Residual Aqueous Phase Research Articles

Co-hydrothermal carbonization with process water recirculation as a valuable strategy to enhance hydrochar recovery with high energy efficiency

This study aims at valorizing the residual aqueous phase from hydrothermal carbonization (HTC) of Sicilian agro-wastes in order to enhance the hydrochar recovery, positively affecting the process energy balance. Process waters (PW) obtained from HTC and co-HTC using orange peel waste and fennel plant residues were used as recycled solvent in experiments carried out at the temperatures of 180 and 230 °C. The results showed that an additional hydrochar formation was promoted during recirculation of solvent, leading to average increments of solid mass yield of 10.5 wt% for tests conducted at 180 °C and 3.9 wt% for 230 °C. After five consecutive recirculation phases in co-HTC runs, the hydrochar yield increased up to 18.2 wt%. The low H/C and O/C atomic ratios values, found after recirculation, indicate that organic acids, accumulated in the PW, may catalyze the process and promote the biomass deoxygenation by boosting dehydration and decarboxylation. The recovered PWs from conversion steps with deionized water were also carbonized in absence of the solid feedstock in order to quantify their contribution in hydrochar formation during recirculation and thus the synergistic interactions. After recirculation, energy recovery averagely augmented by more than threefold, showing that the proposed strategy could significantly improve the sustainability of HTC.

Carbon isotope effects in the sorption of chlorinated ethenes on biochar and activated carbon

As an alternative to activated carbon, biochar is a promising, environmentally friendly sorbent that can be used to remove organic groundwater pollutants, such as chlorinated ethenes (CEs). Stable isotope fractionation in biofilters is used to quantify pollutant degradation and to distinguish degradation from pollutant sorption on e.g. biochar. However, the sorption of CEs on biochar, and the potential abiotic fractionation processes remain to be tested. The sorption process of CEs and ethene on activated carbon and biochar was investigated with regard to the isotope effects for the differentiation from microbial degradation processes. Results from physical and chemical characterization of biochar indicated that biochar feedstock and pyrolysis conditions determined sorption performance depending on the surface chemistry and the pore size distribution of the coarse sorbent particles. The sorption capacity of the activated carbon was significantly higher with highly chlorinated ethenes, but similar to the biochars with low chlorination. Apparent carbon isotope fractionation factors (ε) of +0.1 to −4.4 ‰ were found above measurement uncertainties of GC/IRMS. The extent of isotope enrichment of the 13C bearing isotopologues in the residual aqueous phase (ε < 0) was characteristic for individual pairs of pollutant and sorbent material and could be related to pore-filling processes limited by the micropore size distribution of sorbent materials and the chemical properties of sorbed pollutants. Especially the large isotope fractionation during the sorption of ethene led to the assumption that diffusion processes within the pore matrix of the sorbent particles contributed to the observed isotope effects, but should still be considered a property of sorption. Concluding on the results indicated that sorption processes can have a significant contribution to carbon isotope fractionation in CEs and ethene. These should not be neglected in the evaluation of biofilters for groundwater purification, in which CEs are simultaneously degraded by microbes.

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.

Bio-Crude Production from Protein-Extracted Grass Residue through Hydrothermal Liquefaction

In the present study, the protein-extracted grass residue (press cake) was processed through hydrothermal liquefaction under sub and supercritical temperatures (300, 350 and 400 °C) with and without using a potassium carbonate catalyst. The results revealed that bio-crude yield was influenced by both temperature and the catalyst. The catalyst was found to be effective at 350 °C (350 Cat) for enhancing the bio-crude yield, whereas supercritical state in both catalytic and non-catalytic conditions improved the quality of bio-crude with reasonable HHVs (33 to 36 MJ/kg). The thermal behaviour of bio-crude was analysed and higher volatile contents (more than 50% under the range of 350 °C) were found at supercritical conditions. The overall TOC values in the residual aqueous phase varied from 22 to 38 g/L. Higher carbon loss was noticed in the aqueous phase in supercritical conditions. Furthermore, GCMS analysis showed ketones, acids and ester, aromatics and hydrocarbon with negligible nitrogen-containing compounds in bio-crude. In conclusion, the catalytic conversion of grass residue under subcritical conditions (350 Cat) is favourable in terms of high bio-crude yield, however, supercritical conditions promote the deoxygenation of oxygen-containing compounds in biomass and thus improve HHVs of bio-crude.

Assessment of weed root extracts for allelopathic activity against Orobanche and Phelipanche species

Broomrapes (Orobanche and Phelipanche species) are holoparasitic weeds that infect roots of crop hosts from Asteraceae, Brassicaceae, Apiaceae, Fabaceae, and Solanaceae. The parasitic weeds are difficult to control selectively without crop damage once attached to their roots. Identification of natural compounds with herbicidal activity against pre-attached broomrape stages can provide control alternatives. With the aim to identify plant species with efficacy for broomrape control, organic and residual aqueous phase extracts from roots of seventeen weed species common in south Spanish broomrape-infested fields were assessed as potential inducers of suicidal broomrape germination and as inhibitors of broomrape radicle growth. Assessments were carried out in vitro using seeds and seedlings of four noxious broomrape species, Orobanche crenata Forsk., Orobanche cumana Wallr., Orobanche minor Sm. and Phelipanche ramosa (L.) Pomel. While root extracts from all the weed species did not induce suicidal germination on O. crenata seeds, most of the extracts induced germination of P. ramosa except for those obtained from Amaranthus albus L., Amaranthus retroflexus L. and Convolvulus arvensis L. Moderate levels of germination activity were induced in O. cumana and O. minor seeds by some of the root extracts tested, with strongest induction obtained from Heliotropium europaeum L. on O. cumana seeds, and from Silybum marianum (L.) Gaertn. on O. minor seeds. For root extract inhibition of broomrape radicles, the extract from C. arvensis roots strongly inhibited radicles of all the broomrape species. While extracts from the other weed species induced low or negligible inhibition of O. cumana and O. crenata radicle growth, many inhibited P. ramosa and O. minor radicles. Exceptions were root extracts from Datura stramonium L., Heliotropium europaeum L., Malva sylvestris L., Solanum nigrum L. and Urtica dioica L., which did not inhibit P. ramosa radicles, and those from A. retroflexus, Datura stramonium L., Malva sylvestris L., Portulaca oleracea L. and S. nigrum, which did not inhibit O. minor radicles. Among the active organic extracts assessed, those showing promising chemical profiles were selected for future studies to characterize natural compounds with potential herbicidal activity on early stages of broomrape growth.

Bio-Crude Production Improvement during Hydrothermal Liquefaction of Biopulp by Simultaneous Application of Alkali Catalysts and Aqueous Phase Recirculation

This study focuses on the valorization of the organic fraction of municipal solid waste (biopulp) by hydrothermal liquefaction. Thereby, homogeneous alkali catalysts (KOH, NaOH, K2CO3, and Na2CO3) and a residual aqueous phase recirculation methodology were mutually employed to enhance the bio-crude yield and energy efficiency of a sub-critical hydrothermal conversion (350 °C, 15–20 Mpa, 15 min). Interestingly, single recirculation of the concentrated aqueous phase positively increased the bio-crude yield in all cases, while the higher heating value (HHV) of the bio-crudes slightly dropped. Compared to the non-catalytic experiment, K2CO3 and Na2CO3 effectively increased the bio-crude yield by 14 and 7.3%, respectively. However, KOH and NaOH showed a negative variation in the bio-crude yield. The highest bio-crude yield (37.5 wt.%) and energy recovery (ER) (59.4%) were achieved when K2CO3 and concentrated aqueous phase recirculation were simultaneously applied to the process. The inorganics distribution results obtained by ICP reveal the tendency of the alkali elements to settle into the aqueous phase, which, if recovered, can potentially boost the circularity of the HTL process. Therefore, wise selection of the alkali catalyst along with aqueous phase recirculation assists hydrothermal liquefaction in green biofuel production and environmentally friendly valorization of biopulp.

Modeling of cost optimized process integration of HTL fuel production

Hydrothermal liquefaction (HTL) is an advanced biomass conversion process for biocrude production from a broad variety of organic feedstock, including wet waste streams. The intermediate biocrudes can be further upgraded to liquid hydrocarbon fuels and thereby contribute to the mitigation of greenhouse gases from the transport sector. This work investigates an optimized sub-system integration of transportation fuel production via sub-critical HTL of primary sewage sludge. The plant design integrates HTL conversion, biocrude upgrading via hydrotreatment, and an energetic valorization of the residual aqueous phase from HTL conversion via catalytic hydrothermal gasification (cHTG). The option of on-site hydrogen production via reforming of cHTG gas is examined for the purpose of biocrude upgrading. The modeling results show that the hydrogen demand for hydrotreatment could be covered by the valorization of the HTL by-products. The thermal management of an integrated biofuel plant is optimized with respect to subsystem cost based on in-depth process modeling to quantify mass and energy flows and principles of pinch analysis to design a heat exchanger network. The cost optimized configuration results in an overall process energy efficiency of 40.5%. The results provide a basis for design choices for future HTL plants.

Efficient and sustainable recovery of lipids from sewage sludge using ethyl esters of volatile fatty acids as sustainable extracting solvent

This work focuses on the recovery of resources from urban sewage sludge. Sewage sludge is generated by water treatment plants and contains a significant amount of lipids that can be used in a number of applications in fine chemistry. This study reports the extraction of lipids from sewage sludge using ethyl esters of volatile fatty acids as solvents. A thermodynamic study was first performed using synthetic primary sludge in order to identify the best operating conditions to apply on real samples of urban primary sludge. Ethyl butyrate showed the best separation performance. It was capable of efficiently recovering the lipid component from primary sewage sludge, which typically resulted in 13–23% of total solids. Highly pure calcium soaps can be extracted in high amounts (yield up to 93%), while the exhausted residual aqueous phase resulted as not significantly contaminated by the solvent and could be anaerobically digested easily. Finally, calcium soaps can be directly used as biolubricant or efficiently converted into biodiesel using aluminum chloride hexahydrate as a catalyst (yield 85%).

Renewable Biopolyols from Residual Aqueous Phase Resulting after Lignin Precipitation

The aim of this work was to obtain two biopolyols from the liquid residue resulting from the precipitation of lignin contained in two different black liquors, Eucalyptus globulus organosolv black l...

Mercury and sulfur isotopic composition of sulfides from sediment-hosted lead-zinc deposits in Lanping basin, Southwestern China

The Lanping basin is an important Pb-Zn-Cu-Ag polymetallic province in southwestern (SW) China. Mineralization types in the basin include mainly MVT Pb-Zn deposits, vein-type Cu deposits, and minor quartz vein-type Pb-Zn deposits. In this study, we analyzed the total Hg (THg) content and Hg-S isotopic compositions of sulfides from two types of Pb-Zn deposits in the basin, and investigate the Hg isotope fractionation mechanism and its major controlling factors in the Pb-Zn ore-forming process. At the Shangnuluo quartz vein-type Pb-Zn-Sb deposit, sulfides (especially sphalerite) show a wide δ202Hg range (−0.40 to 2.71‰), suggesting that Hg0 evaporation from hydrothermal fluids occurred during the ore formation. Negative THg vs. δ202Hg correlation in the sphalerites suggests a mixing of Hg from the vapor phase (low δ202Hg, high THg) and the residual aqueous phase (high δ202Hg, low THg). The negative ∆199Hg (−0.42 to −0.08‰) suggests that the Hg was sourced from the metamorphic basement, whereas the negative δ34S values (−13.0 to −2.7‰) suggests that the sulfur was mainly sourced from sedimentary sequences, possibly related to the organic matter decomposition and thermochemical sulfate reduction (TSR). For the Liziping and Fulongchang MVT Pb-Zn deposits, sulfides have relatively narrow δ202Hg range (−1.46 to 0.25‰), suggesting limited Hg0 evaporation during the mineralization. Lower δ202Hg values were observed in the early-stage sulfides from these two deposits, probably due to the preferential precipitation of lighter Hg isotopes in these early-stage sulfides. Sulfides from both deposits have negative ∆199Hg values (−0.24 to 0.01‰), suggesting that the Hg was also derived from the metamorphic basement. Sulfide δ34S values from the two deposits are positive, which also suggests that the sulfur was sourced from sedimentary sequences, but mainly related to TSR under relatively low-temperatures. Sulfides from different Pb-Zn deposit types in the Sanjiang Tethyans Metallogenic Belt fall into distinct fields in the δ34S vs. δ202Hg (or ∆199Hg) diagrams, indicating that the integration of S and Hg isotopes is useful to discriminate different types of Pb-Zn deposits.

Recyclable copper-catalyzed ambient aerobic oxidation of primary alcohols to aldehydes in water using water-soluble PEG-functionalized pyridine triazole as ligand

A water-soluble PEG-PyTa ligand, conveniently derived from commercially available reagents via a simple synthetic approach, could efficiently promote copper/2, 2, 6, 6-tetramethyl piperidine-1-oxyl (TEMPO)-catalyzed aerobic oxidation of primary alcohols to aldehydes in water under room temperature. A number of primary benzylic, allylic alcohols and heteroaryl methanols were selectively converted into their corresponding aldehydes with excellent yields. The oxidation products could be isolated by simple extraction, and the residual aqueous phase containing the catalyst Cu(OTf)2/PEG-PyTa could be reused at least 7 times.

A Highly Efficient and Reusable Palladium(II)/Cationic 2,2'-Bipyridyl-Catalyzed Stille Coupling in Water.

A water-soluble PdCl2(NH3)2/cationic 2,2′-bipyridyl system was found to be a highly efficient catalyst for Stille coupling of aryl iodides and bromides with organostannanes. The coupling reaction was conducted at 110 °C in water, under aerobic conditions, in the presence of NaHCO3 as a base to afford corresponding Stille coupling products in good to high yields. When aryltributylstannanes were employed, the reactions proceeded smoothly under a very low catalyst loading (as little as 0.0001 mol %). After simple extraction, the residual aqueous phase could be reused in subsequent runs, making this Stille coupling economical. In the case of tetramethylstannane, however, a greater catalyst loading (1 mol %) and the use of tetraethylammonium iodide as a phase-transfer agent were required in order to obtain satisfactory yields.

Suzuki–Miyaura reactions promoted by a PdCl2/sulfonate‐tagged phenanthroline precatalyst in water

This work reports Suzuki–Miyaura cross‐coupling reactions of arylboronic acid with aryl halide or aryl dibromide mediated by PdCl2 (0.05 mol%) and sodium 4‐(1H‐imidazo[4,5‐f][1,10]phenanthrolin‐1‐yl)butane‐1‐sulfonate (0.05 mol%) at 100 °C in water. The corresponding cross‐coupling products were obtained in good to excellent yields. The catalytic system was recovered from the organic products by extraction with ether and the residual aqueous catalyst phase showed high activity after reuse of at least four cycles. Copyright © 2014 John Wiley &amp; Sons, Ltd.

The spasmolytic activity of extracts and some isolated compounds from the leaves of Morinda morindoides (Baker) Milne-Redh. (Rubiaceae)

Aim The study was aimed to evaluate the in vitro antispasmodic activity of Morinda morindoides leaves aqueous extract, its soluble fractions and isolated compounds to provide the pharmacological basis for its use for the treatment of constipation and diarrhoea in traditional medicine. Methods The antispasmodic activity of each sample was evaluated on acetylcholine (ACh) and the depolarized KCl solution induced contractions on guinea-pig isolated ileum suspended in Tyrode's solution. Results At a test concentration of 40 μg/ml in organ bath, the aqueous extract and its petroleum ether soluble fraction showed a spasmogenic effect on both agonists. The diethylether, ethyl acetate, n-butanol and residual aqueous phase soluble fractions from the partition of the aqueous extract exhibited spasmolytic activity producing 47–100% inhibition of contractions induced by both agonists with IC 50 values ranged from 6 to 15 μg/ml according to the case. In addition, the n-butanol and residual aqueous phase soluble fractions showed an inhibitory effect of 75 and 66% respectively on low high [K +] (25 mM) and 65 and 60% respectively on high [K+] (80 mM). Crude flavonoids showed spasmolytic on both agonists while crude saponins only showed spasmolytic activity on ACh and displayed spasmogenic effect on KCl. Quercetin, quercitrin and rutin exhibited significant antispasmodic effect with IC 50 values <0.1 μg/ml. Epoxygaertneroside and gaertneroside showed good antispasmodic activity on both agonists (4 < IC 50 < 7 μg/ml). Conclusion Morinda morindoides leaves possess spasmogenic and spasmolytic properties that can at least explain and support its traditional use against constipation and diarrhoea respectively.

Pd(II)-Catalyzed Hiyama Cross-Coupling Using a Water-Soluble Ligand System

A Pd(NH3)2Cl2/cationic bipyridyl catalytic system is able to efficiently catalyze the cross-coupling reaction of aryl bromides with arylsiloxanes in water under aerobic conditions in the presence of NaOH to afford biaryls in good to excellent yields. After extraction, the residual aqueous phase can be used several times with only a minor decrease in catalyst activity.

Isotopic fractionation by diffusion in groundwater

During the last decade, isotopic fractionation has gained acceptance as an indicator of microbiological and chemical transformations of contaminants in groundwater. These transformation processes typically favor isotopically light, compared to isotopically heavy, contaminants, resulting in enrichment of the latter in the residual aqueous phase. In these isotope applications, it has been generally presumed that physical transport processes in groundwater have a negligible effect on isotopic enrichment. It is well known, however, that aqueous phase diffusion generally proceeds faster for isotopically light, compared to isotopically heavy, solute molecules, often resulting in isotopic fractionation in groundwater. This paper considers the potential for isotopic fractionation during transport in groundwater resulting from minute isotopic effects on aqueous diffusion coefficients. Analyses of transport in heterogeneous systems delimit the viable range of isotopic fractionation by diffusion in groundwater. Results show that diffusion can result in similar degrees of depletion and enrichment of isotopically heavy solutes during transport in heterogeneous systems with significant diffusion rate–limited mass transfer between fast‐ and slow‐flow zones. Additional analyses and examples explore conditions that attenuate the development of significant fractionation. Examples are presented for 13C methyl tertiary butyl ether and deuterated and nondeuterated isopropanol and tertiary butyl alcohol using aqueous diffusion coefficients measured by the Taylor dispersion method with refractive index profiling as a part of this study. Examples elucidate the potential for diffusive fractionation as a confounder in isotope applications and emphasize the importance of hydrogeologic analysis for assessing the role of diffusive fractionation in isotope applications at contaminant field sites.

Hiyama reaction of aryl bromides with arylsiloxanes catalyzed by a reusable palladium(II)/cationic bipyridyl system in water

A Pd(NH 3) 2Cl 2/cationic bipyridyl catalytic system catalyzed the cross-coupling reaction of aryl bromides with arylsiloxanes in water under aerobic conditions in the presence of NaOH to afford biaryls in good to high yields. The reaction was performed at 120 °C and the loading amount of catalyst can be as low as 0.001 mol %. After extraction, the residual aqueous phase can be reused several times with only a slight decrease in activity.

Nuclear Field Shift Effect of Chromium(III) in Repeated Extraction Using a Crown Ether

Chromium isotopes were fractionated by continuous extraction using dicyclohexano‐18‐crown‐6 as an extractant. This system was designed for accumulating isotope effect into the aqueous phase. After a long period of operation (∼2 weeks), the Cr isotope ratios in the residual aqueous phase were precisely measured by using a multi‐collector thermal ionization mass spectrometer with the total evaporation technique. The analytical results showed a clear mass‐independent isotope fractionation. The mass‐independent property was consistent with that obtained from a batch extraction. The isotopic mass balance was verified to be preserved in the continuous extraction. The Bigeleisen's 1996 theory gave the consistent explanation on the Cr isotope effect, in which the mass‐independent isotope effect was identified to be the nuclear field shift effect.

Characterization of Pyrazines in Some Chinese Liquors and Their Approximate Concentrations

Pyrazines are very important impact aroma compounds in Chinese liquors. The identification of pyrazine derivatives was carried out by liquid-liquid extraction (LLE). The liquor sample was adjusted to the H(+) concentration of 1 N with 12 N HCl and then concentrated by rotatory evaporator under vacuum condition. The concentrated liquor was extracted by diethyl ether, and the residual aqueous phase was adjusted to pH 10. The basic compounds were detected and identified by gas chromatography (GC)-mass spectrometry (MS). A total of 27 pyrazines were identified in Chinese liquors, mainly alkyl- and acetylpyrazines. A method for determining pyrazines in Chinese liquors was developed. It involves extraction by headspace (HS) solid phase microextraction (SPME) and determination using GC-flame thermionic detector (FTD). The optimum method was that the sample alcohol concentration was diluted to 12% vol by freshly redistilled-deionized water, and the diluted samples were saturated with NaCl and equilibrated at 50 degrees C for 15 min and extracted for 30 min at the same temperature. The developed method enabled detection limits of <200 ng/L. Linearity (R(2) > 0.99) and recovery rate were satisfied in all cases. Pyrazines of 12 commercial typical Chinese liquors were quantified by HS-SPME followed by GC-FTD and had a wide range of concentration.

Determination of poly(dimethyl)siloxane–water partition coefficients for selected hydrophobic organic chemicals using 14C-labeled analogs

Aqueous solutions of 14C-labeled analogs of seven hydrophobic organic chemicals (HOCs) were subject to solid-phase microextraction (SPME) under static conditions to assess their multi-compartment distribution and to compare poly(dimethyl)siloxane (PDMS)–water partition coefficients ( K f values) with previously reported values. To accomplish this, a protocol for quantitative desorption of radiolabelled HOCs from SPME fibers using hexane was developed. Time series extractions indicated that loading of SPME fibers had reached steady-state by day 8 for PCBs 52, 77 and 153, phenanthrene, benzo[a]pyrene, p,p′-DDT and p,p′-DDE. The recovery of spiked radioactivity among the (residual) aqueous phase, the PDMS coating, and all remaining wetted experimental surfaces ranged between 80 and 120%. K f values based on 14C-labeled analogs were in good agreement with previously published values that were determined at (or closely approaching) equilibrium conditions and without significant chemical depletion and/or uncorrected system losses. Because it allows for the direct determination of HOCs associated with the residual aqueous and experimental surface compartments, the use of radiolabelled HOC analogs is a powerful tool in discriminating among competing sorptive compartments encountered in most SPME fiber calibration methodologies employed to date.