CS266261B1 - The smol processing method - Google Patents

The smol processing method Download PDF

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CS266261B1
CS266261B1 CS878119A CS811987A CS266261B1 CS 266261 B1 CS266261 B1 CS 266261B1 CS 878119 A CS878119 A CS 878119A CS 811987 A CS811987 A CS 811987A CS 266261 B1 CS266261 B1 CS 266261B1
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Czechoslovakia
Prior art keywords
sulfur
resins
mercaptobenzothiazole
products
pitch
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CS878119A
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Czech (cs)
Slovak (sk)
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CS811987A1 (en
Inventor
Ladislav Ing Csc Koudelka
Karol Ing Hlinstak
Vladimir Ing Patek
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Koudelka Ladislav
Hlinstak Karel
Vladimir Ing Patek
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Priority to CS878119A priority Critical patent/CS266261B1/en
Publication of CS811987A1 publication Critical patent/CS811987A1/en
Publication of CS266261B1 publication Critical patent/CS266261B1/en

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Abstract

Spósob spracovania sntíl z výroby gumá­ renských urýchlovačov na báze 2-merkaptobenztiazolu tak, že smoly sa za norraálneho alebo zvýšeného tlaku, s výhodou pri 5 až 20 MPa, tepelne štiepia bez přístupu vzduchu alebo kyslíka po dobu 0,2 až 6 h pri teplote 200 až 500 °C a z produktov štiepenia sa oddelia plynné podřely a s výhodou sa z nich získá síra a/alebo sirovodík.A method of processing resins from the production of rubber accelerators based on 2-mercaptobenzothiazole in such a way that the resins are thermally cracked under normal or increased pressure, preferably at 5 to 20 MPa, without access to air or oxygen for a period of 0.2 to 6 h at a temperature of 200 to 500 °C and gaseous by-products are separated from the cracking products and sulfur and/or hydrogen sulfide are preferably obtained from them.

Description

2 CS 266 261 B12 CS 266 261 B1

Vynález sa týká spósobu spracovania organických smolovitých látok, vznikajúcich privýrobě gumárenských urýchlovačov na báze merkaptobenztiazolu tak, že sa podrobuji! tepelnémuštiepeniu a vzniklý plynný podiel sa použije ako zdroj síry a/alebo sírovodíka.BACKGROUND OF THE INVENTION The present invention relates to a process for the treatment of organic pitch substances resulting from the production of mercaptobenzothiazole-based rubber accelerators by subjecting them to the process. thermal cracking, and the resulting gaseous fraction is used as a source of sulfur and / or hydrogen sulfide.

Pri výrobě gumárenských urýchlovačov na báze merkaptobenztiazolu, najmá pri výroběsamotného 2-merkaptobenztiazolu, 2,2'-dibenztiazyldisulfidu, N(morfolinyl)-2-benztiazyl-sulfenamidu a iných prechádza určitá časť surovin a medziproduktov na organické smolovitékondenzáty, technologicky označované ako smoly, ktoré sa z výroby odvádzajú ako nežiadúciodpad a budto sa róznym spósobom spalujú alebo sa skladuji! na skládkách tuhých odpadov.Množstvo týchto smol a ostatných neprchavých odpadov je relativné vysoké, do 35 % vzhladomk výrobě hlavných produktov podlá druhu urýchlovača a spósobu jeho výroby. Obsahuji! vysokýpodiel organicky viazanej siry (do 30 hmot. aj dusíka (až 15 hmot. %) a ich skladovaniealebo spalovanie je preto spojené so značnými ekologickými problémami. V publikovanej odbornej literatúre sa problému spracovania smól venuje len malá poroz-nost. Časť týchto látok sa móže přidávat do čestných asfaltov alebo po zmiešaní napr.s polyvinylchloridom použit ako hydroizolačná hmota. Tieto spósoby však zdaleka nevystihuji!všetky možnosti spracovania týchto látok. Vysoký obsah siry, nevýhodný pri týchto postupocha pri spalovaní smál ako takých, dává předpoklad pre ich výhodné využitie ako zdroj sírya/alebo sírnych zlúčenín.In the production of mercaptobenzothiazole-based rubber accelerators, a particular proportion of raw materials and intermediates are passed to organic pitch-condensates, technologically referred to as pitch, which are commonly referred to as the 2-mercaptobenzothiazole, 2,2'-dibenzothiazide disulfide, N (morpholinyl) -2-benzothiazylsulfenamide and others. they are diverted from production as undesirable waste and will be burned or stored in different ways! in solid waste landfills. The amount of these pitch and other non-volatile wastes is relatively high, up to 35% due to the production of the main products according to the type of accelerator and the way it is produced. Contents! the high proportion of organically bound sulfur (up to 30 wt.% nitrogen (up to 15 wt.%) and their storage or combustion is therefore associated with considerable environmental problems. In the published literature, the problem of the processing of the poles is limited. Highly sulfur content, which is disadvantageous in these combustion processes, makes it a prerequisite for their advantageous use as a source for their use as a waterproofing material. sulfur and / or sulfur compounds.

Podlá tohto vynálezu sa organické smolovité kondenzáty z výroby gumárenských urýchlovačovna báze 2-merkaptobenztiazolu spracovávajú tak, že sa za normálneho alebo zvýšeného tlaku,s výhodou pri 5 až 20 MPa, tepelne štiepia bez přístupu vzduchu alebo kyslíka po dobu0,2 až 6 hodin, s výhodou 0,3 až 3 hodiny, pri teplote 200 až 500 °C, s výhodou 350 až450 °C, z produktov štiepenia sa oddelia plynné podřely a s výhodou sa z nich získá síraa/alebo sirovodík.According to the present invention, the organic pitch-containing condensates from the manufacture of rubber accelerators of 2-mercaptobenzothiazole base are treated such that they are thermally cleaved under normal or elevated pressure, preferably at 5 to 20 MPa, without air or oxygen for 0.2 to 6 hours. preferably 0.3 to 3 hours, at 200 to 500 ° C, preferably 350 to 450 ° C, the gaseous products are separated from the cleavage products and preferably sulfur and / or hydrogen sulfide are obtained.

Termolabilné smoly sa pri zvýšenej teplote rozkladajú na plynné produkty a polotekutýzvyšok. Do plynnej fázy přitom okrem oxidu uhličitého a dusíka prechádza najma vo forměsírovodíka aj část síry, póvodne viazanej do zložitej organickej zlúčeniny a dalej určitýpodiel uhlovodikov, ktoré zvyšuji! energetický obsah plynu. Volbu podmienok pyrolýzy jemožné upravovat tak množstvo a zloženie plynnej fázy ako aj (do určitej miery) konzistenciupyrolýzneho zvyšku. Pri nižších tlakoch je zvyšok polotuhý s obsahom tuhých častíc, zatialčo pri vyššom tlaku prevládajú polotekuté až tekuté zložky až do teplát okolo 450 °C, nadktorými už opat prevládajú tuhé podřely vo zvyšku. Stúpanie teploty podporuje zvýšenú tvorbuplynnej fázy a zlepšuje účinnost přechodu siry do plynu najma vo formě sírovodíka, v menšejmiere ako nízkomolekulárnych sírnych zlúčenín.The thermolabile pitch decomposes to gaseous products and the semi-liquid residue at elevated temperature. In addition to carbon dioxide and nitrogen, some of the sulfur, which is partially bound to the complex organic compound and some of the hydrocarbon additions, is transferred to the gas phase in addition to carbon dioxide and nitrogen. energy content of gas. The choice of pyrolysis conditions can be adjusted by both the amount and composition of the gas phase as well as (to some extent) the consistency of the pyrolysis residue. At lower pressures, the residue is semi-solid with a solids content, while at higher pressures semi-liquid to liquid components predominate up to about 450 ° C, whereby the abutment predominates in solid residues. The temperature rise promotes increased gas phase formation and improves the sulfur-to-gas transition efficiency, especially in the form of hydrogen sulfide, in a smaller proportion than the low molecular weight sulfur compounds.

Pri pyrolýze za normálneho tlaku prechádza do plynnej podoby len menšia část smól,vačšia část produktov v priebehu pyrolýzy destiluje a získá sa ako kvapalný podiel. Pyro- 4 lýzny zvyšok je čierny a tuhý, krehkej konzistencie. Z týchto dóvodov je možné ako optimálně pracovné podmienky uviesť teploty medzi 350 a450 °C, tlaky 5 až 20 MPa a reakčný čas 0,3 až 3 hodiny. Za týchto podmienok přejde doplynnej fázy okolo 50 » síry, prítomnej v pávodných smolách, zatial čo pyrolýzny zvyšokje pri pracovnej teplote nad 80 °C ešte dobré manipulovatelný. Získaný pyrolýzny plyn móže byt použitý ako zdroj síry, pričom obsah uhlovodikov v ňom(prevažne etán a etylén) ulahčuje jeho spracovanie na síru napr. spálením v Clausovej peci.In the case of pyrolysis under normal pressure, only a minor part of the pitch passes into the gaseous form, the greater part of the products being distilled during the pyrolysis and recovered as a liquid fraction. Pyro-4 lysis residue is black and stiff, brittle consistency. For these reasons, temperatures of between 350 and 450 ° C, pressures of 5 to 20 MPa and reaction times of 0.3 to 3 hours can be used as optimum operating conditions. Under these conditions, the gaseous phase passes about 50% of the sulfur present in the pitch pitch, while the pyrolysis residue is still good to handle at operating temperatures above 80 ° C. The pyrolysis gas obtained can be used as a source of sulfur, the content of hydrocarbons in it (predominantly ethane and ethylene) facilitating its processing to sulfur, for example by burning in a Claus furnace.

Je však možné z něho získat síru alebo aj sirovodík niektorým zo známých spósobov, napr.absorpčně, adsorpčne a pod. Výhody postupu podlá vynálezu sú ilustrované v připojených príkladoch. Spočívajú jednakv podstatnom znížení množstva odpadných smól převedením ich značnej časti do zúžitkovatelnejplynnej formy, jednak v ekologicky dóležitom znížení obsahu síry v pyrolýznom zvyšku a ,However, it is possible to obtain sulfur or even hydrogen sulfide from it by any of the known methods, e.g., adsorption, adsorption and the like. The advantages of the process of the invention are illustrated in the accompanying examples. They consist essentially in a substantial reduction in the amount of waste streams by converting a substantial portion thereof into a usable gas form, and in an ecologically important reduction in the sulfur content of the pyrolysis residue, and,

Claims (1)

Spůsob spracovania smol z výroby gumárenských urýchlovačov na báze 2-merkaptobenztiazolu vyznačený tým, že smoly sa za normálneho alebo zvýšeného tlaku, s výhodou pri 5 až 20 MPa, tepelne štiepia bez přístupu vzduchu alebo kyslíka po dobu 0,2 až 6 hodin, s výhodou 0,3 až 3 hodiny, pri teplote 200 až 500 °C, s výhodou 350 až 450 °C, z produktov štiepenia sa oddelia plynné podřely, ktoré sú zdrojom síry a/alebo sirovodíku.Process for processing resins from the production of rubber accelerators based on 2-mercaptobenzothiazole, characterized in that the resins are thermally cleaved at normal or elevated pressure, preferably at 5 to 20 MPa, without access of air or oxygen for 0.2 to 6 hours, preferably 0.3 to 3 hours, at a temperature of 200 to 500 ° C, preferably 350 to 450 ° C, gaseous fractions which are a source of sulfur and / or hydrogen sulfide are separated from the cleavage products.
CS878119A 1987-11-13 1987-11-13 The smol processing method CS266261B1 (en)

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CS266261B1 true CS266261B1 (en) 1989-12-13

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