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MELI?A - NOI 1,ES Nolis?ºNOO 1STWHXE

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MELI?A - NOI 1,ES Nolis?ºNOO 1STWHXE Oct. 8, 1974 TOMIJIRO MORITA ET AL 3, 0,638 FRODUCTION OF GYPSU FROM COMBUSTION EXHAUST GAS Filed Oct. 26, 1971 9H/Nou?ETTOO™IST:NOLLSmy/HXE·HBSOdWOOEO-LITW ONIZIOIXOç?d'A??e!(ELEVÄNA MELI?A - NOI_1,ES NOliS?ºNOO 1STWHXE. TOMIJ IRQ MQR?TA ?SPAG ÈFUNABAS? S?j??i MASAOS SÜgA ·mS?º) INVENTORS ????? ??????? ATTORNEYs 3,840,638 United States Patent Office Patented Oct. 8, 1974 1. 2 3,840,638 In the drawing, the single figure is a schematic diagram PRODUCTION OF GYPSUM FROM COMBUSTON showing the process steps of producing gypsum according EXHAUST GAS Tomijiro Morita, Isao Funabashi, and Masayoshi Sugai, to the present invention. Iwaki, Japan, assignors to Kureha Kagaku Kogyo Kabu In developing the technique of producing gypsum from shiki Kaisha, Tokyo-to, Japan combustion exhaust gas, the following matters were kept Filed Oct. 26, 1971, Ser. No. 192,231 in mind: (1) the absorption tower should not be blocked; Claims priority, application Japan, Oct. 26, 1970, (2) water for processing the material should be well 45/94,125 balanced; and (3) purity and crystal shape of the resultant Int. CI. C01f 1/00, 11/46 gypsum is sufficiently good, as the result of which it has U.S. C. 423-166 1. Claim been noted that acidic alkali sulfite readily reacts with cal 10 cium carbonate or calcium hydroxide to turn into calcium Sulfite and alkali sulfite. ABSTRACT OF THE DISCLOSURE The detailed process steps of producing gypsum accord Process for producing gypsum from combustion exhaust gas by contact-reacting the gas with alkali sulfite to pro ing to the present invention will be described hereinbelow 15 with reference to the drawing. duce acidic alkali sulfite, then reacting acidic alkali sulfite Combustion exhaust gas is first introduced into the dust with calcium carbonate or hydroxide to obtain calcium collection cum moisture-adjustment section of the absorp sulfite, and oxidizing calcium sulfite. tion tower A where it is washed with water which is circu lated by a water pump 3 to remove carbon and other fine This invention relates to a method for producing 20 particles accompanying the gas, and, at the same time, is gypsum, or, more particularly, to a method for producing adjusted its temperature at a level of from 80 to 90° C. gypsum which has recently become highly demanded by and its relative humidity in a range of from 15% to 60%. absorbing and fixing oxide of sulfur contained in combus If the temperature of the exhaust gas is below this lower tion exhaust gas in the form of acidic alkali sulfite, then limit, evaporation of moisture in the gas at the absorption turning it into calcium sulfite by reacting with calcium 25 section 2 of the absorption tower A is poor. On the other carbonate or hydroxide, and oxidizing calcium sulfite. hand, if the temperature is above the upper limit, absorp Strenuous efforts have been made in recent days to tion of sulfur dioxide becomes inferior. Also, with the develop techniques of treating exhaust gas dicharged from relative humidity of below 15%, the dust collection is not various plants and factories such as thermal power plant so effective, and the humidity of above 60% disadvan not only to make it inoxious with a view to reducing air 30 tageously affects concentration of the acidic alkali sulfite pollution which has been one of the most serious problems solution. over the world, but also to produce useful substances by The exhaust gas which has been thus dust-collected, positively utilizing the gas as the raw material in chemical moisture-adjusted, and temperature-lowered is subse industries. For these reasons, however, that exhaust gas quently sent into the absorption section 2 of filling type. from such plants and factories contains low concentration 35 In this absorption section 2 sulfur dioxide contained in the of the oxide of sulfur and that the quantity of the exhaust exhaust gas is caused to react, through a gas/liquid gas to be treated is enormous, desulfurization technique of phase contact, with approximately 20% aqueous solution the exhaust gas in industrialized scale has still been under of alkali sulfite such as sodium sulfite or potassium sulfite study and development. sent into the absorption section 2 from the upper part As the method of producing gypsum from exhaust gas 40 thereof by means of a circulating pump 4 and a liquid containing oxide of sulfur, there has been known from old supplying pump 8, and is absorbed and fixed in the form various ones such that calcium hydroxide or calcium car of acidic alkali sulfite. Upon the contact reaction, both bonate is reacted with sulfur dioxide to turn it into calci acidic alkali sulfite and alkali sulfite are concentrated by um sulfite, which is then oxidized, or calcium carbonate heat energy of the exhaust gas, and they are sent into a in powder form is dispersed in the exhaust gas to cause it 45 double decomposition reactor 6 in the subsequent step by to react with the coexistent oxygen, thereby obtaining means of a liquid supplying pump 5 in the form of ap gypSum. proximately 8% aqueous solution of acidic alkali sulfite These known methods, however, are still not free from and approximately 15% aqueous solution of alkali sulfite. difficulty in practice. That is, in the former method, In this double decomposition reactor, the acidic alkali absorption should be done in slurry form, which causes 50 sulfite solution reacts with calcium carbonate or calcium clogging and scaling of the absorption tower, and the latter hydroxide in slurry form prepared in a dissolving vessel 9 method possesses problems such as blocking of the reac and sent into the reactor 6 by a slurry pump 10 at a tem tion tower, recovery of product, and so forth. In particul perature of from 50 to 90° C. to produce calcium sulfite. lar, clogging of the absorption tower constitutes a fatal In case of using calcium carbonate, carbon dioxide gener defect in the desulfurizing apparatus. 55 ated from the reaction should be discharged outside the It is therefore the primary object of the present inven reactor, or transferred to a process system which utilizes tion to provide an improved method of producing gypsum carbon dioxide as the raw material. from combustion exhaust gas from plants and factories Calcium sulfite crystal and alkali sulfite produced in the without causing clogging of the absorption tower. double decomposition reactor 6 are then separated in a It is another object of the present invention to provide 60 separating and rinsing vessel 7, and the alkali sulfite solu an improved method of producing gypsum by contacting tion is fed back to the absorption section 2 of the absorp the combustion exhaust gas with alkali sulfite to fix sulfur tion tower A together with washing liquid 7a by means of dioxide in the gas in the form of acidic alkali sulfite, then the liquid supplying pump 8. On the other hand, calcium causing acidic alkali sulfite to react with calcium hy sulfite rinsed in the separating and rinsing vessel 7 is trans droxide or calcium carbonate to produce calcium sulfite 65 ferred into a slurry preparation vessel 11 where it is made and alkali sulfite, and oxidizing the separated calcium into approximately 5% slurry of calcium sulfite, and then sulfite in slurry form with a small quantity of air. sent into the top part of an oxidizing tower 13 by means The above objects as well as the details of the present of a slurry pump 12. While the slurry is being charged invention will become more apparent from the following into the oxidizing tower and falling downward to the description when read in connection with a preferred em 70 bottom of the tower dispersing therewithin, air 13a is bodiment thereof and an accompanying drawing. blown into the oxidizing tower from the bottom thereof, 3,840,638 3 4. which reacts with the calcium sulfite slurry to produce solution was reused, upon evaporating 7.2 kg./hr. Of oxidized gypsum. water therefrom, for absorbing and fixing sulfur dioxide The gypsum thus produced is conveyed to a separation contained in the exhaust gas sent into the tower. vessel 14 from the tower bottom, where the gypsum is In the subsequent slurry preparation vessel, crystallized separated in crystallized form, while filtered liquid is re 5 calcium sulfite was made into 5% by weight of slurry by circulated to the slurry preparation vessel 11 by a liquid adding water thereto, and then the slurry was sent into supplying pump 15. an oxidizing tower from the top thereof by means of a The process according to the present invention has re slurry pump, whereas a small quantity of air at a rate of markable advantages in that no clogging of the absorp 2 Nm.8/hr. was blown into the tower from its bottom tion tower occurs in the course of absorbing oxide of 10 through a nozzle so as to carry out the oxidizing reaction sulfur, alkali sulfite solution as the absorbing agent as at a temperature of 80° C. The reaction product was in Well as water for preparing slurry of calcium sulfite can troduced into a separation vessel through the bottom be recycled for repeated use, and balance of water for part of the oxidizing tower, where it was dehydrated to Washing and slurry preparation can be adequately main produce gypsum dihydrate at a rate of 2.7 kg./hr. Gyp tained to produce gypsum from combustion exhaust gas Sum thus obtained assumed planar crystal, and its purity without much difficulty, hence its economical merit is Was 98.4%.
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