CS209567B1

CS209567B1 - Sulfuric acid utilization

Info

Publication number: CS209567B1
Application number: CS135980A
Authority: CS
Inventors: Peter Hauskrecht; Stefan Husar; Anna Violova
Original assignee: Peter Hauskrecht; Stefan Husar; Anna Violova
Priority date: 1980-02-28
Filing date: 1980-02-28
Publication date: 1981-12-31

Abstract

Kyselina sírová obsahujúca alkalický síran, kyselinu dusičnú, 3-metylfenol a jeho nitro-, nitrozo- a sulfoderiváty. sa čistia tak, že.sa 3-metylfenol a jeh.o deriváty .adsorbujú aktívnym uhlím. Druhý stupeň čistenia sa robí s kremičitanmi s aktívnymi adsorbčnými miestami. Z kremičitanov sa používá výhodné aktivovaný hentonit. Kyselina sírová sa zahušťuje odpařením vody, vykrystalizovaný alkalický síran sa oddělí. .Sulfuric acid containing alkali sulfate, nitric acid, 3-methylphenol and its nitro-, nitroso- and sulfoderivatives. are purified by adsorbing 3-methylphenol and its derivatives with activated carbon. The second stage of purification is carried out with silicates with active adsorption sites. Activated hentonite is preferably used from silicates. Sulfuric acid is concentrated by evaporation of water, the crystallized alkali sulfate is separated. .

Description

Vynález., sa týká spósobu čistenia kyseliny sírovej vznikájúcej pri nitračných, oxidačných a sulfonačnýoh prooesoch.The invention relates to a process for the purification of sulfuric acid resulting from nitration, oxidation and sulfonation processes.

Kyselina sírová , ktorá odpadá po nitračných, oxidačných, sulfonačnýoh. procesech, máhmot. konoentráciu 20-80 %. Obsahuje organické látky, kyselinu dusičná,'kysličníky, dusíka•anorganické.sírany, a pod,Takáto kyselina sírová sa. používá pri výrobě minerálhyoh hnojív(superfosfátu, síranu amonného a pod.), v hutníctve pri odstraňovaní nečistdt .z poíxžitejkyseliny sírov Oj'.Kysličníky, dusíka sa odstranujú v denitračných zariadeniach·, alebo saodstranujú z' kyseliny sírovej aoetylánom. Podlá UDR pat. 120 184, sa odstranujú kyslič-níky dusíka z použitéj kyseliny sírovéj močovinou, alebo inýmikarbamidami."Kyselina 3Í- rová o hmot, konoentrácii 70 % po nitrozačaýoh procésoch. sa koncentruje v Paulingovomprístrhji, pričom dochádza k oxidácii organických nečistot kyselinou,sírovou, alebodusičnou. íistenie použitej kyseliny, sírovéj"extrakciou fenolmi. udává ZSSR - AO 3.16· 648.Extrakciou. organických, nečištdt s mastnými alkoholmi, alebo aromatickými hydroxide -.rivátmi udává ZSSR - AO" 416 312. Odstraňovaníe organických, látok z kyseliny sírovéj v,přítomnosti síranov železa,alebo " médi udává ZSSR - AO 564 260. Sposob čistenia upotře-bené j“kyseliny sírovej po nitraoii aromatických zlúčenín obsahujúci fluor, udává čsl.pat. 167 207. Alkalické' sírany a sírany tažkých. kovov sa oddeřujú zo zriedenej kyselinysírovej skoneentrováním kyseliny'sírovej na 96 až 98 %. Zriedená kyselina sírová sapoužívá na výrobu síranu vápenatého, barnatého, sinočnatého va pod. Organické látky saodstranujú"· z kyseliny sírovej extrakciou organickými rozpústadlami. Pri extrakcii vsakčást rozpúšťadla sa.rozpustí v zriedenej kyselině sírovej.Sulfuric acid, which is eliminated after nitration, oxidation, sulfonation. processes, mass. 20-80%. It contains organic substances, nitric acid, 'oxides, nitrogen', inorganic sulphates, etc., Such sulfuric acid. used in the production of mineral fertilizers (superphosphate, ammonium sulphate, etc.), in metallurgy, to remove impurities from the sulfuric acid used, O 2. Oxides, nitrogen are removed in denitration plants, or removed from sulfuric acid by ethylene. According to UDR pat. 120 184, the nitrogen oxides are removed from the sulfuric acid used by the urea or other carbamides. The "sulfuric acid, 70% by weight of the nitroaccharide process, is concentrated in a Pauling resin, oxidizing the organic impurities with acid, sulfuric acid or nitric acid. purifying the used acid by sulfuric extraction with phenols. indicates USSR - AO 3.16 · 648.Extraction. organic, non-purifying with fatty alcohols or aromatic hydroxide derivatives is given in USSR 416 312. The removal of organic substances from sulfuric acid in the presence of iron sulphates or by the medium is indicated by USSR-AO 564 260. "Sulfuric acid after fluorine-containing nitrous aromatic compounds," cf. 167 207. Alkaline sulphates and sulphates of heavy. metals are separated from dilute acid by scintillation of sulfuric acid to 96-98%. Diluted sulfuric acid is used for the production of calcium sulfate, barium sulphate and the like. The organic substances are removed from the sulfuric acid by extraction with organic solvents. However, in the extraction part of the solvent is dissolved in dilute sulfuric acid.

Vyššie uvedené nedostatky sú odstraněné spdsoboňi čistenia použitej kyseliny sírovejpodlá vynálezu. Kyselina sírová , obšahujúca. alkalický síran, kyselinu dusičná, 3-metyl-fenol a jeho nitrozo-, nitro- a sulfodehiváty, sa. regeneruje tak,- že '3-metylf enol a Jehoderiváty sá adsorbujú aktívnym uhlím. Po adsorbcii aktívnym uhlím sa preyádza adsorboia.krěmičitanmi s aktívnymi adso.rbčnými centrami, s výhodou bentonitom. Po adsorbcii sa zkyseliny, sírovej aktivně uhlie a kremičitany oddelia. Podlá počtu, adscrbčných atupňcvobsah.· 3-metylf enolu poklesne prakticky na nulu. Zriedená kyselina sírová sá skoňcentrujo,pričom vykrystalizuje alkalický síran, ktorý sa oddělí,.The above drawbacks are eliminated by the purification of the sulfuric acid used according to the invention. Sulfuric acid, containing. alkaline sulphate, nitric acid, 3-methylphenol and its nitroso-, nitro- and sulphodegenerates, are. it regenerates so that 3-methylphenol and its derivatives are adsorbed with activated carbon. After adsorption with activated charcoal, adsorption of silicates with active admixtures, preferably bentonite, is carried out. After adsorption, the acid, sulfur, and carbon are actively separated. According to the number of adsorbent and free 3-methylphenol drops to virtually zero. The dilute sulfuric acid is concentrated to give the alkaline sulfate, which is separated off.

Obsah 3-metyl-4~nitrofenolu v nitro-, nitrózo- a sulfoderívátoch, 3-metylfenoluje 1 až.100 %. Adsorbent výhodné obsahuje tak. aktivně uhlie ako-i kremičitan 3 aktív-nymi, adsorbčnými centrami. . íistenie kyseliny sírovej adsorbciou 3-metylfenolu a· jeh.o sulfo-, nitro-, nitrózo-derivýtov ha aktívnom uhlí, alebo následnou adsorbciou krěmičitanmi'3'aktívnymi adsórb-čnými centrami dooielime prakticky odstránehie 3-metylfenolu a jeho nitro-, nitrózd-,.sulfoderivátov zó zriedenej kyseliny sírovej. Zriedená kyselina sírová sa meze použit’pri. výrobě "minerálnyoh hnojív, alebo koncentrovat a použit nalubovolné účely. Příklad 1. ' 200 ml použitej· kyseliny sírovej s hmot. obsah.om· kyseliny sírovej. 28,3 .%·, kyselinydusicnej 1,6 %, 0,1 % ky.sličníkov dusíka titrovatelných ako kyselina dusitá,. Ha+ ionov2,7 % »,0,14 %.3->metyl- 4 - nitrofenolu a 0,05 % 3-metylf enolu a jeho nitrózo - sulfo-derivátov sada do. 600 ml kadičky. Přidá sá 3 g aktívneho uhlia. Po 24 hodinách,sa ak-tivně uhlie. Odfiltruje,Kyselina sírová obsahovala 28,3 % kyseliny sírovej, 0,7.% kyae- lihy dusicnej, 2,7 % Sa+ionov, 0,0-12 % 3-metyl-4-nitrofenolu a 0,006 % 3,-metylf enolu ajeho nitrózo a sulfoderivátov.The content of 3-methyl-4-nitrophenol in nitro, nitroso and sulfoderivates, 3-methylphenol 1 to 100%. The adsorbent advantageously comprises such. actively carbon and silicate 3 by active, adsorption centers. . purification of sulfuric acid by adsorption of 3-methylphenol and sulfo-, nitro-, nitroso-derivatives with activated charcoal, or by subsequent adsorption with silicone-active adsorption centers practically eliminates the removal of 3-methylphenol and its nitro-, nitro- sulfoderivatives of dilute sulfuric acid. Diluted sulfuric acid is used as a limit. to produce "mineral fertilizers, or to concentrate and use any purpose. Example 1." 200 ml of sulfuric acid used · sulfuric acid content 28.3% · acidic acid 1.6%, 0.1% ky nitrogen oxides titratable as nitrous acid, Ha + ion2,7% », 0,14% .3-> methyl 4-nitrophenol and 0,05% 3-methylphenol and its nitroso-sulfo derivatives set up to 600 ml 3 g of activated carbon are added After 24 hours, the charcoal is filtered off, the sulfuric acid contained 28.3% sulfuric acid, 0.7% nitric acid, 2.7% Sa + ion, O , 0-12% 3-methyl-4-nitrophenol and 0.006% 3'-methylphenol and its nitroso and sulfoderivatives.

Claims

2 Example. 2 The procedure is the same as the p-odla example. 1, leň. with the difference that the sulfuric acid is concentrated by distillation of the water by filtration of the activated carbon. The excreted alkali sulfate is filtered off. The sulfuric acid obtained had a concentration of 95% sulfuric acid (traces of organic matter 0.1%). EXAMPLE 3 The procedure is the same as in Example 1, except that 5 g of activated bentonite are added to the sulfuric acid after filtration of the activated carbon and after 15 minutes the adsorbed bentonite is filtered off. content. 3-methyl-4-nitrophenol was 0.003% (traces of 3-methylphenol and its nitroso and sulfoderivatives). . The process of the invention can be used to regenerate sulfuric acid used in the production of 3-methyl-4-nitrophenol. Sulfuric acid has not yet been used and discharged wastewater. Purified sulfuric acid can be used in the production of mineral fertilizers or directly in the production of 3-methyl-4-nitrophenyl. SUMMARY OF THE INVENTION. A method of purifying spent sulfuric acid containing 3-methylphenol as its impurity, nitro-, nitroso- and sulfoderivatives thereof, nitric acid, nitrogen oxides, such as nitrous acid and alkaline sulphates having 3 & in that the 3-methylphenol derivatives are adsorbed with activated carbon which are separated from the sulfuric acid after adsorption.

2. Process according to claim 1, characterized in that after the separation of the activated carbon, the residue of 3-methylphenol and its derivatives is adsorbed by the silicates with the active adsorbent and the adsorbed silicates are separated from the sulfuric acid.

3. Point by point. 1 and 2, characterized in that the masses 1 and 2 are characterized by 3-methyl-4-nitrophenol content. nitro-, nitroso-, sulfode-, .beta.-methylphenol, is 1 to 100%.

4. The process of claim 2 wherein the activated bentonite is preferably used from the silicates.

5. The process according to claim 1 or 2, wherein the sulfuric acid is concentrated by evaporation of water after removal of the adsorbents, and the crystallized alkaline sulfur is separated off.

6. Point by point. 1 characterized in that the adsorbent contains, actively carbon and silicate with active adsorbent oentres.