CS218194B1 - Method of cleaning the refuse solutions of the suphuric acid - Google Patents
Method of cleaning the refuse solutions of the suphuric acid Download PDFInfo
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- CS218194B1 CS218194B1 CS579581A CS579581A CS218194B1 CS 218194 B1 CS218194 B1 CS 218194B1 CS 579581 A CS579581 A CS 579581A CS 579581 A CS579581 A CS 579581A CS 218194 B1 CS218194 B1 CS 218194B1
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- Czechoslovakia
- Prior art keywords
- sulfuric acid
- extraction
- solution
- waste
- solutions
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- 238000000034 method Methods 0.000 title claims description 14
- 239000002253 acid Substances 0.000 title description 4
- 238000004140 cleaning Methods 0.000 title 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 66
- 239000002699 waste material Substances 0.000 claims description 33
- 238000000605 extraction Methods 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 15
- 239000012535 impurity Substances 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 10
- PIIZYNQECPTVEO-UHFFFAOYSA-N 4-nitro-m-cresol Chemical compound CC1=CC(O)=CC=C1[N+]([O-])=O PIIZYNQECPTVEO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 238000005191 phase separation Methods 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- -1 xylene amine Chemical class 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 31
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910052920 inorganic sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006396 nitration reaction Methods 0.000 description 1
- 125000000018 nitroso group Chemical group N(=O)* 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000002426 superphosphate Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
Landscapes
- Extraction Or Liquid Replacement (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález sa týká spósobu čistenia odpadových roztokov kyseliny sírovej.The invention relates to a process for purifying waste solutions of sulfuric acid.
Z nitračných, oxidačných alebo sulfonačných procesov odpadajú roztoky kyseliny sírovej obsahuj úce 20 až 80 % hmotnosti kyseliny sírovej, kyselinu dusičnú, kysličníky dusíka, anorganické sírany a organické látky. Takéto roztoky kyseliny sírovej sa dajú využit, napr. pri výrobě minerálnych hnojív ako sú superfosfát, síran amonný a pod., potřebné je z nich však odstrániť organické nečistoty.Sulfuric acid solutions containing 20 to 80% by weight of sulfuric acid, nitric acid, nitrogen oxides, inorganic sulphates and organic substances are omitted from the nitration, oxidation or sulfonation processes. Such sulfuric acid solutions can be used, e.g. in the production of mineral fertilizers such as superphosphate, ammonium sulphate and the like, but it is necessary to remove organic impurities from them.
Organické látky sa z odpadových roztokov kyseliny sírovej oddelujú destiláciu s vodnou parou. Pri tomto postupe sa zároveň odstránia niektoré kysličníky dusíka. Pri destilácii s vodnou parou sa obvykle zriedi odpadový roztok kyseliny sírovej, čo si před opátovným použitím kyseliny vyžaduje zařadit další stupeň, v ktorom sa odstraňuje voda. Regenerácia kyseliny sírovej z kyselinovej rafinácie benzénových uhlovodíkov extrakciou organických nečistot je opísaná v autorskom osvědčení ZSSR č. 174177. Ako extrakčné činidlo sa používá 5 až 10 %-ný roztok kyseliny sírovej nasýtený (ΝΗ^έο^ V patente USA č. 3 180 713 je opísaná extrakaia kvapalných odpadov kyseliny sírovej nasýtených amoniakom. Ako extrakčné činidlo sa používal proo^o-procesu, a to C^-alkoholy v zmesi s C7 až C9 rozpúšťadlami. Extrakcia organických nečistot z odpadovej kyseliny sírovej fenolom sa opisuje v autorskom osvědčení ZSSR č. 316648. Avšak ako sa uvádza v ďalšom riešení podlte autorského osvedčenia č. 41 6312 ZSSR extrakcia fenolom nie je dosť účinná, pretože fenol sa tiež rozpúšťa v odpadovej kyselme sírovej. Čiastočne sa tento problém rieši v uvedenom autorskom osvědčení tým, že sa ako extrakčné činidlo použijú alkoholy, resp. roztoky alkoholov v nepolárných rozpúšťadlách. Použitie rozpúšťadiel, obsahujúcich alkoholy, vedie k peneniú, s čím súvisia, ťažkosti pri rozdělovaní fáz. Tažkosti sú tiež pri regenerácii extrahovadla reextrakciou roztokmi alkalických hydroxidov, pretože do roztoku hydroxidu prechádzajú čiastočne aj alkoholy z póvodnéhp extrahovadla.The organics are separated from the waste sulfuric acid solutions by steam distillation. At the same time, some nitrogen oxides are removed. In water vapor distillation, the waste sulfuric acid solution is usually diluted, which requires a further water removal step before the acid is reused. Regeneration of sulfuric acid from acidic refining of benzene hydrocarbons by extraction of organic impurities is described in the USSR certificate no. 174177. A 5 to 10% saturated sulfuric acid solution is used as the extraction agent (U.S. Pat. No. 3,180,713 describes the extraction of liquid ammonia saturated sulfuric waste. The extraction agent used is a pro-process. , namely C 1-4 alcohols mixed with C 7 to C 9 solvents The extraction of organic impurities from waste sulfuric acid by phenol is described in USSR Authorized Certificate No. 316648. However, as described in the following solution, follow the Author's Certificate No. 41 6312 USSR. phenol extraction is not effective enough because phenol is also dissolved in waste sulfuric acid, which is partially solved in the above-mentioned certificate by using alcohols or solutions of alcohol in non-polar solvents as the extracting agent. it leads to money, which is associated with, difficulties in phase separation and also in regeneration CII extraction solvent reextraction solutions of alkali hydroxides, as sodium hydroxide to undergo the alcohol part of the extraction solvent póvodnéhp.
Z uvedených údajov je vidieť, že sa doteraz nepodařilo úspěšně zvládnut oddeltevanie organických nečistot z odpadových roztokov kyseliny sírovej napriek tomu, že vyriešenie tohoto problému by poskytlo možnost využit odpadové roztoky kyseliny sírovej pri výrobě minerálnych hnojív alebo v iných technologických aplikáciách.From the above data, it can be seen that the separation of organic impurities from sulfuric acid waste solutions has not yet been successfully managed, although solving this problem would provide the possibility of utilizing sulfuric acid waste solutions in mineral fertilizer production or other technological applications.
Uvedené nedostatky sú odstránené u spósobu čistenia odpadových roztokov kyseliny sírovej podlte vynálezu, obsahujúce okrem anorganických solí aj kyselinu dusičnú a kysličníky dusíka od rozpuštěných organických nečistot extrakcióu, ktorého podstatou je, že organické látky sa extrahujú benzénom, chloridom uhličitým, xylénami, uhlovodíkovou frakciou s teplotou varu 80 až 300 °C, alebo z nej vydělenými destilačnými rezmi, alebo zmesami uvedených rozpúšťadiel, s výhodou protiprúdne, v objemovom pomere extrakčného činidla k odpadovým roztokom kyseliny sírovej 4:1 až 1:10, pri teplotách 0 až 100 °C, pričom exťrahovadlo sa před opátovným použitím regeneruje destiláciou, alebo reextrakciou organických nečistot vodným roztokom NaOH, alebo KOH s koncentráciou 0,2—20 % hmotnosti, pri objemovom pomere organickej fázy k vodnému roztoku hydroxidu 10:1 až 1:4 pri teplotách 0 až 60 °C.The above-mentioned drawbacks are eliminated in the process for the purification of waste solutions of sulfuric acid according to the invention, which, in addition to inorganic salts, also comprises nitric acid and nitrogen oxides from dissolved organic impurities, extracting the organic matter by extraction with benzene, carbon tetrachloride, a boiling point of 80 to 300 ° C, or distillation slices separated therefrom, or mixtures of said solvents, preferably countercurrent, in a volume ratio of extracting agent to waste solutions of sulfuric acid of 4: 1 to 1:10, at temperatures of 0 to 100 ° C, prior to re-use, the extractant is regenerated by distillation or reextraction of organic impurities with an aqueous solution of NaOH or KOH at a concentration of 0.2-20% by weight, at a volume ratio of organic phase to aqueous hydroxide solution of 10: 1 to 1: 4 at temperatures of 0 to 60 ° C.
Postup podía vynálezu umožňuje účinné oddelovanie organických látok z odpadových roztokov kyseliny sírovej extrakcióu a regeneráciou extrahovadla. Postup je energeticky a aparatúrne nenáročný a jeho realizácia umožňuje hospodárné využit odpadové roztoky kyseliny sírovej, ktoré sa vo váčšine prípadov po neutralizácii kyseliny vypúšťajú do odpadových vód závodov.The process according to the invention allows the effective separation of the organic matter from the waste solutions of sulfuric acid by extraction and recovery of the extractant. The process is undemanding in terms of energy and equipment, and its implementation enables the economical utilization of waste solutions of sulfuric acid, which in most cases are discharged into the waste water of the plants after acid neutralization.
Výhodou extrakcie podía tohoto vynálezu v porovnaní s vyššie uvedenými extrakčnými postupmi čistenia odpadových roztokov kyseliny sírovej je, že sa znižuje možnosť tvorby pěny a s tým súvisiace ťažkosti rozdelovania fáz na minimum. Používané extrahovadlá šú jednoducho regenerovatelné a zaisťujú minimálnu rozpustnost v odpadových roztokoch kyseliny sírovej.The advantage of the extraction according to the invention in comparison with the above mentioned extraction procedures for the purification of waste sulfuric acid solutions is that the possibility of foam formation and the associated difficulties of phase separation are reduced to a minimum. The extractants used are easily regenerable and ensure minimal solubility in waste sulfuric acid solutions.
Extrakcióu pri postupe podía vynálezu možno uskutočňovať kontinuálně alebo diskontinuálne, pričom z híadiska technickej a ekonomi ckej efektivnosti je oddelovanie organických nečistot z odpadových roztokov kontinuálnou protiprúdovou extrakcióu najvýhodnejšie. Reextrakciou organických látok z extrahovadla možno rovnako ako extrakciou uskutočňovať kontinuálně alebo diskontinuálne. S ohladom n.a to, že pri reextrakcii odstraňované organické látky chemicky reagujú s používaným hydroxidom, je reextrakcia z híadiska aparatúrneho menej náročná ako extrakcia.The extraction of the process according to the invention can be carried out continuously or discontinuously, and in terms of technical and economic efficiency, the separation of organic impurities from the waste solutions by continuous countercurrent extraction is most preferred. Reextraction of organic substances from the extractant can be carried out continuously or discontinuously as well as extraction. In view of the fact that the organic substances to be removed are chemically reacted with the hydroxide used during the re-extraction, the re-extraction from the viewpoint of the apparatus is less demanding than the extraction.
Ako extrakčné činidlo pri postupe podía vynálezu sa používajú benzén alebo toluén, alebo chlorid uhličitý, alebo xylény, alebo uhlovodíková frakcia s teplotou varu 0 až 300 °C, alebo z nej vydělenými destilačnými rezmi, alebo kombinácia uvedených rozpúšťadiel. Výběr toho-ktorého rozpúšťadla závisí od chemického zloženia organických nečistot v odpadových roztokoch a od následného spracovania extraktu. Pri regenerácii extrahovadla destiláciou, pokiaí’ tou umožňujú teploty varu extrahovaných organických látok sa používajú extrahovadlá, alebo destilačné řezy s nižšími teplotami varu.Benzene or toluene, or carbon tetrachloride, or xylenes, or a hydrocarbon fraction having a boiling point of from 0 to 300 ° C, or distillation sections separated therefrom, or a combination of the abovementioned solvents, are used as extraction agents in the process of the invention. The choice of which solvent depends on the chemical composition of the organic impurities in the waste solutions and the subsequent treatment of the extract. Extracters or distillation sections with lower boiling points are used in the recovery of the distillation by distillation so as to allow the boiling points of the extracted organic substances.
Množstvá aplikovaného extrakčného alebo reextrakčného činidla sa móžu měnit vo velmi širokom rozmedzí, pričom uvádzané objemové poměry nie sú limitované, ale predstavujú v podstatě najčastejšie frekventovaný poměr z híadiska dosahovania požadovaného účinku. Menšie relativné množstvá extrakčného alebo reextrakčného činidla sa použijú pri kontinuálnych procesoch, váčšie pri diskontinuálnych procesoch. Z híadiska teploty možno do extraktora privádzať odpadový roztok kyseliny sírovej priamo z príslušnej výroby bez ohladu na jeho teplotu, čo je taktiež významné z híadiska spotřeby energie.The amounts of extraction or reextraction agent applied can vary within a very wide range, with the stated volume ratios being not limited, but are essentially the most frequently used ratio in terms of achieving the desired effect. Smaller relative amounts of extraction or reextraction agent are used in continuous processes, more preferably in discontinuous processes. From the point of view of temperature, the waste solution of sulfuric acid can be fed directly from the respective production to the extractor regardless of its temperature, which is also important in terms of energy consumption.
Příklad 1Example 1
Do extrakčnej nádoby sa navážilo 200 g odpadového roztoku kyseliny sírovej, ktorý obsahoval: 30,5% hmotnosti H2SO4, 0,54% hmotnosti HNÓ3, 0,15 % hmotnosti kysličníkov dusíka titrovatelných ako HNO2, 8 % hmotnosti NaHSO/„ 1025 mg/1 3-metyí-4-nitrofenolu, 985 mg/1 metylfenolu a jeho nitrozo a sulfoderivátov. Potom sa do nádoby přidalo 80 g benzénu a obsah nádoby pretrepával pri 24 °C 3 hodiny. Po oddělení fáz bol obsah 3-metyl-4-nitrofenolu v odpadovom roztoku kyseliny sírovej 455 mg/1.To extraction vessel was charged with 200 g of the waste sulfuric acid solution containing: 30.5% by weight of H2SO4, 0.54% by weight of HNO 3, 0.15% of titratable nitrogen oxide such as HNO 2, 8% by weight of NaHSO / "1025 mg (1 3-methyl-4-nitrophenol, 985 mg / l methylphenol and its nitroso and sulfoderivatives). Then 80 g of benzene was added to the flask and the contents of the flask were shaken at 24 ° C for 3 hours. After phase separation, the 3-methyl-4-nitrophenol content of the waste sulfuric acid solution was 455 mg / l.
Příklad 2Example 2
Do extrakčnej nádoby s 200 g odpadového roztoku kyseliny sírovej, rovnakého zloženia ako v příklade 1, sa, ipridalo 80,2 g toluenu. Po 3 hodinovom třepaní pri 24 °C klesol obsah 3-metyl-4-nitrofenolu v oddelenom odpadovom roztoku kyseliny sírovej na 470 mg/1.To an extraction vessel with 200 g of waste sulfuric acid solution of the same composition as in Example 1 was added 80.2 g of toluene. After shaking for 3 hours at 24 ° C, the content of 3-methyl-4-nitrophenol in the separated sulfuric acid waste solution dropped to 470 mg / l.
Příklad 3Example 3
Do extrakčnej nádoby s 200 g odpadového roztoku kyseliny sírovej, rovnakého zloženia ako v příklade 1, sa přidalo 80,9 g chloridu uhličitého. Po 3 hodinovom třepaní pri 24 °C klesol obsah 3-metyl-4-nitrofenolu v odpadovom roztoku kyseliny sírovej nia 545 mg/1.To an extraction vessel with 200 g of waste sulfuric acid solution of the same composition as in Example 1 was added 80.9 g of carbon tetrachloride. After shaking at 24 ° C for 3 hours, the content of 3-methyl-4-nitrophenol in the waste sulfuric acid waste solution was 545 mg / l.
Příklad 4Example 4
Do extrakčnej nádoby s 200 g odpadového roztoku kyseliny sírovej, rovnakého zlozenia ako v příklade 1, sa přidalo 100 g petroleja na svietenie a obsah nádoby sa třepal 3 hodiny pri 24 °C. Po oddělení fáz bol obsah 3-metyl-4-nitrofenolu v odpadovom roztoku kyseliny sírovej 515 mg/1.To an extraction vessel with 200 g of waste sulfuric acid solution of the same composition as in Example 1, 100 g of light kerosene was added and the contents of the vessel were shaken for 3 hours at 24 ° C. After phase separation, the 3-methyl-4-nitrophenol content of the sulfuric acid waste solution was 515 mg / l.
Příklad 5Example 5
200 g rafinátu z extrakcie toluénom, ktorý sa získal postupom podía příkladu 2 a obsahoval 470 mg/1 3-metyl-4-nitrofenolu, sa pri 24 °C třepalo 3 hodiny s 80,1 g toluénu. Po oddělení fáz rafinát obsahoval 395 mg/1 3-metyl-4-nitrofenolu.200 g of the toluene extraction raffinate obtained by the procedure of Example 2 and containing 470 mg / l of 3-methyl-4-nitrophenol were shaken at 80C for 3 hours with 80.1 g of toluene. After phase separation, the raffinate contained 395 mg / L of 3-methyl-4-nitrophenol.
Příklad 6Example 6
Z 67,6 g extraktu, z extrakcie organických nečistot z odpadového roztoku kyseliny sí3 rovej benzéinom podlá příkladu 1, sa jednoducho destiláciou oddestilovalo 66,9 g čistého benzénu. Maximálna teplota v ba,ňke bola 108 °C. Zvyšok po destilácii 0,2 g bol tmavohnedej farby, čiastočne tekutý. Straty pri destilácii boli 0,5 g.From 67.6 g of extract, from the extraction of organic impurities from the waste acid solution of sulfuric acid to benzene according to Example 1, 66.9 g of pure benzene was simply distilled off. The maximum temperature in the flask was 108 ° C. The distillation residue 0.2 g was dark brown, partially liquid. The distillation losses were 0.5 g.
Příklad 7Example 7
70,1 g extraktu získaného z extrakcie organických nečistot z odpadového roztoku kyseliny sírovej toluénom postupom pódia příkladu 2 sa třepalo 15 minút pri 23 °C s 15 g70.1 g of the extract obtained from the extraction of organic impurities from the waste solution of sulfuric acid with toluene by the procedure of Example 2 was shaken for 15 minutes at 23 ° C with 15 g
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS579581A CS218194B1 (en) | 1981-07-30 | 1981-07-30 | Method of cleaning the refuse solutions of the suphuric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS579581A CS218194B1 (en) | 1981-07-30 | 1981-07-30 | Method of cleaning the refuse solutions of the suphuric acid |
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| Publication Number | Publication Date |
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| CS218194B1 true CS218194B1 (en) | 1983-02-25 |
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| CS579581A CS218194B1 (en) | 1981-07-30 | 1981-07-30 | Method of cleaning the refuse solutions of the suphuric acid |
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| CS (1) | CS218194B1 (en) |
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1981
- 1981-07-30 CS CS579581A patent/CS218194B1/en unknown
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