Valorisation of the residual aqueous phase from hydrothermally liquefied black liquor by persulphate-based advanced oxidation.

Hydrothermal liquefaction of Kraft black liquor is a promising method for the production of valuable organic chemicals. However, the separation of the biochar and biocrude leaves a residual aqueous phase in large volumes, which needs to be properly managed to make the process profitable. In this work, the persulphate-based advanced oxidation was assessed, for the first time ever, as a pretreatment of this aqueous phase to reduce its content of phenolic compounds and alcohols, which hinder further valorisation strategies. Results revealed that the phenolic compounds and the alcohols were oxidised in presence of low persulphate anion concentrations (<50 mM), mainly to quinone-like compounds and organic acids. At higher oxidant concentrations, these intermediates were subsequently oxidised to valuable acetic acid. When Fe (II) was added as the catalyst, low concentrations (<9 mM) enhanced the degradation of both phenolic compounds and alcohols due to the increase of the sulphate radicals, consequently reducing persulphate requirements for their removal. Nevertheless, higher Fe (II) doses produced the sequestration of sulphate radicals, thus decreasing the oxidation performance and generating undesired parallel reactions.

Structure of the humic acid-like compounds of raw and hydrothermally treated sewage sludge.

Humic acids are of great interest in many fields; however, they are inhibitors of fermentative processes applied to hydrothermally treated sewage sludge. Hence, the structure and composition of soluble and bound humic acid-like fractions from raw and hydrothermally treated sewage sludge were studied. Lipid, polysaccharide, protein and aromatic fractions were identified, as well as a high nitrogen content (7-10 %) and low solubility in alkaline media. Thus, they do not strictly meet the chemical definition of 'humic acids'. The soluble humic acid-like compounds had more aromatic and less protein content. Thermal hydrolysis of sewage sludge increased their aromaticity to the detriment of protein and polysaccharide fractions, while wet oxidation caused an increase in all structural fractions. Regarding the bound compounds, lipid, polysaccharide and aromatic fractions increased markedly during both treatments, although oxygen produced higher degradation of the protein fraction and, from 1 h, the partial degradation of aromatic compounds and an increase in the C/N atomic ratio (from 5.0 to 18.7 after 2 h). Therefore, hydrothermal treatments have a positive impact on the hydrolysate biodegradability due to the organic matter solubilisation, but also a negative impact linked to the higher solubilisation of the humic acid-like compounds and their structural changes.

Characterization and reuse of waste from the magnesium nitrate fertilizer industry.

Currently, liquid fertilizers are considered strategic products in the sector, particularly those with nitrogen and magnesium in their composition. During their synthesis, the generated muddy and sticky residue is usually managed as a toxic waste because its properties and feasible valorization methods have not yet been studied. For the first time, this residue has been thoroughly characterized, and, on the results obtained, its possible reuse options have been discussed. This material, with 47 % moisture content, a neutral pH, and a specific density of 0.85, still contains 35 % dry weight of nitromagnesite. These findings, together with a high cation exchange capacity and the presence of iron, aluminium, calcium and silicon as minority components, make its reintroduction into the manufacturing process of fertilizers the most viable option for its valorization, having two alternatives for this purpose. The first is to use it as a feedstock for the production of solid fertilizers by adding 30 % quicklime to the residue to improve its mechanical properties, thus obtaining a fertilizer with 5.7 %, 5.0 % and 24.3 % (dry weight) of magnesium, nitrogen and calcium, respectively. The second option, which focused on obtaining a liquid fertilizer, allowed the recovery of approximately 86 % of the remaining nitromagnesite in the residue by washing it with nitric acid, reducing its initial dry mass by 77 %. Then, the resultant liquid phase, with 16 % magnesium nitrate, could be enriched to the 35 % concentration demanded by liquid fertilizer consumers by a subsequent acid attack of the raw rock.

Heavy metal solubilisation during the hydrothermal treatment of sludge.

The present study analyses the combined effects of temperature (from 160 to 200 °C), and, for the first time ever, type of atmosphere (oxidising or inert) and pressure (from 60 to 100 bar) on the solubilisation of heavy metals during the hydrothermal treatment of wet no-diluted sewage sludge. Results revealed that Cd, Pb, Al and Fe were hardly affected by neither the atmosphere nor temperature, remained almost completely in the solid phase during all the hydrothermal treatments tested; while Cr, Ni, Cu and Zn were partially solubilised, being this solubilisation favoured by the presence of an oxidising atmosphere. In contrast, initial dissolved Hg was partially precipitated under both types of atmosphere, although it was re-dissolved after 30 min under an inert atmosphere. Regarding the working conditions, the highest temperature (200 °C) caused the greatest metal immobilisation, whereas the range of pressures tested barely had any effect on it. Concerning the reaction time, the lowest concentration of metals in the liquid fraction of the hydrolysed sludge was obtained during the initial 30 min of treatment.

Production of carboxylic acids from the non-lignin residue of black liquor by hydrothermal treatments.

The present study assesses, for the first time, the use of the non-lignin residue from Kraft black liquor as a renewable source of carboxylic acids. For this purpose, the liquid fraction obtained after separating the lignin from the black liquor by acid precipitation was subjected to different hydrothermal treatments. It was found that the formation of carboxylic acids can be maximized at 190 °C, 70 bar and under an inert atmosphere, with concentrations after 2 h of 29.0 g/l of oxalic acid, 1.8 g/L of malic acid, 10.0 g/L of lactic acid, 4.1 g/L of formic acid, 11.8 g/L of acetic acid and 3.4 g/L of propionic acid. The presence of an oxidizing atmosphere generated a less concentrated, but more purified, stream of acids than that obtained by thermal hydrolysis, simplifying the subsequent downstream processing.