Maria J. Martin

H2S and VOCs abatement robustness in biofilters and air diffusion bioreactors: a comparative study.

The robustness of a conventional biofilter and an air diffusion bioreactor (ADB) was comparatively evaluated in laboratory-scale plants treating a mixture of H2S, butanone, toluene and alpha-pinene at gas residence times of 50 s. Under steady state conditions, H2S, butanone and toluene were almost completely degraded, while alpha-pinene removal did not exhibit removal efficiencies (REs) higher than 11.0 +/- 2.3%. Fluctuations in temperature from 8 degrees C to 30 degrees C did not impact significantly process performance in any of the biotechnologies tested. However, while the ADB unit was able to cope with three and six fold step increases in pollutant loadings, volatile organic compounds (VOCs) REs noticeably decreased in the biofilter when subjected to a six fold step change (i.e. 90% reduction for butanone and 30% for toluene). A process shutdown of five days resulted in the temporary loss of butanone and toluene RE in the ADB system. A lack of irrigation during five days caused a slight decrease in the biofilter REs, while a failure in the pH control system drastically affected the ADB performance. Finally, process robustness was quantified. The calculated overall risks showed that both biotechnologies were reliable for H2S and VOCs treatment in wastewater treatment plants, ADB diffusion exhibiting a higher robustness towards fluctuations commonly found under routine operation. This robustness was further confirmed by the high stability of the DGGE profiles.

Biogas Upgrading: Optimal Activated Carbon Properties for Siloxane Removal

A total of 12 commercial activated carbons (ACs) have been tested for the removal of octamethylcyclotetrasiloxane (D4) in dynamic adsorption experiments using different carrier gases and D4 concentrations. Characterization of the ACs included several physical and chemical techniques. The D4 adsorption capacities were strongly related with the textural development of the ACs. Results showed that the optimum adsorbent for D4 is a wood-based chemically activated carbon, which rendered an adsorption capacity of 1732 ± 93 mg g(-1) using 1000 ppm (v/v) of D4 with dry N2 as the carrier gas. When the concentration of D4 was lowered to typical values found in biogas, the adsorption capacity was halved. The presence of major biogas compounds (i.e., CH4 and CO2) and humidity further reduced the D4 adsorption capacity. The polymerization of D4 over the surface of all ACs was found to be relevant after prolonged contact times. The extent of this phenomenon, which may negatively affect the thermal regeneration of the AC, correlated reasonably well with the presence of phenolic and carboxylic groups on the carbon surfaces.

Adsorption of volatile sulphur compounds onto modified activated carbons: Effect of oxygen functional groups

The effect of physical and chemical properties of activated carbon (AC) on the adsorption of ethyl mercaptan, dimethyl sulphide and dimethyl disulphide was investigated by treating a commercial AC with nitric acid and ozone. The chemical properties of ACs were characterised by temperature programme desorption and X-ray photoelectron spectroscopy. AC treated with nitric acid presented a larger amount of oxygen functional groups than materials oxidised with ozone. This enrichment allowed a significant improvement on adsorption capacities for ethyl mercaptan and dimethyl sulphide but not for dimethyl disulphide. In order to gain a deeper knowledge on the effect of the surface chemistry of AC on the adsorption of volatile sulphur compounds, the quantum-chemical COSMO-RS method was used to simulate the interactions between AC surface groups and the studied volatile sulphur compounds. In agreement with experimental data, this model predicted a greater affinity of dimethyl disulphide towards AC, unaffected by the incorporation of oxygen functional groups in the surface. Moreover, the model pointed out to an increase of the adsorption capacity of AC by the incorporation of hydroxyl functional groups in the case of ethyl mercaptan and dimethyl sulphide due to the hydrogen bond interactions.

H2O2-based oxidation processes for the regeneration of activated carbons saturated with volatile organic compounds of different polarity

This study reports the sequential regeneration treatment of activated carbons (ACs) saturated with volatile organic compounds (VOCs) of different polarity using H(2)O(2) as oxidizing agent. In this process, VOCs were adsorbed onto the AC and further oxidized by H(2)O(2). A commercial AC was selected and saturated with three different VOCs: two non-polar and hydrophobic VOCs, toluene and limonene, and one polar and hydrophilic VOC, methyl ethyl ketone (MEK). The saturated AC was regenerated with H(2)O(2), and the Fenton reagent for comparison. It was found that regeneration efficiencies obtained with the H(2)O(2) treatment were equal to or even higher than those obtained with the Fenton treatment. The fate of the pre-adsorbed VOCs, once the regeneration process is completed was studied. It was found that this regeneration treatment is limited for non-polar VOCs such as toluene and limonene, as they tend to remain adsorbed onto the ACs after regeneration treatment. Contrarily, MEK tend to be transferred to the bulk phase and react with the generated oxidant species.

Regeneration of siloxane-exhausted activated carbon by advanced oxidation processes.

In the context of the biogas upgrading, siloxane exhausted activated carbons need to be regenerated in order to avoid them becoming a residue. In this work, two commercial activate carbons which were proved to be efficient in the removal of octamethylcyclotetrasiloxane (D4) from biogas, have been regenerated through advanced oxidation processes using both O3 and H2O2. After the treatment with O3, the activated carbon recovered up to 40% of the original adsorption capacity while by the oxidation with H2O2 the regeneration efficiency achieved was up to 45%. In order to enhance the H2O2 oxidation, activated carbon was amended with iron. In this case, the regeneration efficiency increased up to 92%.

Incorporating cleaner production and environmental management systems in environmental science education at the University of Girona

The field of environmental science and engineering is rapidly evolving. The focus has shifted more and more from the end‐of‐pipe to pollution‐prevention oriented strategies for sustainability. Cleaner production requires new attitudes, knowledge and skills for all professionals to assure that preventive environmental strategies are integrated into planning and development activities throughout society. When preparing the curriculum for the new studies in Environmental Sciences at the University of Girona in 1993, it was considered essential to introduce pollution‐prevention‐oriented courses for future graduates. “Compatible Technologies” and “Minimisation of the Industrial Environmental Impact” are two courses supplementing each other to address the integrated approach to industry environmental issues. Describes the objectives of these two courses as well as the main topics included, and the methodology applied.

Linz-Donawitz steel slag for the removal of hydrogen sulfide at room temperature.

Slags collected from the basic oxygen furnaces of two Linz-Donawitz steel making plants were tested as adsorbents for H(2)S removal at room temperature (298 K). Two different particle size fractions, namely <212 and 212-500 μm, were selected from the original slag samples. Dynamic adsorption tests were carried out using a column-bed configuration and retention capacities were calculated after bed exhaustion. Retention capacities as high as 180 mg of H(2)S g(-1) of slag were attained, in spite of the very low specific surface area of the steel slags. As expected, humidity played a crucial role in the removal of H(2)S. Particle size had also an important effect on the capacity of the adsorption beds. Analysis of the exhausted slags revealed considerable amounts of elemental sulfur on the surface of the particles. Sulfates were also found on the exhausted slags, especially on the 212-500 μm size fractions. The characterization of the slags prior and after the H(2)S adsorption experiments allowed us to postulate plausible mechanisms to understand the outstanding capacity of these steel byproduct for H(2)S adsorption.

Optimizing chemical conditioning for odour removal of undigested sewage sludge in drying processes

Emission of odours during the thermal drying in sludge handling processes is one of the main sources of odour problems in wastewater treatment plants. The objective of this work was to assess the use of the response surface methodology as a technique to optimize the chemical conditioning process of undigested sewage sludges, in order to improve the dewaterability, and to reduce the odour emissions during the thermal drying of the sludge. Synergistic effects between inorganic conditioners (iron chloride and calcium oxide) were observed in terms of sulphur emissions and odour reduction. The developed quadratic models indicated that optimizing the conditioners dosage is possible to increase a 70% the dewaterability, reducing a 50% and 54% the emission of odour and volatile sulphur compounds respectively. The optimization of the conditioning process was validated experimentally.

Adsorption of odorous sulfur compounds onto activated carbons modified by gamma irradiation

A commercial activated carbon (AC) was modified by gamma irradiation and was tested as adsorbent for the removal of ethyl mercaptan, dimethyl disulfide and dimethyl disulfide in wet conditions. Modifications were carried out under five different conditions: irradiation in absence of water, in presence of ultrapure water, in ultrapure water at pH=1.0 and 1000 mg L(-1) Cl(-), in ultrapure water at pH=7.5 and 1000 mg L(-1) Br(-), and in ultrapure water at pH=12.5 and 1000 mg L(-1) NO3(-). The chemical properties of each AC were characterized by elemental analysis, temperature programmed desorption and X-ray photoelectron spectroscopy. Outcomes show that a large number of oxygen functional groups were incorporated in the AC surface by gamma irradiation, especially in the AC irradiated in the presence of ultrapure water. The dynamic adsorption test results reveal that the incorporation of oxygen functional groups did not enhance the adsorption capacities for dimethyl sulfide and dimethyl disulfide. A significant improvement in the ethyl mercaptan adsorption capacity was correlated with the incorporation of phenolic groups in the AC surface. Moreover, diethyl disulfide was detected as by-product of ethyl mercaptan oxidation process under wet conditions and its formation depended on the chemical properties of ACs.

Integration of advanced oxidation processes at mild conditions in wet scrubbers for odourous sulphur compounds treatment

The effectiveness of different advanced oxidation processes on the treatment of a multicomponent aqueous solution containing ethyl mercaptan, dimethyl sulphide and dimethyl disulphide (0.5 mg L(-1) of each sulphur compound) was investigated with the objective to assess which one is the most suitable treatment to be coupled in wet scrubbers used in odour treatment facilities. UV/H2O2, Fenton, photo-Fenton and ozone treatments were tested at mild conditions and the oxidation efficiency obtained was compared. The oxidation tests were carried out in magnetically stirred cylindrical quartz reactors using the same molar concentration of oxidants (hydrogen peroxide or ozone). The results show that ozone and photo-Fenton are the most efficient treatments, achieving up to 95% of sulphur compounds oxidation and a mineralisation degree around 70% in 10 min. Furthermore, the total costs of the treatments taking into account the capital and operational costs were also estimated for a comparative purpose. The economic analysis revealed that the Fenton treatment is the most economical option to be integrated in a wet scrubber to remove volatile organic sulphur compounds, as long as there are no space constraints to install the required reactor volume. In the case of reactor volume limitation or retrofitting complexities, the ozone and photo-Fenton treatments should be considered as viable alternatives.