, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co. , Ni, Zn, B, Al, Ga, Si, Ge, Sn, Li, Na, K, Rb, Cs, Re, Ru, Os, lr, Pt, Rh, Pd, Cu, Ag, Au, Cd, In , Tl, Pb, P, As, Sb, Bi, S, Se, Te, and mixtures of these oxides.

The mixture is advantageously suitable as both fiber and matrix material. The fibers and matrix generally do not need to be made of the same material.

In principle, not only binary mixtures, but also ternary and higher mixtures are suitable and of interest. In a mixture, the individual components may be present in equimolar amounts, but advantageous mixtures are those in which the concentrations of the individual components of the mixture differ significantly, with one component, including the doping, being present at a concentration of less than 1%. be.

Particularly advantageous mixtures are binary and ternary mixtures of aluminum oxide, zirconium oxide and yttrium oxide (for example zirconium oxide reinforced aluminum oxide); mixtures of silicon carbide and aluminum oxide; mixtures of aluminum oxide and magnesium oxide (MgO spinel). ; mixture of aluminum oxide and silicon oxide (mullite); mixture of aluminum silicate and magnesium silicate, ternary mixture of aluminum oxide, silicon oxide and magnesium oxide (cordierite); steatite (magnesium silicate); zirconium oxide Reinforced aluminum oxide; stabilizers in the form of stabilized zirconium oxide (ZrO ₂ ), magnesium oxide (MgO), calcium oxide (CaO) or yttrium oxide (Y ₂ O ₃ ); other stabilizers used include oxidized Contains cerium (CeO ₂ ), scandium oxide (ScO ₃ ) or ytterbium oxide (YbO ₃ ); also aluminum titanate (a stoichiometric mixture of aluminum oxide and titanium oxide); silicon nitride and aluminum oxide (silicon aluminum oxide). nitride (silicon aluminum oxynitride) SIALON).

The zirconium oxide-reinforced aluminum oxide used is preferably Al ₂ O ₃ with 10 to 20 mol % ZrO ₂ . ZrO ₂ advantageously contains 10-20 mol%, preferably 16 mol% CaO, 10-20 mol%, preferably 16 mol% MgO, or 5-10 mol%, preferably 8 mol% Y ₂ O ₃ (“completely or with 1 to 5 mol %, preferably 4 mol % Y ₂ O ₃ (“partially stabilized zirconium oxide”). A preferred ternary mixture is, for example, 80% Al ₂ O ₃ , 18.4% ZrO ₂ and 1.6% Y ₂ O ₃ .

Similar to the aforementioned materials (mixtures and individual components), basalt, boron nitride, tungsten carbide, aluminum nitride, titanium dioxide, barium titanate, lead zirconate titanate and/or boron carbide in an oxidized ceramic matrix. Fibers are also considered.

Useful fibers include oxidized, carbonized, nitrided or C fibers, and reinforcing fibers coated with the SiBCN fiber class. More specifically, the fibers of the ceramic composite are aluminum oxide, mullite, silicon carbide, zirconium oxide and/or carbon fibers. Mullite consists of a solid solution of aluminum oxide and silicon oxide. Preference is given to using fibers of oxide ceramics (Al ₂ O ₃ , SiO ₂ , Mullite) or non-oxide ceramics (C, SiC).

It is advantageously possible to use creep-resistant fibers, ie fibers whose residual deformation, ie creep elongation, does not increase over time or is minimal within the creep range (in the temperature range below 1400° C.). 3M has established the following limit temperatures for NEXTEL fibers for 1% sustained elongation (residual elongation) after 1000 hours at a tensile stress of 70 MPa: NEXTEL 440: 875°C, NEXTEL 550 and NEXTEL 610: 1010°C, NEXTEL 720: 1120°C. (Reference: Nextel™ Ceramic Textiles Technical Notebook, 3M, 2004).

The fibers advantageously have a diameter of 1 to 50 μm, preferably 5 to 20 μm, more preferably 8 to 15 μm. They are advantageously woven, usually in a plain or satin weave, to obtain a textile sheet, knitted to form a hose, or as a fiber bundle around a form. Can be wrapped around. For the production of ceramic composite systems, fiber bundles or woven fabrics are impregnated with slips containing, for example, components of the subsequent ceramic matrix, preferably Al ₂ O ₃ or mullite (Schmuecker, M. 2007), Materialwissenschaft und Werkstofftechnik, 38(9), pp. 698-704). Heat treatment above 700° C. results in a high-strength composite structure composed of ceramic fibers and a ceramic matrix, advantageously having a tensile strength of more than 50 MPa, preferably more than 70 MPa, more preferably more than 100 MPa, especially more than 120 MPa. can be obtained.

Preferably, the _ceramic fiber composites used are SiC/ _Al2O3 , SiC/mullite, C _{/ Al2O3 ,} C/mullite _{, Al2O3} / _Al2O3 , _Al2O3 /mullite _. , mullite/Al ₂ O ₃ and/or mullite/mullite. Here, the material before the slash indicates the type of fiber, and the material after the slash indicates the type of matrix. The matrix systems used in ceramic fiber composite structures may also be siloxanes, Si precursors, and a variety of different oxides including, for example, zirconium oxide. Preferably, the ceramic fiber composite material comprises at least 99% by weight of Al ₂ O ₃ and/or mullite.

In the present invention, fiber composite materials based on oxide ceramic fibers, such as 3M(TM) NEXTEL(TM) 312, NEXTEL(TM) 440, NEXTEL(TM) 550, NEXTEL(TM) 610, NEXTEL(TM) 720, Manufacturer Walter E. C. Preference is given to using the MvM 1415N, MvM 1415N-2220, AvM 1415N, AvM 1415N-3000, FW12 and/or FW30 products from Pritzkow Spezialkeramik. Particular preference is given to using the products NEXTEL610, NEXTEL720 and AVM1415N-3000 and/or FW12 and/or FW30. Furthermore, it is advantageously possible to use fibers from Nitivy, Japan.

The matrix advantageously has a fiber loading level (volume proportion of fibers in the composite structure) of 20% to 40%; the total solids content of the composite structure is advantageously 50% to 80%. . Fiber composite ceramics based on oxide ceramic fibers are chemically stable in oxidizing and reducing gas atmospheres (i.e., there is no mass change even when stored in air at 1200 °C for more than 15 hours (reference: Nextel™ Ceramic Textiles Technical Notebook, 3M, 2004)), is thermally stable at temperatures above 1300°C. Fiber composite ceramics have quasi-ductile deformation properties. Therefore, it is stable against thermal cycles and has quasi-ductile fracture characteristics. Therefore, there is an indication of component failure before failure occurs.

の熱伝導率を有する。 The fiber composite material advantageously has a porosity of 20% to 50%; it is therefore not airtight according to the definition of DIN 623-2. The fiber composite material advantageously has a long-term service temperature of up to 1500°C, preferably up to 1400°C, more preferably up to 1300°C. The fiber composite material advantageously has a strength of more than 50 MPa, preferably more than 70 MPa, more preferably more than 100 MPa, especially more than 120 MPa. The fiber composite material advantageously has a yield point of elastic deformation of 0.2% to 1%. The fiber composite material advantageously has thermal cycling stability according to DIN EN 993-11. The fiber composite material advantageously has a coefficient of thermal expansion [ppm/K] of 4 to 8.5. Fiber composite materials are advantageously

It has a thermal conductivity of

Ceramic fiber composites can advantageously be produced by chemical reactions such as the CVI (chemical vapor infiltration) method, pyrolysis, especially the LPI (liquid polymer infiltration) method or the LSI (liquid silicon infiltration) method.

The framework is advantageously designed modularly in the circumferential direction (see FIGS. 2 to 4). The skeleton is advantageously constructed modularly in the upward direction (see FIGS. 5 and 6). Modular units in the circumferential direction are called segments. Modular units in the vertical direction are called layers. The modular framework has at least two different types of bridge types . This first type of bridge radially defines the delimitation (boundary) of a segment , preferably a lining segment. These bridges (Steg) are called lateral bridges . The second type of bridge defines the position of the segment, preferably the lining segment, in the circumferential direction. These bridges are called lateral bridges .

Advantageously, the skeleton may include further bridge-like elements. Such an element is advantageously inserted into a gap between two circumferentially adjacent transverse bridges (see FIG. 5). These elements are also called isolation bridges . Alternatively, the lateral determination of the segments may advantageously be achieved by additional lateral bridges .

Further elements may advantageously be sandwiched horizontally between two mutually overlapping layers of the transverse bridge (see FIG. 7). These elements are called planar bridges . Planar bridges may advantageously form a barrier to the formation of large area convective clusters in the porous structure of the possible lining. Furthermore, the planar bridge advantageously allows locally limited replacement of the bricks capable of lining without disassembling the entire framework .

The transverse bridge advantageously takes the form of a planar or angled rectangular plate or a cylindrical shell (a cylinder is a figure bounded by a cylindrical surface with a closed generatrix and two parallel planes; Bronstein, p. 251, Figure 2.49).

Additionally, the transverse bridge ( transverse element ) may take the form of a corrugated sheet. The waveform may be sinusoidal or triangular. The amplitude is advantageously between 1 mm and 100 mm, preferably between 2 mm and 50 mm, especially between 3 mm and 20 mm. The wavelength is advantageously between 2 mm and 500 mm, preferably between 5 mm and 200 mm, especially between 10 mm and 100 mm.

In top view, the transverse bridge forms one or more polygons, preferably regular polygons, or one or more concentric ellipses, preferably one or more concentric circles. The wavy transverse bridge in top view has the shape of a periodic function or trochoid. The lateral bridges ( lateral elements ) are preferably arranged star-shaped (see FIGS. 2 to 5).

The prisms with polygonal bases advantageously have from 3 to 60 transverse bridges , preferably from 4 to 40 transverse bridges , in particular from 6 to 24 transverse bridges . The cylinder with an oval, in particular circular, base surface advantageously has 3 to 60 oval transverse bridges , preferably 4 to 40 transverse bridges, in particular 6 to 24 transverse bridges , preferably in the form of an arc. It has a horizontal bridge . The diameter of a cylinder, preferably an ellipse, in particular a circle, or a diagonal of a polygon, preferably a regular polygon, is advantageously between 0.2 m and 20 m, preferably between 0.5 m and 15 m, Especially between 1m and 10m.

The size of the gap between two circumferentially adjacent transverse bridges is advantageously between 0 and 200 mm, preferably between 1 and 100 mm, more preferably between 2 and 50 mm, especially between 3 and 20 mm.

Optionally, the ends of circumferentially adjacent transverse bridges may overlap (see FIG. 8). The size of the overlap is advantageously between 200 and 20 mm. The lap joints are advantageously filled with a highly thermostable cement and/or joined with rivets, which are advantageously made from a ceramic fiber composite material, for example OCMC.

The sheet-like or cylindrical transverse bridge advantageously has a height (element height) of from 100 mm to 5 m, preferably from 200 mm to 3 m, in particular from 500 mm to 2 m. The transverse bridge advantageously has a length of 100 mm to 5 m, preferably 250 mm to 3 m, in particular 500 mm to 2 m. The transverse bridge advantageously has a thickness of 0.2 mm to 20 mm, preferably 0.5 mm to 10 mm, in particular 1 mm to 5 mm.

Advantageously, the transverse bridges forming a polygon, preferably a regular polygon, or an ellipse, preferably a circle in top view have the same height, width and thickness. Advantageously, the modular framework is formed from transverse bridges and has a plurality of layers arranged on top of each other in the form of a uniform prism or cylinder, advantageously from 1 to 100 layers. layers, preferably 2 to 50 layers, especially 3 to 30 layers (see Figures 4 and 5).

The overall height of the superimposed elements is advantageously between 100 mm and 50 m, preferably between 200 mm and 20 m, in particular between 500 mm and 10 m.

In a modular framework , the transverse bridge heights of all mutually superposed layers are advantageously the same ( bridge height ).

Advantageously, parallel transverse bridges or concentric elliptical arc-shaped transverse bridges, preferably parallel transverse bridges , arranged in top view as concentric polygons , preferably regular polygons, or concentric ellipses, preferably circles Bridges or concentric arc-shaped transverse bridges can be used (see Figures 2-5). Advantageously, 2 to 20 parallel transverse bridges or concentric elliptical arc transverse bridges are used, preferably 2 to 5 parallel transverse bridges or concentric arc transverse bridges . The distance between radially adjacent polygons, preferably regular polygons , or adjacent ellipses, preferably circular shapes, consisting of transverse bridges is preferably between 10 mm and 1000 mm, preferably between 20 mm and 20 mm. 500 mm, more preferably 40 mm to 250 mm. Advantageously, this distance is the same for all radially adjacent transverse bridges .

The lateral bridges advantageously take the form of flat or corrugated rectangular (rectangular) sheets.

The waveform may be sinusoidal or triangular. The amplitude is advantageously between 1 mm and 100 mm, preferably between 2 mm and 50 mm, especially between 3 mm and 20 mm. The wavelength is advantageously between 2 mm and 500 mm, preferably between 5 mm and 200 mm, especially between 10 mm and 100 mm.

The lateral bridges are advantageously arranged perpendicular to the lateral bridges .

The lateral bridges advantageously have a height ( bridge height ) of from 100 mm to 5 m, preferably from 200 mm to 3 m, in particular from 500 mm to 2 m. The lateral bridges advantageously have a width of 50 mm to 2 m, preferably 100 mm to 1 m, in particular 200 mm to 500 mm. The lateral bridges advantageously have a thickness of 0.2 mm to 20 mm, preferably 0.5 mm to 10 mm, in particular 1 mm to 5 mm.

In the case of multiple lateral bridges stacked on top of each other , the intermediate lateral bridges have the same height, width and thickness (see FIG. 6). The height of the lateral bridges of the intermediate layer is advantageously between 90% and 110% of the bridge height of the lateral bridges , preferably between 95% and 105% of the bridge height of the lateral bridges , more preferably between 95% and 105% of the bridge height of the lateral bridges . It corresponds to 98% to 102% of the height , in particular the same as the bridge height of the transverse bridge . The bridge heights of the bottom and top layers may be different from the bridge heights of the middle layer. Advantageously, the bridge height of the bottom layer is 10% to 90% lower or higher than the bridge height of the intermediate bridges , preferably 20% to 75%, more preferably 30% to 60%. Advantageously, the bridge height of the top layer is 10% to 90% lower or higher than the bridge height of the middle bridge , preferably 20% to 75%, more preferably 30% to 60%. If the lateral bridge of the bottom layer is lower than the middle lateral bridge , the bridge of the top layer is advantageously higher than the middle lateral bridge by the same proportion. If the lateral bridges of the bottom layer are higher than the middle lateral bridges , the bridges of the top layer are advantageously lower by the same proportion than the middle lateral bridges . Advantageously, the upper edge of the lateral bridge ends flush with the upper edge of the uppermost lateral bridge , which means that a vertical offset in the upward or downward direction advantageously reduces the bridge height. This means less than 5%, preferably less than 2% of the diameter. The width and thickness of the lowermost lateral bridge and the uppermost lateral bridge are advantageously the same as the intermediate lateral bridge .

Alternatively, in each layer, the upper edges of the lateral bridges and lateral bridges advantageously end flush , which means that a vertical offset in the upward or downward direction advantageously reduces the bridge height. This means less than 5%, preferably less than 2% of the diameter. In each layer, the heights of the lateral bridges and the lateral bridges are advantageously the same. This configuration is particularly suitable for use with planar bridges .

Advantageously, in the modular framework , the difference between the number of mutually overlapping lateral bridges and the mutually overlapping lateral bridges is less than two, and the numbers are preferably the same.

Any separating bridge advantageously takes the form of a rectangular sheet.

The separating bridges are advantageously arranged between circumferentially adjacent transverse bridges in the form of a prism, preferably a right prism , or a cylinder, preferably a right cylinder (see FIGS. 4 and 5). Advantageously, the separating bridge is inserted into the gap formed between circumferentially adjacent transverse bridges in the form of a prism, preferably a uniform prism (regular prism), or a cylinder, preferably a regular cylinder. .

The separating bridge advantageously has a height of 100 mm to 5 m, preferably 200 mm to 3 m, in particular 500 mm to 2 m. The separating bridge advantageously has a length of 50 mm to 2 m, preferably 100 mm to 1 m, in particular 200 mm to 500 mm. The separating bridge advantageously has a thickness of 0.2 mm to 20 mm, preferably 0.5 mm to 10 mm, in particular 1 mm to 5 mm.

The ratio of the lengths of the separating bridge and the lateral bridges is advantageously between 0.9 and 1.25. The ratio of the heights of the separating bridge and the lateral bridges is advantageously between 0.5 and 50, preferably between 0.75 and 10, more preferably between 0.9 and 5. Advantageously, the upper edge of the separating bridge ends flush with the upper edge of the transverse bridge of the top layer, which means that a vertical offset in the upward or downward direction advantageously reduces the element height. This means less than 5%, preferably less than 2%. Advantageously, on the top layer, the upper edge of the separating bridge ends flush with the upper edge of the lateral bridge , which means that a vertical offset in the upward or downward direction advantageously prevents the bridge height. This means less than 5%, preferably less than 2%.

Any planar bridge depends on the shape of the transverse bridge , which is advantageously a trapezoidal sheet (in the case of a rectangular transverse bridge ) or a sheet in the form of annular segments (in the case of an arc-shaped transverse bridge ).

The planar bridge is advantageously inserted horizontally between two layers of transverse bridges superimposed on each other (see FIG. 7). The planar bridges advantageously have cutouts, preferably slots or openings, especially slots, so that they can be inserted into the lateral bridges . Advantageously, the planar bridge overlies the upper edge of the transverse bridge .

The trapezoidal planar bridge advantageously has a base length of from 100 mm to 5 m, preferably from 200 mm to 3 m, in particular from 500 mm to 2 m. Furthermore, the trapezoidal planar bridge advantageously has a height of between 50 mm and 2 m, preferably between 100 mm and 1 m, in particular between 200 mm and 500 mm. The trapezoidal angle, ie the acute internal angle between the base of the regular trapezoid and the isosceles, advantageously ranges from 30° to 88°, preferably from 45° to 86°, in particular from 60° to 84°. By way of example, 87° is advantageous for 60 segments, 85.5° is advantageous for 40 segments, and 82.5° is advantageous for 24 segments. Furthermore, the trapezoidal planar bridge advantageously has a thickness of between 0.2 mm and 20 mm, preferably between 0.5 mm and 10 mm, in particular between 1 mm and 5 mm.

The planar bridge in the form of annular segments advantageously has an outer radius of 0.1 m to 10 m, preferably 0.25 m to 7.5 m, in particular 0.5 m to 5 m. Furthermore, the planar bridge in the form of annular segments advantageously has a width of from 50 mm to 2 m, preferably from 100 mm to 1 m, in particular from 200 mm to 500 mm. Furthermore, the planar bridge in the form of annular segments has an angular sector (Winkelausschnitt: German) of 6° to 120°, preferably 9° to 90°, more preferably 15° to 60°. Furthermore, the trapezoidal planar bridge advantageously has a thickness of between 0.2 mm and 20 mm, preferably between 0.5 mm and 10 mm, in particular between 1 mm and 5 mm.

The planar bridge and the separating bridge may also advantageously be combined into one element (see FIG. 11).

The framework advantageously consists of bridges (Steg: German) which can be inserted into one another via cutouts, preferably slots or openings, in particular slots. The transverse bridge and the lateral bridge are preferably inserted into each other in a crosswise manner (see FIGS. 4 and 5).

The modularly constructed skeleton advantageously has 1 to 20 radially adjacent transverse bridges , preferably 2 to 10 transverse bridges , more preferably 2 to 5 transverse bridges per segment and layer. Includes horizontal bridge . The modular framework advantageously comprises 1 to 10 lateral bridges , preferably 1 to 5 lateral bridges , more preferably 1 to 3 lateral bridges per segment and layer ( (see Figure 2).

The lateral bridges and lateral bridges of the bottom layer and the middle layer are advantageously offset from one another in terms of height. The vertical deviation (Versatz) between the upper edge of the lateral bridge and the upper edge of the transverse bridge in one layer is between -90% and +90% of the bridge height , preferably between -75% and 75% of the bridge height ; More preferably, it is -60% to +60% of the bridge height . Advantageously , on the top layer, the upper edge of the separating bridge ends flush with the upper edge of the transverse bridge , which means that the vertical deviation in the upward or downward direction is advantageously less than 5% of the bridge height . , preferably less than 2%. As a result, they advantageously support each other and form a rigid, self-supporting shape consisting of a plurality of segments. Transverse bridges define radial segment separations, and lateral bridges define circumferential segment separations.

Advantageously, 3 to 60, preferably 4 to 40, more preferably 6 to 24 identical segments are formed per layer. The segments are advantageously separated from each other over their entire height by separation bridges (see FIG. 5).

The lateral bridges advantageously have cutouts, preferably slots or openings, in particular slots, for each lateral bridge arranged on the same layer of the same segment. In the case of a single lateral bridge , the cutout, preferably the slot or opening, in particular the slot, is arranged in the middle of the lateral bridge . In the case of multiple lateral bridges , the cutouts, preferably slots or openings, in particular the slots, are arranged symmetrically in the center of the lateral bridge , the distance between them being advantageously between 5 mm and 2 m, preferably between 10 mm and 1 m, particularly preferably 20 mm to 500 mm.

The lateral bridges of the intermediate layer advantageously have cutouts, preferably slots or openings, in particular slots, for each lateral bridge advantageously arranged on the same layer of the same segment. In the case of a single transverse bridge , the cutout, preferably a slot or opening, in particular the slot, advantageously lies between 5 mm and 2 m, preferably between 10 mm and 1 m, from the edge of the lateral bridge facing the reactor jacket. , especially located 20mm to 500mm behind . In the case of multiple transverse bridges , the distance between two adjacent cutouts, preferably slots or openings, in particular slots, is advantageously between 10 mm and 2 m, preferably between 20 mm and 1 m, in particular between 30 mm and 500 mm.

Advantageously, all transverse bridge recesses, preferably slots or openings, in particular slots, open downwardly. The cutouts, preferably slots or openings, in particular the length of the slots, of all lateral bridges of one segment and of the lateral bridges of the intermediate layer of one segment are advantageously between 10% and 90% of the bridge height . , preferably corresponds to 25% to 75% of the bridge height , more preferably 40% to 60% of the bridge height , in particular half of the bridge height .

Advantageously, the recesses, preferably slots or openings, in particular the slots, in the lateral bridges of the intermediate layer open downwardly. The length of the lateral bridge cutouts, preferably slots or openings, in particular the slots, of the intermediate layer is advantageously the same as the bridge height and the length of the lateral bridge cutouts, preferably slots or openings, especially the slots. 90% to 110% of the difference between, preferably 95% to 105% of the difference between the bridge height and the transverse bridge cutout, preferably the slot or opening, especially the length of the slot, more preferably the element Corresponding to 98% to 102% of the difference between the length of the height and the transverse bridge cutout , preferably the slot or opening, in particular the slot; in particular the element height and the transverse bridge cutout, preferably the slot or opening , especially the difference between the lengths of the slots.

Advantageously, the lateral bridge does not have a cutout in the bottom layer. Its height is advantageously between 90% and 110% of the height of the transverse bridge notch , preferably between 95% and 105% of the height of the transverse bridge notch , more preferably between 95% and 105% of the height of the transverse bridge notch . Corresponding to 98% to 102% of the notch height; in particular, it is the same as the notch height of the transverse bridge . The lateral bridges of the top layer have cutouts, preferably slots or openings, in particular paired arrangements of slots, on the upper and lower edges. The length of the cutout, preferably the slot or opening, in particular the slot, corresponds to the length of the cutout, preferably the slot or opening, in particular the slot, of the lateral bridge of the intermediate layer.

The box has two radially adjacent transverse bridges in the form of parallel or concentric elliptical arcs, preferably parallel or concentric elliptical arcs, and corresponding lateral bridges, and circumferentially adjacent lateral bridges . is understood to mean the area surrounded by a gap between or a separating bridge advantageously inserted into said gap (hatched area parts 5a-b in FIG. 2; hatched area parts 5a-d in FIG. 3). ; hatched area portions 5a to 5f in FIGS. 4 and 5). In a top view, the box advantageously has a four-sided cross section or a cross section in the form of an annular segment (see FIGS. 2 to 5). Each segment advantageously has 1 to 50 boxes, preferably 2 to 25 boxes, especially 3 to 15 boxes.

This modular framework system of the invention advantageously comprises lining, especially high temperature processes in the temperature range from 150°C to 1900°C, preferably from 400°C to 1700°C, especially from 600°C to 1500°C. It can be used as a skeleton support for the lining of industrial chemical reactors.

This modular framework system of the invention may also be advantageous as a support structure for catalysts, particularly monolith catalysts (ie catalyst baskets used in fixed bed reactors with axial or radial flow).

Furthermore, the modular framework system of the present invention can be used as electrical insulation, particularly inside a reactor.

Furthermore, the modular framework system of the present invention can be used as a radiation shield.

In top view, the modular framework system of the present invention divides the cross-section of the reactor occupied by the lining into box profiles in the shape of rectangular, trapezoidal, or annular segments. The box is advantageously filled with refractory bricks and/or a catalyst, in particular a monolithic catalyst. Alternatively, the box remains unfilled.

The cross section in top view of the box is advantageously filled with 1 to 2000 bricks, preferably 2 to 500 bricks, more preferably 3 to 200 bricks, which are placed next to each other and/or or are arranged consecutively. The sum of bricks in the box is called packing. The packing in top view preferably has a rectangular, trapezoidal or annular segment-like cross section, the radially oriented sides are preferably parallel to each other and the narrow base is preferably oriented inwardly. ing.

The refractory brick advantageously has a hexahedral, preferably prismatic shape. Advantageously, the upper and lower surfaces and the front and rear surfaces are each parallel to each other. Advantageously, the top and bottom surfaces are at right angles to the other sides of the hexahedron.

The bricks are advantageously arranged in layers in the radial direction . In the radial direction, the packing advantageously comprises 1 to 40 layers, preferably 1 to 20 layers, more preferably 1 to 10 layers. The bricks are advantageously arranged vertically in layers. Regarding the height, the packing comprises 1 to 1000 layers, preferably 1 to 500 layers, more preferably 2 to 200 layers, especially 3 to 100 layers.

Circumferentially, 1 to 200, preferably 2 to 150 and especially 3 to 100 bricks are arranged side by side in the box.

Advantageously, the seams between the bricks in the packing are filled with mortar or adhesive or are carried out as dry seams . Preferably, the seams between the bricks are carried out as dry seams , which means that no mortar or adhesives are used for joining the molded bricks.

Advantageously, the packing bricks are laid as a header course, as a stretcher course, as a soldier course, as a low rock course, as a flat course, as a stretcher bond, as a header bond, as a block bond or as a cross bond. (See "Feuerfestbau" from Deutsche Gesellschaft Feuerfest- und Schornsteinbau e.V., p. 76). Preferably, the packing bricks are laid as stretcher bonds, header bonds, block bonds or cross bonds. More preferably, the bricks of the packing are laid as block bonds or cross bonds.

A combination of radial layer-to-layer laying modes is also possible. For example, in the case of a packing with two layers, the radially inner layer can advantageously be implemented as a cross-bond and the outer layer as a grenadier layer (Grenadierschicht (German)). It is. This combination achieves relative offset of the seams between the bricks of the packing. In this way, gaps that may form between adjacent bricks are blocked. In this way, undesired flow of gaseous reaction medium through the lining can be effectively reduced.

There is advantageously one gap between the bricks and the bridge or between the bricks of different packings of the modular framework system . The gap between a brick and an adjacent bridge or between circumferentially adjacent bricks of the packing is advantageously between 1 and 50 mm, preferably between 1 and 25 mm, more preferably between 1 and 10 mm. The effect of this gap is that the individual bricks can move relative to each other. This gap also facilitates the insertion of bricks in the construction of the lining. Furthermore, the gap provides the necessary space for the packing to thermally expand in an unhindered, ie, stress-free, manner.

Optionally, the gap between the bridge and the packing, or between adjacent bricks in the circumferential direction of the packing, can be filled by an insulating mat, as described below.

Advantageously, the vertical deviation between the upper edge of the packing and the upper edge of the skeleton is less than 50 mm, preferably less than 20 mm, more preferably less than 10 mm; The vertical deviation , ie in the upward or downward direction, is advantageously less than 5%, preferably less than 2%, of the height of the transverse bridge . This can be achieved, for example, by cutting the bricks to size in one layer of packing.

Generally, there is a vertical offset between the layer seams of the packing and the seams between the lateral bridges of the superimposed framework lower and intermediate layers. The vertical deviation between two transverse bridges placed directly one on top of the other and the seam of the next layer of packing is advantageously between 0% and 50% of one brick height, preferably between 0% and 50% of one brick height. It is 20% to 50%. In the particular case where planar bridges are used, the seam between two transverse bridges placed one on top of the other is at the level of the joining of the layers between two rows of bricks placed on top of each other. The vertical deviation between the seam between two superimposed transverse bridges and the seam of the nearest layer between two superposed rows of bricks is advantageously less than 10 mm, preferably It is 5 mm or less, more preferably 3 mm or less.

The sides of the brick may advantageously be flat. Alternatively, the side surfaces may have suitably shaped appendages ( springs/springs ) and recesses (grooves), thus forming a form-fitting manner by means of a spring -groove connection (see DIN 1057). Can be joined.

The inner layer of the packing is advantageously in contact with the reaction zone on the front side and is advantageously bounded on the lateral and rear sides by the framework of the invention.

"Refractory bricks" in the context of the present invention are understood to mean ceramic products and materials with a service temperature of 600° C. or higher. According to the definition (DIN 51 060), only materials with a cone drop point (corresponding to approximately 1500° C.) greater than SK 17 (=ISO 150) can be called refractories. This critical temperature roughly corresponds to the melting point of iron and has important implications for customs and mining law purposes.

The bricks on the inside (inner wall) of the brick lining advantageously have the following property profile: (i) good thermal insulation in the temperature range from 1000°C to 1700°C, (ii) high strength, (iii) wear resistance. (iv) low open porosity, (v) thermal cycle stability, (vi) electrical insulation. The heat insulation properties are good when the thermal conductivity is less than 2 W/m/K, preferably less than 1 W/m/K. High strength is provided by a cold compressive strength of more than 5 MPa, preferably more than 10 MPa. High wear resistance is correlated with the hardness of the material. The open porosity of the ceramic foam is low when the proportion of closed pores is 1% or more, preferably 5% or more, more preferably 10% or more. If the material passes the test according to DIN V ENV 820-3, it has a high thermal cycle stability. The electrical insulation is good if the specific electrical resistance is 10 9 Ωm or more, preferably 10 11 Ωm or more.

The properties of bricks, in particular their composition, strength, shape and dimensions, are specified in DIN 1057 (bricks for free-standing chimneys), 1081 (refractory products: rectangular firebricks), 1082 (refractory products: arch bricks). .

Refractory bricks are advantageously molded bricks made from refractory material. The material of the refractory brick should advantageously be selected depending on the process temperature and process conditions. Furthermore, the choice of material should advantageously be chosen depending on the radial position (layer) within the lining.

Preferably, the material of the inner layer in contact with the medium is a ceramic foam according to the DIN EN 12475 classification or a refractory material, in particular an alumina-silica product, such as refractory brick, corundum, mullite, cordierite, or a basic product, such as magnesia. , magnesia-chromium oxide, magnesia spinel, magnesia-zircon, or carbon-bonded basic bricks, especially corundum, mullite, cordierite. Ceramic foams are described, for example, in DE 102015202277 and WO 07/22750. Particularly suitable is the closed pore foam ceramic material given the trade name Halfoam Alumina™.

Most preferably, the molded bricks of the inner layer consist of a foamed ceramic material given the trade name Halfoam Alumina™.

The invention further relates to molded bricks comprising ceramic foams, in particular closed-cell foams. Advantageously, the shaped bricks of the invention are made of alumina-silica products, such as refractory bricks, corundum, mullite, cordierite, or basic products, such as magnesia, magnesia-chromium oxide, magnesia-spinel, magnesia-zircon, or Carbon-bonded basic bricks, especially ceramic foams made from corundum, mullite, cordierite.

The invention further relates to a brick assembly comprising a plurality of layers of brick packing arranged in radial succession.

The material of the second layer from the inside advantageously has the following property profile: thermal stability above 1500° C., thermal conductivity below 1 W/m/K, preferably below 0.5 W/m/K. cold compressive strength of 1 MPa or more, preferably 2 MPa or more. This property profile is that of foams and cast or extruded lightweight refractory bricks. By way of example, commercially available products such as Halffoam, Carath FL®, PROMATON® are used for this layer.

The material of the third layer from the inside advantageously has the following profile of properties: thermal stability above 1200 °C, below 0.5 W/m/K, preferably below 0.2 W/m/K Thermal conductivity of 0.5 MPa or more, preferably 1 MPa or more of cold compressive strength. This profile of properties is advantageously possessed by vacuum formed fibreboards. By way of example, commercial products such as PROMATON® or ALTRA® are used for this layer.

The material of the fourth layer from the inside advantageously has the following profile of properties: thermal stability above 1000 °C, below 0.2 W/m/K, preferably below 0.05 W/m/K thermal conductivity of 0.1 MPa or more, preferably 0.2 MPa or more. This profile of properties is advantageously possessed by vacuum formed fiberboard or microporous fumed silica boards. For this layer, commercial products such as ALTRA® or MICROTHERM® are used, for example.

The present invention further provides that the invention further provides for the formation of radially sequentially arranged (i) foamed ceramic, (ii) sintered cast or extruded ceramic, or (i) foamed ceramic, (ii) sintered cast or extruded ceramic and (iii) ) compressed ceramic fibers, or (i) foamed ceramics, (ii) sintered cast or extruded ceramics, (iii) compressed ceramic fibers, and (iv) vacuum formed fiberboards or boards comprising microporous fumed silica. The present invention relates to a brick assembly including a plurality of brick packings configured.

The surface of the inner layer of the lining made of molded brick, preferably ceramic foam, may be untreated or coated. The coating advantageously seals the surface of the lining and acts as an abrasion protection. A coating, for example a protective layer, is advantageously applied to the end face (front side: Stirnseite: German) and/or the back side and/or the top side and/or the bottom side and/or the left and right sides, preferably on the end side and/or on the left and right sides. Or it is applied to the back surface and/or the top end surface and/or the bottom end surface, more preferably it is applied to the end surface and/or the back surface, and in particular it is applied to the end surface. End face (front face) refers to the side of the molded brick facing the interior of the reactor. The protective layer advantageously consists of a refractory ceramic, for example ZrO ₂ , YO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , preferably Al ₂ O ₃ . The thickness of the protective layer is advantageously between 100 μm and 2 mm, preferably between 200 μm and 1 mm. The porosity (void content) of the coating is advantageously less than 50%, preferably less than 25%, more preferably less than 10%, especially less than 5%. The coating can be applied to the molded brick by coating methods known to those skilled in the art, such as painting, dip coating, flame spraying, plasma spraying.

Advantageously, the coating consists of a multilayer structure, for example one thin layer of non-porous ceramic and one or more thicker layers of porous ceramic.

Examples of suitable coating materials include Aremco Coatings (coating slips): PP-634-AL, 634-SIC, 634-YO, 634-ZO, Oerlikon Metco (flame and plasma spraying), LWK PlasmaCeramic ( (plasma coating), Polytec Cotronics (coating slip, casting compound), etc.

The shaped bricks advantageously have dimensions known to the person skilled in the art according to DIN 1081 (1988) for rectangular bricks and DIN 1082 (1988) for arch or wedge bricks. Optionally, it is possible to cut the bricks to individual dimensions.

In the vertical direction, the refractory bricks may have different heights in different tiers of a course (Schicht: German) . This can be achieved, for example, by laying shaped bricks alternately as bullet and runner layers (Laeuferschicht (German)) . In this way, it is possible to avoid (i) excessive seams in areas of low axial temperature gradients or (ii) high mechanical stresses within individual bricks in areas of high axial temperature gradients. Become.

The edges of the refractory brick packing are advantageously parallel to adjacent bridges or to the gaps between adjacent bridges . The gap between a brick and an adjacent bridge or between packings circumferentially adjoining a brick is advantageously between 1 mm and 50 mm, preferably between 1 mm and 25 mm, more preferably between 1 mm and 10 mm. These gaps are advantageously at least partially filled with an insulating mat made of mineral fibres.

Insulating mats are optionally fixed to the flat sides of the bridge . During installation, the insulation mat is advantageously vacuum-tightly welded to the film and evacuated. The mat thus prepared is advantageously joined to transverse bridges and/or lateral bridges and/or separation bridges and/or transverse bridges , preferably to transverse bridges and/or lateral bridges , more preferably to transverse bridges . be done. After installation, the film is advantageously perforated. As a result, the mat expands and supports the bricks. This procedure is described, for example, in WO2014/125024.

Materials with the following trade names are suitable for the insulation mat: ALSIFLEX-1600, ALSIFLEX-1600 paper, PROMAFELT-1600, SILCAFELT-160, THERMOFRAX blanket (flexible mat), THERMOFRAX board (vacuum forming) or THERMOFRAX felt/paper (ceramic paper and felt).

Advantageously, the framework of the invention is supported by a foundation, for example a foundation plate. The base plate advantageously serves to secure the modular framework and to receive the mass of the refractory packing. The base plate may alternatively be in one-part or segmented form. The base plate is preferably segmented, with each element advantageously supporting a segment of the modular framework system of the invention.

Instead of a foundation, the framework of the invention may be fixed to the roof.

The base plate is advantageously loosely or firmly supported on the lower dome. Preferably, the base plate is removably connected to the flange of the lower dome. More preferably, the base plate is screwed to the flange of the lower dome.

Advantageously, the base plate is annular. Advantageously, the top and bottom surfaces of the base plate are planar and parallel to each other. The thickness of the base plate is between 1 mm and 500 mm, preferably between 2 mm and 300 mm, more preferably between 3 mm and 200 mm. The width of the ring is between 50 mm and 2 m, preferably between 100 mm and 1 m, especially between 200 mm and 500 mm.

In top view, the outer edge of the base plate advantageously projects beyond the outer transverse bridge of the OCMC skeleton . The excess of the outer edge of the base plate over the outer transverse bridge is advantageously between 0 mm and 200 mm, preferably between 5 mm and 100 mm, more preferably between 10 mm and 50 mm. In top view, the inner edge of the base plate is advantageously covered by an inner layer of the lining. The excess of the inner edge of the lining over the inner edge of the base plate is advantageously between 0 mm and 100 mm, preferably between 0 mm and 50 mm, more preferably between 0 mm and 20 mm. The base plate advantageously has a groove on the top surface. The groove advantageously serves as a pedestal for supporting and guiding the transverse bridges , lateral bridges and any separation bridges in the lowest layer of the framework . The arrangement of the grooves advantageously corresponds to the pattern of the bridges in a top view of the skeleton . The groove advantageously has a depth of 1 mm to 500 mm, preferably 2 mm to 300 mm, more preferably 3 mm to 200 mm. The groove advantageously has a width of 0.2 mm to 20 mm, preferably 0.5 mm to 10 mm, in particular 1 mm to 5 mm. The groove is advantageously 1% to 100% wider, preferably 2% to 50%, more preferably 5% to 20% wider than the thickness of the bridge used. Advantageously, the lowermost lateral bridges and transverse bridges of the framework are joined in a fixed manner to the base plate. The connection can be established, for example, by a press-fit method with a threaded connection, a form-fit method with a dowel or an adhesive bond method with an adhesive. Advantageously, the base plate consists of metal, plastic and/or ceramic, preferably metal, more preferably steel. Optionally, the surface of the base plate is electrically conductive or electrically insulating. In the case of metal base plates, the electrically insulating surface layer advantageously consists of enamel, ceramic and/or plastic. Preferably, the surface of the base plate is electrically insulating in areas. More preferably, the top surface and outer periphery of the base plate are electrically insulated.

The base plate advantageously has fixing elements for a lifting device with which the entire lining or segments can be lifted and assembled from the reactor.

Advantageously, it is possible to use what are called multifunctional base plates. The base plate optionally has one or more of the following features. (i) The base plate is advantageously continuous to the middle of the reactor. In the region of the reaction zone, the base plate advantageously has openings for the flow of gases and solids. (ii) The base plate is advantageously configured as a flange of the lower dome. (iii) The base plate advantageously carries the lower electrode of an electrically heated moving bed reactor or a fixed bed reactor.

An advantageous combination is to have insulation on the inside of the reactor jacket ; for example, using an insulation board encapsulated within a metal shell. The insulation board is advantageously porous with a total porosity of 45% or more and less than 99%, preferably 60% or more and less than 99%, more preferably 70% or more and less than 99%. Advantageously, the insulation board comprises calcium silicate, vermiculite, rock wool, glass wool or fumed silica. Advantageously, the insulation board is housed in a closed metal shell. The metal shell advantageously consists of sheets that are folded, welded or soldered into a closed shell. The shell is advantageously provided with fastening elements, preferably hooks and/or loops, on its back side. By means of these fixing elements they are advantageously suspended in corresponding fixtures on the pressure rated reactor shell.

The invention furthermore provides a reactor having an apparatus, preferably a modular framework system according to the invention, and an apparatus jacket carrying a predetermined pressure , preferably a modular framework system according to the invention , a lining and It relates to a reactor jacket section that carries a predetermined pressure .

The cross-sectional area of the reactor is advantageously between 0.005 m ² and 200 m ² , preferably between 0.05 m ² and 100 m ² , more preferably between 0.2 ^{m 2} and 50 m ² and especially between 1 m ² and 20 m ² . The height of the reactor jacket is advantageously between 0.1 m and 100 m, preferably between 0.2 m and 50 m, more preferably between 0.5 m and 20 m, especially between 1 m and 10 m. The ratio of height to equivalent diameter of the reactor jacket is advantageously from 0.01 to 100, preferably from 0.05 to 20, more preferably from 0.1 to 10, most preferably from 0.2 to 5. . The wall thickness of the reactor jacket is advantageously between 1 mm and 300 mm, preferably between 5 mm and 200 mm, more preferably between 10 mm and 100 mm.

Preferred materials for the reactor jacket are, for example, steel alloys with material numbers 1.4541, 1.4571.

Advantageously, there is a continuous gap between the modular framework and the reactor jacket which carries the predetermined pressure . The gap width is advantageously between 0 mm and 100 mm, preferably between 2 mm and 50 mm, more preferably between 5 mm and 50 mm.

The gap between the modular framework structure and the jacket part carrying the predetermined pressure may optionally be filled with a bed of loose particles. The particles may be ceramic or metallic. The particles may be regular in shape, such as spherical, cylindrical, prismatic, or irregular. Particles may be solid, porous or hollow. The particles may be of the same size or of different sizes. The particles of the bed advantageously have an equivalent diameter of 0.05 mm to 100 mm, preferably 0.1 mm to 50 mm, more preferably 0.5 mm to 10 mm. The equivalent diameter of a particle is the diameter of a sphere of equal volume to the particle.

The gap between the modular framework system and the jacket part carrying the predetermined pressure may optionally be purged by a directed gas flow. The purge gases used are advantageously CO ₂ , H ₂ O, N ₂ , H ₂ , N ₂ , diluted air (air diluted with N ₂ ) and/or Ar. The purge gas flow is advantageously introduced annularly through the upper dome and withdrawn through the base plate of the lining. Alternatively, the purge gas flow is introduced annularly through the base plate of the lining and withdrawn through the dome. The purge gas flow advantageously forms a gas curtain that separates the reaction zone from the reactor jacket carrying the predetermined pressure . This makes it possible to prevent the formation of deposits inside the reactor jacket section that carries the predetermined pressure ; furthermore, it is possible to cool the jacket section that carries the predetermined pressure .

Optionally, the modular framework structure may be supported against the side walls of the jacket section, which carry a predetermined pressure . The support may be constructed of OCMC, monolithic ceramic, woven ceramic fibers, metal, or a combination of these materials. They may be loosely guided between the framework and the side wall of the jacket section carrying the predetermined pressure , or they can be rigidly joined to the jacket section of the OCMC framework or the reactor wall carrying the predetermined pressure. You can. The bond may be adhesive or form-fitting. These supports are preferably loosely supported between the modular framework system and the jacket section that carries the predetermined pressure .

In reactors with large axial temperature gradients, modular framework systems are placed only in those areas of the reactor where high thermal stability and function as thermally and electrically insulating delimitation of the reaction volume are required. It may be advantageous to do so. In this case, the edge region of the jacket part which bears a certain pressure can advantageously remain uninsulated.

Advantageously, the reactor is heated electrically (see PCT/EP2019/051466).

Advantageously, the device of the invention has an upper, middle and lower device part, in which at least one pair of electrodes in a vertical arrangement is installed/arranged in the middle part, all electrodes being advantageously electrically conductive. Placed/embedded within solid packing. Advantageously, the upper device part and the lower device part are in the form of a dome and have a specific conductivity of between 10 ⁵ S/m and 10 ⁸ S/m. The intermediate device part is preferably electrically insulated from the solid packing. Advantageously, the upper device part and the lower device part are likewise electrically insulated from the intermediate device part. Advantageously, the upper electrode is connected via the upper device part, the lower electrode is connected via the lower device part, or the electrodes each have one or more connecting elements in electrical contact with these parts. connected via. Advantageously, the ratio of the cross-sectional area of the upper electrode and/or the lower electrode, preferably the upper electrode and the lower electrode, to the cross-sectional area of the corresponding current-conducting element or, if no connecting element is used, the ratio of the cross-sectional area of the upper electrode and/or the lower electrode to the cross-sectional area of the corresponding current-conducting device part; The ratio of the cross-sectional areas of the electrode and/or the lower electrode, preferably the upper electrode and the lower electrode, is between 0.1 and 10, preferably between 0.3 and 3, especially between 0.5 and 2.

In the apparatus of the invention, in particular in the reactor, it is preferred to carry out the following high temperature reactions:
・Preparation of synthesis gas by reforming hydrocarbons with steam and/or carbon dioxide, simultaneous production of hydrogen and pyrolytic carbon by thermal decomposition of hydrocarbons. Suitable carrier materials are in particular carbonaceous granules, silicon carbide-containing granules, nickel-containing metal granules.
- Preparation of hydrogen cyanide from methane and ammonia or from propane and ammonia. Suitable carrier materials are in particular carbonaceous granules.
- Preparation of olefins by steam cracking of hydrocarbons. Suitable carrier materials are in particular carbonaceous granules, silicon carbide-containing granules.
-Preparation of ethylene, acetylene, and benzene by coupling methane.
- Preparation of olefins by catalytic dehydrogenation of alkanes, for example propylene from propane or butene from butane. Suitable support materials are in particular silicon carbide-containing granules coated with dehydrogenation catalysts or iron-containing moldings.
- Preparation of styrene by catalytic dehydrogenation of ethylbenzene. Suitable support materials are in particular silicon carbide-containing granules coated with dehydrogenation catalysts or iron-containing moldings.
- Preparation of diolefins by catalytic dehydrogenation of alkanes or olefins, for example the preparation of butadiene from butene or from butane. Suitable support materials are in particular silicon carbide-containing granules or iron-containing moldings coated with dehydrogenation catalysts.
- Preparation of aldehydes by catalytic dehydrogenation of alcohols, for example the preparation of anhydrous formaldehyde from methanol. Suitable support materials are in particular silver- or silicon carbide-containing granules coated with dehydrogenation catalysts or iron-containing moldings.
- Preparation of CO from CO ₂ and carbon by Boudouard reaction. Suitable carrier materials are in particular carbonaceous granules.
- Preparation of hydrogen and oxygen by catalytic hydrothermal decomposition on a catalyst. Suitable support materials are in particular silicon carbide-containing granules or iron-containing granules coated with a cleavage catalyst, for example ferrite.

1 is a diagram of a reactor segment consisting of a reactor jacket carrying a predetermined pressure around an OCMC framework filled with refractory bricks; FIG. Legend: 1 = Packing consisting of 3 lateral bridges 2a = Lateral bridges in the middle layer 2b = Lateral bridges in the bottom layer 2c = Lateral bridges in the top layer 6 = Packing of refractory bricks inserted in the box of the OCMC framework Packing (one package) 8 = Reactor jacket part that bears the specified pressure FIG. 4 is a top view of a segment of a segmented framework formed from transverse bridges (1) and lateral bridges (2), with four transverse bridges and three lateral bridges per layer; The transverse bridges are finished as cylindrical shells and the side bridges as flat sheets. FIG. 3 is a top view of a segmented skeleton formed from lateral bridges with one lateral bridge per layer ; Left side: 12 segments, lateral bridge finished as flat sheet, 1 lateral bridge per lateral bridge Center: 18 segments, lateral bridge finished as arc, 1 lateral bridge per lateral bridge Right side: 18 segments, lateral bridge finished as arc, 1 lateral bridge per lateral bridge : 12 segments, lateral bridges constructed as angled (bent) shells, 2 lateral bridges per lateral bridge . The hatched area represents the extent of the segments. 5a, 5b, 5c. ．． ．． The part labeled is the box formed by the bridges within the segment. FIG. 3 is a top view of a segmented skeleton formed from lateral bridges with lateral bridges per layer and lateral bridges with two lateral bridges . Left side: 12 segments, transverse bridges finished as flat sheets, one lateral bridge per transverse bridge Center: 18 segments, transverse bridges finished as arcs, one lateral bridge per transverse bridge Right side: 18 segments, transverse bridges finished as arcs, one lateral bridge per transverse bridge : 12 segments, lateral bridges constructed as angled shells, 2 lateral bridges per lateral bridge . The hatched area represents the extent of the segment. 5a, 5b, 5c. ．． ．． The part labeled is the box formed by the bridges within the segment. FIG. 3 is a top view of a segmented skeleton formed from lateral bridges , lateral bridges and isolated bridges with one lateral bridge per layer ; Left side: 12 segments, transverse bridges finished as flat sheets, one lateral bridge per transverse bridge , one loose (loose) separation bridge in each gap between segments Center: 18 segments, finished as arcs transverse bridge , one lateral bridge per transverse bridge , one loose (loose) separation bridge in each gap between segments Right side: 12 segments, transverse bridge constructed as an angled (bent) shell, The hatched area represents the extent of the segments in the case of two lateral bridges per transverse bridge, one loose separation bridge in each gap between the segments. 5a, 5b, 5c. ．． ．． The part labeled is the box within the segment formed by the bridge . FIG. 3 is a perspective view of a segment in a framework consisting of sheet-like transverse bridges and lateral bridges ; In the radial direction , three transverse bridges are arranged in series and connected by a central lateral bridge . The skeleton consists of six layers. Center: Skeleton- element, transverse bridge with slot on the upper side (1, height h), lateral bridge of the middle layer (2a, height h), lateral bridge of the lower layer (2b, height 1.5h) and Upper layer side bridge (2c, height 0.5h). As a result of the different heights of the lower and upper lateral bridges , the bridges of different layers are interdigitated. Right side: perspective view of a cross-section of a segment consisting of a transverse bridge , a lateral bridge and a packing of refractory bricks embedded in an insulating mat. Legend: 1 = Packing consisting of 3 lateral bridges 2a = Lateral bridges in the middle layer 2b = Lateral bridges in the bottom layer 2c = Lateral bridges in the top layer 6 = Packing of refractory bricks inserted in the box of the OCMC framework Packing (one package) 8 = Insulation mat for fixing the OCMC frame firebrick package FIG. 3 is a perspective view of a segment in the framework of sheet-like transverse bridges , lateral bridges and planar bridges ; Radically, three transverse bridges are arranged in series and connected by a central lateral bridge . The skeleton consists of four layers. Lateral bridges are inserted between the layers. Right side: Skeleton- element, transverse bridge with slot on the underside (1, height h), lateral bridge with slot on the top (2, height h), planar bridge with slot on the inside (3). Legend: 1 = Packing consisting of 3 lateral bridges 2 = Lateral bridges 3 = Planar bridges (Corresponding to the example " Scaffold with one row of lateral bridges "): FIG. 2 is a top view of an exemplary skeleton with one row of lateral bridges ; FIG. 3 is an enlarged view showing details of a lap joint between adjacent transverse bridges ; Legend: 9=Rivet 10=Binding cement (Corresponding to the example " Scaffold with multiple transverse bridges as radiation shielding.") Left side: Top view of an exemplary skeleton with a radial row of multiple transverse bridges . Right side: Detailed side view of the lateral bridge (2) and the bundle of lateral bridges (1) inserted into the lateral bridge. ( Scaffolding with profiled lateral bridges ): Left: Top view of an exemplary framework segment with multiple profiled lateral bridges and isolated bridges . Center: Front view of multiple layers arranged one on top of the other. Figure Right side: Side view of several layers placed one on top of the other Legend: 1 = Lateral bridge 2 = Profiled lateral bridge 4 = Separate bridge : A perspective view of a complex (compounded) bridge configuration. Top: Combination of planar bridge and separation bridge.Middle : Combination of planar bridge , separation bridge , and transverse bridge (outside). Bottom: combination of planar bridge , separation bridge and two transverse bridges (inner and outer). FIG. 1 : is a diagram of a reactor with a framework structure partially cut away for the length of the jacket section carrying a given pressure ;

Fiber-reinforced oxide ceramics, especially OCMC, combine high thermal stability with high strength, ductility and thermal shock stability. The material consistently retains these properties up to temperatures above 1200°C. At higher temperatures, the material gradually becomes brittle, but retains its shape and maintains significant residual strength. These materials also have low thermal conductivity and low electrical conductivity , which makes them suitable as insulators . A framework made of OCMC forms a barrier separating the reactor packing , hot fixed bed, or fluidized bed (moving bed or fluidized bed ) from the reactor walls carrying a given pressure . When electrical current is conducted through the reactor packing, the OCMC framework also forms an effective electrical insulation between the reactor packing and the jacket section carrying the predetermined pressure . The form-fit connection between the bridges allows for stress-free thermal expansion of the skeleton . This makes it possible to control the operating conditions within the reactor, which are characterized by high temperatures and significant temperature gradients with respect to location and time.

The properties of the new materials of foamed ceramics and fiber-reinforced oxide ceramics, especially Halffoam and OCMC, offer the following advantages: Foamed ceramics, especially Halffoam, have high strength and good thermal insulation properties, especially at high temperatures above 1000 °C. It combines authenticity of form. This material can be used up to 1700°C. Fiber-reinforced oxide ceramics, especially OCMC, combine high thermal stability with high strength and ductility. The material consistently retains these properties up to temperatures above 1200°C. At higher temperatures, the material gradually becomes brittle, but retains its shape and maintains significant residual strength.

By combining the two materials, a self-supporting lightweight lining of a pressure reactor can be realized. Forces acting on the lining are absorbed by the OCMC skeleton . This allows the shaped bricks to be loosely arranged so that they can flexibly move relative to each other during thermal expansion. The pure form-fitting connection of the OCMC framework and the refractory packing allows for a flexible structure that can be deformed with low stress in case of significant temperature changes (with respect to location and time).

The insulating effect of Halffoam bricks allows temperature reduction from 1500 °C (reaction zone temperature) to below 1200 °C with a thin layer. As a result, there are several advantages: the lining can be made thinner and is much lighter compared to the prior art. The support framework bridge made of OCMC is effectively protected from aging. Due to the low thermal conductivity of OCMC, the fin action of the support framework eliminates thermal bridges (heat transfer path: Kaeltebruecke: German) .

Foamed ceramics and fiber-reinforced oxide ceramics, especially _AlOx- based Halffoam and OCMC, have identical coefficients of thermal expansion. As a result, the gap in the lining does not change over the entire temperature range, which prevents irregular leakage flow through the lining. The embedding of refractory packing in the insulation mat in the OCMC framework allows for a seamless, flexible, and temperature-stable connection.

As a result of the inherent stability achieved, the lining does not require support by the reactor jacket , which carries a given pressure . As a result, it becomes possible to form a continuous gap between the lining and the reactor jacket . The lining can be assembled and disassembled separately from the reactor jacket . As a result, reactor assembly and repair and replacement of wear-prone elements is simplified. More specifically, the lining is preassembled on the outside of the reactor and suspended completely within the reactor. As a result, reactor downtime can be minimized during lining repairs or renewals.

In the case of electrically heated reactors, the material of the lining is an electrical insulator and constitutes an effective insulating layer between the floor of the reaction zone and the reactor jacket , which carries the predetermined pressure . The gap between the lining and the reactor jacket ensures an additional reliable, temperature-independent electrical insulation between the bed and the reactor jacket .

Coating the inside of the lining with a non-porous, smooth outer layer has a positive concomitant effect: the outer layer provides effective protection against abrasion by particles of moving beds, for example. The smooth surface of the outer layer makes it difficult for solid deposits to form on the walls. The deposits are only loosely attached to the surface and can be dislodged by the movement of particles in the moving bed. Permeability through the wall due to bypass of gas from the reaction zone is reduced. Multilayer structures consisting of a thin layer of non-porous ceramic and one or more thick layers of porous ceramic are resistant to cracking as a result of thermal shock.

The layer-by-layer construction of the lining makes it possible to use insulating materials in the individual layers with optimal respective properties with respect to insulation effectiveness and thermal stability. The radial division of the lining by parallel or concentric transverse bridges of the OCMC framework allows for a fault-tolerant construction scheme : even if part of the refractory packing breaks, the layer remains intact. , these prevent breakthrough of the hotbed from the reaction zone to the reactor jacket section carrying the predetermined pressure , thus allowing a controlled shutdown of a damaged reactor.

Particularly relevant in the case of pressure reactors: any sealing of the surface of the OCMC sheets and/or refractory bricks can suppress the formation of large-area convective cycles, which clearly reduces the thermal insulation effect of the lining.

Example:
Prior art:
The industrial reactor was lined with multiple layers of fireproof concrete. The diameter of the reaction zone was 3000 mm. The electrodes for supplying electricity to the bed were vertically spaced 3000 mm apart. The lining consisted of the following layers:

The lining was secured to the reactor jacket by anchors . The inner diameter of the reactor jacket section, which carries the predetermined pressure, was 3640 mm. In the design, the heat transfer coefficient of the lining was 2.14 W/(m ² K). According to the design, the power loss from the reactor was 32 kW/m over the reactor length, and the temperature outside the reactor was 75°C. In reactor operation at a maximum temperature of 1400° C. and an absolute pressure of 1.6 bar, the heat loss increased to 84 kW/m and the temperature outside the reactor locally increased to 300° C. When the reactor was opened, cracks were found in the lining. Visible cracks inside the reactor walls ran irregularly and varied in size and extent . The longest crack measured was 1000 mm; the largest crack width measured was 3 mm. The lining was damaged in some places. This resulted in depressions in the lining having an area of 500 cm ² and a depth of up to 5 cm. This damage is explained by a reduction in the thermal insulation effect of the lining. As a result, reactor performance and process energy consumption decreased. Furthermore, the reactor jacket section , which carries the given pressure , was weakened due to excessive temperature rise. For these reasons, safe operation of the reactor could not be continued.

Example 1: Use of the modular framework of the invention as an electrical insulator inside a reactor This example shows the simplest configuration of the solution of the invention. Moving bed reactors with resistance heated beds are used, for example, for the pyrolysis of hydrocarbons. The diameter of the reaction zone is 3000 mm. The electrodes for powering the floor are arranged vertically with a distance of 3000 mm from each other. The reactor jacket , which carries the predetermined pressure , has an internal diameter of 3100 mm. A cooling coil is installed on the outside of the reactor shell, and water is flowed through the cooling coil so that the jacket temperature is controlled at a maximum of 50°C. The reaction zone is surrounded by a modular framework . The skeletal bridge is made of OCMC. The framework consists of rows of transverse bridges , each supported by a side bridge . The thickness of all bridges is 3mm. The skeleton has six segments and five layers overlapping each other . The transverse bridges of adjacent segments overlap each other in the circumferential direction. The lap joints are filled with thermostable cement and connected with rivets. As a result, the skeleton forms a dust-tight closure of the reaction zone from the annular space between the skeleton and the reactor jacket part carrying the predetermined pressure . CO ₂ flows as a purge gas into the annular space between the skeleton and the reactor jacket carrying the predetermined pressure . The temperature in the center of the reaction zone is 1400°C. The temperature of the skeleton is 425°C. This solution is notable for its compact and lightweight design. The reaction zone occupies 93.5% of the cross-sectional area surrounded by the jacket section which carries the predetermined pressure . The mass of the framework composed of OCMC bridges is 250 kg. Furthermore, the skeleton serves as electrical insulation of the reaction zone with respect to the walls of the reactor , which carry a given pressure . At the same time, the framework has a slight thermal insulation effect. As a result, a sufficiently low temperature is established inside the skeleton to keep it clean from carbonaceous deposits. This enables a reliable steady-state operation mode of the process.

Example 2: Use of the invention as a modular framework as a radiation shield This example shows the construction of the solution of the invention assuming a framework consisting of OCMC bridges . Moving bed reactors with resistance heated beds are used, for example, for the pyrolysis of hydrocarbons. The diameter of the reaction zone is 3000 mm. The electrodes for powering the floor are arranged vertically with a distance of 3000 mm from each other. The reactor jacket , which carries the predetermined pressure , has an internal diameter of 3700 mm. The reactor jacket is not insulated on the outside. The reaction zone is surrounded by a framework of OCMC bridges . The framework includes 12 circumferential segments and 10 superimposed layers. Each layer within each segment includes 60 rows of lateral bridges , each supported by a lateral bridge . The thickness of the inner row of transverse bridges in direct contact with the reaction zone is 3 mm. The inside of these lateral bridges is coated with a plasma sprayed protective layer. The transverse bridges of adjacent segments of the inner row overlap each other in the circumferential direction. The lap joints are filled with thermostable cement and connected with rivets. In the other rows, the transverse bridges are each 1 mm thick and radially spaced from each other at a distance of 2 mm. The ends of these lateral bridges are not fixed. The thickness of the lateral bridges is 3 mm. The CO ₂ flows as a purge gas into the annular space between the skeleton and the reactor jacket carrying the predetermined pressure . This solution is notable for its relatively lightweight and mechanically robust design. The entire framework is constructed from OCMC , which is ductile and resistant to thermal shock. The bridges inserted into each other form a mechanically stable framework that can simultaneously compensate for deformations resulting from thermal stresses. The mass of the framework is approximately 1.6 tn/m over the reactor length. Furthermore, the skeleton serves as electrical insulation of the reaction zone with respect to the walls of the reactor , which carry a given pressure . Additionally, the framework is effective as a thermal insulator due to the transverse bridges arranged in a row from the inside to the outside and serving as a radiation shield. The narrow distance between the lateral bridges allows a layer of gas to stagnate, promoting insulation. The center temperature of the reaction zone is 1350°C. The temperature inside the skeleton is 1200°C. The heat loss due to insulation is 45 kW/m over the length of the reactor. The temperature of the reactor jacket, which carries the predetermined pressure, is 85°C.

Example 3 (Halfoam and lightweight firebrick)
This example shows a solution of the invention that can be directly compared with the basic configuration. This is a 320 mm thick lining consisting of three layers in the radial direction. The inner layer is composed of HALFOAM from the manufacturer Morgan Advanced Materials Haldenwanger GmbH. The second layer consists of molded bricks of the PROMATON 28 type from the manufacturer Etex Building Performances GmbH. The third layer consists of PROMATON 26 type molded bricks from the same manufacturer. The bricks are laid as stretcher bonds. The OCMC skeleton is composed of 18 segments with circular cross-sections. One segment consists of one lateral bridge and two transverse bridges . The inner transverse bridge has a diameter of 3.63 m and surrounds the inner layer of the lining. The outer transverse bridge has a diameter of 4.09 m and surrounds the two outer layers of the lining. The mass of the lining is approximately 3.35 tn/m. A gap with a width of 20 mm is formed between the outer transverse bridge and the reactor wall. The center temperature of the moving bed is approximately 1500°C. The table shows the radial temperature progression of the lining.

The heat loss based on length at a reactor center temperature of 1500° C. was 15.2 kW/m.

In this configuration, the inner layer of the lining significantly reduced the temperature: T = 244K. As a result, the temperature was reduced to such an extent that the OCMC material did not undergo significant aging up to the inner lateral bridge .

The lining of the invention is significantly lighter than the reference configuration of Example 1. A further advantage of the inventive arrangement over the reference arrangement is evident from the thermally insulating effect of the first lining layer.
1. The temperature field across the moving bed cross-section is homogeneous due to the shaft-wall temperature difference ΔT=73K.
2. The temperature outside the first lining layer is reduced to a temperature well below 1200° C. so that the supporting framework made of OCMC material constantly retains its advantageous mechanical properties. A further advantage is the low temperature of the reactor walls. These advantages can be attributed to the superior thermal insulation properties of HALFOAM compared to refractory bricks made of K99 alumina.

Example 4 (Halfoam, lightweight firebrick, super insulation material)
This example shows an optimized version of the inventive solution with respect to insulation efficiency and mass. This is a 320 mm thick lining consisting of four layers in the radial direction. The two inner layers are composed of HALFOAM from the manufacturer Morgan Advanced Materials Haldenwanger GmbH. The third layer consists of molded bricks of the PROMATON 28 type from the manufacturer Etex Building Performances GmbH. The fourth layer consists of MICORTHERM PANEL from the manufacturer Etex Building Performances GmbH, which are bonded to the outside of the outer transverse bridge . The bricks are laid as stretcher bonds. The OCMC framework consists of 18 segments with circular cross sections. One segment consists of one lateral bridge and two transverse bridges . The inner transverse bridge has a diameter of 3.63 m and surrounds the two inner layers of the lining. The outer transverse bridge has a diameter of 4.03 m and surrounds the third layer of lining. The mass of the lining is approximately 3.2 tn/m. A gap with a width of 20 mm is formed between the outer transverse bridge and the reactor wall. The center temperature of the moving bed is approximately 1500°C. The table shows the radial temperature progression of the lining.

The superinsulation material was fixed to the reactor wall with a cassette.

The heat loss is 9.15 kW/m, ie significantly lower than the configurations of Examples 1 and 2. In this configuration, the two inner layers of the lining reduce the temperature to such an extent that the OCMC material does not undergo significant aging. The third layer reduces the temperature to such an extent that superinsulating materials can be used which have a very strong insulating effect but whose thermal stability is limited to about 1000°C.

The lining of the present invention is lighter than the configuration of Example 2 of the present invention. Further advantages of the configuration of the invention over the configuration of Example 2 are a more uniform temperature field across the cross-section of the moving bed (temperature difference: ΔT=36 K) and a lower temperature at the reactor wall (T=58 °C). be. As a result, it is possible to eliminate the need for contact protection on the outside of the reactor, thereby reducing costs and improving accessibility to the reactor.

Claims (16)

consisting of an apparatus jacket section carrying at least one predetermined pressure and at least one modular framework system disposed inside the apparatus jacket section , the modular framework system consisting of two different bridge types : A device that is
A plurality of lateral bridges form at least one prism or cylinder, and a plurality of lateral bridges protrude into the interior of the prism or cylinder, and the lateral bridges and the lateral bridges interdigitate. Device characterized in that the material of the bridge comprises a ceramic fiber composite material, which can be embedded and/or connectable with the help of one or more connecting elements. 2. The apparatus of claim 1, wherein the modular framework is self- supporting . 3. Device according to claim 1 or 2 , characterized in that the material of the bridge comprises a fiber composite oxidized material. Claim characterized in that the transverse bridges take the form of corrugated, angled or planar sheets or of cylindrical shells, and the lateral bridges take the form of corrugated or planar sheets. The device according to any one of items 1 to 3. Device according to any one of the preceding claims, characterized in that the device has a plurality of layers formed from the transverse bridges and arranged one on top of the other . A plurality of parallel or concentric elliptical arc-shaped transverse bridges are used in radial direction, which transverse bridges are polygonal or mutually disposed in top view. Device according to any one of claims 1 to 5 , characterized in that it is arranged as an ellipse. 7. Device according to claim 1 , characterized in that a separation bridge can be inserted into the gap between the circumferentially adjacent transverse bridges . Device according to one of the preceding claims, characterized in that a planar bridge can be inserted between two mutually arranged layers of the transverse bridge . Device according to any one of the preceding claims, characterized in that the device is supported by a base part and is connected to the base part by releasable connection means . Device according to any one of the preceding claims, characterized in that the device has a refractory brick lining arranged within the modular frame system . The framework structure can be divided into a plurality of boxes, one of which, viewed in the radial direction, comprises two adjacent parallel or concentric elliptical arc- shaped transverse bridges and corresponding and a gap between said circumferentially adjacent lateral bridges , or advantageously surrounded by said separating bridge inserted into said gap, and
each box is filled with 1 to 2000 refractory bricks or catalysts, and the bricks are arranged in layers vertically and horizontally, and
11. Device according to claim 10 , characterized in that the bridge demarcating the brick and the box is a gap. the lining of the refractory bricks is arranged in radial succession;
(i) foamed ceramic;
(ii) sintered cast or extruded ceramic; or
(i) foamed ceramics, (ii) sintered cast or extruded ceramics, and (iii) compressed ceramic fibers, or
A plurality of brick packings constructed from (i) foamed ceramic, (ii) sintered cast or extruded ceramic, (iii) compressed ceramic fibers, and (iv) vacuum formed fiberboard or board containing microporous fumed silica. 12. Apparatus according to claim 10 or 11 , characterized in that it comprises a brick assembly comprising a brick assembly. Claims 10 to 10 , characterized in that the gap between the brick and the adjacent bridge and/or the gap between the circumferentially adjacent brick packings is at least partially filled with an insulating mat. 13. The device according to any one of 12. Device according to any one of the preceding claims, characterized in that a continuous gap exists between the modular framework system and the device jacket part carrying the predetermined pressure . 15. Apparatus according to claim 14, characterized in that the gap is purged by a directed gas flow. Use of a device according to any one of claims 1 to 15, comprising:
- Preparation of synthesis gas by reforming hydrocarbons with steam and/or carbon dioxide - Preparation of hydrogen and carbon as by-products from the thermal decomposition of hydrocarbons - Preparation of hydrogen cyanide from methane and ammonia or from propane and ammonia - Preparation of olefins by steam cracking of hydrocarbons - Preparation of ethylene, acetylene and/or benzene by coupling of methane - Preparation of olefins by dehydrogenation of alkanes - Preparation of styrene by dehydrogenation of ethylbenzene - Dehydration of alkanes or olefins - Preparation of aldehydes by dehydrogenation of alcohols - Preparation of carbon monoxide from carbon dioxide and carbon by the Boudouard reaction - Use for the preparation of hydrogen and oxygen by hydrothermal decomposition over catalysts.