A PROCESS FOR TREATING A CHLORINE-CONTAINING EFFLUENT AND AND APPARATUS THEREFOR

Abstract: An effluent-treating apparatus for treating a chlorine-containing effluent discharged from a flue gas desulfurization apparatus uses an electrodialysis apparatus, which comprises: an anode chamber (306) containing an anode (302) and an electrolyte solution, separated by a cation exchange membrane (304); a cathode chamber (307) containing a cathode (303) and an electrolyte solution, separated by a cation exchange membrane (304); an electrodialysis cell provided therein with concentration chambers (336) and dilution chambers (338) formed by alternately arranging a cation exchange member (304) and an anion exchange membrane (305) between said cathode (303) and said anode (302); and a path (310,311) for circulating said electrolyte solution, by which said anode chamber (306) communicates with said cathode chamber (307).

Description: This invention relates to a process for treating a chlorine-containing effluent discharged from a flue gas desulfurization apparatus and to an apparatus therefor. The present application is divided from European Patent Application No. 83307333.1 Publication No. 0139802 which is directed to a flue gas desulfurization process and apparatus therefor, and more particularly to a wet-type desulfurization process and apparatus therefor. Wet type flue gas desulfurization processes have been directed to a process of converting sulfur oxides SO x (usually SO₂ or SO₃) contained in flue gases, into gypsum which is chemically stable and utilizable, with CaCO₃, CaO or Ca(OH)₂ as raw material, which is abundantly existent in nature and cheaply available, to make flue gases harmless. Conventional flue gas desulfurization processes comprise a cooling step, an absorption step, a concentration step and a flue gas heating step. Namely, flue gas is first introduced into the cooling step where it is partly desulfurized, at the same time cooled and dedusted and then sent to the absorption step where it is contacted with a slurry containing limestone and lime (which slurry will hereinafter often be referred to as absorber slurry or limestone slurry) and desulfurized therewith and then sent to the flue gas heating step where it is heated and exhausted. The slurry containing limestone and lime absorbs sulfur oxides in the absorption step and byproduces calcium sulfite (CaSO₃) and calcium hydrogen sulfite (Ca(HSO₃)₂), but since the slurry partly contains unreacted CaCO₃ and slaked lime (Ca(OH)₂, it is recycled to the cooling step where the amounts of CaCO₃, etc. are reduced. Further, a part of CaSO₃ and Ca(HSO₃)₂ as byproducts is oxidized in the absorption step and the cooling step to form gypsum. The slurry used in the cooling step is sent to the concentration step. Water separated therein is reused, while concentrated solids (CaSO₃, Ca(HSO₃)₂ and CaSO₄) are discarded into a pond adjacent to the step. Further, after the solids are precipitated, the resulting water may often be reused. However, according to the above-mentioned conventional processes, the byproducts consist of a mixture of CaSO₃, CaCO₃; hence they, even if recovered, contain a large amount of byproducts so that it is impossible to effectively utilize them. Further, even in the concentration step, since CaSO₃ and Ca(HSO₃)₂ are existent in large amount, particles have particle diameters as small as several µm and also are inferior in settlability; hence as to the concentration apparatus, the apparatus capacity such as that of the settling tank is inevitable to be enormously enlarged. As mentioned above, various problems have been raised. Furthermore, in the case where a slurry of calcium compounds is used as an absorber, calcium sulfite and calcium sulfate as byproducts are a main cause of scaling; hence the problem of scaling is inevitable to require a countermeasure thereto. From such a viewpoint, there has been desired a process by which gypsum can be recovered as byproduct in accordance with its uses; the amount of water used therein is small; effluent treatment can be carried out in a closed system; no scaling occurs; and its reliability is high. Further, in this case, from a viewpoint of process efficiency, a process using an apparatus as minimal as possible has been desired. An object of the present invention is to provide a process by which effluent treatment can be carried out in a closed system and a relating apparatus. In particular, where a desulfurisation apparatus is installed in an inland area it is necessary to remove chloride ions (C1⁻) from the effluent to comply with regulations as to their discharge into rivers. According to a first aspect of the present invention there is provided an effluent-treating apparatus for treating a chlorine-containing effluent discharged from a flue gas cooling means of a flue gas desulfurization apparatus, including an electrodialysis apparatus which comprises: an anode chamber containing an anode; a cathode chamber containing a cathode, both said chambers containing, in use, an electrolyte solution; concentration chambers and dilution chambers through which effluent is passed, formed by alternately arranging cation exchange membranes and anion exchange membranes between said anode and cathode chambers, to thereby form an electrodialysis cell, said anode and cathode chambers each being separated from its adjacent chamber by a cation exchange membrane; and means defining a path by which said anode and cathode chambers communicate, for circulating said electrolyte solution. Preferably a degassing means is provided in said path. Preferably a liquid-discharging means and a liquid-feeding means are provided which communicate with said concentration chambers and said dilution chambers. According to a second aspect of the present invention there is provided a process for treating a chlorine-containing effluent discharged from cooling means of a flue gas desulfurization apparatus by using an electrodialysis apparatus, which process comprises: a step of subjecting the chlorine-containing effluent to electrodialysis in an electrodialysis apparatus to obtain a concentrated effluent and a desalted water. Embodiments of the invention are described by way of example only with reference to the following drawings in which: Fig. 1 shows an illustrative view of the whole of the flue gas desulfurization process using limestone-lime as absorber, according to a dust separation system; Fig.2 shows a flow sheet illustrating the effluent treatment in the case where there is no discharge regulation as to Cl (clorine) ion in the effluent; Fig. 3 shows a flow sheet illustrating the effluent treatment where Cl in the effluent is removed by electro-dialysis, in accordance with an aspect of the present invention; and Fig. 4 shows an illustrative view of an electrodialysis apparatus suitable for treating a chlorine ion-containing effluent, in accordance with the present invention. First, the whole of the flue gas desulfurization process according to a dust separation system will be described by way of Fig. 1. Referring to this figure, a sulfur oxides-containing flue gas 1 is led through a gas heater 3 into a cooling tower 5 wherein dust and acidic gases in the flue gas are removed and cooled, and further led into an absorption tower 7 wherein the gas is contacted with an absorber (limestone, lime, etc.) fed from an absorber slurry tank 9 and the sulfur oxides in the flue gas react with the absorber and are removed in the form of calcium sulfite. The resulting purified gas 11 is led into the gas heater 3 wherein it is reheated by heat exchange with the high temperature flue gas 1, and exhausted into the atmosphere without forming white smoke. On the other hand, the absorber slurry is fed from the tank 9 through a valve 13 to an absorber slurry circulation line 15. The absorber slurry is contacted with the flue gas in the absorption tower 7 wherein SO₂ in the flue gas is removed in the form of CaSO₃ or Ca(HSO₃)₂ according to the following equations: CaCO₃+SO₂+1/2 H₂O CaSO₃·1/2 H₂O+CO₂ CaSO₃·1/2 H₂O+SO₂+1/2 H₂O Ca(HSO₃)₂ The slurry containing calcium sulfite formed in the absorption tower 7 and unreacted absorber is fed through lines 17 and 21, a valve 23 and a line 14 into a pH-adjusting tank 25 wherein the pH of the slurry is adjusted to that required for the subsequent oxidation, with sulfuric acid fed from a line 18, and then fed to an oxidation tower 29 wherein Ca(HSO₃)₂ in the slurry is oxidized by air led through a line 31 to form gypsum (CaSO₄·2H₂O) according to the following equations: Ca(HSO₃)₂+1/2O₂+2H₂O CaSO₄·2H₂O+H₂SO₃ CaSO₃·1/2H₂O+1/2O₂+3/2H₂O CaSO₄·2H₂O The oxidation reaction expressed by the above equations occurs when oxygen in air dissolves in the slurry and contact with Ca S O₃ therein. On the other hand, the solubility of CaSO₃ greatly varies depending on the pH of the slurrry, and the lower the pH, the higher the solubility. However, the solubility of oxygen in the slurry is about 6 ppm at normal temperatures and normal pressures, and even if the pH is considerably lowered, the oxidation rate is not affected so much, and on the contrary, sulfuric acid is wasted. Thus, the preferred pH of the slurry in the oxidation step is 5 or lower, more preferably about 4.5 to 3.5. However, in the oxidation tower, there often is formed S₂O₆²⁻ (dithionic acid) which constitutes the main cause of COD (chemical oxygen demand) in the desulfurized effluent, and if the pH at the time of oxidation is too low, the amount of the acid formed increases. In such a case, it is possible to control the pH in the pH-adjusting step so as to give a pH of 5 to 6 at the exit of the oxidation tower. The theoretical amount of oxygen fed for the oxidation may be calculated from the amount of CaSO₃ at the inlet of the oxidation tower. Further, the oxidation rate in the oxidation tower increases by increasing the amount of air fed, but the particle diameter of gypsum byproduced is affected by the oxidation rate, and if the oxidation rate is higher, the particle diameter becomes finer; hence in view of the grade of byproduct, it is preferred to introduce air in an amount in the range of 1.5 to 3 times the theoretical amount. The pH adjustment of the slurry fed to the pH-adjusting tank 25 and its oxidation in the oxidation tower 29 may be carried out by using the flue gas. When the oxidation is carried out with the flue gas, a reactor 202 may be employed for the oxidation in place of the oxidation tower 29. Namely, a portion of the flue gas after dedusting and cooling is separated by means of a fan 201. This portion together with the slurry 17 withdrawn from the absorption tower 7 at its exit and passed through a valve 19 are led into the reactor 202 where a good contact thereof is effected. As a result, unreacted CaCO₃ in the slurry sent from the exit of the absorption tower 7 reacts with SO₂ in the flue gas to form calcium sulfite, which is then oxidized together with calcium sulfite formed in the absorption tower 7, by the oxygen in the flue gas to form gypsum. In this case, since SO₃ is contained in the flue gas, it is possible to carry out the pH adjustment of the slurry at the same time. As for the reactor 202, an ejector having a good efficiency of gas-liquid contact or a reactor provided with a bubble generating apparatus such as atomizer is preferably employed. The slurry leaving the reactor 202 is then led through a valve 30 into a concentrator 45. In the oxidation tower 29, the slurry containing calcium sulfite is mixed with air with stirring and in this case, there may occur troubles such as incapability of feeding air through the line 31 e.g. due to clogging of the air-feeding line. In such a case, the slurry in the oxidation tower is withdrawn and led through a line 33 and a valve 35 into an urgent flow tank 37 where air is blown therein through a line 39 to prevent the slurry from settling and coagulating. The resulting slurry is again returned to the oxidation tower through a pump 41. The urgent blow tank 37 may also be used as a tank for retaining the slurry of the absorption system and that of the gypsum recovery system. The slurry leaving the oxidation tower 29 or the reactor 202 is then led through a valve 43 or a valve 30 into a concentrator 45 where it is separated into a concentrated slurry and a filtrate. This filtrate is returned through a line 47 and a valve 50 to the limestone slurry tank 9 and used therein for diluting limestone. This filtrate may also be used as water fed to the cooling step or as washing water for various parts of the apparatus. On the other hand, the concentrated slurry is led from the concentrator 45 through a concentration-adjusting tank 91 and a line 51 to a centrifugal separator 53 where solid-liquid separation is effected. Gypsum separated in the centrifugal separator 53 is withdrawn through a line 55, and the filtrate is returned through a line 56, a tank 57 and a pump 59 into the concentrator 45 and a portion of the filtrate is returned through a valve 48 and a line 61 to the absorption tower 7 wherein the gypsum particles in this filtrate are utilized as seed crystals to prevent gypsum scale from forming in the absorption tower. The amount of the filtrate in the centrifugal separator 53 to be returned to the absorption system is preferred to be such an amount that the gypsum concentration in the slurry contained in the absorption system is 5% by weight or higher so that the effectiveness of the seed crystals may be exhibited, and the amount of the filtrate to be finally returned is determined based on the relation thereof with an amount in which CaSO₃ and Ca(HSO₃)₂ are oxidized in the absorption system by O₂ in the flue gas. In order to prevent the absorption system (the absorber slurry tank 9 for the absorption tower and related pipings) from developing gypsum scale the slurry at the exit of the oxidation tower or the concentrated slurry at the exit of the concentrator may be returned to the absorption system. However, most part of the gypsum particles contained in these slurries are crystal particles which have fully grown; and hence they are not so effective as seed crystals. Whereas the gypsum particles contained in the effluent from the centrifugal separator are mostly those which have passed through the filter cloth (or metal gauze); have small particle diameters; and contain a large amount of ungrown fine crystals (nuclei); hence they are notably effective as seed crystals. According to the dust separation system , that is, a system of circulating water in the cooling tower without circulating the CaCO₃-containing slurry therein, to remove dust and acidic gases in the flue gas, a definite amount of slurry is discharged from the cooling tower 5 to the outside of the system and treated in an effluent-treating apparatus 4, is shown in Fig. 1, to prevent the corrosion and abraision of the materials of the cooling tower due to concentration of acidic materials and dust in the cooling tower. Fig. 2 shows an example of flow sheets of such an effluent-treating apparatus. A flocculant 182 is added to the effluent 180 from the cooling step, and the resulting effluent is successively passed through a thickner for removing ss (suspending solids) 181 (ss-removing step), a tank for settling with alkali 183, a heavy metals-removing thickner 185 (these means belong to steps for removing ss, fluorine and heavy metals), a pH-adjusting tank 187, a COD component-adsorbing tank 189 (these means belong to COD-removing step), and a pH-adjusting tank 191, to successively remove ss, heavy metals and COD component. In addition, in this figure, numeral 184 represents a tank for sludge (fly ash); 186, a sludge tank; and 188, a regenerated water. However, in the case where this desulfurization apparatus is installed in a inland area, it is necessary to remove chlorine ion (Cℓ⁻) in the effluent, from a viewpoint of regulations of effluents to rivers. In such a case, in the process of Fig. 2, an electrodialysis apparatus may be provided between a COD-adsorbing tower 189 and a pH-adjusting tank 191 to desalt and concentrate the effluent by means of the electrodialysis apparatus. Fig. 3 shows a flow sheet wherein an electrodialysis apparatus, in accordance with the invention, is used in the effluent-treating apparatus. This apparatus is the same in the steps as far as the COD-adsorbing tank 189, as that of Fig. 2, but two electrodialysis apparatuses 193 and 194 for desalting and concentration are provided after the tank 189 to carry out desalting and concentration, respectively, the resulting desalted water 197 being sent to a pH-adjusting tank 191, and the concentrated slurry 195 concentrated in the apparatus 194 being sent through a concentrated slurry tank 196 to a vaporization-to-dryness step, where solids are recovered, e.g. sodium chloride. The concentrated slurry in the apparatus 193 is fed to the apparatus 194 where it is concentrated to a higher concentration, while the desalted water in the apparatus 194 is recycled to the apparatus 193 where its is desalted to a lower concentration. In this process, since two electrodialysis apparatuses are provided and concentration is carried out in two steps, a higher concentration of concentrated slurry can be obtained to more reduce the energy required for vaporization to dryness of the subsequent step. The effluent (desalted water) freed from chlorine ion in the electrodialysis apparatuses as described above may be reused in the process, e.g. as the cooling water for the cooling step, while the concentrated slurry may be e.g. vaporized to dryness using boiler flue gas as the heat source, or sprayed inside a duct for boiler flue gas, followed by returning the flue gas containing the resulting solids that is obtained by vaporization to dryness to the front of an upstream electrostatic precipitator to render the desulfurization process a complete closed system. A main substance among the COD component-forming substances in the effluent is dithionic acid S₂O₆²⁻ formed from a portion of H₂SO₃⁻ ion contained in the absorbing solution, in the presence of Mn, Fe, etc. As for a process for treating this S₂O₆²⁻, there may be employed a process of adding a strong acid such as sulfuric acid to a blow-down water to adjust the pH to 1.5 or lower, heating to a temperature of 60°C or higher. Further, another process may be employed wherein S₂O₆²⁻ ions are attached onto a weakly basic ion exchange resin, followed-by desorbing them at a pH of 10 or higher, adding a strong acid as described above to adjust the pH to 1.5 or lower, and decomposing it on heating. According the above processes, S₂O₆²⁻ ions contained in the circulating slurries of the absorption tower or the cooling tower or in the effluent may be removed to prevent reduction in the SO₂ absorbability of the circulating slurries and also to thereby avoid a secondary environmental pollution. In addition, the flue gas containing SO₂ formed by decomposition of S₂O₆²⁻ in the effluent-treating apparatus 4 or 49 may be returned to the feed line of the flue gas 1 to purify the gas. According to the dust separation system, it is possible to obtain a high grade of gypsum as byproduct, but on the other hand, since solids such as dust, heavy metals, etc. are discharged through the above-mentioned effluent treatment of the cooling step, a portion of the gypsum concentrated slurry may be mixed with a slurry obtained by adding CaCO₃ and Ca(OH)₂ to the effluent from the cooling tower, to recover a byproduct which is usable as gypsum although its grade is low, and also inhibit discharge of dust, heavy metals, etc. from the effluent-treating apparatus of the cooling step. Thus it is possible to obtain a high grade of gypsum and an optional low grade of gypsum depending on their uses, and also it is possible to inhibit discharge of dust, heavy metals, etc. from the effluent-treating apparatus of the cooling step, and also reduce their amounts discharged. Fig. 4 shows an embodiment of an electrodialysis apparatus 193 or 194 of the present invention employed for treating the effluent discharged from the cooling step of the desulfurization process (see Fig. 3). The electrodialysis cell 301 is provided with an anode chamber 306 and a cathod chamber 307 containing an anode 302 and a cathode 303, respectively, in an electrolyte solution, between which chambers cation exchange membranes 304 and anion exchange membranes 305 are alternately arranged by the medium of spacers 314, between which membranes concentration chambers 336 and dilution chambers (desalting chambers) 338 are alternately formed. Numeral 315 represents a chamber frame. The anode chamber 306 and the cathode chamber 307 are separated from the adjacent chamber by the cation exchange membranes 304, respectively, and also they are connected by communicating pipes 310 and 311, respectively, provided midway, with gas-liquid separators 308 and 309 as a degassing means, to form a circulating path for the electrolyte solution. The concentration chambers 336 and the dilution chambers 338 are respectively provided with a line for feeding the effluent to be treated 330 and on the opposite side, with a line for discharging concentrated water 334 and a line for discharging diluted water 332. The liquid feed to the concentration chambers 336 and the dilution chambers 338 may be uniformly carried out by way of the liquid feeding line 330, as described above, but two kinds of liquids having different concentrations may be separately fed, respectively, that is, a high concentration liquid being fed to the concentration chambers, and another low concentration liquid, to the dilution chambers. As to the gas-liquid separators 308 and 309, the respective gases formed in the anode 302 and the cathode 303 by electrode reaction are exhausted through exhaust pipes 312 and 313. These gas-liquid separators 308 and 309 may be e.g. a liquid storage tank, and are preferred to be those which can effect supply of the electrolyte solution (an aqueous solution of e.g. sodium sulfate but having a small halogen concentration) or water, blowdown of a portion of the electrolyte solution or pH adjustment thereof, as occasion demands, along with degassing. The electrolyte solution may be a solution of soluble salts consisting of the same cation as that contained in the solution to be treated and an anion from which no gas is formed in the anodic oxidation reaction, and sodium phosphate or the like may be used besides sodium sulfate in the present invention. The degassing means (gas-liquid separator) provided in the circulating path of the electrolyte solution may be a liquid storage tank having a liquid storage part and a clearance part for degassing, but a means of merely providing a degassing hole in the electrode chamber or connecting pipe may also be employed. In the electrodialysis apparatus, when an aqueous solution of sodium sulfate is filled in the electrode chamber and an effluent from the desulfurization apparatus, composed mainly of sodium chloride, is fed through a line 330 to carry out electrodialysis operation, then the respective ions in the effluent selectively permeate through the ion exchange membranes 304 and 305 to form concentrated water and diluted water in the concentration chamber 336 and the dilution chamber 338, respectively, and these waters are discharged through lines 334 and 332, respectively. At that time, since the anode chamber contains no halogen ion and yet is separated from the adjacent chamber by the cation exchange membrane, no halogen ion which is anion permeates and hence no halogen gas is formed, and also sodium ion (Na⁺) decreases through the permeation, while there proceeds a reaction by which sulfuric acid and oxygen gas are formed. The solution containing the thus formed sulfuric acid and oxygen gas is fed through the communicating pipe 310 to the cathode chamber 307. The oxygen gas is removed by the midway gas-liquid separator 308 and exhausted through an exhaust pipe 312. On the other hand, in the cathode chamber 307, hydrogen ion is reduced to form hydrogen gas, while Na⁺ permeates from the adjacent chamber into this chamber to form sodium hydroxide, which, however, is neutralized by sulfuric acid fed from the anode chamber 306, to form sodium sulfate. Thus, the solution in the cathode chamber does not become alkaline, and also there occurs no scaling therein due to compounds of Mg, Ca or the like. The solution containing the thus formed sodium sulfate and hydrogen gas is freed from hydrogen gas in the gas-liquid separator 309 midway in the course of communicating pipe 311 through an exhaust pipe 313, and then recycled to the anode chamber 306. According to the above embodiment, when the saline solution-containing effluent from the desulfurization apparatus is subjected to electrodialysis treatment, it is possible to prevent generation of chlorine gas in the anode and scaling in the cathode. Further, the electrolyte solution is, in principle, not consumed; hence it may be sufficient to supply a small amount of water lost by the electrolysis. Accordingly, the amount of agents such as sodium sulfate consumed becomes also small, as well as it is easy to operate and control the apparatus.

Claims: An effluent-treating apparatus for treating a chlorine-containing effluent discharged from a flue gas cooling means of a flue gas desulfurization apparatus, including an electrodialysis apparatus which comprises: an anode chamber (306) containing an anode (302); a cathode chamber (307) containing a cathode (303), both said chambers containing, in use, an electrolyte solution; concentration chambers (336) and dilution chambers (338) through which effluent is passed, formed by alternately arranging cation exchange membranes (304) and anion exchange membranes (305) between said anode and cathode chambers (306)(307), to thereby form an electrodialysis cell, said anode and cathode chambers (306)(307) each being separated from its adjacent chamber by a cation exchange membrane (304); and means defining a path by which said anode and cathode chambers (306)(307) communicate, for circulating said electrolyte solution. An effluent-treating apparatus as claimed in claim 1, wherein a degassing means (308,309) is provided in said path (310,311). An effluent-treating apparatus as claimed in claim 1 or 2, wherein a liquid-discharging means (332,334) and a liquid-feeding means (330) are provided which communicate with said concentration chambers (336) and said dilution chambers (338). An effluent-treating apparatus as claimed in claim 1, 2 or 3, wherein a gas-blowing means (312) for discharging chlorine is provided in communication with said anode chamber (306). A process for treating a chlorine-containing effluent discharged from a flue gas cooling means of a flue gas desulfurization apparatus, which process comprises: a step of subjecting the chlorine-containing effluent to electrodialysis in an electrodialysis apparatus (301) to obtain a concentrated effluent and a desalted water. A process for treating a chlorine-containing effluent according to claim 5, wherein said concentrated effluent is separated into water and solids by a separation means. A process for treating a chlorine-containing effluent according to claim 6, wherein said separation means is a vaporization apparatus. A process for treating a chlorine-containing effluent according to any one of claims 5 to 7, wherein said concentrated effluent is subjected to vaporization, using a flue gas as a heat source therefor to obtain a solid chloride. A process for treating a chlorine-containing effluent according to claim 8, wherein the flue gas, after use as heat source for evaporation of said concentrated effluent, is fed to an electrostatic precipitator for dedusting said flue gas. A process for treating a chlorine-containing effluent according to any one of claims 5 to 9, wherein said chlorine concentrated effluent is sprayed into an inlet duct of an electrostatic precipitator for dedusting a flue gas, to subject the effluent to vaporization. A process for treating a chlorine-containing effluent according to any one of claims 5 to 10, wherein said desalted water is utilized as a process water in a desulfurization system. A process for treating a chlorine-containing effluent according to any one of claims 5 to 11, wherein said chlorine containing effluent is subjected to pretreatment before electrodialysis. A process for treating a chlorine-containing effluent according to claim 12, wherein said pretreatment is selected from steps for removing suspended solids, heavy metal components, and COD components in the effluent. A process for treating a chlorine-containing effluent using the apparatus of claim 1, wherein said effluent is introduced into said concentration and dilution chambers (336,338) at first sides thereof, undergoes electrodialysis therein, and wherein concentrated effluent and desalted water are removed from said concentration and dilution chambers (336)(338) respectively at opposite sides thereof.

Inventors: HASHIMOTO, TAIKI, KURE WORKS OF BABCOCK-HITACHI, KANDA, OSAMU, KURE WORKS OF BABCOCK-HITACHI, KURODA, HIROSHI, KURE WORKS OF BABCOCK-HITACHI, NISHIMURA, TSUKASA, KURE WORKS OF BABCOCK-HITACHI, NISHIMURA,MASAKATSU, KURE WORKS OF BABCOCK-HITACHI, NOZAWA, SHIGERU, KURE WORKS OF BABCOCK-HITACHI, SHIBATA, KENJI, KURE RES. LAB.OF BABCOCK-HITACHI
Applicants: BABCOCK-HITACHI KABUSHIKI KAISHA
Application year: 1983
Main classification: B01D61
IPC codes: B01D53, B01D61, F28D15, C01F11