FLUIDIZED-BED REACTION APPARATUS AND A FLUIDIZING BED REACTION PROCESS USING THE SAME

Abstract: A fluidized-bed reaction apparatus comprising: a perforated plate (3), located in the lower portion of a fluidized-bed reaction tower (1) on which can be formed a fluidized-bed (2) of particles, a gas inlet (5), located below said perforated plate (3), for the supply of heating fluidizing gas, a particle inlet (7), located above said fluidized bed (2), a particle outlet (6) located above said perforated plate (3) and a gas outlet (9) located adjacent the top of said fluidized bed reaction tower (1). At least an outer peripheral portion (B) of said perforated plate (3) has a larger proportional open area than the average proportional open area of the whole plate, the ratio of the area of the portion of the plate having said larger proportional open area to the area of the remainder of the plate being between 1:2 and 1:15, and the average proportional open area of said portion being between 2 and 8 times the average proportional open area of the remainder of said perforated plate.

Description: The present invention relates to fluidized-bed reaction apparatus. There have been the following problems in the treatment accompanying heat generation in fluidized-beds of fluidized-bed reaction towers. In granulation and oxidative ifusibilization of a petroleum pitch, for example, a process of subjecting granulated pitch (pitch particles) to oxidative infusibilization when fluidized by air at a high temperature has been generally employed. However, since an excessive amount of air is required for removing the large quantity of heat generated by the oxidation, if only the fluidizing air is used, even though the fluidized-bed is an excellent apparatus in view its heat-utilizing efficiency because of the low circulating speed of the particles, it can not be said to be ideal. Also, there is a similar problem in endothermic reactions. Further, although disposal of a heat-removing device such as cooling pipes, etc. inside of the fluidized-bed may be considered, such a method is not preferable because the cooling pipes hinder the fluidization of granulated particles thereby causing local heat generation and uncontrollable exothermic reactions. Since a sufficient amount of oxidizing air for forming the fluidized-bed is supplied from a perforated plate, as the size of the apparatus increases, if the movement of the particles slows down the amount of heat generated becomes greater than the amount of heat removed causing rapid reaction. In order to make the movements of the particles vigorous the flow rate of the fluidizing gas should be raised, however in a large scale apparatus, since the height of the fluidized-bed is increased in view of the processing efficiency, the fluidizing gas forms huge gas bubbles which burst in the upper portion of the fluidized-bed, thereby causing remarkable scattering of the particles. Further, the removal of heat by cooling pipes, etc. does not have a rapid response, making it difficult to control the temperature in the case of exothermic reactions such as oxidation which are highly temperature-dependent. The present inventors have applied a method of water-spraying onto the fluidized-bed in the fluidized-bed reaction apparatus, in order to rapidly remove the heat of oxidation in the oxidative infusion reaction for granulated pitch, but it takes a relatively long time for the particles cooled in the upper portion to flow downwardly to near the perforated plate in a large-scale fluidized-bed. This tends to form a temperature differential in the fluidized-bed. A vicious circle is started in which, if a temperature differential is formed, the temperature rises more at places where the temperature is higher. Further, in conventional gas-solid type reaction apparatus, a method of recovering pulverized and scattered particles by a cyclone and returning them to the fluidized-bed only for the purpose of reacting the fluidized particles with gases has been employed. Improvements of this technique have usually been directed towards increasing the superficial gas velocity but no substantial study has been made of moderation of the movement of particles by lowering the superficial gas velocity as far as possible to obtain, from the fluidized bed, products with no pulverized particles. JP-A-(UM) 53-102138 shows fluidized bed apparatus with nozzles extending through a bottom plate. A majority of them are beneath an annular plate provided to circulate the flow. US-A-4425303 shows fluidized bed apparatus with variations in porosity across the width of the plate, but with baffles and deflectors to assist circulation. GB-A-1463377 is concerned with a process for oxidizing coal. According to the present invention there is provided a fluidized-bed reaction apparatus comprising: a perforated plate located in the lower portion of a fluidized-bed reaction tower on which can be formed a fluidized-bed of particles, a gas inlet located below said perforated plate for supply of heating fluidizing gas, a particle inlet located above said fluidized bed a particle outlet located above said perforated plate and a gas outlet located adjacent the top of said fluidized bed reaction tower characterised in that, at least an outer peripheral portion (B) and a geometrical central portion (C) of said perforated plate have respectively a larger proportional open area than the average proportional open area of the whole plate, the ratio of the sum of the areas of the portions of the plate having said larger proportional open area to the area of the remainder (A) of the plate being between 1:2 and 1:15, and the average proportional open area of said portions (B,C) being between 2 and 8 times the average proportional open area of the said remainder (A) of said perforated plate. There is further provided a fluidizing bed reaction process comprising introducing heating-fluidizing gas of a temperature required for the reaction to a fluidized-bed reaction apparatus comprising: a perforated plate located in the lower portion of a fluidized-bed reaction tower on which can be formed a fluidized-bed of particles, a gas inlet located below said perforated plate for the supply of heating fluidizing gas, a particle inlet located above said fluidized bed a particle outlet located above said perforated plate and a gas outlet located adjacent the top of said fluidized bed reaction tower characterised in that, at least an outer peripheral portion (B) and a geometrical central portion (C) of said perforated plate have respectively a larger proportional open area than the average proportional open area of the whole plate, the ratio of the sum of the areas of the portions of the plate having said larger proportional open area to the area of the remainder of the plate being between 1:2 and 1:15, and the average proportional open area of said portions (B,C) being between 2 and 8 times the average proportional open area of the remainder (A) of said perforated plate so as to satisfy the following formulae (I) and (II): 1.2 < (U OA /U mf ) < 2.5 (I) (U OB -U mf )/(U OA - U mf ) > 5 (II) wherein U mf represents the minimum fluidizing velocity, U OB represents an average superficial velocity of gas in each of the portions having said larger proportional area, and U OA represents an average superficial velocity of gas in the portion having proportional open area no greater than the average. The invention will be better understood from the following description which is given by way of example, with reference to the accompanying drawings in which: Figure 1 is a schematic view of a fluidized-bed reaction apparatus similar to that of the present invention and of assistance in understanding the invention; Figures 2a and 2b are views showing states of a fluidized-bed useful in understanding the present invention; Figures 3a and 3b are views showing states of a known fluidized-bed and Figure 4 is a view of a perforated plate for use in a fluidized-bed reaction apparatus as described above and which is according to the present invention. The fluidized-bed reaction tower 1 shown in Figure 1 is similar to apparatus according to the present invention, but differs in that only a peripheral area has a larger opening ratio. It has a perforated plate 3 located at its lower portion on which a fluidized-bed 2 is formed. The perforated plate 3 has regions of different opening ratio (proportional open area). An outer peripheral portion B of the perforated plate 3 has a larger opening ratio (proportional open area) than the average opening ratio of the perforated plate 3. The ratio of the area of the portion having the larger opening ratio to the area of the portion having an opening ratio not more than the average is from 1:15 to 1:2, preferably from 1:10 to 1:3. For example, the ratio of the area of the outer peripheral portion B to the area of an inner portion A is 1:15 to 1:2, preferably 1:10 to 1:3. The average opening ratio of the portion having the larger opening ratio than the average opening ratio is from 2 to 8 times, preferably from 3 to 6 times larger than the average opening ratio of the portion having the opening ratio not more than the average of the whole plate. The opening ratio, or proportional open area, mentioned herein, is the ratio of the open area to the closed area of the surface at the perforated plate 3, the areas of the portions of the perforated plate referred to herein include the area of the openings of the portion of the plate and the peripheral portion is a portion arranged on the periphery of the plate. An outlet 4 of the drain is located at the bottom of the fluidized-bed reaction tower 1, while an inlet 5 of the heating-fluidizing gas is located below the perforated plate 3. An outlet 6 of the particle is located above the perforated plate 3 and in the lower portion of the fluidized-bed 2. Further, an inlet 7 of the particle receiving the reaction in the fluidized-bed 2 is located in the upper portion of the fluidized-bed reaction tower 1 and above the fluidized-bed 2, and a spray nozzle 8 of the cooling water is located at the top of the fluidized-bed reaction tower 1 and above the fluidized-bed 2. An outlet 9 of discharge gas is located at the top of the fluidized-bed reaction tower 1. The outlet 4 of the drain and the spray nozzle 8 of the cooling water are not necessary in the case where the particles receiving the reaction are only subject to endothermic reaction and as will be seen from the later-mentioned, in the case where the removal of the generated heat is possible only by the heating-fluidizing gas due to increase of circulation velocity according to the present invention. For observing the movement of particles and the gas bubbles in the fluidized-bed 2 of the reaction tower 1 shown in Figure 1, each of the perforated plate 3 and the conventional perforated plate 12 is provided on the lower portion of a Semi=circular cylinder (1 m diameter) to which a transparent vinyl chloride plate is fixed, spherical activated carbon particles are charged and air is introduced from the bottom, respectively. Then, the result for the observation of the fluidized state in the respective cases are shown in Figure 2 and Figure 3. Figures 2a and 2b are views showing the fluidized state when using the perforated plate of Figure 1 whereas Figures 3a and 3b are views showing the fluidized state when using the conventional perforated plate. In Figures 3a and 3b, the average grain size of the activated carbon particles used is 600 µm, the minimum fluidizing velocity (U mf ) is 11 cm/S, the height of the stationary bed is 900 mm, the opening ratio of the perforated plate is about 0.8 % and the average superficial gas velocity (U O ) was 15 ∼ 25 cm/s. Figure 3a is a front view and Figure 3b is a cross sectional view taken along line II-II in the upper portion of the fluidized-bed. As the superficial gas velocity is increased, the gas bubbles 14 grow larger and particles are sprung up violently. In the fluidized-bed, there are portions where particles move up and down and portions where they flow downwardly as shown by the arrow, and the portion where they move up and down moves with time. This phenomenon is explained as follows. If gases pass uniformly from each of the points (perforate) on the perforated plate, gas bubbles gather toward the center as is shown in Figure 3a, thereby forming the downward stream for a portion of particles near the wall in the upper portion, whereas the gas bubbles uprise at random and accordingly, the downward flow of the particles is hindered and some amounts of particles go up and down repeatedly in the middle portion of the fluidized-bed. On the other hand, Figure 2a, shows the front view of the fluidized-bed reaction tower 1 with the perforated plate of Figure 1 and Figure 2b is a cross sectional view take along line I-I in the upper portion of the fluidized-bed thereof. By using a perforated plate capable of satisfying the condition that the ratio of an average opening ratio of the peripheral portion of the perforated plate is 2 to 8 times, preferably 3 to 6 times larger than an average opening ratio of the other portion (hereinafter referred to as "internal portion") and the ratio of the area of the peripheral portion of the perforated plate to the area of the internal portion of the perforated plate is 1 : 15 to 1 : 2, preferably 1 : 10 to 1 : 3, constant downward flow of the particles as shown by the arrow in Figure 2a can be obtained even if the average superficial gas velocity U OA of the gas passing through the internal portion of the perforated plate, on the internal portion thereof is as low as 1.2 ∼ 2.5 times of the minimum fluidizing velocity U mf . When such a perforated plate according to Figure 1 is used, since a great amount of gas flows from the vicinity of the wall as shown in Figure 2a, the gas bubbles rise nearer to the wall as compared with the case in Figure 3a, although it somewhat directs to the central part, and the gas bubbles reach the top of the fluidized-bed. Accordingly, gas bubbles are not burst near the central part and the particles are always drawn downwardly along the direction of arrows and then, rise together with the gas bubbles as shown in Figures 2a and 2b. Moreover, by deciding the average superficial gas velocity U OB passing through the peripheral portion of the perforated plate, on the peripheral portion thereof so as to satisfy the following formula: (U OB - U mf )/(U OA - U mf ) > 5 it is possible to raise the circulation velocity of the particles and to attain the treatment of the fluidized-bed which makes the temperature control easy. In the formula, U mf represents a value naturally given in the case of deciding the particles which receive the reaction in the fluidized-bed, the temperature in the fluidized-bed and the pressure in the fluidized-bed, and U OA is limited to 1.2 to 2.5 times of U mf as described before. Moreover, since the ratio of the area of the peripheral portion to the area of the internal portion is limited to 1 : 15 to 1 : 2, the upper limit of U OB is naturally limited. U OA and U OB can be obtained from the average superficial gas velocity in the whole of the fluidized-bed U O , the area ratio of each portion of the perforated plate and the opening ratio of the holes. Hereupon, in the case where the height of the fluidized-bed is small as compared with the internal diameter of the fluidized-bed, since a portion which prevents the circulation of the particles is formed on the geometrical center portion of the perforated plate, it is necessary to make the average opening ratio of the geometrical center portion larger than that of the internal portion in order to circulate the particles at a high speed (refer to Figure 4). In such a case, and according to the present invention, the average opening ratio of the geometrical center portion and the peripheral portion of the perforated plate is larger than the average opening ratio of the internal portion, namely, the ratio of the average opening ratio of the geometrical center portion and the peripheral portion to the average opening ratio of the internal portion is 2 : 1 to 8 : 1, preferably 3 : 1 to 6 : 1, and the ratio of the sum of the area of the peripheral portion and the area of the geometrical center portion to the area of the internal portion is made to be 1 : 15 to 1 : 2, preferably 1 : 10 to 1 : 3. Hereupon, the geometrical center portion means the part including the geometrical center of the surface of the side forming fluidized-bed and has the larger opening ratio than the average opening ratio. The ratio of the area of the peripheral portion to the area of the geometrical center portion is preferably 5 : 1 to 15 : 1. In the case where the height of the fluidized-bed is smaller as compared to the internal diameter of the fluidized-bed, the part which prevents the circulation of the particles occurs in one or multiple number of regions of the perforated plate between the geometrical center portion and the peripheral portion other than the geometrical center portion. In such a case, it is necessary to make the opening ratio of those portions larger than the average opening ratio of the perforated plate. On such occasion, the ratio of the area of the portions having the larger opening ratio than the average opening ratio to the area of the portion having the opening ratio not more than the average opening ratio is 1 : 15 to 1 : 2, preferably 1 : 10 to 1 : 3, and an average opening ratio of the portions having the larger opening ratio than the average opening ratio of the perforate plate is 2 to 8 times, preferably 3 to 6 times larger than an average opening ratio of the portion having the opening ratio not more than the average opening ratio of the perforated plate. Also in the case of using the perforated plate which has the portion having such a large opening ratio in the geometrical center portion as the peripheral portion and, according to circumstances, in other portion than the peripheral portion and the geometrical center portion, the following formulae concerning U OA and U OB should be satisfied. U OA /U mf = 1.2 to 2.5 (U OB - U mf )/(U OA - U mf ) > 5 As a matter of course, in this case, U OB is the average superficial velocity of a gas on the portion having the larger opening ratio than the average opening ratio of the perforated plate in which the gas passes through the portion having the large opening ratio and U OA is the average superficial velocity of the gas on the portion having the opening ratio not more than the average opening ratio of the perforated plate in which the gas passes through the portion having the opening ratio not more than the average opening ratio. As the reaction to which the fluidized-bed reaction apparatus and the reaction process in fluidized-bed according to the present invention is applied, any reaction can be exemplified in the case where the reaction is exothermic or endothermic, however, the present invention is effective in the case of exothermic reactions, particularly in the case of oxidation reaction because of the fear of runaway reaction. As the solid material (particles) which receives the reaction, materials in a wide range from the material having a high melting point such as inorganic materials, for instance, zeolite, zirconia and the like to the material having a low melting point such as petroleum pitch beads, chitin and collagen are used. Further, as the heating fluidizing gas, air, steam, gaseous nitrogen, combustion gas, etc. may be exemplified. The temperature of the heating fluidizing gas may be the temperature necessary for the reaction, and although the temperature differs due to the solid-gas reaction system, for instance, in the case when petroleum pitch beads (i.e. spherical pitch beads of an average particle diameter of 250 to 800 µm) are subjected to oxidative infusibilization, air at 130 to 150°C is suitably used. According to the present invention, even in the case of using a small average superficial gas velocity, it is possible to obtain the reaction process in fluidized-bed and the fluidized-bed reaction apparatus capable of preventing the pulverization and/or entrainment of the particles, and increasing the circulation velocity of the particles. Moreover, the temperature control of the apparatus according to the present invention is easy and the apparatus can be automatically operated while following the established temperature profile. Apparatus according to the present invention, and apparatus having the same but not all features of the invention, will be described more specifically referring to the examples. Example 1 Oxidative infusibilization was conducted for petroleum pitch beads (spherical pitch beads) with the average particle size of 470 µm in the fluidized-bed reaction apparatus shown in Figure 1 having the fluidized-bed of 1200 mm inner diameter and the stationary layer height of about 1000 mm. The perforated plate had an opening ratio of 1.77 % in the outer peripheral portion of 60 mm width (portion B) and had an opening ratio of 0.44 % in the internal portion of 1080 mm diameter (portion A) (the average opening ratio for the entire portion of the perforated plate was 0.69 %). Further, the pore size was 1.5 mm. Five thermocouples 11 were set in the fluidized-bed as shown in Figure 1. The temperature in the fluidized-bed was controlled by an automatic temperature controller and was elevated from 120°C to 300°C at the rate of 0.3°C/min. The elevating of the temperature was carried out by the heated air at 150°C. Since the temperature elevating rate in the fluidized-bed became higher than the predetermined rate from about 150°C due to the oxidizing heat-generation, water spray was conducted for temperature control so that the rate matched with the temperature profile. A thermocouple (a) was set at the central portion above the perforated plate at a distance of 1000 mm therefrom, a thermocouple (b) was set at the central portion above the perforated plate at a distance of 50 mm therefrom, a thermocouple (c) was set at a position 50 mm above the perforated plate and apart by 200 mm from the wall, a thermocouple (d) was set just above the thermocouple (c) and aparted by 1000 mm from the perforated plate, and a thermocouple (e) was set within the same level as the thermocouple (c) and at a position deviated with 90° by the angle of center and above the perforated plate apart by 50 mm therefrom. The thermocouples (a) - (e) were connected with a pen-writing recorder for continuously recording the temperature at each of the positions. As a result, the temperature at the position of the thermocouples (a) and (d) was lowered substantially simultaneously with the water spray, while the temperature at the position of the thermocouple (b) was lowered 1.5 - 3 sec thereafter, and the temperature at the positions of the thermocouples (c) and (e) caused temperature change 2 - 4 sec thereafter. The temperatures at the positions of the thermocouples (a) - (b) were substantially identical within five sec after stopping the spray. Since U mf of the pitch beads was set to 7.0 cm/s, and the average superficial gas velocity U O over the entire fluidized-bed was set to 21.0 - 25.0 cm/s, U OA was from 13.4 to 16.0 cm/s and U OB was from 53.6 to 63.8 cm/s, while (U OA /U mf ) = 1.9 ∼ 2.3 and (U OB - U mf )/(U OA - U mf ) = 6.3 ∼ 7.3. It was possible for automatic operation in accordance with the temperature profile set under the conditions and, further, fluidized-bed reaction could be conducted with small amount of particle pulverization and scattering. Comparative Example In the same device as in Example 1 except for changing the perforated plate with a perforated plate of a uniform pore distribution having an opening ratio of 0.69% reaction was conducted under the same temperature profile as in Example 1 with the average superficial gas velocity U O in the fluidized-bed of from 21 to 25 cm/s. Particles of substantially the same particle size were used. As a result, there was often found a difference from 3 to 15 sec between the fall of the temperature at the positions of the thermocouples (a) and (d) and the fall of the temperature at the positions of the thermocouples (b), (c) and (e) after water spraying although U O /U mf = 3 ∼ 3.6, which sometimes showed a delay of greater than 30 sec and no stationary circulation of particles was obtained. When the oxidative infusibilization was conducted under this state, since the temperature at the point (e) was made higher by greater than 5°C than the temperature at the measuring-end point of the temperature controller and the difference of the temperature tended to be greater, the amount of water spray was manually increased and U O was also increased temporarily to 30 cm/s to unify the internal temperature of the fluidized-bed. The operation had to be conducted 4 times till the completion of the reaction. Example 2 Oxidative infusibilization for petroleum pitch beads (spherical pitch beads) was conducted by disposing a perforated plate having an outer peripheral portion (portion B) of 60 mm width with a central portion (portion C) of 300 mm diameter shown in Figure 4 to the fluidized-bed of 2700 mm diameter. The ratio between the area in the portion A and the sum of the area of the portion (B) and the portion (C) was about 9 : 1, and the ratio of the opening ratio of the portion (A) to each of the opening ratio of the portion (B) and the opening ratio of the portion (C) was set to 1 : 4. Reaction was conducted for the particles with the average particle size of 600 µm, U mf = 11 cm/s at the average superficial gas velocity U O over the entire fluidized-bed = 20 ∼ 25 cm/s and automatic operation was conducted in accordance with the temperature profile set to 8 hours from 150°C to 300°C. Under this condition, U OA /U mf = 1.4 ∼ 1.7 ; (U OB - U mf )/(U OA - U mf ) = 8.1 ∼ 11.8. There was rare pulverization and/or scattering of the particles.

Claims: A fluidized-bed reaction apparatus comprising: a perforated plate (3), located in the lower portion of a fluidized-bed reaction tower (1) on which can be formed a fluidized-bed (2) of particles, a gas inlet (5), located below said perforated plate (3), for supply of heating fluidizing gas, a particle inlet (7), located above said fluidized bed (2), a particle outlet (6) located above said perforated plate (3) and a gas outlet (9) located adjacent the top of said fluidized bed reaction tower (1), characterised in that, at least an outer peripheral portion (B) and a geometrical central portion (C) of said perforated plate have respectively a larger proportional open area than the average proportional open area of the whole plate, the ratio of the sum of the areas of the portions of the plate having said larger proportional open area to the area of the remainder (A) of the plate being between 1:2 and 1:15, and the average proportional open area of said portions (B,C) being between 2 and 8 times the average proportional open area of the said remainder (A) said perforated plate. A fluidized-bed reaction apparatus according to claim 1, wherein the ratio of the area of the peripheral portion (B) of said perforated plate to the area of the geometrical central portion (C) thereof is from 5:1 to 15:1. Apparatus according to claim 1, or 2 including a spray nozzle (8) for cooling liquid in the upper part of the tower, and an outlet drain (4) below the perforated plate. A fluidizing bed reaction process, comprising introducing heating-fluidizing gas of a temperature required for the reaction to a fluidized-bed reaction apparatus comprising: a perforated plate (3), located in the lower portion of a fluidized-bed reaction tower (1) on which can be formed a fluidized-bed (2) of particles, a gas inlet (5), located below said perforated plate (3), for the supply of heating fluidizing gas, a particle inlet (7), located above said fluidized bed (2), a particle outlet (6) located above said perforated plate (3) and a gas outlet (9) located adjacent the top of said fluidized bed reaction tower (1), characterised in that, at least an outer peripheral portion (B) and a geometrical central portion (C) of said perforated plate have respectively a larger proportional open area than the average proportional open area of the whole plate, the ratio of the sum of the areas of the portions of the plate having said larger proportional open area to the area of the remainder (A) of the plate being between 1:2 and 1:15, and the average proportional open area of said portions (B,C) being between 2 and 8 times the average proportional open area of the said remainder (A) of said perforated plate so as to satisfy the following formulae (I) and (II): 1.2 < (U OA /U mf ) < 2.5 (I) (U OB -U mf )/(U OA - U mf ) > 5 (II) wherein U mf represents the minimum fluidizing velocity, U OB represents an average superficial velocity of gas in each of the portions having said larger proportional area, and U OA represents an average superficial velocity of gas in the portion having proportional open area no greater than the average. A fluidizing bed reaction process according to claim 4, wherein a spray nozzle (8) for cooling liquid is located on the upper part of said reaction tower, a drain outlet (4) is disposed on the bottom part of said reaction tower, the particles participating in the reaction in said fluidized-bed are spherical pitch beads and the heating-fluidizing gas is air, said spherical pitch beads being oxidized and infusibilized by the reaction in said fluidized-bed. A fluidizing bed reaction process according to claim 5, wherein the average particle diameter of said spherical pitch beads is between 250 and 800 µm and the temperature of said fluidizing gas is 130 to 150°C.

Inventors: OKAMOTO, TSUNEO, SAKAGUCHI, YASUO
Applicants: KUREHA KAGAKU KOGYO KABUSHIKI KAISHA
Application year: 1988
Main classification: B01J8
IPC codes: B01J8, C10C3