CS208338B1

CS208338B1 - Process for the production of sulphates from the sulfuric acid used

Info

Publication number: CS208338B1
Application number: CS136080A
Authority: CS
Inventors: Anna Violova; Peter Hauskrecht; Stefan Husar
Original assignee: Anna Violova; Peter Hauskrecht; Stefan Husar
Priority date: 1980-02-28
Filing date: 1980-02-28
Publication date: 1981-09-15

Abstract

Vynalez sa týká výroby síranov z použitéj kyseliny sírovej, vznikájúoej po nitračných, alebo oxidačnýoh prooesoch.The invention relates to the production of sulfates from spent sulfuric acid, resulting from nitration or oxidation processes.

Description

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Kyselina sírová, ktorá odpadá po nitračných, oxidačnýoh, sulfonačných procesoch má·hmotnostnú konoentráoiu 20-80 %. Obsahuje organické l'átky, kyselinu dusičnú, kysličníkydusíka, anorganické sírany a pod. Takáto kyselina sírová sa používá pri výrobě minerál-nych hnojív (superfosfátu, síranu amonného,a pod. ) a v hutníctve pri odstraňovaní kys-ličníkov kovov. Sú známe postupy k odstraňovaniu nečistot z použitej kyseliny sírovej.Kysličníky dusíka sa odstraňujú v denitračných zariadeniach, alebo sa odstraňujú z ky-seliny acetylénom.. Podlá NDR - patentu 120 184, sa odstraňujú kysličníky dusíka z pou-žité j kyseliny sírovéj močovinou, alebo inými karbamidami. Kyselina sírová o hmotnostnějkoncentrácii 70 % po nitrozačných procesoch sa koncentruje v Paulingovom přístroji, pri-čom doohádza k oxidácii organických nečistSt kyselinou sírovou, alebo dusičnou. Cisteniepoužitej kyseliny sírovej extrakciou fenolmi sa popisuje v sovietskom autorskom osvědče-ní 316 648. Extrakcia organických nečistót mastnými alkoholmi, alebo aromatickými hydro-xiderivátmi. sa popisuje v sovietskom autorskom osvědčení 416 312. Odstraňovanie organic-kých látok z kyseliny v přítomnosti síranov železa, alebo médi sa popisuje v sovietskomautorskom osvědčení 564.260. Sposob čistenia upotrebenej kyseliny sírovej po nitráciiaromatických, zlúčenín obsahujúci fluor sa popisuje v Csl. patente 167 207. Alkalickésírany a sírany ťažkých kovov sa oddelujú zo zriedenej kyseliny sírovej skoneentrovanímkyseliny sírovej na hmot. konoentráoiu 96 až 98 %. Zriedená kyselina sírová sa používána výrobu.síranu vápenatého, barnatého, zinočnatého a pod.Sulfuric acid, which is eliminated after nitration, oxidation, sulfonation processes, has a weight ratio of 20-80%. It contains organic substances, nitric acid, nitrogen oxides, inorganic sulphates and the like. Such sulfuric acid is used in the production of mineral fertilizers (superphosphate, ammonium sulfate, etc.) and in metallurgy to remove metal oxides. Procedures for removing impurities from the sulfuric acid used are known. Nitrogen oxides are removed in denitration plants or removed from the acetylene acid. According to GDR patent 120,184, nitrogen oxides are removed from the sulfuric acid used by urea, or other carbamides. Sulfuric acid at 70% by weight after nitrosation processes is concentrated in a Pauling apparatus to oxidize organic impurities with sulfuric acid or nitric acid. The purification of the used sulfuric acid by phenol extraction is described in Soviet patent 316 648. Extraction of organic impurities with fatty alcohols or aromatic hydroxides. is described in Soviet copyright 416,312. The removal of organic matter from the acid in the presence of iron sulphates or by the medium is described in the Soviet Certificate of Authentication 564.260. A method for purifying spent sulfuric acid after nitro-aromatic, fluorine-containing compounds is described in Csl. Alkali sulphates and sulphates of heavy metals are separated from dilute sulfuric acid by scintillating sulfuric acid to mass. 96% to 98%. Diluted sulfuric acid is used to produce calcium, barium, zinc, and the like.

Použitá kyselina sírová sa často používá pri výrobě minerálnych hnojív, alebo niek-torých technicky doležitých síranov. Nevýhoda je, že minerálně hnojivo obsahuje organickélátky, ktoré v niektorých prípadoch nemožno v danej koncentrácii tolerovat.The sulfuric acid used is often used in the production of mineral fertilizers or some technically important sulphates. The disadvantage is that mineral fertilizer contains organic substances, which in some cases cannot be tolerated in a given concentration.

Vyššie uvedené nedostatky sú odstránené spósobom výroby síranov z použitej kyselinysírovej, obsahujúcej ako nečistoty 3-metylfenol a jeho nitro-, nitrozo- a sulfoderiváty,kyselinu dusičná, kysličníky dusíka a alkalické sírany. Podstata vynálezu je v tom, žesa kyselina sírová zneutralizuje a 3-metylfenol a jeho nitro-, nitrozo- a sulfoderivátysa od vzniklých síranov oddelia.'Kyselina sírová sa zneutralizuje hydroxidom alkalickéhokovu, amoniakom, alebo uhličitanom, alebo síričitanom alkalického kovu, alebo síričitanom,alebo uhličitanom amonným. Koncentrácia vzniklého síranu je nižšia ako koncentrácia jehonasýteného roztoku a hodnota pH je nižšia ako 7, pričom sa vzniklej suspenzie 3-metyl -fenolu a jeho derivátov tieto látky oddelia. Zvyšný 3-metylfenol a jeho nitro-, nitrózo-.a sulfoderiváty sa z roztoku síranov oddelia adsorbciou aktívnym uhlím.The aforementioned drawbacks are eliminated by the method of producing sulphates from the used acidic acid, containing as impurities 3-methylphenol and its nitro-, nitroso- and sulfoderivatives, nitric acid, nitrogen oxides and alkali sulphates. SUMMARY OF THE INVENTION Sulfuric acid is neutralized and 3-methylphenol and its nitro, nitroso and sulfoderivates are separated from the sulphates formed. The sulfuric acid is neutralized with alkali hydroxide, ammonia, or an alkali metal carbonate or sulphite, or a sulphate, or ammonium carbonate. The concentration of the resulting sulfate is lower than the concentration of the saturated solution and the pH is less than 7, with the resulting suspension of 3-methylphenol and its derivatives being separated. The remaining 3-methylphenol and its nitro, nitroso and sulfoderivatives are separated from the sulphate solution by adsorption with activated carbon.

Kyselina sa zneutralizuje hydroxidom, alebo uhličitanom kovu alkalických zemin. HodnotapH vzniklej suspenzie sa upraví nad hodnotu 8. Vyzrážané sírany sa oddelia. Vo filtrátesa upraví minerálnou kyselinou hodnota pH na hodnotu nižsiu ako 6. Vyzrážaný 3-metylfenola jeho nitro-, nitrózo- a sulfoderiváty sa oddelia a zvyšný 3-metylfenol a jeho nitro-,nitrózo- a sulfoderiváty sa adsorbujú,aktívnym uhlím.The acid is neutralized with hydroxide or an alkaline earth carbonate. The pH of the resulting suspension was adjusted to above 8. The precipitated sulphates were separated. The pH of the filtrates is adjusted to less than 6 with mineral acid. The precipitated 3-methylphenol and its nitro, nitroso and sulfoderivatives are separated and the remaining 3-methylphenol and its nitro, nitroso and sulfoderivatives are adsorbed with activated carbon.

Kycelina sírová sa zneutralizuje hydroxidom, uhličitanom, alebo kysličníkom kovu alkalic-kých zemin, pričom hodnota pH je nižšia než 6, vyzrážané sírany sa oddelia a premyjú roz-,tokom alkalického hydroxidu, alebo uhličitanom. Pri reakcii uhličitanu kovu alkalickýchzemin s kyselinou sírovou sa použije zmes' kyseliny sírovej a chlorovodíkovej. Kyselinasírová sa neutralizuje roztokom amoniaku v amonných soliach kyselin, s výhodou v dusič-nane amónnom. 3-metylfenol a jeho nitro-, nitrozo-, sulfoderiváty sa adsorbujú kremičitan-mimi s aktívnymi adsorbčnými miestami. Hmotnostná koncentrácia 3-metyl-4-nitrofenolu v 3-metylfenole a jeho nitro-, nitrozo- a sulfoderivátoch je 1 až 99,99 %. 3-metylfenola jeho nitro-, nitrozo- a sulfoderiváty sa oddelia od síranov v přítomnosti aktívneho .uhlia a kremičitanov s aktívnymi adsorbčnými miestami. Výhodou ; 'Ssobu podlá vynálezu je výroba síranov z odpadnej kyseliny sírovej. Síranyobsahujú malt ;.možstvo organických látok, ktoré je možné tolerovat. Výroba síranov podlá vynálezu má význam hlavně pri výrobě síranu amonného a vápena-tého. Vzniklý síran amonný nájde uplatnenie ako zložka v kombinovaných minerálnych hno-jivách. Síran vápenatý nájde uplatnenie v stavebníctve. 3-metylfenol a hlavně jeho 3-me-tyl-4-nitrofenol je cenný a nájde uplatnenie pri výrobě přípravkou na ochranu rastlín. 208 338 2 Příklad 1The sulfuric acid is neutralized with hydroxide, carbonate or alkaline earth metal oxide, the pH being less than 6, the precipitated sulphates are separated and washed with an alkali hydroxide or carbonate solution. The reaction of the alkaline earth metal carbonate with sulfuric acid is carried out using a mixture of sulfuric acid and hydrochloric acid. The acid kinase is neutralized with a solution of ammonia in the ammonium acid salts, preferably in ammonium nitrate. 3-Methylphenol and its nitro, nitroso, sulfoderivatives are adsorbed with silicates with active adsorption sites. The concentration of 3-methyl-4-nitrophenol in 3-methylphenol and its nitro-, nitroso- and sulfoderivatives is 1 to 99.99%. The 3-methylphenol nitro-, nitroso- and sulfoderivatives thereof are separated from the sulfates in the presence of active carbon and silicates with active adsorbent sites. Advantage ; According to the invention, there is provided the production of sulphates from waste sulfuric acid. Sulphate contains mortar, a range of organic substances that can be tolerated. The production of sulphates according to the invention is of particular importance in the production of ammonium sulphate and calcium sulphate. The resulting ammonium sulphate finds application as a component in the combined mineral fertilizers. Calcium sulphate finds application in the construction industry. 3-Methylphenol and especially its 3-methyl-4-nitrophenol is valuable and will find application in the production of plant protection products. 208 338 2 Example 1

Do banky sa dá 100 ml použitej kyseliny s nasledujúcim hmotnostným obsahom 26,2 %kyseliny sírovej, 0,7 % kyseliny dusičnéj, 0,04 % kysličníkov dusíka, 7,2 % NaHSO^, 0,13 % 3-metyl- 4 -nitrofenolu a 0,09 % 3-metylfenolu a jeho sulfo- a nitroderivátov. K vodnému roztoku kyseliny sírovej sa přidal 5 %-ný vodný roztok NaOH, dokial hodnotapH neholá 4. Zo vzniklej suspenzie sa časť usadila za 24 hodin. Roztok síranu sa zlial.Obsahoval zlúčeniny s nasledujúcim hmotnostným obsahom 0,02 % 3-metyl-4-nitrofenolu a0,0J5 % 3-metylfenolu a jeho nitrozo-, a sulfoderivátov. K roztoku sa přidalo 2 g aktív-neho uhlia. Po 24 hodinách sa odfiltrovalo. Eiltrát obsahoval zlúčeniny s nasledujúoimhmotnostným obsahom 0,0005 % 3-metyl-4-nitrofenolu a 0,002 % 3-metylfenolu a jeho nitrozoa sulfoderivátov. Příklad 2The flask was charged with 100 ml of the acid used, followed by 26.2% sulfuric acid, 0.7% nitric acid, 0.04% nitrogen oxides, 7.2% NaHSO3, 0.13% 3-methyl-4 - nitrophenol and 0.09% 3-methylphenol and its sulfo and nitro derivatives. A 5% aqueous NaOH solution was added to the aqueous sulfuric acid solution until a shear of 4 was obtained. The sulphate solution was decanted and contained 0.02% by weight of 3-methyl-4-nitrophenol and 0.05% of 3-methylphenol and its nitroso- and sulfoderivatives. 2 g of activated carbon was added to the solution. After 24 hours, it was filtered off. The filtrate contained compounds with a weight content of 0.0005% 3-methyl-4-nitrophenol and 0.002% 3-methylphenol and its nitrosoa sulfoderivatives. Example 2

Postup je rovnaký ako u příkladu 1, iba s tým rozdielom, že sa použil na neutraliza-oiu roztok amoniaků s hmotnostným obsahom 20,2 % a časť 3-metylfenolu a jeho nitro-,nitrozo- a sulfoderivátov sa zo suspenzie odstředila- po přidaní bentonitu. K roztoku sapotom přidalo 2 g aktívneho uhlia, ktoré sa po 24 hodinách z roztoku odfiltrovalo aroztok síranu amčnneho so síranom sodným s hmotnostnými obsahmi 0,006 % 3-metyl-4nitro-fenolu a 0,004 % 3-metylfenolu a jeho nitrozo- a sulfoderivátov. Příklad 3The procedure is the same as in Example 1, except that a 20.2% ammonia solution was used for neutralization and a portion of the 3-methylphenol and its nitro-, nitroso- and sulfoderivatives were centrifuged after the addition. bentonite. To the solution was added 2 g of activated carbon, which after 24 hours from the solution was filtered off and a solution of ammonium sulfate with sodium sulfate containing 0.006% 3-methyl-4-nitro-phenol and 0.004% 3-methylphenol and its nitroso- and sulfoderivatives. Example 3

Postup bol rovnaký ako u příkladu 1, iba na neutralizáciu sa noužil roztok amonia-katu dusičnanu amonného s hmotnostným obsahom 10,2 % amoniakatu a 25,3 % dusičnanu amon-ného. Po odfiltrovaní aktívneho uhlia, roztok obsahoval 0,006 % 3-metyl-4-n'itrof enolua 0,005 % 3-metylfenolu a jeho nitrozo- a sulfoderivátov. Na druhý stupen adsorboie sapoužilo 2 g aktivovaného bentonitu. Po odfiltrovaní , roztok obsahoval 0,003 % 3-metyl--4-nitrofenolu. Příklad 4The procedure was the same as in Example 1, only a solution of ammonium ammonium nitrate containing 10.2% ammonia and 25.3% ammonium nitrate was used for neutralization. After filtering out the activated carbon, the solution contained 0.006% 3-methyl-4-nitrophenolate and 0.005% 3-methylphenol and its nitroso- and sulfoderivatives. 2 g of activated bentonite was used for the second stage of adsorption. After filtration, the solution contained 0.003% 3-methyl-4-nitrophenol. Example 4

Postup bol rovnaký· ako u příkladu 1, iba na neůtralizáciu sa použila suspenziehydroxidu vápenatého s hmotnostnou konoentráciou 5 % a hodnota pH po neutralizáciibola 5,6. Vyzrázený síran vápenatý sa odfiltroval a premyl 300 ml vodným roztokom NaOHs hmotnostným obsahom 1Síran vápenatý- obsahoval 3-metyl-4-nitrofenolu s hmotnostnýmobsahom 0,007 %. Vo filtráte po filtrácii síranu vápenatého sa 3-metylfenol a jeho deri-váty adsorbovali 2 g aktívneho uhlia. Příklad 5The procedure was the same as in Example 1, only a calcium hydroxide suspension of 5% by weight and a pH of 5.6 after neutralization was used for non-neutralization. The precipitated calcium sulfate was filtered off and washed with 300 ml of an aqueous solution of NaOH with a content of calcium sulfate of 3-methyl-4-nitrophenol containing 0.007% by weight. In the filtrate after filtration of calcium sulfate, 3-methylphenol and its derivatives were adsorbed with 2 g of activated carbon. Example 5

Postup bol rovnaký ako u příkladu 4, iba hodnota pH bola 8,5. Vyzrážaný síran saodfiltroval, premyl 300 ml vody, -Vo filtráte sa kyselinou chlorovodíkovou s hmotnostnýmobsahom 5 % upravila hodnota pH na 4,5 i vyzrážaný 3-metylfenol a jeho deriváty saodfiltrovali. Získalo sa 0,07 g zmesi 3-metylfenolu a jeho derivátov s hmotnostným ob-sakom ?č>,2 % 3-metyl-4-nitrofenolu.The procedure was the same as in Example 4, only the pH was 8.5. The precipitated sulphate was filtered, washed with 300 ml of water, and the pH was adjusted to 4.5 with 5% hydrochloric acid. The precipitated 3-methylphenol and its derivatives were filtered off. 0.07 g of a mixture of 3-methylphenol and its derivatives were obtained with a weight of 2% of 3-methyl-4-nitrophenol.

Claims

Example 6 The procedure was the same as in Example 1, only a 0% sodium carbonate solution was used for neutralization. After the activated charcoal was filtered off, the solution contained 3-methyl-4-nitrophenol and its nitroso- and sulphodivatives with a content of 0.007% and 3-methylphenol with a content of 0.006%. EXAMPLE 7 The procedure was the same as in Example 1, only 5 ml of 32% hydrochloric acid was added to sulfuric acid, and calcium carbonate was used for neutralization, and the pH after neutralization was 2.0. The precipitated calcium sulfate was filtered off, washed with 200 ml of NaOII with a content of 1% and 1.00 ml of water. Calcium sulfate contained 3-methyl-4-nitrophenol with a content of 0.0008%. The invention can be used in the utilization of waste-like 3iric acid formed in the production of 3-methyl-4-nitrophenol. Currently, this sulfuric acid is not used and flows into wastewater. waters. Sulfuric acid can be used to produce technical sulphates, mainly calcium, with a very high content of 3-methylphenol and its derivatives and a solution of ammonium and sodium sulphate, which can be used in the production of multi-component mineral fertilizers. can be used to produce 3-methyl-4-nitrophenol and other 3-methylphenol derivatives. BACKGROUND OF THE INVENTION

Process for producing sulphates from used sulfuric acid, comprising as impurities 3-methylphenol and its nitro-, nitroso- and sulfoderivatives, nitric acid, nitrogen oxides and alkali sulphates characterized in that the sulfuric acid is neutralized and 3-methylphenol and its nitro, nitroso, sulfoderivatives 3a are separated from the resulting sulphates.

2. Process according to claim 1, characterized in that the sulfuric acid neutralizes the alkali metal hydroxide, the ammonia or the carbonate or the sulphate alkaline or ammonium carbonate or sulphite, the concentration of the resulting sulphate being lower than that of its saturated solution and the value of The pH of the solution is greater than 7, separating the 3-methylphenol and its derivatives from the resulting suspension of 3-methylphenol and its derivatives, separating the 3-methylphenol and its nitro, nitroso- and sulfodivatives from the sulphate solution by adsorption with activated carbon,

3. Process according to claim 1, characterized in that the sulfuric acid is neutralized with the hydroxybenzoate and the alkaline earth metal carbonate, the pH of the resulting suspension being 8, the precipitated sulphates are separated, the pH is adjusted to below 6 in the filtrate, the precipitated 3-methylphenol and its nitro-, nitroso- and sulfoderivatives are separated and the 3-methylphenol and its nitro, nitroso- and sulfodivatives are separated with adsorbent carbon. 208 338 4

4. Process according to claim 1, characterized in that the sulfuric acid is neutralized with a hydroxide, a carbonate or an alkaline earth metal oxide, whereby the pH is less than 6, the precipitated sulphates are separated and washed with a solution of alkali hydroxide or carbonate.

5. Process according to claim 4, characterized in that a mixture of sulfuric acid and hydrochloric acid is used in the reaction of the alkaline earth metal carbonate with sulfuric acid.

6. Process according to claim 2, characterized in that the sulfuric acid is neutralized with a solution of ammonia in the ammonium salts of mineral. acids, preferably ammonium nitrate.

7. A method according to claim 2, wherein the 3-methylphenol and its nitro, nitroso, and sulfoderivatives are adsorbed with silicates with active adsorbent sites.

8. The method of clauses 1, 2, 3 and 6 wherein the concentration of 3-methyl-4-nitro-enol in 3-methylphenol and its nitro-, nitroso- and sulfoderivoryto is 1 to 99.99%.

9. The process of claim 2 wherein the 3-methylphenol and its nitro, nitroso and sulfoderivatives are separated from the suspension in the presence of large-surface inert substances, preferably in the presence of activated carbon and silicates with active adsorbent oentres.