Submerged-arc welding slags: characterization and leaching strategies for the removal of aluminum and titanium.

In the present study, submerged-arc welding slags were characterized by applying a variety of methods, including X-ray fluorescence, X-ray diffraction, particle size, Raman spectroscopy, and scanning electron microscope with energy dispersive X-ray analysis. The content of Al proved to be quite similar within neutral and acid slags (10-14%), while that of Ti proved to be much higher in acid slags (approximately 10%) than in neutral slags (<1%). The presence of spinel structures associated with Al species could also be identified in the analyzed samples. This characterization study was accompanied by leaching tests performed under changing operating conditions in an attempt to evaluate to what extent the Al and Ti bearing components could be removed from the slags. The leaching work involved three distinct strategies: (i) NaOH leaching followed by H(2)SO(4) leaching, (ii) acid leaching (HCl and H(2)SO(4)) using oxidizing/reducing agents, and (iii) slag calcination followed by H(2)SO(4) leaching. In the best result, 80% of Al was extracted in one single leaching stage after calcination of the acid slag with NaCl+C at 900 °C. By contrast, the removal of Ti proved to be unsatisfactory.

Leaching of the fine fraction of the argon oxygen decarburization with lance (AOD-L) sludge for the preferential removal of iron.

The fine fraction of the argon oxygen decarburization with lance (AOD-L) sludge is a hazardous waste generated by the stainless steel industry which is normally disposed in landfills. Due to the relative high content of Fe, Cr and Ni as well as its low granulometry, a hydrometallurgical route based on sequential leaching steps is being investigated to treat it. In this paper, an attempt made to remove Fe from the sludge and concentrate Cr and Ni in the solid is highlighted. Leaching was carried out at atmospheric pressure using H(2)SO(4) and HCl at varying temperature (25, 40, 55 and 70 degrees C) and acid concentration (3, 6 and 12%, v/v). For both acids, leaching rate increased with temperature and acid concentration, and higher dissolutions of Fe and Ni were obtained in comparison with that of Cr. HCl was found more selective for Fe over Ni and Cr. The content of Fe was reduced nearly 50% (w/w) at 70 degrees C and HCl 12% (v/v), while Cr remained mostly in the solid; however, around 40% (w/w) of Ni was dissolved and it may hinder such leaching step in the studied route. The study points out that total metal leaching of sludge under high temperature and pressure conditions must be considered.

Alternativas para o tratamento de efluentes da indústria galvânica / Alternatives for the galvanic wastewater treatment

Os métodos de precipitação química, cristalização e extração líquido-líquido foram aplicados visando propor alternativas para o tratamento de efluentes líquidos gerados pela indústria de galvanoplastia. Efluentes de diversas empresas do setor, localizadas no estado de Minas Gerais (Brasil), foram coletados e caracterizados. O efluente estudado, proveniente de empresa de galvanização de zinco a quente, continha cerca de 90 g/L de ferro total, 35 g/L de zinco e menores quantidades de Al, Ni e Cu, em meio ácido clorídrico (pH = 0,6). A separação seletiva entre ferro e zinco não se mostrou eficiente por precipitação, sendo a técnica adequada somente no tratamento do efluente, ao contrário da cristalização e extração líquido-líquido utilizando-se TBP como agente extratante. A integração destas técnicas ainda requer estudos mais detalhados visando à otimização de custos e das condições operacionais.

Separation methods such as chemical precipitation, crystallization and liquid-liquid extraction have been investigated aiming to treat effluents generated by the galvanic industry. Effluent samples generated by several companies located in the state of Minas Gerais (Brazil) were collected and chemically characterized. For this work, a typical zinc hot-dip galvanizing effluent containing about 90 g/L of total iron, 35 g/L of zinc and minor amounts of Al, Ni, Cu, in HCl medium (pH = 0.6) was treated. A selective separation between metals zinc and iron was not achieved by chemical precipitation, which was found adequate to threat water only. On contrary, zinc and iron was separated very efficiently by crystallization and liquid-liquid extraction using TBP as extractant agent. The integration of these methods to recover zinc and iron from effluent still requires more detailed studies.

Selective extraction of zinc(II) over iron(II) from spent hydrochloric acid pickling effluents by liquid-liquid extraction.

The selective removal of zinc(II) over iron(II) by liquid-liquid extraction from spent hydrochloric acid pickling effluents produced by the zinc hot-dip galvanizing industry was studied at room temperature. Two distinct effluents were investigated: effluent 1 containing 70.2g/L of Zn, 92.2g/L of Fe and pH 0.6, and effluent 2 containing 33.9 g/L of Zn, 203.9g/L of Fe and 2M HCl. The following extractants were compared: TBP (tri-n-butyl phosphate), Cyanex 272 [bis(2,4,4-trimethylpentyl)phosphinic acid], Cyanex 301 [bis(2,4,4-trimethylpentyl) dithiophosphinic acid] and Cyanex 302 [bis(2,4,4-trimethylpentyl) monothiophosphinic acid]. The best separation results were obtained for extractants TBP and Cyanex 301. Around 92.5% of zinc and 11.2% of iron were extracted from effluent 1 in one single contact using 100% (v/v) of TBP. With Cyanex 301, around 80-95% of zinc and less than 10% of iron were extracted from effluent 2 at pH 0.3-1.0. For Cyanex 272, the highest extraction yield for zinc (70% of zinc with 20% of iron extraction) was found at pH 2.4. Cyanex 302 presented low metal extraction levels (below 10%) and slow phase disengagement characteristics. Reactions for the extraction of zinc with TBP and Cyanex 301 from hydrochloric acid solution were proposed.

Characterization of the fine fraction of the argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry.

The argon oxygen decarburization with lance (AOD-L) sludge generated by the stainless steelmaking industry is a hazardous waste due to the presence of chromium. While its coarse fraction is usually recycled into the own industrial process, the fine fraction is normally disposed in landfills. Techniques such as briquetting or magnetic separation were found to be inadequate to treat it for reuse purposes. So, in this work, the fine fraction of the AOD-L sludge was characterized aiming to find alternative methods to treat it. This sludge consists of a fine powder (mean diameter of 1 microm) containing 34 +/- 2% (w/w) of iron, 10.2 +/- 0.9% (w/w) of chromium and 1.4 +/- 0.1% (w/w) of nickel. The main crystalline phases identified in this study were chromite (FeCr(2)O(4)), magnetite (Fe(3)O(4)), hematite (Fe(2)O(3)) and calcite (CaCO(3)). In the digestion tests, the addition of HClO(4) has favored the dissolution of chromite which is a very stable oxide in aqueous media. Nickel was found in very fine particles, probably in the metallic form or associated with iron and oxygen. The sludge was classified as hazardous waste, so its disposal in landfills should be avoided.