发酵产氢的动力学模型

发酵产氢已经建立和应用了一些动力学模型.对描述批次发酵产氢过程的动力学模型,描述各种因子对其影响的动力学模型,以及探讨基质降解速率、产氢细菌(HPB)生长速率和产物形成速率关系的动力学模型进行了综述分析.分析表明,改进的Gompertz模型被广泛用于描述批次发酵产氢过程;Monod模型则广泛应用于描述基质浓度对基质降解...     

H(2) production through anaerobic mixed culture: effect of batch S(0)/X(0) and shock loading in CSTR

Biological production of H(2) has received considerable attention lately. The present study was undertaken to observe the effects of substrate/seeding ratios (S(0)/X(0)) on batch H(2) generation. The H(2)-producing seeding spores were obtained from the heat treatment (88 degrees C for 12h) of the compost from a grass composting facility. A dehydrated brewery mixture was used as feed substrate. The results indicate that the pattern of the cumulative H(2) production with time is similar to the growth curve with a typical lag, exponential and stationary phase; the results were successfully modeled with a modified Gompertz equation. It appears that maximum H(2) yield potential (27ml g(-1)COD(added)) occurs at an S(0)/X(0) ratio of about 4, whereas the maximum specific H(2) yield (205ml g(-1) VSSd(-1)) occurs at approximately S(0)/X(0)=3. The S(0)/X(0) ratios higher than 4 would inhibit H(2) production. An attempt was made to waste a certain amount of reactor content and replaced it with fresh substrate in order to enhance H(2) production. After this medium replacement, the H(2) production was initially inhibited and the system then exhibited a long lag before it reached an active H(2) production stage. For a continuous-stirred tank-reactor (CSTR) system, the results of replacing 25% of the reactor content indicate that there is still a lag time before a sudden increase in H(2) production after the addition of the new substrate feed. The major low molecular weight acids identified are HAc and HBu with total volatile acids of about 6000-8000mg l(-1). The ratio of HAc/HBu in the present study is relatively constant (about 5) and appears not significantly affected by the medium replacement. The concentration of total alcohols is about 2000mg l(-1). All in all, the CSTR system is able to recover to its previous performance after such a dramatic 25% medium replacement.     

Hydrogen peroxide-assisted UV photodegradation of Lindane

Aqueous solutions of gamma-hexachlorocyclohexane (Lindane) were photolyzed (lambda=254 nm) under a variety of solution conditions. The initial concentrations of hydrogen peroxide (H(2)O(2)) and Lindane varied from 0 to 20 mM and 0.21 to 0.22 microM, respectively, the pH ranged from 3 to 11, and several concentration ratios of Suwannee River humic acid and fulvic acid were dissolved in the irradiated solutions. Lindane rapidly reacted, and the maximum reaction rate constant (9.7 x 10(-3) s(-1)) was observed at pH 7 and initial [H(2)O(2)]=1 mM. Thus, 90% of the Lindane is destroyed in approximately 4 min under these conditions. In addition, within 15 min, all chlorine atoms were converted to chloride ion, indicating that chlorinated organic by-products do not accumulate. The reactor was characterized by measuring the photon flux (7.04 x 10(-6) E s(-1)) and the cumulative production of *OH during irradiation. The cumulative *OH production during irradiation was fastest at an initial [H(2)O(2)]=5 mM (k=0.77 micro M s(-1)).     

Degradation behaviour of pyrazosulfuron-ethyl in water as affected by pH

Pyrazosulfuron-ethyl, a new herbicide belonging to the sulfonylurea group, is used for weed control in rice crops growing in areas varying from acidic to alkaline soils. This study was undertaken to determine the degradation behaviour of pyrazosulfuron-ethyl in distilled water and buffer solutions at pH 4, 7 and 9. Degradation was pH-dependent and herbicide was least persistent in acidic pH followed by alkaline and neutral pH. The half-life of pyrazosulfuron-ethyl varied from 2.6 days (pH 4) to 19.4 days (pH 7) and half-life in distilled water was comparable to half-life at pH 7 buffer. HPLC analysis of different pH samples showed the formation of three metabolites viz., 5-(aminosulfonyl)-1-methyl-1H-pyrazole-4-carboxylic acid; ethyl 5-(aminosulfonyl)-1-methyl-1H-pyrazole-4-carboxylate and 2-amino-4,6-dimethoxy pyrimidine. The formation of pyrazosulfuron acid [5-([([(4,6-dimethoxy-2 pyrimidinyl)-amino]-carbonyl) amino]-sulfonyl)-1-methyl-1H-pyrazole-4-carboxylic acid] was not observed at any pH. The study indicated that the herbicide was least stable under acidic conditions and the predominant degradation route of pyrazosulfuron-ethyl in water is hydrolysis of sulfonamide linkage.     

Complexation of the antibiotic tetracycline with humic acid

The effect of solution chemistry and sorbate-to-sorbent ratio on the interaction of the antibiotic tetracycline with Elliott soil humic acid (ESHA) was investigated using equilibrium dialysis and FITEQL modeling. Tetracycline speciation strongly influenced its sorption to ESHA. Sorption was strongly pH-dependent with a maximum around pH 4.3, and competition with H+ and electrolyte cation (Na+) was evident. The pH-dependent trend was consistent with complexation between the cationic/zwitterionic tetracycline species and deprotonated sites in ESHA (mainly carboxylic functional groups). Modification of ESHA by Ca2+ addition increased tetracycline sorption suggesting that ternary complex formation (ESHA-metal-tetracycline) may be important at higher concentrations of multivalent metal cations. The macroscopic data (pH-envelope and sorption isotherms) were successfully modeled using a discrete logK function with the FITEQL 4.0 chemical equilibrium program indicating that ESHA-tetracycline interaction could be reasonably represented as complex formation of a monoacid with discrete sites in humic acid. Sorption-desorption hysteresis was observed; both sorption and desorption isotherms were well described by the Freundlich equation.     

Atrazine removal by ozonation processes in surface waters

Atrazine (6-chloro-N-ethyl-N'-isopropyl-1,3,5-triazinedyl-2,4-diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continuously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O3/H2O2 process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O3/H2O2 and O3/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

Evidence for the contribution of methane in the formation of aromatics and soot in fuel-rich pre-mixed combustion

Experimental results from an isothermal laminar flow reactor at atmospheric pressure are presented on the chemical composition in the post-oxidative region of two sooting fuel-rich pre-mixed mixtures diluted in nitrogen. A base case composed of n-heptane and O2 in N2 at 1425 K with a C/O of 2.85 was perturbed by substituting 10% of the carbon in n-heptane with carbon as CH4. While these changes would intuitively reduce aromatics and soot formation by increasing H2 and decreasing C2H2 concentrations, we observe the opposite. The concentrations of individual aromatic species are observed to actually increase by up to 50% and the soot yield increases by 80%.     

Production of hydrogen-rich gas from methane by thermal plasma reform

This study investigated the reforming characteristics and optimum operating condition of the high-temperature plasma torch (so called plasmatron) for hydrogen-rich gas (syngas) production. At the optimum condition, the composition of produced syngas was 45.4% hydrogen (H2), 6.9% carbon monoxide (CO), 1.5% carbon dioxide (CO2), and 1.1% acetylene (C2H2). The H2/CO ratio was 6.6, hydrogen yield was 78.8%, and the energy conversion rate was 63.6%. To obtain the optimum operating condition, parametric studies were carried out examining the effects of O2/CH4 ratio, steam/CH4 ratio, and Ni catalyst addition in reactor. When the steam/CH4 ratio was 1.23, the production of hydrogen was maximized and the methane conversion rate was 99.7%. The syngas composition was determined to be 50.4% H2, 5.7% CO, 13.8% CO2, and 1.1% C2H2. The H2/CO ratio was 9.7, hydrogen yield was 93.7%, and the energy conversion rate was 78.8%. Hydrogen production with catalyst was effective, compared with no catalyst.     

Hydrogen sulfide gas treatment by a chemical-biological process: chemical absorption and biological oxidation steps

In order to remove high concentrations of hydrogen sulfide (H2S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H2S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H2S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe2+ concentrations, pH, and glucose concentrations on Fe2+ oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H2S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass-transfer was verified as the rate-determining step in the chemical reaction through model validation. The Fe2+ production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35 degrees C in which more than 90% Fe3+ formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe2+ oxidation and the growth of T. ferrooxidans CP9.     

Performance of an innovative two-stage process converting food waste to hydrogen and methane

This study was conducted to evaluate the performance of an innovative two-stage process, BIOCELL, that was developed to produce hydrogen (H2) and methane (CH4) from food waste on the basis of phase separation, reactor rotation mode, and sequential batch technique. The BIOCELL process consisted of four leaching-bed reactors for H2 recovery and post-treatment and a UASB reactor for CH4 recovery. The leaching-bed reactors were operated in a rotation mode with a 2-day interval between degradation stages. The sequential batch technique was useful to optimize environmental conditions during H2 fermentation. The BIOCELL process demonstrated that, at the high volatile solids (VS) loading rate of 11.9 kg/m3 x day, it could remove 72.5% of VS and convert VS(removed) to H2 (28.2%) and CH4 (69.9%) on a chemical oxygen demand (COD) basis in 8 days. H2 gas production rate was 3.63 m3/m3 x day, while CH4 gas production rate was 1.75 m3/m3 x day. The yield values of H2 and CH4 were 0.31 and 0.21 m3/kg VS(added), respectively. Moreover, the output from the post-treatment could be used as a soil amendment. The BIOCELL process proved to be stable, reliable, and effective in resource recovery as well as waste stabilization.     

A comparative study of the effects of chloride, sulfate and nitrate ions on the rates of decomposition of H2O2 and organic compounds by Fe(II)/H2O2 and Fe(III)/H2O2

The effects of chloride, nitrate, perchlorate and sulfate ions on the rates of the decomposition of hydrogen peroxide and the oxidation of organic compounds by the Fenton's process have been investigated. Experiments were conducted in a batch reactor, in the dark at pH < or = 3.0 and at 25 degrees C. Data obtained from Fe(II)/H2O2 experiments with [Fe(II)]0/[H2O2]0 > or = 2 mol mol(-1), showed that the rates of reaction between Fe(II) and H2O2 followed the order SO4(2-) > ClO4(-) = NO3- = Cl-. For the Fe(III)/H2O2 process, identical rates were obtained in the presence of nitrate and perchlorate, whereas the presence of sulfate or chloride markedly decreased the rates of decomposition of H2O2 by Fe(III) and the rates of oxidation of atrazine ([atrazine]0 = 0.83 microM), 4-nitrophenol ([4-NP]0 = 1 mM) and acetic acid ([acetic acid]0 = 2 mM). These inhibitory effects have been attributed to a decrease of the rate of generation of hydroxyl radicals resulting from the formation of Fe(III) complexes and the formation of less reactive (SO4(*-)) or much less reactive (Cl2(*-)) inorganic radicals.     

Hydrogen peroxide mediated photodegradation of phenol as studied by a flash photolysis/HPLC technique

The technique of flash photolysis followed by high-performance liquid chromatography has been applied to the study of the photodegradation of phenol (I) in the presence of hydrogen peroxide. Progress of the reaction of I (0.1 mM) in undegassed aqueous solution ([H2O2]/[I] = 200/l) was observed by using multiple flashes (16 J). Analysis after a single flash indicated that catechol and hydroquinone were the primary products of the reaction. The reaction was found to be independent of pH in the range 7.0-9.0, but the yield of degradation decreased at pH > 9.0 and at pH < 7.0. The effects of the hydrogen peroxide concentration and flash energy on the chemical yield of the pollutant degradation, and product formation, were investigated as well. The mechanism of the reaction is discussed. A possibility of the application of flashlamps as powerful sources of the UV irradiation in industrial reactors for wastewater treatment is suggested.     

Factors on the formation of disinfection by-products MX, DCA and TCA by chlorination of fulvic acid from lake sediments

[3-Chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone] (MX) and chlorinated acetic acids such as dichlorinated acetic acid (DCA) and trichlorinated acetic acid (TCA) have always been the focus of disinfection by-products (DBPs) studies. In order to find out the influences of reaction time, TOC, chlorine dose, pH and temperature on the formation of MX, DCA and TCA, we extracted fulvic acid (FA) from the sediment of Tai Lake, and conducted simulated chlorination of samples rich in FA. Results showed positive relationship between TOC and the yields of MX, DCA and TCA. But the influences of pH, chlorine dose, reaction time, and temperature are quite complex. The optimal chlorination condition for the formation of MX is pH = 2, T = 45 degrees C, C/Cl2 = 1/4, t = 12 h. Lower pH, longer time, greater chlorine dose can result in greater yield of both DCA and TCA, and there is a strong linear relationship between the formation of DCA and TCA.     

Reduction of Cr(VI) by caffeic acid

In the soil-plant system, the Cr(VI) toxicity can be moderated through redox reactions involving phenolic substances. In such a context, we report the reducing activity of caffeic acid (CAF) towards Cr(VI) in aqueous phase. The redox reaction between Cr(VI) and CAF was studied as a function of both time and pH at different initial metal concentrations. The reaction was particularly effective at pH 2.5. The kinetic data indicate that the reaction proceeds through two steps: the first is faster and involves four electrons, the latter, which is slower, five electrons. The chromatograms evidence the formation of oxidation products (OP) with a different redox activity towards Cr(VI). A yield of Cr(III) equal to that obtained at pH 2.5 and pH 3.1 in about 7 and 25 h, respectively, was reached at pH 4.2 only after a much longer reaction time (50h). At pH>4.2 the reaction occurred even more slowly, and its kinetic trend was more and more difficult to study at pH values higher than 5.0 due to the formation of precipitates. Other phenolics investigated (o-, m-, p-coumaric acids) showed a reducing activity negligible compared to that of CAF: about 30% of p-coumaric acid was oxidized at pH 2.5 only after two months of reaction.     

Buffering processes in a boreal dissolved organic carbon-rich stream during experimental acidification

The role of organic acids on surface water acidity as well as their buffering during anthropogenic acidification and subsequent recovery was studied in a field experiment on a total organic carbon (TOC)-rich stream draining the Svartberget catchment in northern Sweden. H(2)SO(4) was added to the stream to increase SO(4)(2-) concentration by 90 microeq l(-1) for 30 h. About 60% of the added H(+) was buffered by protonation of organic acids, another 20% was buffered by base cations released from the surface of the stream channel and only ca. 20% of the added acid remained unbuffered. TOC concentrations (27 mg l(-1)), and site density of carboxylic groups--8.6 microeq (mg TOC)(-1)--remained stable during the experiment. Two models of organic acid dissociation (a triprotic model and a monoprotic pH-dependent pKa model) were fitted to the experimental results. These models explained the observed variations in organic anions, but the model parameters were quite different from those reported by studies in Northern America and Central Europe. This experiment had substantially more buffering effect of TOC between pH 4.4 and 5.3, which is an environmentally important pH range.     

UV/H2O2工艺降解环丙沙星的研究

采用UV/₂O₂工艺去除水体中的喹诺酮类抗生素环丙沙星（CIP）。考察了溶液pH值、₂O₂投加量以及水体基质对环丙沙星降解效率的影响,分析了降解产物的生成情况。研究表明,环丙沙星的降解符合拟一级反应动力学模型。降解速率受溶液pH值的影响,酸性及中性条件,有利于环丙沙星的降解。₂O₂投加量的增大,使得降解速率逐渐增大,但速率增幅逐渐变缓;最佳₂O₂/环丙沙星摩尔比为2 000。实际水体中存在的NOM、NO^-₃,促进了单独UV作用下,环丙沙星的降解。水体中的?OH焠灭剂,抑制了UV/₂O₂联合作用下,环丙沙星的降解;实际水体中的光解速率常数低于超纯水中的光解速率常数。GC-MS分析表明,UV/₂O₂工艺,使环丙沙星氧化降解生成氨基乙酸、丙二酸、丙三醇和对苯二甲酸等小分子有机物。     

Ozonation of aqueous solution of alpha endosulfan

Ozonation of alpha endosulfan and the effects of some parameters such as pH, temperature and partial pressure on ozonation were investigated and the kinetic constants were calculated in this study. Alpha endosulfan solutions were ozonated in a lab-scale semi-batch reactor under variable experimental conditions. Increase in dissolved ozone concentration had a positive effect on oxidation rate. Alpha endosulfan could be removed up to 94% at pH 4 for an ozonation time of 60 minutes. The oxidation reaction was found to be of second order and of first order with respect to both ozone and alpha endosulfan. The temperature dependent reaction expression of alpha endosulfan was obtained as kd = (1.889 exp(- 2.21 x 10(-3)/T). It was concluded that, although the rate of reaction was lower than the rate of other pesticide oxidation reported in the literature. alpha endosulfan presented an obvious reaction to ozonation.     

Inhibition of heavy metals on fermentative hydrogen production by granular sludge

This study was conducted to investigate the toxicity of six electroplating metals on the H(2)-producing activity of a granular sludge sampled from an H(2)-producing upflow reactor treating sucrose-containing wastewater. The H(2) production activities of the sludge were measured in serum vials using wastewater containing not just sucrose and proper nutrient, but also individual heavy metals at concentrations ranging 0-5000 mg l(-1). The relative toxicity to H(2) production was found in the following order: Cu (most toxic)>Ni approximately Zn>Cr>Cd>Pb (least toxic). The C(I,50) values, at which the bioactivity of the sludge was reduced to 50% of the control, for individual heavy metals were Cu 30 mg l(-1), Ni and Zn 1600 mg l(-1), Cr 3000 mg l(-1), Cd 3500 mg l(-1), and Pb >5000 mg l(-1). Compared with the literature data, H(2)-producing sludge exhibited in general higher resistance to metal toxicity than methanogenic granular sludge.     

Bacterial leaching of heavy metals from sewage sludge-bioreactors comparison

More than 50% of municipal sewage sludges cannot be used on agricultural land because of their heavy metals content. Therefore, microbial leaching of heavy metal from municipal sludge was studied in a continuously stirred tank reactor without recycling (CSTR) or with sludge recycling (CSTRWR) at residence times of 1, 2, 3 and 4 days. The reactor CSTRWR is supposed to be more efficient for bacterial process due to the recycling of active bacteria from the settling tank to the reactor. The CSTRWR and the CSTR with 1 g litre(-1) FeSO(4).7H(2)O addition were equally efficient because of copper reprecipitation or recomplexation in the settling tank of the CSTRWR. In the CSTR, about 62% of copper and about 77% of zinc were dissolved in 3 days residence time compared to 50% of copper and 64% of zinc in the CSTRWR, if 3 g litre(-1) FeSO(4).7H(2)O was added. Thus with larger amount of substrate, the CSTR was more efficient than the CSTRWR. Residence time and pH were the main factors for zinc solubilization while for copper, the redox potential was also a major factor. The effect of FeSO(4).7H(2)O concentration on bacterial activity to solubilize heavy metals was also studied, increased concentration of FeSO(4).7H(2)O yielded better copper solubilization while it had no effect or a negative effect on zinc. This supports the hypothesis of a direct mechanism for zinc solubilization and of an indirect mechanism for copper solubilization.     

Gas-phase reaction of CCl2F2 (CFC-12) with methane

Gas-phase reaction of CFC-12 (CCl2F2) with methane was carried out in a plug flow reactor over the temperature range of 873-1123 K. The major organic halocarbons formed during the reaction were C2F4, C2H2F2, CHClF2, CH3Cl, C3H2F6 and CCl3F. The formation of all products except C2H2F2 decreased with temperature, while the selectivity to C2H2F2 (difluoroethylene) increased with temperature and reached approximately 80% at 1123 K. Under these reaction conditions, methane acts as hydrogen and carbon source, resulting in the formation of an unsaturated C2 hydrofluorocarbon from two C1 precursors.