METHODS FOR NEUTRALIZING DYESTUFF-SLUDGES AND WASTE PRODUCTS

Abstract: Method for neutralizing dyestuff-sludges and/or waste products containing comminutable organic components, mainly resins, wherein the neutralization is performed by oxidizing pyrolysis in a system with mobile or fixed beds at a temperature of 300 to 800 DEG C, in course of pyrolysis, dwelling time of dyestuff-sludges and/or waste containing comminutable organic components, mainly resin, amounts to 20 to 50 sec, the amount of the medium used for pyrolysis containing 21 % oxygen reaches 3 to 5 m<3>/one kg solid substance. After having performed pyrolysis a waste with gaseous phase and solid phase is obtained, which are separated in a way known in itself, solid phase is recycled to the process of dyestuff-manufacturing, while the gaseous phase is led directly through a reactor working with a method of thermic or catalytic oxidation or with a combination thereof. Thereafter it is led into the atmosphere or substances being harmful for the enrivonment are recovered in an absorbent wash-system or in an absorbent column, following recovery gaseous media left behind are led through a reactor using a method of thermic or catalytic oxidation or the combination thereof, wherefrom they are led into the atmosphere.

Description: METHODS FOR NEUTRALIZING DYE5TUFF -SLUD3E5 AND WASTE PRODUCTS TECHNICAL FIELD The invention relates to the neutralization of dyestuff- sludges and/or waste products containing comminutable organic components, mainly resins. BACKGROUND ART Specification of technological solutions relating to the transformation of dyestuff-sludges and other wastes uccupies internationally an ever increasing field. lϋ Technological solutions generally used are utmost different, as it becomes obvious from the comprehensive technical literature of the authors Olesak-Szabό with the title "Energy gained from waste" /published by the Technical Publishers, Budapest, 1984/, as well as from the lecture hold 15 by Dr. Wal ϋller "Thermic neutralization of wastes and /harmful/ wastes" on the occasion of the Austro-Huπgarian Meeting on Ecology in 1987/. Cited technical literatures present a variety of tech¬ nological specifications and solutions for the recovery 20 and neutralization of diverse waste types. The Patent Specification CH-PS 658 449 relates to the drying of wet sludges; the essence of the drying method lies in that materials having been evaporated are utilized for energetic purposes. Wet sludge containing combustible ma¬ ' " terials is oxidized under pressure and at a high temperature. DISCLOSURE OF INVENTION The object of the present invention is to provide a complex technological solution, wherein in a closed system oxidizing conversion of dyestuff-sludges and different wastes is taking place, simultaneously arising atmospheric contaminations are removed, at the same time residues nf combustion are processed resp. neutralized in a closed system. In accordance with the invention we proceed so, in so far as in the processing plant neutralization of the dyestuff-sludges arriving in a closed unit and/or of the waste containing comminutable organic components, mainly resins, is taking place after drying and pre-treatment by pyrolysis, in a system with movable or fixed beds at a temperature in the range between 300 and 800 C ; in course of pyrolysis dwelling time dyestuff-sludges and/or wastes containing comminutable organic components, in particular resisn, amounts to 20 to 50 seconds; quantity of the medium with an oxigen content of 21 % used for pvrolysis amounts to 3 to 5 m related to one kg of the solid substance; after having performed pyrolysis we obtain a gaseous and a solid waste to be separated; the solid phase is recycled to the process of dyestuff- maπufacturing, while the gaseous phase is led directlv through a reactor working with thp thermic or catalytic method of oxidation or the combination thereof; thereafter it is l°o into the atmosciere; in case, if the gaseous phase contained s hstaπces being harmful for the environment, these are removeα in an aosorbent wash-system or in an adsorbent column; gaseous media left back after recovery are led through a reactor using the thermic or catalytic method of oxidization or the combina ion thereof, thereafter the are led into the atmosphere. Pyrolysis may be performed in a fluidizatioπ system with a mobile bed using a carrier meGium wherein sand grains or ceramic grains with a grain diameter of 0,1 to 5 mm, glass-grains or catalytically active metal oxide grains used to be applied as heat-carrier media. Pyrolysis is preferably taking place in a system with movable beds, wherein the pyrolysing bed performs a rotary or horizontal motion; in dependence of requirements of pyrolysis bed temperature may be changed in the range between 300 and 800 C°. Pyrolysis may be realized in a system with a fixed bed and a grate too, wherefrom solid product of combustion formed as a final product is forwarded continuously by means of a conveyor chain or it can be removed periodically by putting the combustion grate into motion. Flue gases ana solid substances arising in course of pvrolysis in fluidi/ing or mobile beds preferable used to be separated into gaseous and solid substance by means of separators based on the cycloπ system or by precipitation. Gaseous phases are introduced advantageously into an absorbent wash-system, in which contaminating hydro- 5 carbons over C. , primarily aliphatics and aromatics with large carbon chains are separated, using a wash-fluid oil or hydrocarbons with low tension, so e.g. fuel oils etπylene glycol, glycerine, softeπeres; in course of recirculation temperature of the absorbent medium is lfi kept in the range between 20 and 40 C in a separate neating and cooling system. Parts of the gaseous phase are bound preferably in an adsorption column, mostly on active carbon or silica gel or aluminium oxide; in dependence of the length of 15 the carbon chain, temperature lies in the range between 20 and 40 C°, flow velocity amounts to 0,2 -0,5 m /sec; regeneration of adsorbents used to be performed either ther ically, maximally up to 300 C or by introducing steam, in the latter case water and solid phase are 20 separated in a separator. Particles of the gaseous phase or flue gases leaving the absorbent or adsorbent equipments are oxidized pre¬ ferably thermically or catalytically , in course of the catalytic combustion temperature in the reactor lie- -5 in the range between 250 and 450 C . MODES FDR CARRYING UL 1HE 1NVENTI0', Examples of application: Example 1 45 kg dyestuff-sludge or any otner equivalent material with identical carbon content are oxidized with air of the quantity of 211 kg/h in a fluidization pyrolysing system, wherefrom 16 kg/h solid residue and 240 kg/h flue gases are leaving, i-lue gases and dusty materials are cleaned from solid substance in a cvclon with a 95 % eff ciency, that means that 15 kg/h solid substance will be further processed. 1 kg/h solid material contained in the flue gas and 240 kg/h gas get rid of the dusty content in a dry cyclon or in an electrofil er , while dusty com¬ ponent will be introduced into the solid material for subsequent processing. 240 kg/h flue gases - consisting of 211 kg/h gas mixture with changing oxigen content and 29 kg/h de¬ composition products - are led into an oily washer, wherein contaminations are separated with a 75 % efficiency at least. Gas mixture leaving the oily wash system and containing 7,25 kg/h decomposition products is led into the catalytic combustion system coupled to the direct burniπg-in kiln, wherein - by adding supplementary air resp. oxigen in case uf necessity - contaminating cι>m- poneπts are transformed with a 98 % efficiency Practi - Cdliy, gases leaving the catalytic reactor oo not contain hvdrocarbon contaminations. Example 2 45 kg/h dyestuff-sludge or equivalent waste with identical carbon content and 211 kg/h air are led into a discoπtinuously or continuously operated mechanic pvro- lysing equipment /with a rotary drum, movable and im¬ movable bed/, wherein organic substances are transformed hv oxidizing pyrolysis and after having separated solid substance and flue gases further processing may take place. In course of subsequent mechanic purification of the flue gases solid substances appearing as fly dust are separated, thereafter flue gases in a total quantity of 240 kg/h - consisting of 211 kg/h gas with changing oxigen content and 29 kg/h decomposition pro¬ duct - are led into the oily washer, wherein contaminants are flushed with 75 % efficiency. Gaseous substances leaving the wash-system containing 7,2 kg/h decomposi- tion product get rid of organic contaminants in the catalytic after-combustion system with the direct burning-in kiln with an efficiency over 98 %. Example 3 We proceed as described in Example 1 and 2 wi + the difference that instead of the oily wash-system flue gases are led through an absorber filled with active carbon, aluminium oxide or silica gel or artificial and natural zeolites, wherein decomposition products are bound wi h an efficiency of at leas + 80 %; gaseous suostances leaving the absorber are transformed in the catalytic after-combustion equipment with the direct burning- in kiln. Periodical regeneration of the absorber is taking place with a warm inert or oxigen-containing gas, in dependence of the filler at a temperature in the range between 200 and 300 C° , with direct or indirect heating. In course of regeneration the air leaving the ad¬ sorber is led into the catalytic combustion system combined with the burπing-in kiln, wherein these are transformed into components being unharmful for the eπviroment. The main advantage of the method according to the invention lies in that materials containing dyestuff- -sludge and other combustible components can be utilized as raw materials, by converting the residues by oxidizing pyrolysis new products, product groups may be αbtained / sr e.g. priming ompos i t i oπs , fil l ers. , -÷: π.ϋltane' * usl -. i n a closed cycle materials oeing harmful i n respect to ecology can be utilized.

Claims: CLAIMS 1. Method for neutralizing dyestuff-sludges and/or waste products containing comminuta le organic components, mainly resins, c h a r a c t e r i z e d in that neutraliza¬ tion is performed by oxidizing pyrolysis in a system with mobile or fixed beds at a temperature of 300 to 800 C°, in course of pyrolysis dwelling time of dye¬ stuff-sludges and/or waste containing comminutable organic components, mainly resin, amounts to 20 to 50 sec, the amount of the medium used for pyrolysis containing 3 21 % oxigen reaches 3 to 5 m one kg solid substance, after having performed pyrolysis we obtain a waste with gaseous phase and solid phase, which are separated in a way known in itself, solid phase is recycled to the process of dyestuff-manufacturiπg , while the gaseous phase is led directly through a reactor working with a method of thermic or catalytic oxidation or with a combination thereof, thereafter it is led into the atmosphere or substances being harmful for the environ¬ ment are recovered in an absorbent wash-system or in an adsorbent column, following recovery gaseous media left behind are led through a reactor using a method of thermic or catalytic oxidation or the combination thereof, wherefrom they are led into the atmosphere. 2 Method as claimed in claim 1, c h a r a c t e r i z e d in that pyrolysis is realized in a fluidizatioπ system with mobile bed sing a carrier medium, while as heat carrier 'f.edium sand grains with a grain diameter of 0,1 - 5 mm, ceramic grains, glass-grains or catalytically active metal oxide grains are used. 5 3. Method as claimed in claim 1, c h a r a c t e r i z e d in that pyrolysis is taking place in a system with mobile bed, wherein pyrolvsing bed performs a rotary or horizontal motion, while the temperature of the bed in dependence of requirements of pyrolysis lies in the range between 300 IP and 800 C°. 4. Method as claimed in claim 1, c h a r a c t e r i z e d in that pyrolysis is taking place in a system with fixed bed and a grate, wherefrom solid combustion product formed as a final product is forwarded continuously by means of 5 a coπweyor chain or it is removed discontiπuously by putting the combustion grate into motion. 5. Method as claimed in claim 1, c h a r a c t e r i z e d in that flue gases and solid substances arising after fluidization or pyrolysis in the mobile bed used to be 0 separated into gas and solid substance in a cyclon or by means of precipitation. 6. Method as claimed in claim 1, c h a r a c t e r i z e d in that gaseous components are led into an adsordeπt wash-system, wherein contaminant hydrocarboπats higher, - 11 - than C. , in particular aliphatics and aro atics with longer carbon chains are separated, as wash-liquid oil or hydrocarbons with low tension using, so e.g. fuel oil, ethylene glycol, glycerine, softener, in course of re- circulation temperature of the absorption medium is kept in the range between 20 and 40 C° in a pooling or heating system. 7. Method as claimed in claim 1, characteri ze d in that gaseous components are bound in an adsorbent column, most frequently on active carbon, silica gel or aluminium oxide, in dependence of the length of the carbon chain, temperature lies in the range between 20 to 40 C°, flow velocity amounts to 0,2 - t),5 /sec, regeneration of adsorbens is realized thermically up to max. 300 C° or by introducing steam, in the latter case water and organic phase are separated in a separator. 8. Method as claimed in claim 1, characteri zed in that flue gases leaving the absorption resp. adsorption systems are oxidized by using thermic or catalytic method °r the combination thereof, in course of catalytic combustion, temperature of the reactor lies in the range between 250 and 450 C°.

Inventors: BALOGH ANDRAS, DOBOS GABOR, LACSNY BALINT, MOLNAR BELA, MOLNAR MIHALYNE, MOZES GYULA, SCHMID FERENC, SZOKE ELEK, WAGNER JOZSEF, BALOGH, ANDRAS, DOBOS, GABOR, LACSNY, BALINT, MOLNAR, BELA, MOLNAR, MIHALYNE, MOZES, GYULA, SCHMID, FERENC, SZOKE, ELEK, WAGNER, JOZSEF
Applicants: IKARUS KAROSSZERIA, MAGYAR ASVANYOLAJ ES FOELDGAZ, IKARUS KAROSSZERIA ES JARMUGYAR, MAGYAR ASVANYOLAJ ES FOELDGAZ KISERLETI INTEZET
Application year: 1991
Main classification: B09B3
IPC codes: A62D3, A62D101, B09B3, C02F11, C10B53, F23G7