Search

Microwave-assisted method was used to synthesize successfully a series of new surfactants. Maleic anhydride, ethylenediamine, polyoxyethylene lauryl ether (number of polymerization of ethylene oxide = 3, 5, 7, 9, 12) and sodium sulfite were used. The optimal reaction conditions for synthesizing five new surfactant products were obtained by response surface design. The chemical structure of five new surfactant products were confirmed by Fourier transform infrared spectroscopy (FT-IR), mass spectrometry, elementary analysis and 1H-nuclear magnetic resonance (1H-NMR) analysis. The critical micelle concentration (CMC), surface tension, emulsifying power and foaming capacity in aqueous solution were studied. The microemulsion cutting fluid was also prepared by micro-emulsification of self-made new anionic–nonionic Genimi surfactant. The influence of the different structural unit of ethoxy (EO) and additives on the surface properties of five new prepared products was researched. CMC and γcmc of five new prepared products were in the scope of 3.39×10−4~3.48×10−4 mol/L and 21.9~23.4 mN/m respectively. Oxalamide polyoxyethylene(12) lauryl biether succinate sodium sulfonate was the optimum foamability and foam stability among five new prepared surfactants. Oxalamide polyoxyethylene( 3) lauryl biether succinate sodium sulfonate was the best emulsification power in the five new product. The cutting fluid prepared by self-made Gemini surfactant showed good performance. Experimental results show that it is expected to be a wide range applications in oil emulsification and other fields for new Gemini surfactants.

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).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.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.

Ethyl cyanoacetate is an important chemical intermediate and has been used widely. Ethyl cyanoacetate was prepared by esterification of cyanoacetic acid and absolute ethanol with mixed catalyst (the same proportion of silicotungstic and p-toluene sulfonic acid as catalyst). The influence factors of the amount of catalyst, n(cyanoacetic acid): n ( absolute ethanol), reaction time and reaction temperature on the esterification rate was investigated by orthogonal experiment of four factors and three levels. The product was analyzed by gas chromatography to determine the optimum reaction conditions.

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.

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.

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 0 . α-Fe 0 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.

180 p. Chlorinated benzenes are widely used in synthesis of dyes, pesticides and other chemicals, as space deodorants and moth repellent, and as solvent. Because of their biorefractory nature, they tend to accumulate in the environment and in animal tissues. Biodegradation requires well controlled growth conditions for the indigenous microorganisms, and may take a long period to degrade these contaminants. Recently, destruction of halogenated hydrocarbons in water by means of abiotic reductive dehalogenation with zero-valent iron (ZVI) has been proved to be a promising technology. Doctor of Philosophy (CEE)

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≈silicaperchloratecarbonatenitratephosphatenitritesulfitesulfide. Mineralogical analysis with XRD, morphological study with SEM-EDX, and spectroscopic analysis with FTIR spectrometer of the fresh and reacted Pd/Fe samples were conducted to examine the influences of the various anions on the Pd/Fe surface. Silica and sulfate did not show any significant short-term effect on reactivity of the nanoscale Pd/Fe, because the 124TCB dechlorination reaction was only dependent on the reactivity of the Pd site that was apparently not passivated by the anions. However, sulfide and sulfite could immediately terminate the 124TCB dechlorination process. Based on the natures of their inhibitory effects on 124TCB dechlorination by the Pd/Fe, the anions can be classified as: (1) adsorption-precipitation passivating species (e.g., phosphate and carbonate), (2) redox-active species (e.g., nitrate, nitrite, and perchlorate), and (3) catalyst poisons (e.g., sulfide and sulfite).

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 ( −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.

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 TCBDCBsMCB, while among the DCBs the order was 1,4-dichlorobenzene1,3-dichlorobenzeneor = 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.

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.

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.

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.