SHAPED CATALYST BODY IN THE FORM OF TETRALOBES HAVING A CENTRAL THROUGH-PASSAGE

Abstract

The invention relates to a shaped catalyst body in the form of a tetralobe having four outer through-passages and a ratio of diameter to height of the shaped body of from 0.25 to 1.0 and having a central fifth through-passage. It is used for the oxidation of S02 to S03.

Claims

1.-14. (canceled)

15. A shaped catalyst body in the form of a tetralobe having four outer through-passages and a ratio of diagonal diameter D to height E of the shaped body of from 0.25 to 1.0, wherein the cross section of the tetralobe having four outer through-passages is formed by four partly overlapping annular rings whose midpoints lie on a circular line having a diameter y, with the four annular rings being bounded by an outer circular line having an outer diameter x1 and a concentric inner circular line having an inner diameter x2, wherein all annular rings have the same external diameter x1 and the same internal diameter x2, wherein the outer wall thickness B of the outer through-passages is 0.5 to 1.25 times the spacing F between 2 adjacent outer through-passages and wherein the body has a central fifth through-passage.

16. The shaped catalyst body according to claim 15, wherein the central through-passage and the four outer through-passages are present in a quincunx arrangement.

17. The shaped catalyst body according to claim 15, wherein the body has 4-fold rotational symmetry.

18. The shaped catalyst body according to claim 15, wherein the diameter of the central through-passage is smaller than the diameter of the outer through-passages.

19. The shaped catalyst body according to claim 15, wherein the wall thickness of the outer walls of the outer through-passages is essentially equal to the spacing between two adjacent outer through-passages.

20. The shaped catalyst body according to claim 15, wherein all through-passages are circular.

21. The shaped catalyst body according to claim 20, wherein the diameter of the central through-passage is essentially equal to the spacing between two adjacent outer through-passages.

22. The shaped catalyst body according to claim 15, wherein the central through-passage is square and the four outer through-passages are circular.

23. The shaped catalyst body according to claim 15, wherein the ratio of the diagonal diameter D of the shaped body to the height E of the shaped body is from 0.4 to 0.75.

24. The shaped catalyst body according to claim 15, wherein the diagonal diameter D of the shaped body is from 5 to 80 mm.

25. The shaped catalyst body according to claim 15, wherein the body comprises vanadium, at least one alkali metal and sulfate on a silicate support material.

26. The shaped catalyst body according to claim 15, obtainable by extrusion of a catalyst precursor composition by means of an extrusion tool which represents the geometry of the cross section of the shaped catalyst body to form shaped catalyst precursor bodies, drying and calcination thereof.

27. A process for the oxidation of SO.sub.2 to SO.sub.3, which comprises bringing into contact a gas mixture comprising oxygen and sulfur dioxide at a temperature in the range from 340 to 680 C. with a bed of shaped catalyst bodies according to claim 15.

Description

[0039] FIG. 1 shows a shaped body which is not according to the invention and has 4 through-passages, as is described in WO16156042A1.

[0040] FIGS. 2a, b show an embodiment of the shaped catalyst body of the invention. Here, the outer wall thickness B is equal to the spacing F between 2 adjacent outer through-passages and is also equal to the diameter G of the circular central through-passage. A is the diameter of the outer through-passages, C is the lateral diameter, D is the diagonal diameter and H is the inner wall thickness, i.e. the spacing between the central through-passage and the outer through-passages.

[0041] FIG. 3 shows a further embodiment of the shaped catalyst body of the invention. Here, the outer wall thickness B is likewise equal to the spacing between 2 adjacent outer through-passages. However, the shaped body has a square central through-passage having the side length G.

[0042] Values of B are preferably in the range from 0.5 to 1.25 F, particularly preferably in the range from 0.9 to 1.10 F; for example B=F.

[0043] Values of A in the case of a circular inner through-passage are preferably in the range from 1.4 to 1.8 G, particularly preferably from 1.5 to 1.7 G, for example 1.6 G, and in the case of a square through-passage are preferably in the range from 1.8 to 2.4 G, particularly preferably from 2.0 to 2.2 G, for example 2.1 G.

[0044] Values of H are preferably in the range from 0.4 to 0.6 G, particularly preferably from 0.45 to 0.55 G, for example 0.5 G.

[0045] Values of F are preferably in the range from 0.8 to 1.2 G, particularly preferably from 0.9 to 1.1 G, for example 1.0 G.

[0046] FIGS. 4a, 4b, 4c, 4d, 5a and 5b show horizontal projections of the dies used for producing shaped bodies according to the invention.

[0047] FIGS. 6 and 7 show photographs of the shaped bodies according to the invention. It is clear from the photographs that the extruded shaped bodies can also have, as a result of the production process, some curvature along the longitudinal axis (extrusion direction). This can lead to reduced rotational symmetry of the shaped body, but generally without being disadvantageous for the effect according to the invention of the shaped bodies.

[0048] The shaped catalyst bodies of the invention can be produced by extrusion of a corresponding catalyst precursor composition comprising vanadium, at least one alkali metal and sulfate on a silicon dioxide support material through an extrusion tool which represents the geometry of the cross section of the shaped body, drying and calcination of the extruded shaped catalyst precursor bodies. The cross section of the opening of the extrusion tool accordingly has an ideal geometry formed by 4 partly overlapping annular rings which are bounded by an outer circle having an external diameter x1 and an inner circle having an internal diameter x2 and whose midpoints lie on a circular line having the diameter y, the cross section having a central (preferably circular or square) recess.

[0049] The ideal shape of the shaped bodies of the invention is defined by the geometry of the extrusion tool through which the catalyst precursor composition is extruded. In general, the geometry of actual extruded shaped bodies deviates from this ideal shape, but the actual shaped bodies have essentially the above-described geometric features. In general, the axes of the hollow-cylindrical convexities are parallel. However, the actual shaped bodies can, for example, be slightly curved in the z direction. The holes (through-passages) of the shaped bodies of the invention can deviate from a perfect circular or square shape. If a large number of actual shaped bodies is present, individual through-passages in some few shaped bodies can be closed. In general, the end face of the shaped bodies in the xy plane is, due to the production process, not a smooth surface but more or less irregular. The length of the shaped bodies in the z direction (maximum extension in the z direction) is generally not equal for all shaped bodies but instead has a distribution which is characterized by an average length z (arithmetic mean).

[0050] The process for producing shaped catalyst bodies comprising vanadium, at least one alkali metal and sulfate on a silicate support material includes the extrusion of a catalyst precursor composition comprising vanadium, at least one alkali metal and sulfate on a silicate support material through the opening of an extrusion tool, the cross section of which represents the shaped catalyst body geometry, wherein the cross section of the opening of the extrusion tool is formed by 4 partly overlapping annular rings which are bounded by an outer circle having an external diameter x1 and an inner circle having an internal diameter x2 and whose midpoints lie on a circular line having the diameter y and the opening furthermore has a central (preferably circular or square) recess having a diameter or lateral length x3.

[0051] In general, the catalysts comprise not only vanadium but also alkali metal compounds, especially potassium compounds but optionally also sodium compounds and/or cesium compounds, and also sulfate. Porous oxides such as silicon dioxide, SiO.sub.2, are used as support for the abovementioned components.

[0052] As inert support materials, use is made of, in particular, porous materials based on SiO.sub.2. Here, it is possible to use synthetic variants of SiO.sub.2 and also natural forms of SiO.sub.2 or mixtures thereof.

[0053] The content of vanadium, calculated as V.sub.2O.sub.5, is generally from 3 to 10% by weight, the content of alkali metals (M), calculated as M.sub.2O, is from 5 to 30% by weight, with the molar ratio of alkali metal to vanadium (M/V ratio) usually being in the range from 2 to 6. The content of potassium, calculated as K.sub.2O, is usually in the range from 6 to 15% by weight and the content of sulfate is in the range from 12 to 30% by weight. In addition, it is possible for further elements such as chromium, iron, aluminum, phosphorus, manganese and boron to be comprised.

[0054] A preferred support material comprises naturally occurring diatomaceous earth. The support material particularly preferably comprises at least two different naturally occurring, uncalcined diatomaceous earths which differ in terms of the structure type of the diatoms on which they are based, with the various structure types being selected from plate-shaped, cylindrical and rod-shaped structure types.

[0055] The catalysts produced therefrom have a particularly good mechanical stability.

[0056] Preferred diatomaceous earths should have a content of aluminum oxide Al.sub.2O.sub.3 of less than 5% by weight, preferably less than 2.6% by weight and in particular less than 2.2% by weight. Their content of iron(III) oxide Fe.sub.2O.sub.3 should be less than 2% by weight, preferably less than 1.5% by weight and in particular less than 1.2% by weight. Their total content of alkaline earth metal oxides (magnesium oxide MgO+calcium oxide CaO) should be less than 1.8% by weight, preferably less than 1.4% by weight and in particular less than 1.0% by weight.

[0057] Uncalcined diatomaceous earth has not been treated at temperatures above 500 C., preferably not above 400 C. and in particular not above 320 C., before mixing with the active components.

[0058] A characteristic feature of uncalcined diatomaceous earth is that the material is essentially amorphous, i.e. the content of cristobalite is <5% by weight, preferably <2% by weight and particularly preferably <1% by weight, determined by X-ray diffraction analysis.

[0059] Of course, the naturally occurring, uncalcined diatomaceous earth can have been subjected to various treatment steps apart from calcination, for example slurrying, washing, extraction, drying and/or sifting, after mining and before use as support material.

[0060] The production of the catalysts is effected by mixing aqueous solutions or suspensions of the various active components, for example appropriate vanadium compounds (V.sub.2O.sub.5, ammonium polyvanadate, ammonium metavanadate, alkali metal vanadates or vanadyl sulfates) with alkali metal salts (nitrates, carbonates, oxides, hydroxides, sulfates), optionally with sulfuric acid and other components which can function as pore formers or lubricants, for example sulfur, starch or graphite, with the support material. The mixing operation is not restricted further and can, for example, be carried out in a kneader, a screw mixer, a paddle mixer or a Mix Muller in which the components are mixed by means of rotating wheels and scrapers.

[0061] The resulting composition is, in the next step, extruded to give the shaped bodies according to the invention, dried and calcined. The type of extruder is not restricted further here. It is possible to use, for example, ram extruders, screw extruders, cascade extruders or planetary gear extruders. Preference is given to using screw extruders, in particular screw extruders having one or two screw shafts. The screw shafts can be optimized in respect of their geometry, for example in respect of their nominal diameter, the flight depth and/or the pitch, so that they produce very uniform extrudates. The material of the screw shaft or its surface and also the material of the barrel or its surface and of the extrusion tool or its surface can, for example, be optimized so that it has a very high resistance to the composition to be extruded. Owing to the low pH of the composition, corrosion- and acid-resistant materials are particularly preferred. The materials to be processed can be continuously or discontinuously supplied to the screw from above via a hopper. Reproducible metering and fill height in the hopper can lead to improved quality of extrusion.

[0062] The type of extrusion is likewise not restricted further. For example, cold extrusion, warm extrusion or hot extrusion can be used. At the inlet into the extruder, the composition to be extruded typically has a temperature of from 10 to 90 C. The extruder housing with the barrel can be cooled by means of a cooling medium, for example water, in order to prevent components from being deformed by excessively high temperatures. In such a case, the temperature of the cooling medium fed to the extruder is typically from 0 to 80 C. The temperature of the extrudate immediately after leaving the extruder is typically from 10 to 90 C. The speed of rotation of the screw is typically from 1 to 100 revolutions per minute, often from 2 to 30 revolutions per minute. The pressure in the extruder upstream of the extrusion tool is typically from 20 to 500 bar. The torque imparted by the screw is typically from 50 to 5000 Nm.

[0063] Extrusion tools can consist of one or more components. In a preferred embodiment, they consist of a die and insert pins, with the die as far as possible determining the shape, size and position of the outer convexities and the insert pins determining the shape, size and position of the four outer through-passages and of the central through-passage. The insert pins can be inserted into the die. The translatory and rotary centering of the insert pins in the dies can be achieved by means of a suitable construction of die and insert pins, for example by means of a groove in one component and a tongue in the other component. Centering can also be effected with the aid of an additional centering tool.

[0064] If the extrusion tool consists of a plurality of components, the components can consist of the same material or of different materials. In a preferred embodiment, the die consists of a very acid-resistant plastic, for example PTFE and the insert pins consist of an acid-resistant stainless steel. The dies can be produced inexpensively by, for example, injection molding.

[0065] The shaped bodies are generally subjected to a drying step after extrusion. Here, the type of oven is not restricted further. It is possible to use, for example, stationary convection ovens, rotary tube ovens or belt ovens. The duration of drying is generally from 0.5 to 20 hours and the temperature is generally from 50 to 200 C.

[0066] The shaped bodies are generally subjected to a calcination step after drying. Here, the type of oven is not restricted further. It is possible to use, for example, stationary convection ovens, rotary tube ovens or belt ovens. The duration of the calcination is generally from 0.5 to 20 hours and the temperature is generally from 200 to 800 C.

[0067] After the calcination or even at other points during the process for producing the catalyst, it can be advantageous to sort the shaped bodies according to their dimensions and utilize only a suitable size fraction. Such sorting can be effected, for example, by means of suitable sieves. Shaped bodies which are larger or smaller than the desired dimensions can, for example, be recirculated as recycle material to suitable points in the process. It can be advantageous to subject this recycle material to one or more further process steps, for example milling, before recirculation.

[0068] The present invention also provides for the use of the shaped catalyst bodies for the oxidation of SO.sub.2 to SO.sub.3.

[0069] The present invention further provides a process for the oxidation of SO.sub.2 to SO.sub.3, wherein a gas mixture comprising oxygen and sulfur dioxide is brought into contact at a temperature in the range from 340 to 680 C. with a bed of the shaped catalyst bodies of the invention.

[0070] Tray reactors (see, for example, H. Muller, Sulfuric Acid and Sulfur Trioxide in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, 2012; DOI: 10.1002/14356007.a25_635) are typically used as reactors. These tray reactors have a plurality of reaction trays in which SO.sub.2 is brought into contact with shaped catalyst bodies. The reactor typically comprises from 1 to 6, usually from 3 to 5, trays. The tray reactors generally behave approximately adiabatically, i.e. the heat liberated in the oxidation of SO.sub.2 to SO.sub.3 largely heats the reaction gas. The exothermic oxidation of SO.sub.2 to SO.sub.3 is limited by thermodynamic equilibrium which is shifted in the direction of the starting materials with increasing temperature. After passage through a tray, the reaction gas is therefore cooled, for example in suitable heat exchangers, before being fed to the next tray. Furthermore, there are processes in which the SO.sub.3 formed is largely removed from the reaction gas, for example by absorption in concentrated sulfuric acid, between two trays in order to increase the conversion of remaining SO.sub.2 in the subsequent trays.

[0071] The concentration of SO.sub.2 in the reaction gas before the latter enters the first tray is generally from 2 to 20% by volume; depending on SO.sub.2 source, it is typically in the range from 5 to 15% by volume. The concentration of O.sub.2 in the reaction gas before the latter enters the first tray is likewise generally 2-20% by volume; depending on SO.sub.2 source, it is typically in the range from 5 to 15% by volume. The volume flows are generally from 10 000 to 500 000 standard m.sup.3/h, typically from 30 000 to 350 000 standard m.sup.3/h. The diameter of the reactors is typically from 2 to 15 m, normally from 3 to 10 m. The volume of the catalytic bed per tray is generally from 10 to 500 m.sup.3, usually from 20 to 350 m.sup.3. The height of the catalytic bed per tray is generally from 0.3 to 3 m, typically from 0.5 to 2.5 m. The space velocity of gas in standard m.sup.3/h, based on the catalyst volume in m.sup.3 (GHSV), is generally from 100 to 5000 h.sup.1, usually from 500 to 2500 h.sup.1. The flow is typically in the laminar range, and the Reynolds number of the flow in the tray is generally from 10 to 1000, typically from 30 to 500. The pressure drop over the bed in a tray is generally from 2 to 100 mbar, typically from 5 to 50 mbar.

[0072] It is economically advantageous for the pressure drop over the process, in particular over reactor, heat exchanger and optionally absorption tower, to be low in order to have low costs for compression of the reaction gas and in order to minimize the pressure rating requirements for the components. A catalytic bed which displays a low pressure drop and a high activity is advantageous here.

[0073] The invention is illustrated in more detail by the following examples.

EXAMPLES

[0074] Simulation of the Pressure Drop

[0075] In Examples 1 and 2, the relationship between pressure drop and shape and size of the catalysts was calculated by means of a numerical flow simulation which fully resolves the flow in the intermediate spaces of the catalyst bed. The method gives very good agreement with experimental data for cylindrical bodies. The procedure comprises three successive steps. Firstly, the geometry of the bed is established. For this purpose, a CAD (computer-aided design) model of a single shaped catalyst body was set up using any CAD program. This fixes the shape of the catalyst (e.g. cylinder, ring, flower, etc.). A tube having an internal diameter typical of an industrial reactor is used as outer container for the bed. Both the digital container geometry and also the digital catalyst geometry are loaded into another simulation program which makes it possible to calculate the movement of the catalysts on introduction into the container using the Newtonian equations of motion. The pressure drop calculations were carried out assuming air at ambient temperature and various space velocities of gas (GHSV, gas hourly space velocity). For the thermodynamic and transport properties of the gas, literature values for air at a constant operating pressure of 1 bar and temperature of 20 C. were used. In the following, an example according to the invention (Example 2) is compared with a comparative example (Example 1).

Example 1 (Comparative Example)

[0076] Tetralobes having 4 through-passages and a cross section as per FIG. 1, with the following dimensions:

[0077] A=3.0-3.2 mm

[0078] B=2.1-2.2 mm

[0079] C=11.5-12 mm

[0080] D=12.0-12.9 mm

[0081] F=0.95-1.05 mm

[0082] The height of the tetralobes (E) was assumed to be 20 mm.

[0083] Geometric surface area of the bed: 431.6 m.sup.2/m.sup.3 (corresponds to 100%), height of the bed: 2 mm

[0084] Simulated pressure drop per meter: 4.24 Pa/m (corresponds to 100%)

Example 2 (According to the Invention)

[0085] Tetralobes having 5 through-passages as per FIGS. 2a, 2b, with the following dimensions:

[0086] A=3.2 mm

[0087] B=2.0 mm

[0088] C=13.0 mm

[0089] D=14.9 mm

[0090] F=2.0 mm

[0091] G=2.0 mm

[0092] H=1.0 mm

[0093] The height (E) of the tetralobes was assumed to be 20 mm.

[0094] Geometric surface area of the bed: 401.5 m.sup.2/m.sup.3 (corresponds to 93%), height of the bed: 2 mm

[0095] Simulated pressure drop per meter: 3.84 Pa/m (corresponds to 90.6%) as compared to example 1

[0096] Example 2 according to the invention displays a 9.4%-lower pressure drop at a 7%-smaller geometric surface area.

Example 3

[0097] Production of the Catalyst Composition

[0098] 0.8991 kg (30% by weight based on the mixture of the diatomaceous earths) of a diatomaceous earth of the type MN from EP Minerals, 1.4985 kg (50% by weight based on the mixture of the diatomaceous earths) of a diatomaceous earth of the type Masis from Diatomite SP CJSC and 0.5994 kg (20% by weight based on the mixture of diatomaceous earths) of a diatomaceous earth of the type Diatomite 1 from Mineral Resources Ltd are mixed for 30 minutes at 45 revolutions per minute in a drum hoop mixer (from Engelsmann, container volume 32 liters). The mixture of the diatomaceous earths is placed in a Mix-Muller (from Simpson, year of construction 2007, container volume 30 liters) and processed for 2 minutes at 33 revolutions per minute. A first solution consisting of 1.3706 kg of aqueous KOH solution (47.7% by weight) and 0.532 kg of ammonium polyvanadate (from Treibacher) is then added over a period of 2 minutes and the mixture is processed further for 1 minute. 2.1025 kg of 48 percent strength sulfuric acid is added over a period of 2 minutes and the mixture is processed for a further minute at 33 revolutions per minute. As next step, 0.3 kg of K.sub.2SO.sub.4 (from K+S Kali GmbH) is introduced into 1.587 kg of a 50 percent strength aqueous Cs.sub.2SO.sub.4 solution, introduced over a period of 2 minutes into the Mix-Muller and processed for 1 further minute at 33 revolutions per minute and 180 g of a starch solution (7.39% by weight of potato starch in DI water) are then added while continuing to process. The composition obtained is processed further at 33 revolutions per minute until the total processing time from introduction of the diatomaceous earth is 15 minutes altogether.

[0099] Production of the Shaped Catalyst Bodies

Example 4 (Comparative Example)

[0100] The geometry of the shaped body is determined by a die through which the composition to be extruded is conveyed under high pressure. The extruded shaped body had the geometry shown in FIG. 1, with the following dimensions:

[0101] A=3.2 mm

[0102] B=2.1 mm

[0103] C=11.5 mm

[0104] D=12.9 mm

[0105] F=0.95 mm

[0106] E=15-30 mm

[0107] A screw extruder with a screw is used here. The introduction of solids into the screw is effected from above. The extruder is cooled by means of water. The rotation speed of the transport screw in the extruder is 10 revolutions per minute. The temperature of the solid on introduction and of the shaped bodies on leaving the extruder is about 50 C. The throughput through one extruder is 6000 kg per day. Since, inter alia, the speed of transport of the extrudates is not constant, a uniform length is not obtained but instead a length distribution is obtained. Furthermore, the average length is dependent on the geometry of the die. The shaped bodies are subsequently dried at 120 C. for 2 hours and calcined at 475 C. for 3 hours. Oversize and undersize shaped bodies are removed by means of screening devices.

[0108] The lateral compressive strength was determined in accordance with DIN/ISO on the extruded shaped body, both for the still-moist shaped body immediately after extrusion and also after calcination. This was

[0109] after extrusion: 1.9 N (corresponds to 100%)

[0110] after calcination: 110 N (corresponds to 100%)

Example 5 (According to the Invention)

[0111] Example 4 was repeated. A die as per FIGS. 4a, 4b was used. The extruded shaped bodies had the geometry shown in FIG. 2a, with the following dimensions:

[0112] A=3.2 mm

[0113] B=2.0 mm

[0114] C=13.0 mm

[0115] D=14.9 mm

[0116] E=15-30 mm

[0117] F=2.0 mm

[0118] G=2.0 mm

[0119] The lateral compressive strength was likewise determined on the extruded shaped body both for the still-moist shaped body immediately after extrusion and also after calcination. This was

[0120] after extrusion: 2.7 N (corresponds to 142%)

[0121] after calcination: 143 N (corresponds to 130%)

Example 6

[0122] Tetralobes having 5 through-passages as per FIG. 3, with the following dimensions:

[0123] A=3.2 mm

[0124] B=1.5 mm

[0125] C=11.2 mm

[0126] D=12.9 mm

[0127] F=1.5 mm

[0128] G=1.5 mm

[0129] H=0.75 mm

[0130] The height (E) of the tetralobes was assumed to be 20 mm.

[0131] Geometric surface area of the bed: 453.6 m.sup.2/m.sup.3 (corresponds to 105%). Height of the bed: 2 mm

[0132] Simulated pressure drop per meter: 2.15 Pa/m (corresponds to 50.7% as compared to example 1)

[0133] Example 6 according to the invention displays a 49.3%-lower pressure drop at a 5%-higher geometric surface area.