• Title/Summary/Keyword: Reductive degradation

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A Complete, Reductive Depolymerization of Concentrated Sulfuric Acid Hydrolysis Lignin into a High Calorific Bio-oil using Supercritical Ethanol

  • Riaz, Asim;Kim, Jaehoon
    • KEPCO Journal on Electric Power and Energy
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    • v.2 no.3
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    • pp.447-452
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    • 2016
  • It is imperative to develop an effective pathway to depolymerize lignin into liquid fuel that can be used as a bioheavy oil. Lignin can be converted into liquid products either by a solvent-free thermal cracking in the absence air, or thermo-chemical degradation in the presence of suitable solvents and chemicals. Here we show that the solvent-assisted liquefaction has produced promising results in the presence of metal-based catalysts. The supercritical ethanol is an efficient liquefaction solvent, which not only provides better solubility to lignin, but also scavenges the intermediate species. The concentrated sulfuric acid hydrolysis lignin (CSAHL) was completely liquefied in the presence of solid catalysts (Ni, Pd and Ru) with no char formation. The effective deoxy-liquefaction nature associated with scEtOH with aid hydrodeoxygenation catalysts, resulted in significant reduction in oxygen-to-carbon (O/C) molar ratio up to 61%. The decrease in oxygen content and increase in carbon and hydrogen contents increased the calorific value bio-oil, with higher heating value (HHV) of $34.6MJ{\cdot}Kg^{-1}$. The overall process is energetically efficient with 129.8% energy recovery (ER) and 70.8% energy efficiency (EE). The GC-TOF/MS analysis of bio-oil shows that the bio-oil mainly consists of monomeric species such as phenols, esters, furans, alcohols, and traces of aliphatic hydrocarbons. The bio-oil produced has better flow properties, low molecular weight, and high aromaticity.

Treatment of TNT and Parathion Using Constructed Wetland Microcosms

  • Choi, Jong-Kyu;Kim, Se-Kyung;Oh, Se-Hee;Lee, Eun-Sook;Zoh, Kyung-Duk
    • Proceedings of the Korean Environmental Health Society Conference
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    • 2004.06a
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    • pp.160-164
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    • 2004
  • This study was carried out to investigate the removal of TNT (2,4,6-trinitrotoluene) and parathion in the batch and the continuous constructed wetland microcosms consisting of marsh and pond. The batch system study showed that TNT was almost reduced in the marsh and pond system within 20 days and parathion was within 8 days. The major reductive metabolites of TNT includes 2,4-diamino-6-nitrotoluene (24DANT) >2,6-diamino-4-nitrotoluene (26DANT) >4-diamino-2,6-nitrotoluene(4ADNT) > 2-diamino-4,6-nitrotoluene (2ADNT), and the concentrations of these metabolites were decreased during further operation. The generation rates of 4-nitrophenol, the major metabolite of parathion, were 82% and 15% in the bottom of marsh and pond system, respectively. In the continuous system study, although TNT/parathion degradation pattern was similar to the batch's, marsh-pond system showed the most stable TNT/ parathion removal among various continuous reactor combinations.

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Identification of Active Agents for Reductive Dechlorination Reactions in Cement/Fe (II) Systems by Using Cement Components (시멘트 구성성분을 이용한 시멘트/Fe(II)의 TCE 환원성 탈염소화 반응의 유효반응 성분 규명)

  • Jeong, Yu-Yeon;Kim, Hong-Seok;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.13 no.1
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    • pp.92-100
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    • 2008
  • Experimental studies were conducted to identify the active agents for reductive dechlorination of TCE in cement/Fe(II) systems focusing on cement components such as CaO, $Fe_2O_3$, and $Al_2O_3$. A hematite that was used to simulate an $Fe_2O_3$ component in cement was found to have degradation efficiencies (k = 0.641 $day^{-1}$) equivalent to that of cement/Fe(II) systems in the presence of CaO/Fe(II), only when it contained an aluminum impurity$(Al_2O_3)$. When the effect of $Al_2O_3$ content of hematite/CaO/$Al_2O_3$/Fe(II) system was tested, the mole ratio of $Al_2O_3$ to CaO affected the rate of TCE degradation with an optimum ratio around 1 : 10 that resulted in a rate constant of 0.895 $day^{-1}$. In the SEM images of hematite/CaO/$Al_2O_3$/Fe(II) systems, acicular crystals were also found that were also observed in cement/Fe(II) systems. Thus it was suspected that these crystals were reactive reductants and that they might be goethite or ettringite that are known to have acicular structures. An EDS element map analysis revealed that these crystals were not goethite crystals. A subsequent experiment that tested reactivities of compounds formed during the ettringite synthesis showed that ettringite and minerals associated with ettringite formation are not reactive reductants. These observations conclude that a mineral containing CaO and $Al_2O_3$ with a acicular structure could be a major reactive reductant of cement/Fe(II) systems.

Production and Characterization of Keratinolytic Proteases by a Chicken Feather-Degrading Thermophilic Strain, Thermoactinomyces sp. YT06

  • Wang, Lin;Qian, Yuting;Cao, Yun;Huang, Ying;Chang, Zhizhou;Huang, Hongying
    • Journal of Microbiology and Biotechnology
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    • v.27 no.12
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    • pp.2190-2198
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    • 2017
  • Thermoactinomyces sp. strain YT06 was isolated from poultry compost and observed to degrade integral chicken feathers completely at $60^{\circ}C$, resulting in the formation of 3.24 mg/ml of free amino acids from 50 ml of culture containing 10 g/l chicken feathers. Strain YT06 could grow and secrete keratinase using feather as the only carbon and nitrogen sources without other supplement, but complementation of 10 g/l sucrose and 4 g/l $NaNO_3$ increased the production of the keratinolytic enzyme. The maximum protease activity obtained was 110 U/ml and for keratinase was 42 U/ml. The keratinase maintained active status over a broad pH (pH 8-11) and temperature ($60-75^{\circ}C$). It was inhibited by serine protease inhibitors and most metal ions; however, it could be stimulated by $Mn^{2+}$ and the surfactant Tween-20. A reductive agent (${\beta}$-mercaptoethanol) was observed to cleave the disulfide bond of keratin and improve the access of the enzyme to the keratinaceous substrate. Zymogram analysis showed that strain YT06 primarily secreted keratinase with a molecular mass of approximately 35 kDa. The active band was assessed by MALDI-TOF mass spectrometry and was observed to be completely identical to an alkaline serine protease from Thermoactinomyces sp. Gus2-1. Thermoactinomyces sp. strain YT06 shows great potential as a novel candidate in enzymatic processing of hard-to-degrade proteins into high-value products, such as keratinous wastes.

Degradation of Chlorinated Phenols by Zero Valent Iron and Bimetals of Iron: A Review

  • Gunawardana, Buddhika;Singhal, Naresh;Swedlund, Peter
    • Environmental Engineering Research
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    • v.16 no.4
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    • pp.187-203
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    • 2011
  • Chlorophenols (CPs) are widely used industrial chemicals that have been identified as being toxic to both humans and the environment. Zero valent iron (ZVI) and iron based bimetallic systems have the potential to efficiently dechlorinate CPs. This paper reviews the research conducted in this area over the past decade, with emphasis on the processes and mechanisms for the removal of CPs, as well as the characterization and role of the iron oxides formed on the ZVI surface. The removal of dissolved CPs in iron-water systems occurs via dechlorination, sorption and co-precipitation. Although ZVI has been commonly used for the dechlorination of CPs, its long term reactivity is limited due to surface passivation over time. However, iron based bimetallic systems are an effective alternative for overcoming this limitation. Bimetallic systems prepared by physically mixing ZVI and the catalyst or through reductive deposition of a catalyst onto ZVI have been shown to display superior performance over unmodified ZVI. Nonetheless, the efficiency and rate of hydrodechlorination of CPs by bimetals depend on the type of metal combinations used, properties of the metals and characteristics of the target CP. The presence and formation of various iron oxides can affect the reactivities of ZVI and bimetals. Oxides, such as green rust and magnetite, facilitate the dechlorination of CPs by ZVI and bimetals, while oxide films, such as hematite, maghemite, lepidocrocite and goethite, passivate the iron surface and hinder the dechlorination reaction. Key environmental parameters, such as solution pH, presence of dissolved oxygen and dissolved co-contaminants, exert significant impacts on the rate and extent of CP dechlorination by ZVI and bimetals.

Degradation of energetic compounds using an integrated zero-valent iron-Fenton process

  • Oh Seok-Young;Kim Byung J.;Chiu Pei C.;Cha Daniel K.
    • 한국지구물리탐사학회:학술대회논문집
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    • 2003.11a
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    • pp.493-500
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    • 2003
  • The effect of reductive treatment with elemental iron on the extent of mineralization by Fenton oxidation was studied for the explosive 2,4,6-trinitrotoluene (TNT) and hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX) using a completely-stirred tank reactor (CSTR). The results support the hypothesis that TNT and RDX are reduced with elemental iron to products that are oxidized more rapidly and completely by Fenton's reagent. Iron pretreatment enhanced the extent of TOC removal by approximately $20\%\;and\;60\%$ for TNT and RDX, respectively. Complete TOC removal was achieved for TNT and RDX solutions with iron pretreatment under optimal conditions. On the other hand, without iron pretreatment, complete mineralization of TNT and RDX solutions were not achieved even with much higher $H_2O_2$ and $Fe^{2+}$ concentrations. The bench-scale iron treatment-Fenton oxidation integrated system showed more than $95\%$ TOC removal for TNT and RDX solutions under optimal conditions. The proposed zero-valent iron-Fenton process was evaluated with pink water from the Iowa Army ammunition plant. Results from batch and column experiments show that TNT, RDX, and octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine (HMX) were completely removed from the pink water and that triaminotoluene (TAT) and ${NH_4}^+$ were recovered as products in reduction with zero-valent iron. By using an integrated system, $83.3\pm4.2\%$ of TOC was removed in a CSTR with 10 mM of $Fe^{2+}$ and 50 mM of $H_2O_2$. These results suggest that the reduction products of TNT and RDX are more rapidly and completely mineralized by Fenton oxidation and that a sequential iron treatment-Fenton oxidation process may be a viable technology for pink water treatment.

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Optimal Remediation of TCE-contaminated Groundwater using Direct Current and Fe$^0$ (직류전원과 0가 철을 이용한 지하수내 TCE정화효율의 최적화 연구)

  • Moon, Ji-Won;Moon, Hi-Soo;Roh, Yul;Kim, Heon-Ki;Song, Yun-Goo
    • Economic and Environmental Geology
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    • v.35 no.3
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    • pp.229-239
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    • 2002
  • The objective of this study was to design an optimal electro-remediation system for TCE contaminated water using zero talent iron (ZVI) and direct current (DC). A series of column experiments were conducted to evaluate the effects of electrode arrangement and the location of permeable iron barrier in the column on the TCE removal efficiency and iron corrosion process. In twelve different combinations of ZVI and/or DC application in the test columns, the rate of reductive degradation of TCE was improved with simultaneous application of both ZVI and DC compared to that used ZVI only. The moot effective arrangement of electrode and ZVI for TCE removal from water was a column set with ZVI and cathode installed at the down gradient, respectively.

Synthesis of Oxidation Resistant Core-shell Nanoscale Zero-valent Iron by Controlled Air Contact (공기접촉 제어를 통한 산화방지 Core-Shell 나노영가철의 제조)

  • Ahn, Jun-Young;Kim, Hong-Seok;Hwang, In-Seong
    • Journal of Soil and Groundwater Environment
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    • v.13 no.6
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    • pp.93-102
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    • 2008
  • Experimental studies were conducted to characterize the synthesized nanoscale zero-valent iron (NZVI) which is resistant to oxidation in the atmospheric environment. XRD, XPS, and TEM analyses revealed that the oxidation-resistant NZVI particles formed under various controlled air contact conditions (4, 8 and 12 mL/min) have shells with ${\sim}$5 nm thickness. The shells consist of magnetite (${Fe_3}{O_4}$) and maghemite (${\gamma}-{Fe_2}{O_3}$), predominantly. No substantial differences were found in the shell components and thickness among NZVI particles formed under the various air flow rates. On the other hand, shell was not detected in the TEM image of rapidly oxidized NZVI particles. NZVI particles synthesized under the various air flow rates showed similar TCE degradation performances ($k_{obs}$= 0.111, 0.102, and 0.086 $hr^{-1}$), which are equivalent to approximately 80% of those obtained by the fresh NZVI particles. TCE degradation efficiencies of the NZVI particles(fresh, controlled air contact and rapidly oxidized) were improved after equilibrating with water for one day, indicating that depassivation of the shells occurred. The performances of NZVI particles decreased to 90% and 50% of those of the fresh NZVI particles, when they were equilibrated with the atmosphere for a week and two months, respectively. The NZVI particles synthesized under the controlled air contact would have advantages over traditional NZVI particles in terms of practical application into the site, because of their inertness toward atmospheric oxygen.

The Rate of Superoxide Radical (${O_2}^-$.) Production in Normal Fenton's Reagent at Different pHs (펜톤반응에서 pH의 변화에 따른 superoxide radical (${O_2}^-$.)의 생성)

  • 김용수;공성호;김재호
    • Journal of Soil and Groundwater Environment
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    • v.7 no.2
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    • pp.73-81
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    • 2002
  • In normal Fenton's reagent, the reductive mechanism of carbon tetrachloride (CT) with superoxide radical (${O_2}^-$.) was observed and the rate of ${O_2}^-$. production was investigated as a function of $H_2O$$_2$ concentration and pH. As pH was increased, the rate of 1-hexanol degradation was rapidly decreased from 90% (at pH 3) to 5% (at pH 11). On the other hand, more degradation of carbon tetrachloride was observed at higher pH regimes indicating Fenton's reaction is an oxidant-reductant co-existing system at neutral pHs. The rate of $O_2^{-}$ . production was observed at different $H_2$$O_2$ concentrations and at different pHs. The rate increased from (45.3$\pm$7.8) x $10^{-6}$ M/s to (151.0$\pm$26.2) x $10^{-6}$ M/s ($294mM H_2$$O_2$) at pH 11: the rate 3150 increased from (22.1$\pm$3.8) x $10^{-6}$ M/s at pH 7 to (151.0$\pm$26.2) x $^10{-6}$ M/s at pH 11 with 294mM $H_2$$O_2$, These results showed that Fenton's reagent could be applied at wide pH regimes. Especially, carbon tetrachloride, which can not be easily adsorbed to soils and then can be dissolved into groundwater causing a cancer, could be efficiently treated by Fenton's reagent.reagent.

Diversity of Uncultured Microorganisms Associated with the Anaerobic Pentachlorophenol Degradation Estimated by Comparative RELP Analysis of PCR-Amplified 16S rDNA Clones (16S rDNA 클론들의 RFLP 비교분석에서 얻어진 Pentachlorophenol의 혐기성 분해에 따른 미생물군집의 변화)

  • 성창수;권오섭;박영식
    • Korean Journal of Microbiology
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    • v.33 no.2
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    • pp.149-156
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    • 1997
  • We have employed comparative RFL,P(Restriction Fragment Ixngth Pol~iniorphism) analysis and molecular phylogenetic techniques to investigate the diversity of uncultured microorganisms associated with the anaerobic PCP degradation in PCP-adapted enrichment cultures inoculated by samples from anaerobic cewage sludgc(Jangrim, Pusan) and leachate of landfill site(Kimhae). 16s rDNA cloncs were obtairted by PCR amplification of mixed population DNAs extracted directly from the nonactive and active stage ol each PCP-adapted culture. After three rounds of comparative RFLP analyses. two RFLP types. designated as Ala and Hld, were found prevalent and common in both active stage samples. Thc analysis of phylogenctic diversity bawd on the 5'-terminal 180 nt of sequences from whole clones of the Ala and Bld RFLP types showed close similarity among themselves. In case of Bld clones, 7XQ of them shared identical sequences. Thcse resuliq suggest that the clones of both RFLP types wcre originated from highly affiliated microorganisms which are e~iriched as a result of metabolic activity to PCP. The full-length 16s rRNA sequence of each representative clone from both RFLP types was determined. and an Ala clone w i n found to he related to Clo.strrdiurn ulfutzac~(Genk~ank No. Z69203) and a Bld clone to Thermobacteroides proteolyticus(Genbank No. X09335), with sequence similarities of 89%' and 97%. respectively.

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