Fixed-bed study for bone char adsorptive removal of refractory organics from electrodialysis concentrate produced by petroleum refinery.

Water reuse in industrial processes has been an increasing need encouraged in recent years. However, as the streams are recycled, solutes accumulate, thus requiring purification techniques. Membrane processes (reverse osmosis and electrodialysis) have been implemented and in order to increase the reuse of water at its highest level, crystallization has been evaluated to remove salts from the concentrate produced and get a feasible disposal. Nevertheless, contaminants affect the crystallization performance, thus making the removal of residual organics important for both the efficiency of crystallization and the increase of water reuse. In this context, aiming at establishing a sustainable virtuous circle, bone char (0.5-1.4 mm particle size, mesoporous structure) was used to remove refractory organics from an electrodialysis concentrate effluent (C-EDR) from a Brazilian petroleum refinery, at a lab-scale, in a fixed-bed adsorption column. Bone char selectively and partially removed the refractory organics, a complex mixture of long-chain hydrocarbons, aromatic compounds, carboxylic acids, amines and amides. The maximum adsorption capacity increased with the increase in bed depth and reduction in flow rate. A maximum removal of 35.60 mg g-1 was achieved for the highest bed depth evaluated (12.9 cm). The breakthrough curves indicated that bone char could adsorb part of the organic compounds from the C-EDR. The scaling up was possible for the C/C0 ratios of 0.55, 0.60 and 0.65, providing a service time at about 16 days for 45% removal efficiency for typical real operational conditions used in the refinery.

Aspectos do coprocessamento de resíduos em fornos de clínquer / Aspects of waste co-processing in clinker kilns

A prática do coprocessamento de resíduos na indústria de cimento tem se expandido devido à necessidade crescente de uma destinação ambiental e socialmente mais adequada de resíduos perigosos provenientes de diversos processos industriais. O objetivo deste trabalho foi realizar uma revisão sobre o coprocessamento de resíduos em fornos de clínquer, no Brasil e no mundo, visando contribuir para a otimização dos processos, identificando os aspectos já estudados e os que ainda demandam pesquisas. Foram abordados aspectos socioambientais e tecnológicos do coprocessamento, bem como a análise do ciclo de vida (ACV) na produção de cimento, e a produção técnico-científica sobre o coprocessamento.

The practice of co-processing of residues has increased due to the requirement of environmental and social friendly disposal of dangerous wastes from several industrial processes. The aim of this work was to perform a revision of co-processing of residues in Brazil and in the world, aiming at process optimization and also to identify the aspects already studied as well as those which still request research efforts. Social, environmental, and technological aspects of co-processing were discussed in the present work as well as the life cycle analysis (LCA) in the cement production and the technical and scientific literature about co-processing.

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.