硅藻土颗粒在处理煤气废水活性污泥系统中的作用

Diatomite is a kind of natural low-cost mineral material. It has a number of unique physical properties and has been widely used as an adsorbent in wastewater treatment. This study was conducted to investigate the aerobic biodegradation of coal gasification wastewater with and without diatomite addition. Experimental results indicated that diatomite added in the activated sludge system could promote the biomass and also enhance the performance of the sludge settling. The average mixed-liquor volatile suspended solids (MLVSS) is increased from 4055 mg•L－1 to 4518 mg•L－1 and the average settling volume (SV) are changed only from 45.9% to 47.1%. Diatomite additive could enhance the efficiency of chemical oxygen demand (COD) and total phenols removal from the wastewater. The COD removal increased from 73.3% to near 80% and the total phenols removal increased from 81.4% to 85.8%. The mechanisms of the increase of biomass and pollutants removal may correlates to the improvement of bioavailability and sludge settlement characteristics by diatomite added. Micrograph of the sludge in the diatomite-activated sludge system indicated that the diatomite added could be the carrier of the microbe and also affect the biomass and pollutant removal.     

用CuO/A12O3/堇青石催化剂选择性催化还原脱硝的实验和动力学研究

The CuO/γ-Al2O3/cordierite catalyst, after being sulfated by sulfur dioxide (SO2) at 673 K, exhibits high activities for selective catalytic reduction (SCR) of nitrogen oxide (NO) with ammonia (NH3) at 573-723 K. The intrinsic kinetics of SCR of NO with NH3 over CuO/γ-Al2O3/cordierite catalyst has been measured in a fixed-bed reactor in the absence of internal and external diffusions. The experimental results show that the reaction rate can be quantified by a first-order expression with activation energy of 94.01 kJ•mol1 and the corresponding pre-exponential factor of 3.39×108 cm3•g1•s1 when NH3 is excessive. However, when NH3 is not enough, an Eley-Rideal kinetic model based on experimental data is derived with Ea of 105.79 kJ•mol1, the corresponding A of 2.94×109 cm3•g1•s1, heat of adsorption ΔHads of 87.90 kJ•mol1 and the corresponding Aads of 9.24 cm3•mol1. The intrinsic kinetic model obtained was incorporated in a 3D mathematical model of monolithic reactor, and the agreement of the prediction with experimental data indicates that the present kinetic model is adequate for the reactor design and engineering scale-up.     

新筛选菌种Sphingopyxis sp.USTB-05对微囊藻毒素的生物降解

A promising bacterial strain for the biodegradation of Microcystins (MCs) was isolated from Dianchi lake in China and identified as Sphingopyxis sp. USTB-05 by the analysis of 16s rDNA. Initial MC-RR of 42.3 mg&;#8226;L－1 was completely degraded by USTB-05 within 36 h, which was a relatively high biodegradation rate of MC-RR. With the cell-free extract (CE) of Sphingopyxis sp. USTB-05, MC-RR was biodegraded at a more rapid biodegradation rate compared with its strain, so that initial MC-RR of 42.3 mg&;#8226;L－1 was completely biodegraded within 10 h. During the bio-reaction of MC-RR catalyzed by CE, two intermediate metabolites and a dead-end product of MC-RR were observed on HPLC profiles and all of them had similar scanning profiles in the wavelength from 200 to 300 nm, indicating that the group of Adda in all products of MC-RR remained intact.     

氨改性的介孔二氧化硅的直接合成和CO2吸附

Amine-functionalized mesoporous silica was prepared by using lauric acid and N-stearoyl-l-glutamic acid as structure directing agents via the SN+-I mechanism and applied to CO2 adsorption at room temperature. With γ-aminopropyltriethoxysilane as co-structure directing agent and due to the direct electrostatic interaction with anionic surfactant, most of the amino groups were uniformly distributed at the inner surface of pores and the performance was stable. The amine-functionalized mesoporous silica was characterized by Fourier transform infrared spectrometer, X-ray diffraction, nitrogen physisorption and thermogravimetric analysis. The CO2 adsorption capacity was measured by digital recording balance. At the room temperature and under the atmospheric pres-sure, the adsorption capacity of LAA-AMS-0.2 for CO2 and N2 is 1.40 mmol•g1 and 0.03 mmol•g1, respectively, indicating high separation coefficient of CO2/N2.     

硫酸铁改性颗粒活性氧化铝除氟的等温线研究

The adsorption equilibrium of a fluoride solution on 1-2 mm granular activated alumina modified by Fe2(SO4)3 solution was investigated. The experiments were conducted using a wide range of initial fluoride concentrations (0.5 to 180 mg•L1 at pH ~7.0) and an adsorbent dose of 1.0 g•L1. The application of Langmuir and Freundlich adsorption isotherm models (linear and nonlinear forms) generally showed that a single Langmuir or Freundlich equation cannot fit the entire concentration gap. Experimental data on low equilibrium concentrations (0.1 to 5.0 mg•L1) was in line with both Langmuir and Freundlich isotherm models, whereas that of high equilibrium concentrations (5.0 to 150 mg•L1) was more in line with the Freundlich isotherm model. A new Langmuir- Freundlich function was used for the entire concentration gap, as well as for low and high concentrations.     

ZnAl类水滑石制备温度对吸附剩余污泥脱水液中磷酸根的影响

A group of Zn-Al layered double hydroxides (LDHs) were synthesized at different temperatures from 25–90 °C in order to investigate the influence of synthesis temperature on characteristics of the LDHs and their phosphate adsorption behaviour. The results reveal that an increase in the synthesis temperature generally improves the specific surface area of the sample and the phos-phate adsorption capacity. The significantly enhanced crystallinity of the Zn-Al-30, synthesized at 30 °C, leads to a remarkable de-crease in the specific surface area and consequently a poor phosphate adsorption capacity. It is suggested that the surface adsorption plays an important role in the phosphate uptake by the Zn-Al LDHs. Zn-Al-70 presents a relatively higher crystallinity and a lower specific surface area, compared with Zn-Al-60 and Zn-Al-80, but the highest phosphate adsorption capacity, indicating that surface adsorption is only one of the pathways for phosphate removal. The phosphate adsorption by the Zn-Al follows a pseudo-second-order kinetic equation. The adsorption isotherms fit Langmuir models, and the maximum adsorption capacities of the Zn-Al-25, Zn-Al-50 and Zn-Al-70 are estimated to be 17.82, 21.01 and 27.10 mg•g1 adsorbent, respectively.     

过氧化叔戊醇对苯并噻吩类衍生物的氧化

Homogeneous oxidation using an oil-soluble oxidant, tert-amyl hydroperoxide (TAHP), for ultra-deep desulfurization was performed under mild conditions in the presence of molybdenum oxide catalysts. Dibenzothio-phene (DBT), benzothiophene (BT) and 4, 6-dimethyl-dibenzothiophene (DMDBT), which are the refractory sulfur compounds for hydrodesulfurization (HDS), were employed as model substrates for a simulated diesel fuel. Activ-ity of molybdenum oxide supported on a macroporous weak acidic resin was investigated. The mass conversion of DBT reached near 100% at 90°C and a TAHP/DBT molar ratio of 3 with 1% of molybdenum oxide supported on Amberlite IRC-748 resin for 1 h. It was further found that the activities of the model substrates decreased in the or-der of DMDBT＞DBT＞BT. In the flow oxidation using TAHP as the oxidant, mass conversion of DBT increased remarkably from 61.3% to 98.5% when dropping the weight hourly space velocity (WHSV) from 40 h－1 to 10 h－1. A series of experiments dealt with selectivity of this oxidation using TAHP revealed that the model unsaturated compounds, i.e. 4, 6, 8-trimethyl-2-nonylene, and 2-methylnaphthalene did not affect the oxidation of DBT. Car-bazole had nearly no effect on the conversion of DBT using TAHP, but had some influence on the one using tert-butyl hydroperoxide (TBHP). The mass conversion of DBT decreased remarkably from 75.2% to 3.6% when the content of carbazole increased from 0 to 500 μg•g－1. In the flow oxidation using TAHP as the oxidant, the con-centration of DBT in model fuels was reduced from 500 µg•g－1 to 7.2 µg•g－1 at WHSV of 10 h－1, and then reduced to 3.8 µg•g－1 by adsorption of Al2O3.     

PDMS/陶瓷复合膜用于正丁醇-水体系的渗透汽化分离

Pervaporation has attracted considerable interest owing to its potential application in recovering biobutanol from biomass acetone-butanol-ethanol (ABE) fermentation broth. In this study, butanol was recovered from its aqueous solution using a polydimethylsiloxane (PDMS)/ceramic composite pervaporation membrane. The effects of operating temperature, feed concentration, feed flow rate and operating time on the membrane pervaporation per-formance were investigated. It was found that with the increase of temperature or butanol concentration in the feed, the total flux through the membrane increased while the separation factor decreased slightly. As the feed flow rate increased, the total flux increased gradually while the separation factor changed little. At 40 C and 1% (by mass) butanol in the feed, the total flux and separation factor of the membrane reached 457.4 g•m2•h1 and 26.1, respec-tively. The membrane with high flux is suitable for recovering butanol from ABE fermentation broth.     

甲苯液相空气氧化过程中[Co2+]/[Co3+]的测定及其对反应的影响

Liquid phase oxidation of toluene is an environmental benign route for the production of benzoic acid. In a mm bubble column reactor, the commercial process of toluene liquid phase oxidation was conducted with Co(CH3COO)2&#8226;4H2O as catalyst. The Co2+ concentration [Co2+] was determined by extraction spectrophotometry and hereby the Co3+ concentration [Co3+] was obtained by mass balance. The results showed that [Co3+] reached the maximum at about 25-30 min. [Co3+] increased with increasing Co catalyst amount at total Co concentration <150 mg&#8226;L－1 of toluene. The conversion of toluene, yield and selectivity of benzoic acid increased with the increasing [Co3+/Co2+]max. A high [Co3+] and a high [Co3+]/[Co2+] ratio are beneficial to the reaction.     

生物活性泡沫乳液反应器处理被苯、甲苯、二甲苯污染的空气

A novel bioactive foam emulsion bioreactor for benzene, toluene and xylene (BTX) contaminated air streams treatment has been developed. The gas-liquid interfacial area by biocompatible foam and driving force for mass transfer by a water immiscible organic phase were increased in this reactor. The effect of several parameters such as gas residence time, oxygen content, and organic phase concentration on bioreactor performance was studied. Experimental results showed an average elimination capacity (EC) of 220 g&;#8226;m－3&;#8226;h－1 with removal efficiency (RE) of 89.59% for BTX inlet concentration of 1 g&;#8226;m－3 at 15 s gas residence time in the bioreactor. The statistical developed model predicted that the maximum elimination capacity of the reactor for BTX could be reached to 423.45 g&;#8226;m－3&;#8226;h－1. Continues operation of the bioreactor with high EC and RE was demonstrated by optimizing the operational parameters of the bioreactor. Overall the results suggest that the bioreactor developed can be very effective systems to treat BTX vapors.     

External-loop fluidized bed airlift bioreactor (EFBAB) for the cometabolic biotransformation of 4-chlorophenol (4-cp) in the presence of phenol

The advantages from a 4-l external-loop inversed fluidized bed airlift bioreactor (EIFBAB) reported by Loh and Liu [2001. Chemical Engineering Science 56, 6171-6176] was synergized with preferential adsorption by granular activated carbon (GAC) for the enhanced cometabolic biotransformation of 4-chlorophenol (4-cp) in the presence of phenol as a growth substrate. This was achieved by incorporating a GAC fluidized bed in the lower part of the riser with the gas sparger relocated above this fluidized bed to avoid the presence of a 3-phase flow in the fluidized bed consequently providing larger gas holdup. Expanded polystyrene beads (EPS) were used as the supporting matrix for immobilizing Pseudomonas putida ATCC 49451, in the downcomer of the bioreactor. The hydrodynamics of the bioreactor system was characterized by studying the effect of the extent of valve opening, under cell-free condition, on gas holdup and liquid circulation velocity at different gas velocities and solids loading (EPS and GAC). The experimental data for gas holdup were modeled using power law correlations, while a Langmuir-Hinshelwood kinetics model was used for the liquid circulation velocity. The bioreactor was tested for batch cometabolic biotransformation of 4-cp in the presence of phenol at various concentration ratios of phenol and 4-cp (ranging from phenol: 4-cp to phenol: 4-cp) at 9% EPS loading and 2.8% (10 g) GAC loading. The 4-cp and phenol biotransformations were achieved successfully in the bioreactor system, which ascertained the feasibility of the bioreactor. Biotransformation of high 4-cp and phenol concentrations, which was oxygen limited, was also effectively achieved by increasing the gas holdup in the riser. This was possible in the current EFBAB system because of the synergistic effect of the GAC fluidized bed, the globe valve and cell immobilization by EPS.     

苯酚液相臭氧化动力学特性的研究

应用Stopped-flow光谱仪对苯酚在288－313K温度和pH=3.2-9.3的液相臭氧化反应动力学特性进行了实验研究。通过实验及分析认为：苯酚的O3氧化降解反应，O3与苯酚的计量比为3；在不同酸度的实验条件下，苯酚的液相O3氧化降解的途径及动力学不同。     

A KINETIC STUDY OF SULFURIC ACID-CATALYZED LIQUEFACTION OF WOOD INTO PHENOL

The powders of monarch birch wood (Betula maximowiczina Regel) were liquefied into phenol using sulfuric acid as a catalyst at various temperatures and reaction times. Typical kinetic parameters of the degrading reaction of wood in the presence of phenol and the acid were determined using typical kinetic models. In addition, the activation parameters of the liquefaction of wood were determined according to transition-state theory. The results of showed percent liquefied wood that about 100% of the wood could be liquefied into phenol at a temperature of 150°C for about 2 h. However, about 68% of phenol was found to react mainly with wood components along with sulfuric acid and phenol itself. The kinetic studies showed that the liquefaction of wood into phenol using sulfuric acid obeyed a bimolecular type second-order reaction and Arrhenius law. The activation energy of the liquefaction was 68.5 kJ mol^-1. Furthermore, the findings related with activation enthalpy showed that the liquefaction of wood possessed a primarily endothermic reaction nature.     

A KINETIC STUDY OF SULFURIC ACID-CATALYZED LIQUEFACTION OF WOOD INTO PHENOL

The powders of monarch birch wood (Betula maximowiczina Regel) were liquefied into phenol using sulfuric acid as a catalyst at various temperatures and reaction times. Typical kinetic parameters of the degrading reaction of wood in the presence of phenol and the acid were determined using typical kinetic models. In addition, the activation parameters of the liquefaction of wood were determined according to transition-state theory. The results of showed percent liquefied wood that about 100% of the wood could be liquefied into phenol at a temperature of 150°C for about 2 h. However, about 68% of phenol was found to react mainly with wood components along with sulfuric acid and phenol itself. The kinetic studies showed that the liquefaction of wood into phenol using sulfuric acid obeyed a bimolecular type second-order reaction and Arrhenius law. The activation energy of the liquefaction was 68.5 kJ mol^?1. Furthermore, the findings related with activation enthalpy showed that the liquefaction of wood possessed a primarily endothermic reaction nature.     

2，6-二叔丁基对仲丁基酚的合成

以磺酸阳离子树脂为催化剂,以对仲丁基苯酚和异丁烯为原料合成了2,6-二叔丁基对仲丁基苯酚。探讨了不同催化剂、反应温度、反应时间、物料配比和催化剂用量对反应的影响。最优的反应条件:催化剂的质量分数为3%～5%(以对仲丁基苯酚质量计,下同),n(对仲丁基苯酚)∶n(异丁烯)=1∶2,反应温度90～100℃,反应压力0.15～0.2 MPa,反应时间4 h,在该条件下,产物选择性达95%以上,精馏分离得到色谱纯度大于97.5%的2,6-二叔丁基对仲丁基苯酚,总收率达95%以上。     

琥珀酸十二醇聚氧乙烯醚单酯二乙醇酰胺合成与红外光谱表征

从顺丁烯二酸酐出发,经过单酯化、酰胺化等一系列过程,合成了一种具有防锈、润滑双重性能的水基合成切削液添加剂———琥珀酸十二醇聚氧乙烯醚单酯二乙醇酰胺。酯化条件为:酸酐/AEO9(物质的量比)1.0∶1.1,反应温度为85～95℃,反应时间为3～4 h;酰胺化条件为:琥珀酸十二醇聚氧乙烯醚单酯/二乙醇胺(摩尔比)为1∶1.2,反应温度为150～160℃,反应时间为2～3 h。采用红外光谱法对原料、中间体和产物进行表征,确定了合成的最佳工艺路线和工艺条件。     

工业碱木素热化学转化制备酚类化学品

引言 工业碱木素是碱法制浆过程中产生的重要副产物之一,其排放污染问题越来越受到关注,目前工业处理方法只是将其浓缩燃烧以回收能源和残碱.木质素是一种化学结构复杂的天然高分子聚合物(主要由愈创木基丙烷、紫丁香基丙烷和对羟苯基丙烷通过醚键和碳碳共价键相联),其分子量从几千至几十万,数量上仅次于纤维素,利用潜力较大.     

4种DSA阳极的制备及其电催化性能比较

制备了Ti/SnO2+Sb2O3, Ti/PbO2, Ti/Fe-PbO2和Ti/SnO2+Sb2O3/Fe-PbO2四种形稳阳极材料,对其表面形貌进行了表征,同时测试了其在H2SO4溶液中的极化曲线. 以苯酚为目标污染物,用其进行了电催化降解实验. 结果表明,Ti/SnO2+Sb2O3/Fe-PbO2电极催化活性最好,苯酚降解率可达95%. 添加锡锑中间层后,Ti/SnO2+Sb2O3/Fe-PbO2电极寿命显著提高,可达16 h. 苯酚在4种阳极上的电催化降解反应遵循一级反应动力学规律.     

4-叔戊基-2-(α-甲苄基)苯酚的合成

以对叔戊基苯酚和苯乙烯为起始原料,浓磷酸作催化剂,设计合成铷、铯萃取剂4-叔戊基-2-(α-甲苄基)苯酚。考察反应温度、反应时间、原料配比和催化剂用量为对4-叔戊基-2-(α-甲苄基)苯酚产率的影响。确定最佳反应条件为:反应温度140℃,反应时间3 h,n(苯乙烯)∶n(对叔戊基苯酚)=1.4,催化剂用量为对叔戊基苯酚质量的24.63%。此条件下,4-叔戊基-2-(α-甲苄基)苯酚产率为58.76%。     

对甲苯磺酸催化合成2，2-双（3-苯基-4-羟基苯基）丙烷研究

以主催化剂对甲苯磺酸及助催化剂巯基丙磺酸来催化丙酮和邻苯基苯酚,经过缩合反应合成了2,2-双（3-苯基-4-羟基苯基）丙烷（双OPP-A）,实验过程中研究了原料配比、反应温度、催化剂用量、反应时间等因素对产物的影响,得到合成2,2-双（3-苯基-4-羟基苯基）丙烷的最优工艺条件为：丙酮、邻苯基苯酚、对甲苯磺酸和巯基丙磺酸物质的量比为1：4：O．25：O．25,最佳反应时间为7h、最佳反应温度为60℃,2,2-双（3-苯基-4-羟基苯基）丙烷收率达到74．2％,经重结晶纯度达99．5％。通过红外光谱、核磁共振和熔点等分析手段对产物结构进行了确证。