RU2798072C2 - Device with a pressure-receiving casing and a frame system inside it - Google Patents

Abstract

FIELD: insulation of high-temperature reactors.

SUBSTANCE: group of inventions relates to a device for electrical and/or thermal insulation of high-temperature reactors, as well as to its application. The device consists of at least one pressure-receiving housing and at least one modular frame system of ceramic fibrous composite materials located inside the housing. Modular lining contains refractory bricks in addition to the modular frame system.

EFFECT: group of inventions improves the thermal and physical properties of the device.

16 cl, 12 dwg, 3 tbl

Description

The invention relates to a device consisting of at least one pressure-receiving casing and at least one modular frame system made of ceramic fibrous composite materials located inside the casing, to a modular lining, which, in addition to the modular frame system, contains refractory bricks, as well as to the use of this device for high-temperature reactors, in particular, for high-temperature reactors with electric heating.

Highly endothermic reactions are often the initial links in the value chain in the chemical industry, for example, in the cracking of petroleum fractions, the reforming of natural gas or oil, the dehydrogenation of propane, the dehydroaromatization of methane to benzene, or the pyrolysis of hydrocarbons. To achieve technically and economically acceptable yields, the temperature of such processes should be from 500 to 1700°C. The reason for this is mainly the thermodynamically determined limit of the equilibrium transformation.

Due to the high temperatures of endothermic reactions implemented in the chemical industry in order to produce marketable products, it is necessary to ensure effective thermal isolation of the reactor from the environment. In addition, some reactions should be carried out in pressure-resistant reaction zones, for which it is necessary to hermetically isolate the reaction chamber from the environment, excluding entrances to and exits from the reaction chamber. Some of the above endothermic reactions proceed under reducing conditions. In addition, endothermic reactions require efficient heat input. In the case of direct electrical heating, it is additionally necessary to electrically isolate the interior of the reactor, for example, the bulk layer, relative to the reactor shell.

German patent DE 8714113 U1 describes a modular pressure vessel, the pressure-receiving casing of which consists of flat metal rings stacked on top of each other, if necessary connected to each other by vertically arranged fasteners. The bottom and/or the lid of the tank, if necessary, can be formed by separate ribbed elements, tightly adjacent to each other and arranged in a star-like manner in the direction from the walls of the tank to its axis. On the inner walls of the tank there may be a flat insulating layer of ceramic material, which may also be protected by a thin metal layer (so-called inner jacket). The disadvantage of the cited prior art is that the ceramic insulating layer is firmly connected to the pressure-receiving casing. In addition, the metal inner jacket separating the ceramic layer from the reaction volume conducts electric current and has a lower thermal stability than the ceramic lining. In this regard, the cited technical solution cannot be applied to reactors with electrically heated packing. In addition, the cited document lacks information on how to equalize the thermal expansion of the elements of a structural assembly consisting of a pressure-receiving casing, a ceramic insulating layer and a metal inner jacket.

US Pat. No. 2,982,622 discloses an electrical heating solution for endothermic reactions. To do this, electrically conductive particles in the form of a moving layer are passed through the reaction chamber. Electric current is passed through the electrodes through the bulk layer of particles, which thus acts as a resistance heater, providing direct heating of the reaction chamber. Due to the counterflow of gas and particles inside the apparatus, effective thermal integration is achieved, in which a high temperature range is localized in the middle part of the reaction chamber, while the upper and lower edges of the reactor remain cold. This principle applies to many technically important endothermic reactions. The implementation of electrical heating is specified in the application PCT/EP2019/051466, which describes a heated compact device for carrying out endothermic reactions, wherein vertically located electrodes are located in an electrically conductive nozzle made of solid material and are attached throughout the top, respectively, the bottom cover of the reactor, and moreover, conductive connecting elements have large areas of contact with the electrodes.

To carry out high temperature reactions in reactors, linings are commonly used that protect the pressure-receiving metal jacket from high temperatures, reduce heat loss, and/or protect the jacket from electrical current. Such linings must, in some cases, resist very high temperatures and pressures, chemical corrosion, particle erosion, and alternating thermal loads. The latter may be due, for example, to the implementation of the process in batch mode, as well as the introduction of cold process materials.

Thus, the requirements for the refractory lining used to carry out high-temperature chemical reactions are diverse and in some cases contradict each other. On the one hand, such a lining must have a high insulating capacity and low bulk density, respectively, high porosity, and, on the other hand, it is necessary that it has a sufficiently high mechanical strength and workability. In addition, the lining must have high thermal stability in a wide variety of atmospheric conditions.

Reactors designed to avoid the use of heat-insulating linings, such as Lurgi's high-pressure gas generators, have a double-walled pressurized casing with forced water cooling. The advantages of such a technical solution include ease of assembly and low weight of the reactor, as well as low thermal load on the reactor shell. Its disadvantages include structural complexity, complexity of automatic control and insufficient reliability of the cooling system. In addition, this technical solution is unsuitable for reactors with direct electrical heating, in which it is necessary to pass an electric current through the bulk layer. In this case, a short circuit would occur between the bulk bed and the pressure-receiving jacket of the reactor.

Refractory bricks are usually used for lining. Such fired refractory products are obviously characterized by open porosity, with the content of open pores being in the approximate range of 13 to 20% by volume. Technological materials can penetrate into open pores, for example, slags, melts or gases, which, due to chemical reactions, can destroy bricks and / or completely change the thermomechanical properties of the structure. Variable chemical influences, as well as variable thermal and thermomechanical loads, cause accelerated wear and damage, for example, chipping of large pieces from the lining, the thickness of which can be several millimeters. As a result, the corresponding lining has a limited service life and, once a certain degree of wear has been reached, must be replaced in a time-consuming and costly manner.

Another disadvantage of such porous materials is that at elevated reaction pressures (about 10 bar and above) convection currents can occur in the bricks, which can increase heat transfer to the casing walls and, consequently, reduce the effectiveness of the insulation. The refractory brick materials known from the prior art include Al ₂ O ₃ (corundum), phosphate-bonded Al ₂ O ₃ , cement-bonded Al ₂ O ₃ , chromium corundum Al ₂ O ₃ -Cr ₂ O ₃ (“Aurex 75”, “Aurex 90 ”, “Radex-BCF”), MgO-Cr ₂ O ₃ , Cr ₂ O ₃ , Al ₂ O ₃ -Cr ₂ O ₃ -ZrO ₂ ("Zichrom 60"), Cr ₂ O ₃ -ZrO ₂ ("Zichrom 90"), AlPO ₄ , CrPO ₄ ("Aurex 95Р") [see dissertation Gehre P. "Korrosions-und thermoschockbestandige Feuerfestmaterialien fur Flugstromvergasungsanlagen auf Al ₂ O ₃ -Basis-Werkstoffentwicklung und Korrosionsuntersuchungen", 2013, Technical University of the Mining Academy, Freiberg, chapter 2.3.1]. Other known refractory materials are silicon carbide and carbon, preferably in the form of graphite. Particularly resistant to thermal shock refractory bricks contain 6% of the mass. ZrO ₂ -Cr ₂ O ₃ -Al ₂ O ₃ .

In addition, German patent DE 102015202277 and international application WO 89/5285 describe refractory bricks made of foamed ceramic materials. The disadvantage of a lining design made only of refractory bricks is that in order to absorb horizontal forces, for example, loads due to a bulk layer, such a structure must be supported. Along with this, the lining, consisting only of refractory bricks, is prone to cracking due to thermal expansion of the structure. In the absence of support, bricks may fall out of the lining. The consequence of this may be structural weakening and failure of the lining and/or loss of its insulating effect, which in turn may cause damage to the casing of the apparatus.

The search for heat-resistant support structures is also known from publications concerning the processes of heat treatment of structural elements. International applications WO 2011/18516 and WO 2004/111562 describe planar modular support structures consisting of ribbed fibrous ceramic materials, such as carbon fiber reinforced plastics. The disadvantage of such support structures is that they are only movably mounted on a support base. Without strong anchoring, they are not able to absorb horizontal forces, such as the load caused by the bulk layer. In addition, such support structures do not function as thermally and electrically insulating layers.

US Pat. No. 8,211,524 describes a ceramic fiber composite anchor structure that connects a metal substrate to a ceramic insulating layer. The ceramic fiber composite structure is embedded in the metal layer or the ceramic layer and is positively connected to these layers. The disadvantage of such an anchor structure is that it is rigidly connected to both the ceramic and the metal layer. Such a rigid connection cannot be broken without destroying the structure.

At present, lining is carried out for commercial purposes, for example, for blast-furnace processes, in the partial oxidation of hydrocarbons in order to obtain synthesis gas and in metallurgy (carbide technology). So, for example, individual zones of a blast furnace are lined as follows: (i) top - fireclay containing from 39 to 42% of the mass. Al ₂ O ₃ (conventional), or chamotte of higher refractoriness (newer material), (ii) mine - chamotte containing from 39 to 42% of the mass. Al ₂ O ₃ (the usual version), or corundum and SiC-Si ₃ N ₄ (newer materials), (iii) steam - fireclay with 62% of the mass. Al ₂ O ₃ , mullite (common) or SiSiC (newer material), (iv) shoulders - fireclay containing from 42 to 62% of the mass. Al ₂ O ₃ , mullite, carbon (common) or SiC, chromium corundum (newer materials), (v) horn - chamotte containing from 42 to 62% of the mass. Al ₂ O ₃ , mullite, carbon (common) or carbon/graphite (with super micropores (new material).

From the prior art, various variants of the design of the fastening of the lining are known (“Refractory Design”, Deutsche Gesell-schaft Feuerfest- und Schornsteinbau e.V.):

In industrial apparatuses, refractory materials are usually connected to a supporting structure, such as a metal structure, by means of anchors. Anchors can be made of ceramic or metal materials. Ceramic anchors are always connected to the metal structure by means of a metal fastener. At the same time, the quality of the fixing (anchor) stones must correspond to the quality of the material of the hot (inner) side. The choice of type and material is determined by the requirements for the design of the part, as well as the thermal and corrosive effects exerted on it.

It is also known that refractory brickwork is fastened to a metal wall at certain intervals by means of special steel anchors. To fix the brickwork and control thermal expansion, heat-resistant steel metal brackets must be spaced at regular intervals to support the bricks. Bricks, the dimensions of which approximately correspond to those of fired bricks, are joined in the usual way by means of mortar.

In addition, it is known to fasten each brick to the wall of the shell to be protected by means of a support in the form of a plate. One side of each plate, for example, rests on a pin welded to the shell wall and is fixed towards the wall, while the other side of the plate is glued to the wall with SiC mortar. In another variant, each plate is suspended on a support in the form of a pin directed upwards from the wall of the shell at an angle to the wall. In addition, heat-insulating linings of industrial furnaces with refractory blocks and steel anchors are known, and on the narrow sides of each brick a groove extending along the perimeter is made, and the tops of the steel anchors engage with the groove of the block and the blocks are fastened to each other along the perimeter by means of a hardened refractory material. with geometric closure.

Any liners known in the art are supported by the pressure-receiving reactor shell, most commonly by metal walls. The advantage of using the pressure-receiving walls as a support for the lining is the simplicity of the corresponding design.

The weak points of linings are the connections of metal anchors with anchor stones. Due to the different coefficients of expansion of the materials, in combination with temperature differences and mechanical stress, weakening of these connections can occur. As a result, there may be a violation of the fastening of the lining over a large area. This, in turn, may be accompanied by the loss of blocks from the lining. The resulting gaps can cause indirect damage. Thus, for example, the thermal insulation between the reaction zone and the pressure-receiving walls of the reactor is weakened, which leads to overheating of the latter. In addition, for example, particles from the bulk bed of the reaction zone can penetrate into the gaps, which can cause a short circuit between the bulk bed and the pressure-receiving wall of the reactor.

A problem often encountered with lined systems is that the lining tends to be damaged if the temperature changes too quickly, since the lining and pressure-bearing reactor walls, for example, have different coefficients of thermal expansion and, moreover, heat up at different rates. Since individual bricks, due to their fixation, have limited freedom of movement, deformation or displacement of bricks free from mechanical stress during abrupt changes in temperature can be so difficult that the bricks crack or their fixation is disturbed. A similar phenomenon can already occur with a single rapid local change in temperature, for example, in the event of an accident.

According to the prior art, different thermal expansions are equalized by using expansion joints between the lining bricks. The disadvantage of this technical solution is the formation of gaps in the lining structure, into which particles and gases can penetrate from the reaction zone. As a consequence, undefined and unwanted bypass flows may occur. To avoid this problem, the equipment should be heated at an extremely low rate during start-up, typically less than 3 K/min. However, the resulting long start-up periods can have a tangible negative impact on the effective production capacity of high-temperature reactors.

The mechanical connection of the lining to the pressure walls limits the suitability of the reactor for assembly, as well as its accessibility and suitability for repair. So, for example, it is impossible to raise the reactor casing above its bottom. In addition, individual damaged bricks can only be repaired or replaced after the lining has been completely dismantled.

Thus, in the case of linings known from the prior art, the following problems remain unsolved:

Insufficient efficiency of electrical insulation of the lining.

Active cooling of the reactor vessel is critical from a safety point of view (poor fault immunity, contamination of the reactor contents and unwanted side reactions).

Fluctuations in temperature and/or pressure can cause the destruction of the lining and, as a consequence, significant structural damage to the reactor.

The heavy weight of the lining makes it difficult to maintain the reactor.

Mounting and dismantling, for example, in the event of a malfunction, are difficult and complex.

Starting and stopping are slow and inertial (for example, when a fault occurs, equipment needs to be cooled down).

So, for high-temperature reactions implemented under pressure, there are no technical solutions to ensure optimal thermal insulation and low gas permeability of the lining in the high-temperature region, as well as the possibility of mechanical and electrochemical separation of the lining from the pressure-receiving casing.

In view of the foregoing, the object of the present invention was to provide a modular self-supporting device that performs the function of electrical and/or thermal insulation and is mechanically separated from the pressure-receiving reactor shell. Another object of the present invention was to provide a modular self-supporting framework for lining high temperature reactors, mechanically separating the lining from the shell. Another object was to propose a lining which makes it possible, in a technically simple manner, to electrically isolate the reaction zone located in the interior of the reactor from the pressure-receiving reactor shell. Another challenge was to provide a lining capable of withstanding reaction pressures of up to 60 bar while providing reliable thermal insulation. Another objective was to provide a lining which, due to its improved resistance to chemical corrosion, is characterized by a long service life, high resistance to temperature cycling and increased resistance to cracking.

Unexpectedly, it was possible to find a device, in particular a reactor, consisting of at least one pressure-receiving casing and at least one modular frame system of partitions of at least two different types located inside the casing, characterized in that several transverse partitions form at least one prism or cylinder, moreover, several side partitions protrude inside the prism or cylinder, and the transverse partitions and side partitions can be inserted into one another and/or connected to each other by means of one or more connecting elements, and the material of the partitions contains ceramic fibrous composite materials.

In addition, a self-supporting frame system containing ceramic fiber composites has been found, which includes refractory bricks containing foamed ceramic materials, the bricks being supported by the modular frame system according to the invention.

The modular frame system located inside the casing is discussed in more detail below.

The transverse baffles preferably form a uniform prism with a polygon as a base or a uniform cylinder with a circle as a base.

The recesses in the partition walls are preferably in the form of slots or holes, preferably in the form of holes (see DIN 24041), for example oblong holes, preferably multi-faceted oblong holes or oblong holes with rounded corners.

As connecting elements for connecting the transverse partitions and the side partitions to each other, it is preferable to use form-fitting and/or permanent connections, for example, combined detachable connections and adhesive connections, with tenon and groove connection, groove connection or tenon connection being preferred.

In accordance with the present invention, "framework" refers to vertical baffles, which are preferably cross-connected to each other and are able to planarly (that is, in two coordinates) receive lateral forces due to the possible presence of a lining. By means of the frame, the lining can advantageously be divided into segments which can be delimited in both the radial and circumferential directions.

In accordance with the present invention, "self-supporting" is a frame that does not need support, in particular, lateral support on the walls, including at pressures up to 60 MPa. Inside the frame, due to pressure losses and forces due to the possible presence of bulk layers (the so-called "silo effect"), stresses of about 0.5 MPa can prevail.

By "pressure-receiving casing of the device or pressure-receiving casing of the reactor" is meant the boundary zone of the tank, which is subjected to a pressure difference between the inside of the tank and the environment surrounding the tank. The pressure-receiving reactor shell includes three main parts: the lower part, the upper part, and the side walls of the reactor.

By “lining” is meant a protective structure consisting of sheets, bricks or molded articles that can be bonded to each other by means of mortar or mastic, including sealing or insulating intermediate layers; in addition, "lining" refers to any applied layers and ceramic built-in parts that have maximum resistance to mechanical, thermal and chemical influences (standards DIN 28060 and DIN 28071). In 1986, the term "lining" was replaced by the term "lining" (DIN 28071 standard).

The term "segment" refers to the modular frame elements in the circumferential direction. The transverse baffles define the delimitation of the segments in the radial direction. The side baffles determine the position of the segments in the circumferential direction, with the gaps between adjacent transverse baffles in the circumferential direction, respectively inserted into these gaps dividing baffles, limit the segment in the circumferential direction (see Fig. 2-4).

By "nest" is meant a region which includes two radially adjacent transverse baffles in the form of parallel or concentric arcs of an ellipse, preferably parallel or concentric arcs of a circle, and respective side baffles, and optionally also a gap between the transverse baffles adjacent in circumferential direction, respectively. preferably inserted into this gap dividing wall (see Fig. 2-4).

The terms "front" or "front side" are used when referring to the surface facing the inside of the reactor. The terms "behind", "outside" or "back side" are used when referring to the surface facing the outer circumference of the reactor. The definitions "top", "bottom" and "side" refer to a vertically standing reactor. The terms "lower", "middle" and "upper" are used in the geodetic sense.

By "ceramic fibrous composite materials" is meant fibre-reinforced ceramic, in particular oxide ceramic materials, as described, for example, in M. Schmücker's publication "Faserverstärkte oxidkeramische Werkstoffe", Materialwissenschaf-ten und Werkstofftechnik, 2007, 38, No. 9, 698- 704. Ceramic fibrous composite material contains a fibrous frame, fabric, canvas, knitted fabric and/or woven material from ceramic fibers, as well as a filling matrix of sintered ceramic powder.

Thus, fibrous composite materials are characterized by the presence of a matrix of ceramic particles, between which ceramic fibers are embedded, in particular continuous fibers with a length of more than 50 mm in the form of yarn packages or in the form of a textile material. These are fibre-reinforced ceramics, composite ceramics or fiber ceramics. In this case, the matrix and fibers can in principle be made of any known ceramic materials, carbon being also considered as a ceramic material.

By "oxide fibrous composite ceramics or oxide fibrous composites" is meant a matrix of oxide ceramic particles containing ceramic, oxide and/or non-oxide fibres.

Preferred fiber and/or matrix oxides are oxides of an element selected from the group consisting of Be, Mg, Ca, Sr, Ba, rare earth metals, Th, U, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W , Mn, Fe, Co, Ni, Zn, B, Ai, Ga, Si, Ge, Sn, Li, Na, K, Rb, Cs, Re, Ru, Os, Ir, Pt, Rh, Pd, Cu, Ag , Au, Cd, In, Ti, Pb, P, As, Sb, Bi, S, Se, Te, as well as mixtures of the corresponding oxides.

Blends are preferably suitable as both fiber and matrix material. The fibers and the matrix generally do not have to be made of the same material.

In principle, not only binary mixtures are suitable and important, but also mixtures consisting of three or more oxides. The mixtures may contain the same molar amounts of the individual components, however, in the preferred embodiment, the concentrations of the individual components differ significantly from each other and may be less than 1%, that is, they may correspond to the contents characteristic of impurities.

Particularly preferred are binary and ternary mixtures of alumina, zirconium oxide and yttrium oxide (eg zirconia-reinforced alumina); mixtures of silicon carbide and aluminum oxide; mixtures of aluminum oxide and magnesium oxide (MgO-spinel); mixtures of aluminum oxide and silicon oxide (mullite); a mixture of aluminum silicates with magnesium silicates; a ternary mixture of aluminum oxide, silicon oxide and magnesium oxide (cordierite); steatite (magnesium silicate); zirconia-reinforced alumina; stabilized zirconium oxide (ZrO ₂ ) (while magnesium oxide (MgO), calcium oxide (CaO) and yttrium oxide (Y ₂ O ₃ ), and in some cases also cerium oxide (CeO ₂ ), scandium oxide ( SCO ₃ ) or ytterbium oxide (YbO ₃ ), aluminum titanate (stoichiometric mixture of aluminum oxide with titanium oxide), silicon nitride and aluminum oxide (SIALON).

As reinforced with zirconium oxide, alumina is preferably used Al ₂ O ₃ containing from 10 to 20 mol%. ZrO ₂ . To stabilize ZrO ₂ preferably you can use from 10 to 20 mol.%, preferably 16% mol. CaO, from 10 to 20% mol., preferably 16% mol. MgO, from 5 to 10% mol., preferably 8% mol. Y ₂ O ₃ (fully stabilized zirconium oxide) or from 1 to 5% mol., preferably 4% mol. Y ₂ O ₃ (partially stabilized zirconium oxide). A preferred ternary mixture is, for example, a mixture consisting of 80% Al ₂ O ₃ , 18.4% ZrO ₂ and 1.6% Y ₂ O ₃ .

In addition to the materials mentioned above (mixtures and individual components), fibers of basalt, boron nitride, tungsten carbide, aluminum nitride, titanium dioxide, barium titanate, lead zirconate titanate and/or boron carbide can also be used in the oxide ceramic matrix.

Suitable fibers are reinforcing fibers which belong to the classes of oxide, carbide and nitride fibers (respectively carbon fibers and SiBCN fibers). In particular, the fibers contained in the ceramic composite material are fibers of alumina, mullite, silicon carbide, zirconium oxide and/or carbon. In this case, mullite consists of mixed crystals of aluminum oxide and silicon oxide. It is preferable to use oxide ceramic fibers (Al ₂ O ₃ , SiO ₂ , mullite) or non-oxide ceramic fibers (C, SiC).

Creep-resistant fibers are preferred, i.e. fibers which, in the creep range (temperature range up to 1400° C.), are characterized by the absence or minimal increase in permanent deformation (creep elongation) over time. According to 3M data, NEXTEL fibers are characterized by the following temperature limits for residual elongation of 1% after 1000 hours of exposure to a tensile load of 70 MPa: NEXTEL 440-875°C, NEXTEL 550, respectively NEXTEL 610-1010C, NEXTEL 720-1120°C ( see Nextel™ Ceramic Textiles Technical Notebook, 3M, 2004).

The fiber diameter is preferably 1 to 50 µm, preferably 5 to 20 µm, particularly preferably 8 to 15 µm. The fibers are preferably woven together into textile materials (usually plain or satin weave), knitted into sleeves, or wound around a mould. For the manufacture of a combined ceramic system, fiber bundles or fibrous fabric are impregnated with a slurry that contains, for example, components of the future ceramic matrix, preferably aluminum oxide or mullite (Schműcker, M. (2007), Faserverstärkte oxidkeramische Werkstoffe, Materialwissenschaft und Werkstofftechnik, 38(9), 698-704). As a result of the final heat treatment at a temperature above 700°C, a high-strength composite structure of ceramic fibers and a ceramic matrix is obtained, the tensile strength of which is preferably more than 50 MPa, preferably more than 70 MPa, more preferably more than 100 MPa, in particular more than 120 MPa.

Preferably, the system SiC/Al ₂ O ₃ , SiC/mullite, C/Al ₂ O ₃ , C/mullite, Al ₂ O ₃ /Al ₂ O ₃ , Al ₂ O ₃ /mullite, mullite/Al ₂ O ₃ and/or mullite/mullite. In this case, before the slash, the material of the fibers is indicated, and after the slash, the material of the matrix. Siloxanes, silicon precursors and a wide variety of oxides can also be used as the matrix of the ceramic fiber composite material, including also, for example, zirconium oxide. Ceramic fibrous composite material preferably contains at least 99% of the mass. alumina and/or mullite.

In accordance with the present invention, fiber composites based on oxide ceramic fibers, for example, 3M™ NEXTEL™ 312, NEXTEL™ 440, NEXTEL™ 550, NEXTEL™ 610, NEXTEL™ 720 fibers, or MvM 1415N, MvM 1415N- 2220, AvM 1415N, AvM 1415N-3000, FW12 and/or FW30 from Walter E.C. Pritzkow Spezialkeramik. Particularly preferred is the use of NEXTEL 610, NEXTEL 720 fibers as well as AvM 1415N-3000 and/or FW30 fibers. In addition, fibers from the Japanese company Nitivy can preferably be used.

The degree of filling of the matrix with fibers (volume fraction of fibers in the structure of the composite material) is preferably from 20 to 40%, while the total solids content in the structure of the composite material is preferably from 50 to 80%. Fibrous ceramic composite materials based on oxide ceramic fibers are characterized by chemical resistance in an oxidizing and reducing gas atmosphere, that is, no change in mass after exposure to air at 1200 ° C for 15 hours (see Nextel™ Ceramic Textiles Technical Notebook, 3M, 2004) and thermal stability up to 1300°C. Fibrous ceramic composite materials are characterized by quasi-plastic behavior during deformation. Consequently, they are characterized by resistance to thermal cycling and quasi-ductile fracture behavior. Thus, signs of failure of the corresponding structural element are detected before its destruction occurs.

The fibrous composite preferably has a porosity of 20 to 50% and is therefore not gas-tight as defined in DIN 623-2. The long-term operating temperature of the fibrous composite preferably reaches 1500°C, preferably 1400°C, particularly preferably 1300°C. The strength of the fibrous composite material is preferably more than 50 MPa, preferably more than 70 MPa, particularly preferably more than 100 MPa, in particular more than 120 MPa. The limiting elongation of the fibrous composite material under elastic deformation is preferably from 0.2 to 1%. The fibrous composite material is preferably characterized by resistance to temperature fluctuations according to DIN EN 993-11. The thermal expansion coefficient of the fibrous composite is preferably 4 to 8.5 ^ppm /K. The thermal conductivity of the fibrous composite material is preferably 0.5 to 5 W/(m⋅K).

The ceramic fiber composite can preferably be produced by chemical vapor impregnation or pyrolysis, in particular by liquid polymer impregnation or by chemical reaction (eg liquid silicone impregnation).

The frame in the circumferential direction preferably has a modular structure (see Fig. 2-4). The framework in the vertical direction preferably has a modular structure (see FIGS. 5 and 6). Modular elements located in the circumferential direction are called segments. Modular elements arranged in a vertical direction are called layers. The modular framework includes at least two different types of baffles, the first type of baffles defining the delimitation of the segments, preferably the lining segments, in the radial direction. These partitions are called transverse partitions. The second type of baffles define the position of the segments, preferably the lining segments, in the circumferential direction. These partitions are called side partitions.

The frame may preferably include other elements in the form of partitions. Such elements are preferably inserted into the gaps between two circumferentially adjacent transverse baffles (see FIG. 5). Such elements are also called dividing partitions. In another embodiment, the lateral closure of the segments can preferably be realized by means of additional side partitions.

Other elements can preferably be inserted horizontally between two layers of transverse baffles located one above the other (see Fig. 7). Such elements are called flat partitions. The flat baffles can preferably act as an obstacle to the formation of extensive convective currents in the porous structure of a possibly present lining. In addition, flat baffles preferably allow locally limited replacement of bricks of possibly existing lining without having to dismantle the entire carcass.

Transverse partitions preferably have the form of flat or curved rectangular sheets or cylindrical shells (“a cylinder is a body bounded by a cylindrical surface with a closed guide and two bases in the form of parallel planes”, Bronstein, p. 251, Fig. 2.49).

In addition, the transverse partitions may be in the form of corrugated sheets. Waves can be sinusoidal or triangular in shape. The wave amplitude is preferably 1 to 100 mm, preferably 2 to 50 mm, in particular 3 to 20 mm. The wavelength is preferably 2 to 500 mm, preferably 5 to 200 mm, in particular 10 to 100 mm.

The transverse partitions in plan view form one or more polygons, preferably regular polygons, or one or more concentric ellipses, preferably one or more concentric circles. Wavy transverse partitions in horizontal projection have the form of a periodic function or trochoid. The side baffles are preferably arranged in a star-like arrangement (see FIGS. 2-5).

The polygonal base prism preferably comprises 3 to 60, preferably 4 to 40, in particular 6 to 24 transverse baffles. A cylinder with a base in the shape of an ellipse, in particular in the shape of a circle, preferably comprises from 3 to 60, preferably from 4 to 40, in particular from 6 to 24 transverse partitions in the shape of an ellipse, preferably in the shape of an arc of a circle. The diameter of a cylinder with a base preferably in the form of an ellipse, in particular in the form of a circle, respectively, the diagonal of a polygon, preferably a regular polygon, is preferably from 0.2 to 20 m, preferably from 0.5 to 15 m, in particular from 1 to 10 m.

The gap between two circumferentially adjacent transverse baffles is preferably 0 to 200 mm, preferably 1 to 100 mm, more preferably 2 to 50 mm, in particular 3 to 20 mm.

The edges of circumferentially adjacent transverse baffles can be overlapped if necessary (see FIG. 8). The overlap is preferably 200 to 20 mm. The lap joints are preferably filled with a high temperature resistant mastic and/or connected with rivets, preferably made of ceramic fiber composites, for example OCMC (Oxide Ceramic Matrix Composite).

The height of the transverse baffles in the form of sheets or cylindrical shells is preferably from 100 mm to 5 m, preferably from 200 mm to 3 m, in particular from 500 mm to 2 m. The length of the transverse baffles is preferably from 100 mm to 5 m, preferably from 250 mm to 3 m, in particular 500 mm to 2 m. The thickness of the transverse partitions is preferably 0.2 to 20 mm, preferably 0.5 to 10 mm, in particular 1 to 5 mm.

The transverse partitions, which in plan view form a polygon, preferably a regular polygon, or an ellipse, preferably a circle, preferably have the same height, width and thickness. The modular frame preferably includes several layers formed in the form of uniform prisms or cylinders of one above the other transverse partitions, preferably from 1 to 100, preferably from 2 to 50, in particular from 3 to 30 layers (see Fig. 4 and 5) .

The overall height of the stacked elements is preferably 100 mm to 50 m, preferably 200 mm to 20 m, in particular 500 mm to 10 m.

The height of the transverse partitions of all layers arranged one above the other in a modular frame is preferably identical.

Preferably, parallel or concentric transverse baffles in the form of an arc of an ellipse can be used, preferably parallel or concentric transverse baffles in the form of an arc of a circle, which are arranged in a horizontal projection in the form of polygons located one in the other, preferably regular polygons, respectively, in the form of ellipses located one in the other, preferably circles (see Fig. 2-5). Preferably, 2 to 20, preferably 2 to 5 parallel or concentric elliptical arc-shaped transverse baffles, preferably parallel or concentric circular arc-shaped transverse baffles are used. The distance between radially adjacent polygons, preferably regular polygons, or radially adjacent ellipses, preferably circles, respectively formed by transverse partitions, is preferably 10 to 1000 mm, preferably 20 to 500 mm, particularly preferably 40 to 250 mm. Said distance is preferably identical for all radially adjacent transverse baffles.

The side partitions are preferably made in the form of flat or corrugated rectangular sheets.

Waves can be sinusoidal or triangular in shape. The amplitude of the waves is preferably 1 to 100 mm, preferably 2 to 50 mm, in particular 3 to 20 mm. The wavelength is preferably 2 to 500 mm, preferably 5 to 200 mm, in particular 10 to 100 mm.

The side baffles are preferably arranged perpendicular to the transverse baffles.

The height of the side partitions is preferably 100 mm to 5 m, preferably 200 mm to 3 m, in particular 500 mm to 2 m. The width of the side partitions is preferably 50 mm to 2 m, preferably 100 mm to 1 m, in particular, from 200 mm to 500 mm. The thickness of the side partitions is preferably 0.2 to 20 mm, preferably 0.5 to 10 mm, in particular 1 to 5 mm.

In the case of several side partitions arranged one above the other, the middle side partitions have the same height, width and thickness (see FIG. 6).

The height of the side baffles in the middle layers is preferably 90 to 110%, preferably 95 to 105%, particularly preferably 98% to 102% of the height of the transverse baffles, in particular identical to the height of the transverse baffles. The height of the side baffles in the lowermost layer and in the uppermost layer may differ from the height of the side baffles in the middle layers. The height of the side baffles in the lowest layer is preferably greater or less than the height of the middle baffles by 10 to 90%, preferably 20 to 75%, particularly preferably 30 to 60%. The height of the side baffles in the uppermost layer is preferably greater or less than the height of the middle baffles by 10 to 90%, preferably 20 to 75%, particularly preferably 30 to 60%. If the height of the side baffles in the lowermost layer is less than the height of the middle side baffles, the height of the baffles in the uppermost layer preferably exceeds the height of the middle side baffles in a similar proportion. If the height of the side baffles in the lowermost layer is greater than the height of the middle side baffles, the height of the baffles in the uppermost layer is preferably less than the height of the middle side baffles in a similar proportion.

In the topmost layer, the top edges of the side baffles are preferably coplanar with the top edges of the transverse baffles, i.e. the vertical displacement up or down is preferably less than 5%, preferably less than 2% of the height of the baffles.

The width and thickness of the lowermost and uppermost side baffles is preferably identical to the width and thickness of the middle side baffles.

Alternatively, the top edges of the side baffles in each layer are preferably coplanar with the top edges of the transverse baffles, i.e. the vertical displacement up or down is preferably less than 5%, preferably less than 2% of the height of the baffles. In this case, the height of the transverse baffles and the side baffles is preferably identical in each layer. Such a configuration is particularly suitable for the introduction of flat baffles.

In a modular frame, the difference between the number of side baffles located one above the other and the number of transverse baffles located one above the other is preferably less than two, with an identical number of corresponding baffles being preferred.

If necessary, the dividing walls used are preferably in the form of rectangular sheets.

The partition walls are preferably arranged in a prism, preferably a homogeneous prism, or in a cylinder, preferably in a circular cylinder, between circumferentially adjacent transverse partitions (see FIGS. 4 and 5). The partition walls are preferably inserted into gaps which are formed in a prism, preferably a homogeneous prism, or in a cylinder, preferably in a circular cylinder, between circumferentially adjacent transverse partitions.

The height of the partition walls is preferably 100 mm to 5 m, preferably 200 mm to 3 m, in particular 500 mm to 2 m. The length of the partition walls is preferably 50 mm to 2 m, preferably 100 mm to 1 m, in particular from 200 to 500 mm. The thickness of the partition walls is preferably 0.2 to 20 mm, preferably 0.5 to 10 mm, in particular 1 to 5 mm.

The ratio of the length of the partition walls to the length of the side walls is preferably 0.9 to 1.25. The ratio of the height of the partition walls to the height of the side partitions is preferably 0.5 to 50, preferably 0.75 to 10, particularly preferably 0.9 to 5. of the transverse baffles, i.e. the vertical displacement up or down is preferably less than 5%, preferably less than 2% of the height of the baffles. In the uppermost layer, the upper edges of the partition walls are preferably located in the same plane as the upper edges of the side walls, i.e. the vertical displacement up or down is preferably less than 5%, preferably less than 2% of the height of the partitions.

If necessary, the flat partitions used, depending on the shape of the transverse partitions, are preferably made in the form of trapezoidal sheets (in the case of rectangular transverse partitions) or in the form of sheets having the form of annular segments (in the case of transverse partitions in the form of circular arcs).

The flat baffles are preferably inserted horizontally between two layers of transverse baffles located one above the other (see FIG. 7). The flat baffles are preferably provided with recesses, preferably in the form of slots or openings, in particular in the form of slots, which allow the flat baffles to be inserted into the side baffles. The flat baffles preferably bear against the upper edges of the transverse baffles.

The base length of the trapezoidal flat baffles is preferably 100 mm to 5 m, preferably 200 mm to 3 m, in particular 500 mm to 2 m. The height of the trapezoidal flat baffles is preferably 50 mm to 2 m, preferably 100 mm to 1 m, in particular from 200 to 500 mm. The internal angle of an isosceles trapezoid (ie the angle between its base and sides) is preferably 30° to 88°, preferably 45° to 86°, in particular 60° to 84°. For example, in the case of 60 segments, the internal angle is preferably 87°, in the case of 40 segments, it is preferably 85.5°, and in the case of 24 segments, it is preferably 82.5°. The thickness of the trapezoidal flat baffles is preferably 0.2 to 20 mm, preferably 0.5 to 10 mm, in particular 1 to 5 mm.

The outer radius of the flat baffles in the form of annular segments is preferably from 0.1 to 10 m, preferably from 0.25 to 7.5 m, in particular from 0.5 to 5 m. 50 mm to 2 m, preferably from 100 mm to 1 m, in particular from 200 to 500 mm. The sector angle of the flat partition in the form of an annular segment is from 6° to 120°, preferably from 9° to 90°, particularly preferably from 15° to 60°. The thickness of the flat baffles in the form of annular segments is preferably 0.2 to 20 mm, preferably 0.5 to 10 mm, in particular 1 to 5 mm.

Flat baffles and baffles can preferably also be combined to form one structural element (see Fig. 11).

The frame consists of partitions, which can preferably be inserted into each other by means of recesses, preferably slots or holes, in particular slots. The transverse and side partitions are inserted into each other preferably crosswise (see Fig. 4 and 5).

The modular frame preferably comprises 1 to 20, preferably 2 to 10, particularly preferably 2 to 5 radially adjacent transverse baffles per segment or layer. The modular frame preferably comprises 1 to 10, preferably 1 to 5, particularly preferably 1 to 3 side partitions per segment or frame layer (see FIG. 2).

In this case, the side and transverse partitions in the lowest and middle layers are preferably offset relative to each other in the vertical direction. The vertical offset between the upper edges of the side and transverse baffles in the layer is -90 to +90%, preferably -75 to 75%, particularly preferably 60 to +60% of the height of the baffles. The upper edges of the partition walls and the upper edges of the transverse walls in the uppermost layer preferably lie in the same plane, i.e. the vertical displacement of the partition walls up or down is preferably less than 5%, preferably less than 2% of their height. Due to this, the partitions preferably bear on each other, forming a rigid self-supporting profiled structure of several segments. The transverse baffles define the delimitation of the segments in the radial direction, while the lateral baffles define the delimitation of the segments in the circumferential direction.

Each layer preferably has 3 to 60, preferably 4 to 40, particularly preferably 6 to 24 identical segments. The segments are preferably separated from each other over their entire height by dividing walls (see FIG. 5).

The transverse baffles are preferably provided with one recess, preferably a slot or opening, in particular a slot, for each side element which is located in the same layer of the same segment. In the case of a single side partition, a recess, preferably a slit or opening, in particular a slit, is located in the middle of the cross member. In the case of several side partitions, recesses, preferably slots or openings, in particular slots, are located in the transverse partitions symmetrically about their middle, the distance between the recesses being preferably 5 mm to 2 m, preferably 10 mm to 1 m, in particular from 20 to 500 mm.

The side baffles in the middle layers are preferably provided with one recess, preferably a slit or opening, in particular a slit, per transverse baffle, which is preferably located in the same layer of the same segment. In the case of a single transverse baffle, the recess, preferably a slit or opening, in particular the slit is preferably located at a distance from the rear edge of the side baffle facing the reactor shell, at a distance of 5 mm to 2 m, preferably 10 mm to 1 m, in in particular, from 20 to 500 mm. In the case of several transverse partitions, the distance between two adjacent recesses, preferably slots or holes, in particular slots, is preferably 10 mm to 2 m, preferably 20 mm to 1 m, in particular 30 to 500 mm.

Recesses, preferably slits or openings, in particular slits, provided in all transverse baffles are preferably open at the bottom. The length of the recesses, preferably slots or openings, in particular slots, made in all transverse partitions of the segment and side partitions located in the middle layers of the segment, preferably corresponds to from 10 to 90%, preferably from 25 to 75%, especially preferably from 40 to 60 % of the height of the partitions, in particular half the height of the partitions.

Recesses, preferably slits or openings, in particular slits, provided in the side walls of the middle layers are preferably open at the bottom. The length of the recesses, preferably slots or holes, in particular the slots, made in the side walls of the middle layers, preferably corresponds to 90 to 10%, preferably 95 to 105%, particularly preferably 98 to 102% of the difference between the height of the partitions and the length of the recesses, preferably slits or openings, in particular slits of the transverse baffles, said length being in particular identical to the difference between the height of the baffles and the length of the recesses, preferably the slits or openings, in particular the slits of the transverse baffles.

The side partition in the lowest layer is preferably not recessed. The height of this side partition preferably corresponds to 90 to 110%, preferably 95 to 105%, particularly preferably 98 to 102% of the height of the recess made in the transverse partitions, the height of this side partition being in particular identical to the height of the recess in the transverse partitions.

The side partition located in the uppermost layer is provided with recesses, preferably slots or holes, in particular slots located in pairs, respectively, in the upper edge and the lower edge of this partition. The length of these recesses, preferably the slots or holes, in particular the slots, corresponds to the length of the recesses, preferably the slots or holes, in particular the slots in the side walls located in the middle layers.

By seat is meant a region which includes two radially adjacent transverse baffles in the form of parallel or concentric arcs of an ellipse, preferably in the form of parallel or concentric arcs of a circle, and the corresponding side baffles, as well as a gap between the transverse baffles adjacent in the circumferential direction, respectively preferably inserted into this lumen of the dividing wall (shaded areas 5a-b in Fig. 2, shaded areas 5a-d in Fig. 3, shaded areas 5a-f in Fig. 4 and 5). The nests in plan view preferably have a rectangular or annular segment cross section (see FIGS. 2-5).

Each segment preferably comprises from 1 to 50, preferably from 2 to 25, in particular from 3 to 15 sockets.

The modular frame system according to the invention described above can preferably be used as a frame support for linings, in particular chemical reactor linings, intended for high-temperature processes in the temperature range from 150 to 1900°C, preferably from 400 to 1700°C, in particular , from 600 to 1500°С.

In addition, the modular frame system according to the invention can preferably be used as a support structure for catalysts, in particular monolithic catalysts (ie catalyst baskets used in axial or radial flow fixed bed reactors).

The modular frame system according to the invention can also be used as electrical insulation, in particular in the interior of reactors.

In addition, the modular frame system according to the invention can be used as a radiation shield.

The modular frame system according to the invention in plan view divides the cross section of the reactor occupied by the lining into pockets having a rectangular shape, a trapezoid shape or an annular segment shape. The nests are preferably filled with refractory bricks and/or catalysts, in particular monolithic catalysts. Alternatively, the nests are left unfilled.

The cross section of the nest in plan view is filled with bricks arranged parallel to each other and/or in series, the number of which is preferably from 1 to 2000, preferably from 2 to 500, particularly preferably from 3 to 200. The set of bricks inside the nest is called a pack. The cross section of the bag in plan view is preferably rectangular, trapezoidal or annular segment shaped, with the radially oriented sides preferably parallel to each other and the narrow side preferably directed inwards.

Refractory bricks preferably have a hexagonal, preferably prismatic shape. The top and bottom surfaces and the front and back surfaces, respectively, are preferably parallel to each other. The top and bottom surfaces are preferably perpendicular to the other surfaces of the hexagon.

The bricks in the radial direction are preferably arranged in layers of masonry. The stacks in the radial direction preferably comprise 1 to 40, preferably 1 to 20, particularly preferably 1 to 10 masonry layers.

Bricks in the vertical direction are preferably arranged in layers of masonry. The stacks in the vertical direction contain from 1 to 1000, preferably from 1 to 500, particularly preferably from 2 to 200, in particular from 3 to 100 layers of masonry.

Preferably, from 1 to 200, preferably from 2 to 150, in particular from 3 to 100 bricks are arranged parallel to each other in the circumferential direction in the nest.

The seams between the bricks of the package are preferably filled with mortar or adhesive, or they are made in the form of dry seams. The seams between the bricks are preferably made as dry seams, i.e. no mortar or adhesive is used to join the bricks. The bricks of the package are preferably laid in the form of a tie row, a spoon row, a row of bricks placed on the end, a row of bricks placed on the edge, a row of bricks laid flat, and also in the form of a spoon ligation, a tie ligation, a chain ligation or a cross ligation (see " Feuerfestbau", Deutsche Gesellschaft Feuerfest- und Schornsteinbau e.V., p. 76). The stack bricks are preferably laid in the form of a spoon tie, a bond tie, a chain tie or a cross tie. The stack bricks are particularly preferably laid in the form of a chain tie or a cross tie.

In addition, it is possible to combine types of brick laying layer by layer in the radial direction. Thus, for example, in the case of a package with two layers of masonry, the inner layer in the radial direction can preferably be laid in the form of a cross ligation, and the outer layer is preferably in the form of masonry on the end. As a result of such a combination, the seams between the bricks of the package are shifted relative to each other. Due to this, gaps that may arise between adjacent bricks are interrupted. This, in turn, makes it possible to effectively reduce the incorrect flows of the gaseous reaction medium passing through the lining.

There are preferably gaps between the bricks and the partitions or between the bricks of different packages of the modular frame system. The gap between bricks and adjacent partitions or between bricks of circumferentially adjacent stacks is preferably 1 to 50 mm, preferably 1 to 25 mm, particularly preferably 1 to 10 mm. The presence of this clearance contributes to the fact that individual bricks can move relative to each other. In addition, due to the presence of this gap during the lining, the introduction of bricks is simplified. Along with this, due to the presence of gaps, there is free space necessary for unhindered thermal expansion of the package, that is, expansion of the package without stress.

The gaps between the partitions and the package, respectively the gaps between the bricks of the packages adjacent in the circumferential direction, if necessary, can be filled with insulating mats, as described below.

The vertical offset between the top edges of the bag and the top edges of the frame is preferably less than 50 mm, preferably less than 20 mm, particularly preferably less than 10 mm, with the top edges of the bag and the top edges of the frame in particular located in the same plane, i.e. the vertical displacement upwards or down is preferably less than 5%, preferably less than 2% of the height of the transverse baffle. This can be realized, for example, by properly cutting the bricks used in the stack layer.

In this case, between the layered seams of the package and the seams located between the transverse partitions located one above the other of the lower and middle layers of the frame, as a rule, there is a vertical displacement. The vertical offset between two immediately above the other transverse partitions and the next layer seam of the package is preferably from 0 to 50%, preferably from 20 to 50% of the height of the brick.

In the special case where flat partitions are used, the seam between two transverse partitions located one above the other is at the level of a horizontal seam located between two layers of bricks located one above the other. The vertical offset between the joint located between two transverse partitions located one above the other and the next horizontal joint located between two layers of bricks located one above the other is preferably less than 10 mm, preferably less than 5 mm, particularly preferably less than 3 mm.

The sides of the bricks may preferably be flat. As an alternative, the sides of the bricks can be provided with appropriately designed tongues and grooves, and therefore the respective bricks can be positively connected to each other by a tongue-and-groove connection (see DIN 1057).

The front side of the inner layer of the bag is preferably in contact with the reaction zone, while the sides and back of the inner layer of the bag is preferably limited by the frame according to the invention.

In accordance with the present invention, "refractory bricks" refers to ceramic products and materials with a service temperature in excess of 600°C. According to the definition given in DIN 51060 (see also ISO 150), only those materials should be considered refractories that have a Seger cone (SK) point of incidence greater than 17, which corresponds approximately to a temperature of 1500°C. This temperature limit is close to the melting point of iron and is important for customs law and the mining industry.

Bricks on the inner side of the lining preferably have the following set of properties: (i) good thermal insulation ability in the temperature range from 1000 to 1700°C, (ii) high strength, (iii) abrasion resistance, (iv) low open porosity, (v) resistance to temperature fluctuations, (vi) good electrical insulating ability. Good thermal insulation means that the thermal conductivity is less than 2 W/m/K, preferably less than 1 W/m/K. High strength means that the cold compressive strength is more than 5 MPa, preferably more than 10 MPa. High abrasion resistance correlates with the hardness of the material. Ceramic foams have little open porosity if the content of closed cells is more than 1%, preferably more than 5%, particularly preferably more than 10%. The material is highly resistant to temperature fluctuations if it passes the test according to DIN V ENV 820-3. Good electrical insulating ability of the material means that its electrical resistivity is more than 109 ohm⋅m, preferably more than 1011 ohm⋅m.

The characteristics of the bricks, in particular the composition, strength, shape and dimensions, are given in DIN 1057 (“Building materials for free-standing chimneys”), DIN 1081 (“Ceramic refractory materials: refractory rectangular bricks”) and DIN 1082 (“ Ceramic refractory materials: refractory wedge (pivot) bricks).

The refractory bricks are preferably shaped bricks made of refractory materials. The material of the refractory bricks should preferably be selected depending on the process temperatures and process conditions. In addition, the material of the refractory bricks should preferably be selected depending on the radial position (layer of masonry) within the lining.

The materials of the inner layer of the masonry that come into contact with the medium are preferably ceramic foam or refractory materials according to the classification given in DIN EN 12475, in particular products based on alumina-silica, such as chamotte, corundum, mullite and cordierite, base products, such as magnesia , magnesia-chromium oxide, magnesia-spinel, magnesia-zirconium silicate, or base products with fixed carbon, especially corundum, mullite and cordierite. Ceramic foams are described, for example, in German patent DE 102015202277 and international application WO 07/22750. Closed-cell ceramic foams sold under the trade name Halfoam Alumina™ are particularly suitable.

The shaped bricks of the inner layer of the masonry are most preferably made of a foamed ceramic material available under the trade name Halfoam Alumina™.

In addition, the present invention relates to shaped bricks containing ceramic foam, in particular closed-cell ceramic foam. The shaped bricks according to the invention preferably comprise ceramic foams made from alumina-silica based products such as chamotte, corundum, mullite and cordierite, base products such as magnesia, magnesia-chromium oxide, magnesia-spinel, magnesia-zirconium silicate, or base products with fixed carbon, primarily corundum, mullite and cordierite.

The present invention also relates to a combination of bricks comprising several layers of stacks of bricks arranged in series in the radial direction.

The materials of the second layer (inward direction) preferably have the following set of properties: heat resistance above 1500° C., thermal conductivity less than 1 W/m/K, preferably less than 0.5 W/m/K, and cold compressive strength greater than 1 MPa, preferably more than 2 MPa. Foam materials, as well as cast or extruded refractory lightweight bricks, have this set of properties. In the second layer, for example, commercial products Halfoam, Carath FL® or PROMATON® are used.

The materials of the third layer (inward direction) preferably have the following set of properties: heat resistance above 1200° C., thermal conductivity less than 0.5 W/m/K, preferably less than 0.2 W/m/K, and cold compressive strength more than 0.5 MPa, preferably more than 1 MPa. Vacuum-formed fibreboards preferably have this set of properties. In the third layer, for example, commercial products PROMATON® or ALTRA® are used.

The materials of the fourth layer (inward direction) preferably have the following set of properties: heat resistance above 1000° C., thermal conductivity less than 0.2 W/m/K, preferably less than 0.05 W/m/K, and cold compressive strength more than 0.1 MPa, preferably more than 0.2 MPa. Vacuum-formed fibreboards or microporous fumed silica boards preferably have this set of properties. The fourth layer uses, for example, commercial products ALTRA® or MICROTHERM®.

The invention also relates to a combination of bricks comprising a plurality of stacks of bricks arranged in series in the radial direction of (i) foamed ceramics and (ii) sintered cast or extruded ceramics, of (i) foamed ceramics, (ii) sintered cast or extruded ceramics and (iii) ) pressed ceramic fibers, or from (i) foamed ceramics, (ii) sintered cast or extruded ceramics, (iii) pressed ceramic fibers and (iv) vacuum formed fibreboards or panels containing microporous fumed silica.

The surface of the inner layer of the lining, which consists of shaped bricks, preferably ceramic foams, may be untreated or may be provided with a coating. The coating is preferably intended to seal the surface of the lining and protect it from abrasion. The coating, for example a protective layer, is preferably applied on the front side, back side, top side, bottom side and/or on the left and right side surfaces, preferably on the front side, back side, top side and/or bottom side, especially preferably on front side and/or back side, in particular on the front side. Under the end side is meant the surface of the shaped brick, facing the inside of the reactor. The protective layer is preferably made of refractory ceramic materials such as ZrO ₂ , YO ₂ , Si ₃ N ₄ , Al ₂ O ₃ , preferably Al ₂ O ₃ . The thickness of the protective layer is preferably 100 µm to 2 mm, preferably 200 µm to 1 mm. The porosity of the coating (void content) is preferably less than 50%, preferably less than 25%, particularly preferably less than 10%, in particular less than 5%. The coating can be applied to the shaped bricks by methods known to those skilled in the art, for example by spreading, dipping, flame spraying or plasma spraying.

The coating preferably has a multi-layer structure, for example, consists of a thin layer of non-porous ceramic and one or more thick layers of porous ceramic.

Examples of suitable coating materials are Aremco Coatings brushable products (PP-634-AL, 634-SIC, 634-YO, 634-ZO), Oerlikon Metco flame or plasma sprayed products, LWK PlasmaCera-mic plasma sprayed products, and Polytec Cotronics products (brush application, potting compounds).

The shaped bricks preferably have dimensions known to those skilled in the art (DIN 1081 (1988) for rectangular bricks and/or DIN 1082 (1988) for wedge bricks). If necessary, bricks can be cut to individual dimensions.

Refractory bricks located in different layers of the same row may have different heights in the vertical direction. This can be realized, for example, by alternately laying shaped bricks on edge and laying bricks. This avoids (i) unnecessary seams in areas with low axial temperature gradients or (ii) high mechanical stresses inside individual bricks in areas with significant axial temperature gradients.

The edges of the stack of refractory bricks are preferably parallel to the edges of adjacent baffles or gaps between adjacent baffles. The gap between the bricks and the adjacent partition or the gap between the bricks of the circumferentially adjacent stack is preferably 1 to 50 mm, preferably 1 to 25 mm, particularly preferably 1 to 10 mm. Said gaps are at least partially preferably filled with insulating mats of mineral fibers.

Insulating mats, if necessary, are fixed on the flat sides of the partitions. During installation, the insulating mats are preferably vacuum-tight welded into the foil and evacuated. The mats prepared in this way are preferably glued to transverse partitions, side partitions, partition walls and/or transverse partitions, preferably to transverse partitions and/or side partitions, particularly preferably to transverse partitions. After installation, the film is preferably pierced. As a result, the mats expand and wedged the bricks. This technology is described, for example, in international application WO 2014/125024.

Suitable materials for the insulation mats described above are: ALSIFLEX-1600, ALSIFLEX-1600 (cardboard), PROMAFELT-1600, SILCAFLEX 160, THERMOFRAX blanket (flexible mats), THERMOFRAX board (vacuum formed products) or THERMOFRAX felt/paper (ceramic building cardboard and felt).

The framework according to the invention preferably rests on a foundation, for example on a foundation slab. The base plate preferably serves to anchor the modular frame and bear the weight of the refractory package. The foundation slab can be monolithic or segmented. The base slab is preferably segmented, with each element of the segmented base slab preferably supporting a segment of the frame system according to the invention.

As an alternative to a foundation, the frame according to the invention can be attached to the ceiling.

The base plate is preferably freely or rigidly mounted on the lower roof. The base slab is preferably connected to the flange of the lower arch by means of a detachable connection. The base plate is particularly preferably bolted to the flange of the lower roof.

The base plate is preferably annular. The top and bottom sides of the base plate are preferably flat and parallel to each other. The thickness of the base plate is 1 to 500 mm, preferably 2 to 300 mm, particularly preferably 3 to 200 mm.

The width of the ring is from 50 mm to 2 m, preferably from 100 mm to 1 m, in particular from 200 to 500 mm.

The outer edge of the foundation slab, in plan view, preferably protrudes beyond the outer transverse baffles of the OSMS-ceramic frame. The outer edge of the base plate protrudes beyond the outer transverse partitions by an amount preferably 0 to 200 mm, preferably 5 to 100 mm, particularly preferably 10 to 50 mm. The inner edge of the foundation slab in plan view is preferably covered by an inner lining layer. The inner edge of the lining overlaps the inner edge of the base plate by an amount preferably 0 to 100 mm, preferably 0 to 50 mm, particularly preferably 0 to 20 mm.

The upper side of the base plate is preferably provided with grooves. The grooves preferably serve to support and pass through the transverse, lateral and, if appropriate, dividing partitions of the lowest frame layer. The location of the grooves preferably corresponds to the location of the partitions on the horizontal projection of the frame.

The depth of the grooves is preferably 1 mm to 500 mm, preferably 2 to 300 mm, particularly preferably 3 mm to 200 mm. The width of the grooves is preferably 0.2 mm to 20 mm, preferably 0.5 mm to 10 mm, in particular 1 mm to 5 mm. The width of the grooves preferably exceeds the thickness of the partitions inserted into them by 1 to 100%, preferably 2 to 50%, particularly preferably 5 to 20%.

The side baffles and transverse baffles of the lowest frame layer are preferably rigidly connected to the base plate. A force-locking connection can be realized, for example, by means of bolts, a form-fitting connection by means of a locating pin, and a permanent connection by means of gluing. The base plate is preferably made of metal, polymer and/or ceramic material, preferably metal, particularly preferably steel.

The surface of the foundation slab, if necessary, is electrically conductive or electrically insulating. In the case of a metal base plate, the electrically insulating surface layer is preferably made of enamel, ceramic material and/or polymer. The surface of the foundation slab is electrically insulating, preferably in places. Particularly preferably, the upper side and the outer perimeter of the base plate are electrically insulating.

The base plate is preferably provided with elements for attaching a lifting device, by means of which it is possible to remove from the reactor and mount the lining as a whole or in segments.

Preferably, a so-called multifunctional base plate can be used. Such a foundation slab optionally has one or more of the following features: (i) The foundation slab preferably extends continuously to the center of the reactor. In the area of the reaction zone, it is preferably provided with holes for the passage of gas and solid material, (ii) The base plate is preferably made in the form of a flange of the lower dome, (iii) The base plate is preferably provided with a bottom electrode located in an electrically heated moving or stationary bed reactor.

The combination with thermal insulation on the inside of the reactor shell is preferred, for example by thermal insulation panels sealed in metal sheaths. The thermal insulation panels are preferably porous, with a total porosity of more than 45% and less than 99%, preferably more than 60% and less than 99%, particularly preferably more than 70% and less than 99%. Thermal insulation panels preferably contain calcium silicate, vermiculite, mineral wool, glass wool or fumed silica. Thermal insulation panels are preferably enclosed in solid metal shells. The metal shells are preferably made of sheets which are bent, welded or soldered to form a continuous shell. The reverse side of the shells is preferably provided with fasteners, preferably with hooks and/or staples. By means of these fasteners, the shells are preferably hung from appropriate fixtures on the pressure-receiving reactor shell.

Furthermore, the invention relates to an apparatus, preferably a reactor, which comprises a modular frame system according to the invention and a pressure-receiving reactor shell, preferably a modular frame system according to the invention, a lining and a pressure-receiving reactor shell.

The cross-sectional area of the reactor is preferably 0.005 to 200 m ² , preferably 0.05 to 100 m ² , particularly preferably 0.2 to 50 m ² , in particular 1 to 20 m ² . The height of the reactor shell is preferably 0.1 to 100 m, preferably 0.2 to 50 m, particularly preferably 0.5 to 20 m, in particular 1 to 10 m. The ratio of the height to the equivalent diameter of the reactor shell is preferably in the range from 0.01 to 100, preferably from 0.05 to 20, particularly preferably from 0.1 to 10, even more preferably from 0.2 to 5. The wall thickness of the reactor shell is preferably from 1 to 300 mm, preferably from 5 to 200 mm, particularly preferably 10 to 100 mm.

Preferred reactor shell materials are steel alloys, eg alloys 1.4541, 1.4571.

Preferably, there is a through gap between the modular frame system and the reactor pressure housing. The width of this gap is preferably 0 to 100 mm, preferably 2 to 50 mm, particularly preferably 5 to 50 mm.

The gap between the modular frame system and the pressure-receiving reactor shell, if necessary, can be filled with a loose bulk layer of particles. The particles may be ceramic or metallic. The particles may be given a regular, for example, spherical, cylindrical or prismatic shape, or they may have an irregular shape. The particles may be solid, porous or hollow. The particles may have the same or different sizes. The bulk layer particles preferably have an equivalent diameter of 0.05 to 100 mm, preferably 0.1 to 50 mm, particularly preferably 0.5 to 10 mm. The equivalent diameter of a particle is the diameter of a sphere whose volume is identical to that of the particle.

The gap between the modular frame system and the reactor pressure housing can be purged with a directional gas stream if necessary. The purge gas preferably used is carbon dioxide, steam, nitrogen, lean air (air diluted with nitrogen) and/or argon. The purge gas stream is preferably annularly introduced through the upper dome and discharged through the base plate of the lining. Alternatively, the purge gas stream is introduced annularly through the base plate of the lining and exited through the roof. The purge gas stream preferably forms a gas curtain which separates the reaction zone from the pressure-receiving reactor shell. Due to this, it is possible to prevent the formation of deposits on the inner surface of the pressure-receiving casing, and also to cool the pressure-receiving casing.

The block frame system can optionally be supported on the side walls of the pressure-receiving casing. The support elements can be made of OSMS-ceramics, monolithic ceramics, ceramic fiber textiles, metal, or a combination of these materials. The support elements may be freely positioned between the frame and the side walls of the pressure-receiving reactor shell, or may be rigidly connected to the OCMS-frame or the walls of the pressure-receiving reactor shell. The connection can be made permanently or positively. The support members are preferably freely positioned between the modular frame system and the side walls of the pressure-receiving reactor shell.

In a reactor with significant axial temperature gradients, it may be advantageous to position the modular scaffold system only in the zone of the reactor in which said system is required to function as a high temperature resistant, thermally and electrically insulating restriction of the reaction volume. In this case, the edge zones of the pressure-receiving reactor shell can preferably remain uninsulated.

The reactor is preferably an electrically heated reactor (see application PCT/EP 2019/051466).

The device according to the invention preferably consists of an upper, a middle and a lower part, wherein at least one vertical electrode pair is mounted/placed in the middle part, and all electrodes are preferably placed/embedded in an electrically conductive package of solid materials. The top and bottom of the device are preferably domed and have a conductivity in the range of 10 ⁵ S/m to 10 ⁸ S/m. The middle part of the device is preferably electrically isolated from the package of solid materials. The upper and lower parts of the device are also preferably electrically isolated from the middle part of the device. The upper electrode is preferably connected via the upper part of the device and the lower electrode via the lower part of the device, or the respective electrodes are connected via one or more connecting elements electrically in contact with said parts. The ratio of the cross-sectional area of the upper and/or (preferably "and") lower electrode to the cross-sectional area of the corresponding conductive connector, or - without the use of a connector - the ratio of the cross-sectional area of the upper and/or (preferably "and") lower electrode to the area of the cross section of the respective conductive part of the device is preferably 0.1 to 10, preferably 0.3 to 3, in particular 0.5 to 2.

In the device according to the invention, in particular the reactor, the following high-temperature reactions are preferably carried out:

• Production of synthesis gas by reforming hydrocarbons with steam and/or carbon dioxide, combined production of hydrogen and pyrolysis carbon by pyrolysis of hydrocarbons. Suitable carrier materials are, in particular, carbon-containing granules, silicon carbide-containing granules and nickel-containing metal granules.

• Production of hydrocyanic acid from methane and ammonia, or from propane and ammonia. Suitable carrier materials are, in particular, carbonaceous granulates.

• Obtaining olefins through steam cracking of hydrocarbons. Suitable carrier materials are, in particular, granulates containing carbon and granulates containing silicon carbide,

• Coupling reaction of methane to form ethylene, acetylene and benzene.

• Obtaining olefins by catalytic dehydrogenation of alanes, for example, obtaining propylene from propane or butylene from butane. Suitable carrier materials are, in particular, granulates containing silicon carbide coated with dehydrogenation catalysts or iron-containing shaped articles.

• Obtaining styrene by catalytic dehydrogenation of ethylbenzene. Suitable carrier materials are, in particular, granulates containing silicon carbide coated with dehydrogenation catalysts or iron-containing shaped articles.

• Obtaining diolefins by catalytic dehydrogenation of alkanes or olefins, for example, obtaining butadiene from butylene or butane. Suitable carrier materials are, in particular, granulates containing silicon carbide coated with dehydrogenation catalysts or iron-containing shaped articles.

• Obtaining aldehydes by catalytic dehydrogenation of alcohols, for example, obtaining anhydrous formaldehyde from methanol. Suitable carrier materials are, in particular, silver-containing granules, dehydrogenation catalyst-coated granules containing silicon carbide, or iron-containing shaped articles.

• Obtaining carbon monoxide from carbon dioxide and carbon by the Boudouard reaction. Suitable carrier materials are, in particular, carbonaceous granulates.

• Obtaining hydrogen and oxygen by means of thermal splitting on catalytic contacts. Suitable carrier materials are, in particular, granulates containing silicon carbide or iron-containing granules coated with a cleavage catalyst, for example ferrite.

Blueprints

Fig. 1 Diagram of a reactor segment consisting of a pressure-receiving reactor shell surrounding an OSMS-frame filled with refractory bricks

Positions:

1 pack of three cross baffles

2a side baffles in the middle layers

2b side baffles in the lowest layer,

2 with side baffles in the topmost layer

6 pack of refractory bricks inserted into the nests of the OSMS frame

7 reactor pressure housing

Fig. 2 Plan view of a segmented frame segment formed by transverse baffles (1) and side baffles (2), each layer comprising four transverse baffles and three side baffles. The transverse partitions are made in the form of side surfaces of a circular cylinder, the side partitions are made in the form of flat sheets.

Fig. 3 Plan view of a segmented framework consisting of transverse and side baffles, with one transverse baffle per layer

Left: 12 segments, transverse baffles are made in the form of flat sheets, one side baffle per transverse baffle.

In the middle: 18 segments, transverse partitions are made in the form of circular arcs, one side partition per transverse partition.

Right: 12 segments, transverse partitions are made in the form of curved sheets, two side partitions per transverse partition.

The shaded area indicates the area of the segment.

Zones 5a, 5b, 5c ... respectively mean nests formed by partitions in the segment.

Fig. 4 Plan view of a segmented frame consisting of transverse and side baffles, with two transverse baffles per layer

Left: 12 segments, transverse baffles are made in the form of flat sheets, one side baffle per transverse baffle.

In the middle: 18 segments, transverse partitions are made in the form of circular arcs, one side partition per transverse partition.

Right: 12 segments, transverse partitions are made in the form of curved sheets, two side partitions per transverse partition

The shaded area indicates the area of the segment.

Zones 5a, 5b, 5c ... respectively mean nests formed by partitions in the segment.

Fig. 5 Plan view of a segmented framework consisting of transverse, side and dividing baffles, with two transverse baffles per layer

Left: 12 segments, transverse baffles are made in the form of flat sheets, one side baffle per transverse baffle, one loose baffle in each gap between the segments.

In the middle: 18 segments, transverse partitions are made in the form of circular arcs, one side partition per transverse partition, one loose dividing partition in each gap between the segments.

Right: 12 segments, transverse baffles are made in the form of curved sheets, two side baffles per transverse baffle, one loose dividing baffle in each gap between the segments.

The shaded area indicates the area of the segment.

Zones 5a, 5b, 5c ... respectively mean nests formed by partitions in the segment.

Fig. 6 General view of the segment in the frame, consisting of transverse partitions in the form of sheets and side partitions. In the radial direction, three transverse baffles are sequentially connected to the central side baffle. The framework consists of six layers.

In the middle: frame elements, transverse partitions with a slot on the upper side (item 1, height h), side partition of the middle layers (item 2a, height h), side partition of the lower layer (item 2b, height 1.5h), side partition of the upper layer (position 2c, height 0.5h). Due to the different heights of the lower and upper side partitions, the partitions of the different layers are engaged with each other.

Right: General view of part of a segment consisting of cross baffles, side baffles and a pack of refractory bricks fixed with insulating mats.

Positions:

1 pack of three cross baffles

2a side baffles in the middle layers

2b side baffles in the lowest layer

2 with side baffles in the topmost layer

6 pack of refractory bricks inserted into the nests of the OSMS frame

8 insulating mats for fixing the stack of refractory bricks in the OSMS frame

Fig. 7 General view of the segment in the frame, consisting of transverse partitions in the form of sheets, side partitions and flat partitions. In the radial direction, three transverse baffles are sequentially connected to the central side baffle. The framework consists of four layers. Transverse partitions are inserted between the layers.

Right: frame elements, cross partitions with a slot on the underside (item 1, height h), side partitions with slots on the upper side (item 2, height h), flat partitions with a slot on the inside (item 3).

Positions:

1 pack of three cross baffles

2 side partitions

3 flat baffles

Fig. 8 (refers, for example, to "framing with a series of transverse partitions"): a plan view of an example of a framework with a series of transverse partitions. An enlarged scale shows in detail the connection of adjacent transverse partitions with an overlap.

Positions:

9 rivets

10 grout

Fig. 9 (refers, for example, to "framework with several transverse baffles as protection against radiation").

Left: Plan view of an example frame with several rows of transverse baffles in the radial direction.

Right: Detailed side view of a side baffle (2) and a group of transverse baffles (1) inserted into the side baffle.

Fig. 10 Example of a framework with profiled side partitions.

Left: horizontal view of a frame segment with a large number of profiled side and dividing partitions.

Middle: Front view of several stacked layers.

Right: side view of several stacked layers.

Positions:

1 cross partitions

2 profiled side partitions

4 dividing walls

Fig. 11 General view of combinations of partitions of various shapes

Above: a combination of a flat partition and a partition wall.

Middle: Combination of flat baffle, baffle and cross baffle (on the outside).

Below: a combination of a flat baffle, a baffle and two transverse baffles (on the inside and outside).

Fig. 12 Diagram of a reactor with a frame system, the length of which is less than the length of the pressure-receiving reactor shell.

Fibre-reinforced oxide ceramic materials, in particular FSMS, have high thermal stability combined with high strength, plastic deformation capacity and thermal shock resistance. Such materials retain these properties for a long time at temperatures up to 1200°C. At higher temperatures, they gradually become brittle, but retain their shape and a significant part of the residual strength. In addition, these materials are characterized by low thermal conductivity and low electrical conductivity, which allows them to be considered insulators. The SSMS frame forms a barrier that separates the reactor packing, hot fixed bed, or moving (fluidized) bed from the pressure-receiving walls of the reactor. In addition, when an electric current is passed through the reactor packing, the OCMS frame forms an effective electrical isolation between the packing and the reactor pressure housing. The connection of the partitions to each other with positive locking contributes to the thermal expansion of the frame without internal stresses. This makes it possible to control the operating mode of the reactor, which is characterized by high temperatures, as well as significant local and temporal temperature gradients.

The properties inherent in new ceramic foams and fiber-reinforced oxide ceramics, in particular Halfoam and OSMS, allow the following advantages to be achieved:

Foamed ceramic materials, in particular Halfoam, combine high strength and shape retention with optimum thermal insulation performance, especially at high temperatures in excess of 1000°C. Such material can be used up to a temperature of 1700°C.

Fibre-reinforced oxide ceramic materials, in particular OCMS ceramics, combine high heat resistance with high strength and plastic deformation capability. Such materials retain these properties for a long time at temperatures up to 1200°C. At higher temperatures, they gradually become brittle, but retain their shape and a significant part of the residual strength.

The combination of both materials makes it possible to form a self-supporting lightweight lining for high pressure reactors. The forces acting on the lining are perceived by the frame made of OSMS. This makes possible the free laying of shaped bricks, which, in turn, contributes to their easy displacement relative to each other during thermal expansion. The connection of the framework of OSMS and the refractory package with a purely geometrical closure allows you to create an elastic structure that, with significant temperature fluctuations (local or temporary), is able to deform without stress.

The thermally insulating effect of Halfoam bricks allows, when using a thin layer, to reduce the temperature from 1500°C (temperature of the reaction zone) to temperatures below 1200°C. This achieves the following benefits:

In contrast to the prior art, the lining can be thinner and much lighter.

Partitions of the supporting frame made of OSMS are effectively protected from aging.

Since OSMS ceramics have low thermal conductivity, thermal bridges due to the ribbed effect of the support frame are eliminated.

Foamed ceramics and fibre-reinforced oxide ceramic materials, in particular Halfoam and AlOx-based OCMS, have identical coefficients of thermal expansion. Due to this, the gaps in the lining remain unchanged over the entire temperature range and undefined flows through the lining are prevented.

The sealing of the refractory stack with insulating mats in the frame of OSMS allows for a seamless, but nevertheless flexible and heat-resistant connection.

Due to the inherent stability achieved, the lining does not need to be supported on the pressure-receiving reactor shell. As a result, a through gap may form between the lining and the reactor shell.

The lining can be mounted and dismantled independently of the reactor shell. This simplifies the installation of the reactor, as well as the repair and replacement of worn parts. In particular, the lining can be pre-assembled outside the reactor and then transferred as an assembly to the reactor. This makes it possible to minimize the downtime of the reactor when repairing or updating the lining.

In the case of electrically heated reactors, the lining materials are electrical insulators and form an effective insulating layer between the bulk material in the reaction zone and the pressure-bearing reactor shell.

The gap between the lining and the reactor shell provides additional reliable and temperature-independent electrical insulation between the bulk bed and the reactor shell.

Coating the inner surface of the lining with a non-porous and smooth facing layer provides the following positive effects:

The liner provides effective protection to the inside of the lining against abrasion by particles, such as particles of the moving layer. The smooth surface of the facing layer hinders the formation of hard deposits on the wall. The deposits adhere weakly to the surface and, due to the movement of particles of the moving layer, can be separated from it.

In addition, the permeability of the wall for bypass gas flows from the reaction zone is reduced.

The multi-layer structure of a thin layer of non-porous ceramic material and one or more thick layers of porous ceramic is resistant to thermal shock cracking.

The layered structure of the lining allows the use of different insulating materials in separate layers with the corresponding optimal set of properties, namely, heat-insulating effect and heat resistance.

Separation of the lining in the radial direction by means of parallel or concentric transverse baffles of the OSMS carcass contributes to the tolerance of the structure in relation to failures. Even in the event of destruction of individual parts of the refractory package, the layers remain intact, and the breakthrough of the hot bulk layer from the reaction zone to the pressure-receiving reactor shell is excluded, due to which a controlled shutdown of the damaged reactor is possible.

A circumstance that is especially important for high-pressure reactors is that, if necessary, the sealing of the surface of the OSMS baffles and/or refractory bricks makes it possible to prevent the occurrence of intense convective circulation flows that can significantly reduce the insulating effectiveness of the lining.

Examples

Prior Art Example

The production reactor is lined with a multilayer refractory concrete lining. The reaction zone diameter is 3000 mm. The electrodes for power supply of the bulk layer are located vertically at a distance of 3000 mm from each other. The lining consists of the layers indicated in the table.

The lining is attached to the reactor shell with anchors. The internal diameter of the reactor pressure housing is 3640 mm. The design heat transfer coefficient of the lining is 2.14 W/(m2 K). The power loss of the reactor, according to the calculation, should be 32 kW/m of the length of the reactor, and the temperature on the outside of the reactor should be 75°C. During operation of the reactor at a maximum temperature of 1400°C and an absolute operating pressure of 1.6 bar, heat losses reach 84 kW/m, and the temperature on the outer side of the reactor rises in places to 300°C. When opening the reactor, cracks were found in the lining. Visible cracks on the inner surface of the reactor walls are arranged irregularly and have different sizes and lengths. The length of the longest cracks is 1000 mm, the maximum width is 3 mm. The lining is partially destroyed. The depressions formed as a result of this in the lining with an area of 500 cm have a depth of up to 5 cm. The defects listed above explain the deterioration in the insulating ability of the lining. As a result, the production capacity of the reactor and the energy consumption of the process are reduced. In addition, as a result of exceeding a predetermined temperature, the strength of the pressure-receiving reactor shell decreases. In this regard, further operation of the reactor becomes unsafe.

Example 1 Use of the modular frame according to the invention as electrical insulation in the interior of a reactor

In this example, the simplest version of the technical solution proposed in the invention is presented. The resistively heated moving bed reactor is used, for example, for the pyrolysis of hydrocarbons. The diameter of the reaction zone of the reactor is 3000 mm. The electrodes used for power supply of the bulk layer are vertically located at a distance of 3000 mm from each other. The internal diameter of the pressure-receiving jacket of the reactor is 3100 mm. The reactor casing is equipped with a cooling coil located on the outer surface with water passing through it, which makes it possible to set the casing temperature not higher than 50°C. The reaction zone is limited by a modular framework. Partitions of the frame are made of OSMS. The frame consists of a series of transverse partitions, which are respectively supported by side partitions. The thickness of all partitions is 3 mm. The frame includes six segments and five layers arranged one above the other. The transverse partitions of adjacent segments in the circumferential direction are overlapped with each other. The lap joints are filled with high temperature resistant mastic and connected with rivets. Thus, the frame provides dust-tight isolation of the reaction zone relative to the annular space between the frame and the pressure-receiving reactor shell. Carbon dioxide is passed through the annulus between the frame and the reactor pressure housing as a purge gas. The temperature in the center of the reaction zone is 1400°C. The frame temperature is 425°C. The technical solution described above is compact and light in design. The reaction zone occupies 93.5% of the cross section surrounded by the pressure-receiving reactor shell. The weight of the frame made of OSMS-partitions is 250 kg. In addition, the frame performs the function of electrically isolating the reaction zone relative to the pressure-receiving walls of the reactor. At the same time, the frame has a small heat-insulating effect. Due to this, the temperature on the inside of the frame is so low that there is no contamination of the frame with carbonaceous deposits. This, in turn, allows the technological process to be carried out in a reliable stationary mode.

Example 2 Use of the modular frame according to the invention as radiation protection

In this example, a variant of the technical solution proposed in the invention is presented, which involves the use of a frame made of OSMS partitions. The resistively heated moving bed reactor is used, for example, for the pyrolysis of hydrocarbons. The diameter of the reaction zone of the reactor is 3000 mm. The electrodes used for the power supply of the bulk layer are located vertically at a distance of 3000 mm from each other. The internal diameter of the pressure-receiving jacket of the reactor is 3700 mm. The reactor shell is not insulated from the outside. The reaction zone is limited by a framework of OSMS partitions. The frame includes twelve segments in the circumferential direction and ten layers arranged one above the other. Each layer in each segment includes sixty rows of transverse baffles, which respectively rest on the side baffles. The thickness of the transverse baffles of the inner row, which are in direct contact with the reaction zone, is 3 mm. A protective layer is deposited on the inner side of these transverse partitions by means of plasma spraying. The transverse partitions of adjacent segments in the inner row are overlapped to each other in the circumferential direction. The lap joints are filled with high temperature resistant mastic and connected with rivets. The thickness of the transverse baffles in the remaining rows is respectively 1 mm, and the baffles are spaced from each other in the radial direction by 2 mm. The edges of these transverse partitions are not fixed. The thickness of the side partitions is 3 mm. Carbon dioxide is passed through the annulus between the frame and the reactor pressure housing as a purge gas. The technical solution described above is characterized by exceptionally high mechanical reliability and relatively light construction. The overall frame is made of ductile and thermal shock-resistant OSMS-ceramics. The partitions inserted one into the other form a mechanically stable frame, which is simultaneously able to equalize the deformations caused by thermal expansion. The frame weight is about 1.6 t/m of the reactor length. In addition, the frame performs the function of electrically isolating the reaction zone relative to the pressure-receiving walls of the reactor. The frame is also effective as a thermal insulation, and the transverse baffles, arranged in a row from the inside to the outside, perform the function of protecting against radiation. Small distances between the transverse partitions contribute to the absence of movement of gas layers, which enhances the insulating effect of the frame. The temperature in the center of the reaction zone is 1350°C. The temperature on the inside of the frame is 1200°C. The heat loss of the insulation is 45 kW/m of the reactor length. The temperature of the pressure-receiving jacket of the reactor is 85°C.

Example 3 (Halfoam material and refractory lightweight bricks)

This example shows a variant of the technical solution proposed in the invention, directly comparable to the basic variant. This is a lining with a thickness of 320 mm, consisting of three layers arranged in the radial direction. The inner layer is made of HALFOAM (Morgan Advanced Materials Haldenwanger GmbH). The second layer is made of PROMATON 28 shaped bricks (manufacturer Etex Building Performances GmbH). The third layer is made of PROMATON 26 shaped bricks from the same manufacturer. Bricks are laid by means of a spoon dressing. OSMS frame consists of eighteen segments with an annular cross section. The segment consists of one side partition and two transverse partitions. The inner transverse baffle, which is 3.63 m in diameter, includes an inner lining layer. The outer transverse baffle, which is 4.09 m in diameter, includes two outer layers of lining. The weight of the lining is about 3.35 t/m of the reactor length. Between the outer transverse baffle and the walls of the reactor there is a gap 20 mm wide. In the center of the moving layer, a temperature of about 1500°C prevails. The table shows the radial temperature profile of the lining.

At a temperature in the center of the reactor 1500°C heat loss is 15.2 kW/m length of the reactor.

In this embodiment, the presence of the inner lining layer causes a significant decrease in temperature: T = 244 K. Due to this, the temperature to the inner transverse partition is reduced so much that the OSMS material does not undergo significant aging.

The lining according to the invention is much lighter than in the basic variant described in Example 1. Other advantages of the variant proposed in the invention in comparison with the basic variant, which are due to the heat-insulating effect of the first lining layer, include the following:

1. More uniform temperature field over the cross section of the moving layer (temperature difference between the axis and the walls ΔT is 73 K).

2. The temperature of the outer side of the first layer of the lining is reduced to values much lower than 1200°C, and, consequently, the supporting frame of OSMS materials retains its preferred mechanical properties for a long time. Another advantage is the lower temperature at the walls of the reactor. These advantages may be due to the better insulating properties of HALFOAM compared to K99 alumina refractory bricks.

Example 4 (Halfoam Material, Lightweight Fire Bricks and Heavy Duty Insulation)

This example shows a variant of the technical solution according to the invention, optimized with regard to the insulating effect and weight. This is a lining with a thickness of 320 mm, consisting of four layers arranged in the radial direction. The two inner layers are made of Halfoam (Morgan Advanced Materials Haldenwanger GmbH). The third layer is made of PROMATON 28 shaped bricks (manufacturer Etex Building Performances GmbH). The fourth layer is assembled from MICORTHERM PANEL panels (manufactured by Etex Building Performances GmbH) glued to the outside of the outer transverse partitions. Bricks are laid by means of a spoon dressing. OSMS frame consists of eighteen segments with an annular cross section. The segment consists of one side partition and two transverse partitions. The inner transverse baffle, which is 3.63 m in diameter, includes two inner layers of lining. The outer transverse baffle, whose diameter is 4.03 m, includes three layers of lining. The weight of the lining is about 3.2 t/m. A gap 20 mm wide is formed between the outer transverse baffle and the walls of the reactor. In the center of the moving layer, a temperature of about 1500°C prevails. The table shows the radial temperature profile of the lining.

Heavy-duty insulation is fixed in cassettes on the walls of the reactor.

The heat loss is 9.15 kW/m, i.e., much lower than in the variants of examples 1 and 2. Due to the presence of two inner layers, the lining temperature in this embodiment decreases so much that the OSMS material does not undergo significant aging. Due to the presence of the third layer, the temperature is reduced to such an extent that it becomes possible to use heavy-duty insulation with an extremely strong insulating effect, which, however, has a thermal resistance limited to a temperature of about 1000°C.

The inventive lining is lighter than the inventive variant of example 2. Other advantages of the inventive variant compared to the variant of example 2 include a more uniform temperature field across the moving bed (temperature difference ΔT is 36 K) and lower temperature at the walls of the reactor (58°C). This makes it possible to dispense with contact protection on the outside of the reactor, and thus reduce costs and increase the availability of the reactor.

Claims (26)

1. Device for electrical and/or thermal insulation of high-temperature reactors, consisting of at least one pressure-receiving casing of the device and at least one modular frame system of partitions of two different types located inside the casing, characterized in that several transverse partitions form at least at least one prism or cylinder, moreover, several side partitions protrude inside the prism or cylinder, moreover, the transverse partitions and side partitions are made with the possibility of inserting them into one another and / or connecting to each other by means of one or more connecting elements, and moreover, the material of the partitions contains ceramic fibrous composite materials. 2. The device according to claim 1, characterized in that the modular frame system is a self-supporting system. 3. The device according to claim. 1, characterized in that the material of the partitions contains oxide fibrous composite materials. 4. The device according to claim 1, characterized in that the transverse partitions are in the form of corrugated, curved or flat sheets or in the form of cylindrical shells, and the side partitions are in the form of corrugated or flat sheets. 5. The device according to claim. 1, characterized in that it includes several layers located one above the other, formed by transverse partitions. 6. The device according to claim 1, characterized in that several parallel or concentric transverse partitions in the form of an elliptical arc are used in the radial direction, which are located on a horizontal projection in the form of polygons or ellipses located one inside the other. 7. The device according to claim. 1, characterized in that the dividing partitions are made with the possibility of inserting them into the gaps between the transverse partitions adjacent in the circumferential direction. 8. The device according to claim. 1, characterized in that the flat partitions are made with the possibility of insertion between two layers of transverse partitions located one above the other. 9. The device according to claim 1, characterized in that it rests on a foundation to which it is connected via a detachable connection. 10. The device according to claim 1, characterized in that it includes a lining of refractory bricks located inside a modular frame system. 11. The device according to claim 10, characterized in that the frame system is made with the possibility of dividing into nests, and the nest means an area that includes two transverse partitions adjacent in the radial direction in the form of parallel or concentric arcs of an ellipse and the corresponding side partitions, as well as a gap between circumferentially adjacent transverse baffles, or preferably a partition wall inserted into this gap; and said pockets are respectively filled with 1 to 2000 refractory bricks or catalysts, and the bricks are arranged in vertical and horizontal directions in the form of layers, and there is a gap between the bricks and the partitions limiting the nests. 12. Apparatus according to claim 10, characterized in that the refractory brick lining comprises a combination of bricks, which in turn includes a plurality of stacks of (i) foamed ceramic and (ii) sintered cast or extruded ceramic bricks arranged in series in the radial direction. , of (i) ceramic foam, (ii) sintered, cast or extruded ceramic, and (iii) pressed ceramic fibers, or (i) foamed ceramic, (ii) sintered, cast or extruded ceramic, (iii) pressed ceramic fibers, and (iv) ) vacuum formed fibreboards or panels containing microporous fumed silica. 13. The device according to one of paragraphs. 10-12, characterized in that the gap between bricks and adjacent partitions and/or between bundles of bricks adjacent in the circumferential direction is at least partially filled with insulating mats. 14. The device according to one of paragraphs. 1-12, characterized in that there is a through gap between the modular frame system and the pressure-receiving casing of the device. 15. The device according to claim 14, characterized in that the gap is purged with a directed gas flow. 16. The use of the device according to one of paragraphs. 1-15 for: - obtaining synthesis gas by reforming hydrocarbons with steam and/or carbon dioxide, - obtaining hydrogen and carbon as joint products through the pyrolysis of hydrocarbons, - obtaining hydrocyanic acid from methane and ammonia or from propane and ammonia, - production of olefins by steam cracking of hydrocarbons, the reaction of the combination of methane with the formation of ethylene, acetylene and / or benzene, - obtaining olefins by dehydrogenation of alkanes, - obtaining styrene by dehydrogenation of ethylbenzene, - obtaining diolefins by dehydrogenation of alkanes or olefins, - obtaining aldehydes by dehydrogenation of alcohols, - obtaining carbon monoxide from carbon dioxide and carbon by the Boudouard reaction, - production of hydrogen and oxygen by means of thermal splitting on catalytic contacts.

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