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    © All Rights Reserved
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    5 views24 pages

    Untitled

    Uploaded by

    Oppi Mabela 1807110819

    Copyright:

    © All Rights Reserved
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    Office de la Propriéts Canadian CA 2345092 C 2009/0818 Intellectuelle Intellectual Property du Canada Office «nen 2 345 092 Un erganisme ‘An agency of BREVET CANADIEN (2) industie Canada Industry Canada " CANADIAN PATENT a (06) Date de dépdt PCTIPCT Filing Date; 1999/09/09 (51) Clint int. Cl. BO7J 10/00 (2006.01), (87) Date publication PCT/PCT Publication Date: 2000/03/30 ea eis abe DO CO a ses (2006.01) (72) Inventeurs/inventors: (45) Date de délvrance/issue Date: 2009/08/18 eters (05) Entrée phase nationale/National Entry: 2001/03/21 SCHUTTE, RUDIGER, DE (08)N° demande PCTIPCT Application No.: EP 1999/006626| (73) Proprétaire/Owner: (@7)N* publication PCTIPCT Publication No.: 2000/017098 EVONIK DEGUSSA GMBH, DE (20) Prionte/Priorty: 1998/0912 (DE198 43 573.8) (74) Agent: MARKS & CLERK (64) Titre : COLONNE A BULLES ET UTILISATION Y FAISANT APPEL (64) Title: BUBBLE COLUMN AND USE THEREOF (67) Abrége/Abstract: The invention relates to a bubble column with perforated bottoms. Said bubble column can be operated in a counter flow. The ‘space-time yield of gas-iquid reactions can be increased substantially when the perforated bottoms (5) have substantially the same + Ottawa-Hull KLA 0C9 + hutp:/cipo.ge.ca Canada CA 2345092 C 2009/0818 «nen 2 345 092 aye (67) Abrégé(suite)/Abstract(continued): distribution of holes, the cross sectional surfaces of the individual holes range from 0.003-3mm2, especially 0.01-0.5 mm2, the open surface of the bottoms amounts to 3-2 %, especially 3-10 % and the bubble column is provided with flow passages (6) for liquids between adjacent liquid areas, The bubble column can be used to perform gas-liquid reactions such as oxidation reactions with air, whereby preferably gas and liquid are conducted in a cocurrent flow through said bubble column. ‘ea 02945092 2001-03-21 ABSTRACT The invention relates to a bubble column with perforated bottoms. Said bubble column can be operated in a counter flow. The space-time yield of gas-liquid reactions ‘can be increased substantially when the perforated bottoms (5) have substantially the same distribution of holes, the cross sectional surfaces of the individual holes range from 0.003-3mm2, especially 0.01-0.5 mm2, the open surface of the bottoms amounts to 3-2 %, especially 3-10 % and the bubble column is provided with flow passages (6) for liquids between adjacent liquid areas. The bubble column can be used to perform gas- liquid reactions such as oxidation reactions with air, whereby preferably gas and liquid are conducted in a cocurrent flow through said bubble column. tw 5 25 30 35 ca 02345092 2009-05-06 Bubble column and use thereof bubble column which can be counter-current flow, comprising horizontally erforated trays in its middle part and to the use thereof for carrying cut gas-liquid reactions. one wards the oxidation stage of special use is oriented ¢: or the production of hydrogen the anthraquinone proces peroxide. in the s vessi mn n form cf bubbles comes intc contact with a liquid, wher erred from one phase into the ubstance. are mostiy tran other chase. Accordingiy, bubble columns are also used for chemical reactions between components in a liquid phase 2nd components gaseous phase. In order to y mass transfer between the phases and to reduce intens rality of perforated trays effects, back-mixil dispesed one above another can also be used in bubble Pp columns (Ullmann's Encyclopedia of Industrial Chemistry Sth Ed. (1992), Vol. 24, 276-278). large-scale industrial bubble The perforated trays of columns, namely those with a diameter of at least 1 m, are usually sieve plates with a hole diameter between 2 and 5 mm or dual flow trays with a hole diameter of up to 20 mm. Grids with a thin layer of customary packing material situated thereon are also used instead of sieve plates. The space-time yield of gas-liquid reactions is strongly dependent on the gas content in the gas-liquid mixture flowing through the column. When employing bubble columns with the 2forementioned sieve plates, it has not 10 ny ao 30 35 ‘ea 02945092 2001-03-21 WO 00/17908 PCT/EP99/06626 proved possible to increase the gas content above certain iting values, and the space-time yield has thereby been limited. Therefore, there has been no lack of ns aimed at reasing the space-time yield other b ° components and/or by means of special injection means for the gas. However, the construction of bubble columns is made considerably more an indust 1 scale by the use of the other componen x instance static toned above, DE 694 03 618 T2, which is a translation of EP 0 659 474 Bl, teaches at a method of for bringing a gas stream into tact with a uid phase and an apparatus therefor. @ appar: comprises a column with perforated sieve re total surface area of the perforations ‘ays, wherein is between one 1/40 and 1/300 of the cross-section which is available for perforations. The height of the liquid layer which is retained on the eve trays and which is lls sted by means of weirs for ample, preferably he range from 200 to 600 mm. The cross-sectional area of the individual perforations falls within the range from 0.5 to 3.5 mm. AT-PS 236 346 teaches special, perforated trays for columns such as those which are used for distillation and absorption processes. In addition to vertical apertures, the trays additionally contain a small number of apertures with walls which are inclined at a slant to the main face. The cross-sectional area of the apertures is a given as 0.155 to 31.7 mm’, and the surface area is 0.363 mm, for example. In operation, a liquid flows over the trays. This document does not teach that the column is operated as a bubble column. 16 30 35 ‘ea 02945092 2001-03-21 _3VO 0017908 PCT/EP99/06626 ~ DE-AS 10 28 096 teaches a method for the continuous reaction of finely distributed solids with liquids and/or gases. A column is used which is sperated in co-current , which is completely filled with liquid and which comprises sieve trays, the holes in which have é diameter an 1mm. A gas cushion inhibits the passage of quid. The column does not a comprise devices for operation in counter-current flow. The pubbie column cascade reactor according to 25-0 21 737 is substantially equivalenc to the reactor jowledged above. The tctal free hole area is preferably less than 5 % of the reactor cross-section, and thers che hole diameters which are quoted in the 0.78 to 12.56 mm). This document examples are 2 or 4 mm does not sention counter-current operation and devices erefor. One large-scale industrial process based on a gas-liquid reaction is the oxidation stage in the anthraquinone process (30 process) for @ production of hydrogen gercxide. As is known, this process comprises a aydrogen. age and an extraction nm stage, an oxidation s stage - a review is given in Ullmann’s Encyclopedia of + (1988), Vol. A13, 447-457. In the hydrogenation stage, a reaction medium which is Industrial Chemistry 5th E based on one or more 2-alkylanthraquinones and/or tetrahydro derivatives thereof, and which is dissolved in a solvent system, is partially hydrogenated to form the corresponding hydroquinones, and in the oxidation stage the hydroquinones contained in the hydrogenated working solution are re-oxidised to quinones by a gas containing 02, generally air, with the formation of hydrogen peroxide. The reaction in the oxidation stage should be as quantitative as possible with the avoidance of decomposition reactions of components of the working 10 20 30 35 ‘ea 02945092 2001-03-21 VO 00/17908 PCT/EP99/0626 4 should consume as on. Moreover, i ttle energy as possible and it should be capable of being conducted with igh space-time yield. ation is first conducted in AO process, oxii cation towers disposed in series, using fresh air each case. This is both costly on an industrial scale and relatively uneconomic. According to US Patent Specification 3,073,680, the rate of oxidation can in act be increased by maintaining defined bubble sizes vhich can be obtained by means of fine-pored gas such as = $, and by maintaining defined conditions of cross-sectional loading. However, the separation of the resulting foam gas-liquid phase separation. Recording to German Patent Specification 20 03 268, the rementioned problems associated with the AO process can be solved by means of an oxidation column which is subdivided into two to six sections. In each section of s column, the working solution and the oxidising gas are passed from the bottom to the top in co-current flow, but in the column as a whole the gas and the liquid move in countercurrent flow in relation to each other. In order to achieve intimate mixing, the individual sections contain suitable built-in components such as sieve plates or meshes, or are packed with packing elements. As an attempt to reduce the pressure drop in the aforementioned cascade-type arrangement of columns, European Patent Specification 0 221 931 proposes that oxidation be conducted in a tubular co-current reactor, which contains no built-in components apart from a special gas distributor element. This gas distributor element results in the formation, from the working solution and the oxidising gas, of a system in which 10 20 25 30 35 ca 02345092 2008-08-11 bubbles are inhibited from coalescing and which has a high gas content. If the gas content is too high and/or if the gas bubbles are particularily small, problems can gas-liguid separation. It has been shown in at the specific reactor volume to be gasified {in m per tonne H02) i quite large, which results in a reduced space-time yield and also results in a high hold- up of costly working solution. The object of t e present invention is to provide a bubble column comprising perforated trays and which can be operated in counter-current flow,with which gas-liquid reactions can be conducted with a higher space-time yield than when using columns comprising customary sieve plates. bu e column should be of simple construct n. further object is oriented towards the ase of the bubble column in the oxidation stage of the AO process for the production of hydrogen peroxide, wherein the conversion is improved compared with known processes, the space-time yield with respect to the reactor volume and the volume > working solution is improved, and the formation of a gas-liquid mixture which is difficult to separate is avoided. This object is achieved by a bubble column comprising a columnar vessel (1) having a bottom (3), middle (2) and top part (4), one or more perforated trays (5) horizontaily disposed in the middle part, and devices for feeding and discharging a liquid phase (9 and 10) and a gas phase (11 and 12) in order to operate the bubble column in co-current flow or counterflow, which is characterised in that the perforated trays (5) have a substantially uniform distribution of holes over the cross-section of the column, the cross-sectional area of the individual holes is 0.003 to 3 mm’, and the open area of the trays is 2 to 20 %. The subsidiary claims are 10 35 ‘ea 02945092 2001-03-21 Wo 00/17908 PCT/EP99/06626 oriente towards preferred embodiments of the bubble column. Compared with bubble columns comprising conventional eve plates, the bubble columns according to the invention are character by trays with fine holes or fine slits. The rably contain holes with a Ol to 1 mm’, particularly 0.05 to 0.5 mm’, the open area preferably falls within the range from 3 to 15 %, particularly 2 to 10 %, most preferably the holes is arbitrary, but the holes are usually round, triangular to semi- elliptical, or slit-shaped construction. The trays comprising fine holes or fine slits can be constructed as complete column trays, but usually consist of a supporting grid and of a plate which is fixed thereon, which comprises fine holes or fine slits and which is of the desired plate thickness and degree of perforation. Plates of this type compri sing fine holes or slits are in fact used n sieving and filtration technology and as fluidising bases in fluidised bed technology. Their use as trays in bubble columns has never been considered previously, however. As determined by their manufacture, the holes in the plates are preferably of tapered construction in the direction of passage of the gas and/or the holes are inclined in addition for the purpose of achieving a directed flow during the passage of the gas. A directed flow can additionally be effected by the scale which is formed on the surface of the plate due to the manufacture thereof. The bubble column is divided by the finely perforated trays into a plurality of zones, which in the operating state in the middle part of the bubble column, with the 8 25 30 35 ‘ea 02945092 2001-03-21 WO 00/17908 PCT/EP99/06626 7 exception of a thin gas cushion, are completely filled with liquid or with the liquid-gas mixture. So that operation without problems can be ensured when using counter-current flow, the bubble column comprises, on each tray, at least one tubular or well-shaped liquid passageway (6), termed a downcomer, between adjacent zones. These passageways, which advantageously begin directly on the tray, and which therefore make a weir unnecessary, dip into the liquid in the zone below the respective tray or are connected thereto. They are designed so that no gas flows through them in the opera state. This is achieved, for example, py arranging for the downcomers to ce in the form of round pipes or segmenc-shaped wells which are disposed on the perforated tray, and for @ corresponding free cross- secticn =Hereof lead into an immersion pocket. Alternatively, external pipes which each connect two adjacent zones can also be used. The bubbie column is usually constructed so that it can be operated in counter-current flow, wherein a liquid is fed in at the top and a gas is fed in at the bottom. In the presence of @ device (6)for the passage of liquid, the bubble column can also be operated in co-current flow, wherein the liquid-gas mixture flows from the bottom te the tes. The tray spacing in the bubble column according to the invention depends on the specific application and on the diameter-to-height ratio of the bubble column. In general, the tray spacing falls within the range from 0.1 to 10 times, particularly 0.5 to 5 times, the tray diameter. In large-scale industrial bubble columns, such as those which are employed in the use according to the invention for the production of hydrogen peroxide for example, the tray spacing of the trays comprising fine 25 30 35 ‘ea 02945092 2001-03-21 WO 00/17908 PCT/EP99/06626 holes or fine slits advantageously falls within the range rom 0.5 times to twice the tray diameter. Apart from said ys, which for operation in countercurrent flow are advantageously each equipped with at least one tubuiar or well-like liquid passage, the middle part of the column can be free from built-in components. According to one preferred embodiment, however, it is also possible for heat exchangers to be disposed bet! ween individual trays. These are advantageously plate heat exchangers comprising vertically placed plates. Bubble columns of this type, which are equipped with trays comprising fine holes and with heet exchangers, can be used particularly advantageously Zor carrying out gas-liquid reactions for h the enthalpy of reaction is high. The bubble columns according to the invention can be equipped in the manner familiar to one skilled in the art for operation in co-current or countercurrent flow, preferably in countercurrent flow. A cascade-like arrangement is also possible. the As can be seen from the examples according to invention and from the comparative examples, extraord nary, unforeseeable advantages are achieved due to the design according to the invention comprising perforated trays in the bubble column: * gasifica on of a liquid situated above the plates comprising fine holes or slits is extremely uniform; © small bubbles with a narrow range of diameters are produced uniformly over the entire cross-section of the bubble column; 20 25 30 35 ‘ea 02945092 2001-03-21 WO 00/17908 PCT/EP99/06626— 9 the efficiency of the intensive mass transfer which is due to the trays enables the specific gasification volume effective reactor volume) to be reduced compared with bubble columns comprising sieve plates; the gas content of the gas-liquid mixture which can be attained in practice is significantly greater than the gas contents which can ce obtained when using onal sieve plates and conver other gasification technicues, without this resulting in problems in gas- ° liguid phase separati the mass transfer area, and the extent of mass transfer which is achieved therewith, is very high; compared with conventional columns, the hold-up of the liguid chase is significantly reduced; in particular, this is a considerable advantage if the liguid phase is mult: re, for instance the component mixt! working solution of the AO process: a higher reaction conversion is achieved per m of reactor volume compared with competing processes; a higher reaction conversion is achieved per m? of liquid phase (e.g. the vorking solution in the AO process); the pressure drop across the trays is about 300 to 500 Pa (3-5 mbar) per tray, and is therefore low compared with the hydrostatic pressure drop in the column; a gas cushion with a depth of only 1 to 5 cm is formed under the trays, so that practically the complete apparatus volume the middle part of the column) can be utilised for the reaction. 20 25 30 35 ca 02345092 2008-08-11 10 The Figure is a diagram of a preferred bubble column 1 according to the invention, which is particularly suitable for coun’ rcurrent flow operation and which in its middle part 2 contains three heat exchangers 16 in addition to six trays comprising fine holes 5. Apart from the gasified ddle part 2, the column comprises a bottom part 3 with a cap-shaped gas distributor device 8 and a top part 4 with a device 7 for distributing the liquid phase and a gas- liquid separation device 13 connected to 14. A well-shaped element 6 in the shape of a segment for the passage of liquid is disposed on each finely perforated tray in the zone below the tray. The liquid phase is supplied via line 9 at the top of the column and is discharged via line 10 at the bottom part. The gas is supplied via line 11 to the gas distributor device 8, from which fine gas bubbles emerge. After passing through the column, the gas is separated from the liquid phase in the gas separation device, which is schematically illustrated as a centrifugal separator here, and is discharged as an off- gas via line 12. It is possible to check whether foam has been formed in the region of the column top by means of the sight glasses 15. The flow and return lines 17; 18 of each heat exchanger supply the heat exchanger with a heat transfer medium. The bottom and top parts of the bubble column can be designed in any desired manner. In particular, customary units can be incorporated for supplying a gas and a liquid and for phase separation. The bubble column according to the invention can be used for carrying out reactions between a component of a gas phase and a component of a liquid phase. Gas-liquid reactions such as these can comprise oxidation, reduc n, addition or neutralisation reactions, for 10 20 25 30 35 ‘ea 02945092 2001-03-21 wo 00/17908 PCT/EP99/06626 YW example, vherei: he liquid phase can be aqueous or organic. During the reaction, the two phases can be brought into centact with each cther in co-current flow or in countercurrent flow, preferably in countercurrent flow, in che bussie column. At the same time, a plurality of bubble columns can be connected in series in the form of a cascade. Aeart from one cr more reaction components, the liquid phase can additiona y contain a catalyst in dissolved or suspended form. When substances are suspended in the liquid phase, their particle diameters must be significantly smaller than the diameter of the holes in che t comprising fine holes or fine slits. Accerding <0 o1 preferred use, the bubble column according

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