Production of 1,3-propanediol and lactic acid from crude glycerol by a microbial consortium from intertidal sludge.

OBJECTIVES: To select a microbial consortium from intertidal sludge and evaluate its ability to convert crude glycerol from biodisel to high value-added products such as 1,3-propanediol (1,3-PDO) and lactic acid (LA). RESULTS: A microbial consortium named CJD-S was selected from intertidal sludge and exhibited excellent performance for the conversion of crude glycerol to 1,3-PDO and LA. The composition of CJD-S was determined to be 85.99% Enterobacteriaceae and 13.75% Enterococcaceae by 16S rRNA gene amplicon high-throughput sequencing. In fed-batch fermentation with crude glycerol under nonsterile conditions, the highest concentrations of 1,3-PDO and LA were 41.47 g/L and 45.86 g/L, respectively. CONCLUSIONS: The selected microbial consortium, CJD-S, effectively converted crude glycerol to 1,3-PDO and LA under nonsterile conditions and can contribute to the sustainable development of the biodiesel industry.

Preparation and property analysis of antioxidant of carbazole derivatives.

Carbazole derivatives can be used as antioxidants in the lubricating oil industry. The alkylation of carbazole with 2-chloro-2-methylpropane and 2-bromopropane catalyzed by anhydrous aluminum chloride was studied. Initially, 3,6-di-iso-propylcarbazole and 3,6-di-tert-butylcarbazole were using dichloromethane and dibromomethane as solvents at room temperature, respectively. The synthesis conditions were optimized. Subsequently, the effects of reaction time, catalyst dosage, and molar ratio of carbazole to alkylating agent were investigated, and orthogonal experiments were performed. The structures of the carbazole derivatives were characterized by Fourier infrared spectroscopy (FT-IR), mass spectrum (MS) and nuclear magnetic resonance spectroscopy (NMR). The thermal stability of the synthesized carbazole derivatives was investigated by differential scanning calorimetry (DSC). The carbazole derivatives were added into the lubricating oil with a mass fraction of 0.8% and the miscibility, stability and oxidation resistance of the mixed system were evaluated by mechanical stirring and a rotary pressure vessel oxidation test (RPVOT). The DSC results showed that there was good thermal stability for the carbazole derivatives. The mechanical stirring method revealed good solubility and stability for the mixture of oil and carbazole derivatives. The RPVOT results showed that isopropyl carbazole derivatives could increase the oxidation induction period of lubricating oil to 1.39 times, and tert-butyl carbazole derivatives could increase the oxidation induction period of lubricating oil to 1.91 times. The antioxidant effect of tert-butyl carbazole derivatives was better than that of isopropyl carbazole derivatives.

Kinetic and mechanistic examinations of reductive transformation pathways of brominated methanes with nano-scale Fe and Ni/Fe particles.

In this study, carbon tetrabromide (CTB), bromoform (BF) and dibromomethane (DBM) were the target compounds investigated for their reduction kinetics and pathways with nano-scale Fe and Ni/Fe particles synthesized in laboratory. The BET surface areas of these nano-scale particles were around two orders of magnitude higher than that of the commercial micro-scale Fe particles. Batch reduction experiments were carried out with a metal loading of 2.5gl(-1) for the nano-scale particles, and 125gl(-1) for the commercial micro-scale Fe. The nano-scale Ni/Fe was the most reactive for reductive dehalogenation of the brominated methanes. The rates of bromide ion liberated during the reduction of the brominated methanes were usually higher than the disappearance rates of the parent compounds, indicating occurrence of concerted debromination mechanism. Analysis of the reduction kinetics showed that CTB and BF were mainly reduced through hydrogenolysis reaction, while over 76% of DBM was reduced through concerted reductive debromination to methane. Addition of Ni to Fe increased the specific reduction rates of the target compounds and reactive intermediates, but only marginally changed the distribution of their end products. Through comprehensive kinetic and mechanistic examinations of the reduction dehalogenation of various brominated methanes, a scheme summarizing their overall reduction pathways with the nano-scale Fe and Ni/Fe is proposed.

Reductive dechlorination of 1,2,4-trichlorobenzene with palladized nanoscale Fe(zero-valent) particles supported on chitosan and silica.

In this study, nanoscale Pd-Fe particles, with diameters less than 100 nm, were synthesized and dispersed over the chitosan and silica supports. Three different Pd-Fe particles were synthesized, namely 0.1% Pd-Fe, 0.5% Pd-Fe and 1.0% Pd-Fe. SEM images confirmed that the Pd-Fe particles were dispersed over the surface of the supports while SEM-EDX confirmed evenly distribution of Pd over Fe(zero-valent). alpha-Fe(zero-valent) crystallites were identified by means of XRD and observed in TEM. Reductive dechlorinations of 1,2,4-trichlorobenzene (1,2,4-TCB) with the nanoscale Pd-Fe/chitosan and Pd-Fe/silica were carried out in the batch experiment system. Disappearance of the parent species and formation of the reaction intermediates and end product were monitored at discrete times. The results show that the nano-scale Pd-Fe particles were able to completely dechlorinate the chlorinated benzenes within a very short timescale. Complete dechlorinations of 1,2,4-TCB to benzene were achieved within 60 min with the 1.0% Pd-Fe/chitosan and within 100 min with the 1.0% Pd-Fe/silica. Reaction rates were observed to increase with increasing Pd content of the Pd-Fe/support. The reactions apparently followed pseudo-first-order kinetics with respect to the 1,2,4-TCB transformation. A kinetic model is constructed to fit the experimental results for the reactions, enabling identification of the major and minor dechlorination pathways of 1,2,4-TCB. The model suggests that the 1,2,4-TCB transformation mainly followed the primary pathway of direct reductive dechlorination to benzene and secondary pathway of sequential hydrogenolysis to 1,2-dichlorobenzene (1,2-DCB) and then chlorobenzene (CB) or benzene.

Synergistic effect of palladium and oxygen vacancies in the Pd/perovskite catalysts synthesized by the spc method.

A series of oxygen-deficient perovskite-supported palladium catalysts were prepared by the "solid phase crystallization" (spc) method and investigated with XRD, TPR, TPD, TEM, XPS, BET analysis and CO oxidation. It was found that Pd/perovskite catalysts synthesized by the spc method were more active for CO oxidation than the calcined LaCo0.95 Pd0.05 O3, where Pd dispersed in the solid solution. H2-reducing treatment in the spc method could yield not only high-dispersed fine Pd particles on the perovskite surface but also oxygen-deficient structure. In these perovskite-supported Pd catalysts, oxygen vacancies adsorbed, activated and supplied oxygen to the active Pd sites, where the oxidation occurred with adsorbed CO. The high activities were due to the cooperative action of Pd and oxygen vacancies.

Effects of anions on the kinetics and reactivity of nanoscale Pd/Fe in trichlorobenzene dechlorination.

Influences of anionic co-solutes on dechlorination of 1,2,4-trichlorobenzene (124TCB) by the nanoscale Pd/Fe particles were investigated in batch experiments in the presence of an anionic solute such as nitrate, nitrite, perchlorate, phosphate, carbonate, silica, sulfate, sulfite, or sulfide. Based on the extent of inhibitory effects on the 124TCB dechlorination, the anions can be ranked in the order of: control≈sulfate≈silica

Reduction of chlorinated methanes with nano-scale Fe particles: effects of amphiphiles on the dechlorination reaction and two-parameter regression for kinetic prediction.

The influences of amphiphiles, including humic acid (HA) and various types of surfactants, on dechlorination of carbon tetrachloride (CTC) and chloroform (CF) by the nano-scale Fe particles were investigated. Since the amphiphiles would modify the surface tension between the liquid-liquid and solid-liquid interface, in the presence of amphiphile matrix solution the Fe corrosion rate and the parent compound dechlorination rate would be different from those in the ultrapure water. Among the four amphiphile solutions, Fe corrosion rate was the highest in the anionic surfactant sodium dodecyl sulfate (SDS) solution, presumably due to the existence of chemisorption between the hydrophilic head of SDS and Fe particles. The dechlorination rates of CTC and CF could be described with the pseudo-first order kinetic model. The influences of amphiphiles on the dechlorination reaction rate were related to the species of parent compound and concentration of the matrix solution. The influences of HA on the dechlorination of CTC and CF were the most significant compared to other matrix solutions. At relatively low HA concentration (<0.1 g L(-1)), the HA molecules (serving as electron transfer mediator) would significantly accelerate the dechlorination rate of CF. The two-parameter regression with energy of the lowest unoccupied molecular orbital (E(LUMO)) and HA concentration as the descriptors was developed to predict the specific reduction rate constants of chlorinated methanes in HA solution. The analysis of variance (ANOVA) indicated the existence of significant relationship between the dechlorination rate constants and the two descriptors.

Influences of amphiphiles on dechlorination of a trichlorobenzene by nanoscale Pd/Fe: adsorption, reaction kinetics, and interfacial Interactions.

The influences of amphiphiles on the catalytic dechlorination of 1,2,4-trichlorobenzene (124TCB) bythe nanoscale Pd/Fe particles were comprehensively examined. The fresh and reacted Pd/ Fe particles were characterized with XRD, TEM, SEM, FTIR spectrometry, and goniometry. Adsorption of amphiphiles on the Pd/Fe particles, iron dissolution, and H2 evolution in the Pd/Fe-water system were quantified to expound the influences of the various amphiphiles on the dechlorination process. The Langmuir-Hinshelwood model is used to elucidate the dechlorination kinetics, and it provides insight into the influence of amphiphiles on 124TCB partitioning to the interfacial layer and the resulting dechlorination rates. The rate constants increased by a factor of 1.5--2.5 with the presence of cationic cetyltrimethylammonium bromide (CTAB). In the anionic sodium deodecyl sulfate(SDS) or nonionic nonylphenol ethoxylate (NPE) and octylphenolpoly (ethylene glycol ether)x (TX-100) surfactant solutions, the 124TCB dechlorination rates were slightly increased over those observed in ultrapure water. However, when concentrations of the surfactants were above their CMCs, the dechlorination rates decreased. The findings also showed that DPC (dodecylpyridinium chloride) and NOM (natural organic matter) might be the competitive H2 acceptors to 124TCB, and they significantly retarded its catalytic dechlorination by the Pd/Fe particles. CTAB at a concentration below the CMC appeared to be the most benign to the 124TCB dechlorination.

Catalytic reduction of chlorobenzenes with Pd/Fe nanoparticles: reactive sites, catalyst stability, particle aging, and regeneration.

Monochlorobenzene (MCB), dichlorobenzenes (DCBs), and 1,2,4-trichlorobenzene (124TCB) dechlorination experiments in water were carried out with freshly synthesized Pd/Fe particles. The pre- and postreacted Pd/Fe samples were characterized by applying various analytical techniques (XRD, SEM, TEM, and XPS). Chlorinated benzenes could be completely reduced by the Pd/Fe to benzene and the reaction followed the pseudo-first-order kinetics. The reaction rates followed the order TCB < DCBs < MCB, while among the DCBs the order was 1,4-dichlorobenzene >1,3-dichlorobenzene > or = 1,2-dichlorobenzene. Insignificant reactions were observed with the unpalladized iron, suggesting that Pd was the only reactive site in the Pd/Fe particles. The aged Pd/Fe particles exhibited significant decrease in its dechlorination reactivity. The loss of Pd/Fe reactivity could be due to Pd dislodgment from the aged Pd/Fe particles and Pd islets encapsulation by the iron oxides film developed over aging period. Reactivity of the aged Pd/Fe could be only partially restored after HCI treatment, while regeneration with the NaBH4 reduction method could not restore its activity, although zerovalent state of the iron was reinstated.

[Preparation method of Pd/Ce0.5Zr0.5O2 three-way catalysts].

1% Pd/Ce0.5Zr0.5O2(CZ) catalysts were prepared by deposition-precipitation (DP), mixing (MIX) and conventional impregnation (IMP) methods, and the effects of the preparation methods on the three-way catalytic behaviors were investigated. Hydrogen temperature-programmed reduction (H2-TPR) and in situ diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) were performed to understand the Pd-support interaction and the three-way catalytic reaction mechanisms. The experiments results reveal that the catalyst prepared by deposition-precipitation (DP) method shows the strongest Pd-support interaction and the best light-off performance. In situ DRIFTS results suggest that there exists alternative route of NOx reduction over Pd-DP catalyst. And it is supposed that Pd-support interaction leads to the difference of reaction mechanism and then the diversity of light-off performances.