水碳化变化对汽油氧化重整制氢影响的研究

本文用正辛烷代替汽油从理论和实践两方面研究了碳化变化对汽油氧化重整制氢反应的影响。理论研究表明，在绝热反应条件下，对应确定的反应湿度存在一个最佳的氧油比及水碳比；实验研究表明，在非绝热反应体系中，在一定的氧油比及反应温度条件下，反应体系的转化率及生成氢的选择性均随水碳化的增加与增加，为实现燃料电池汽油制氢自热反应，反应体系应在一定水碳比条件下,实验条件下最佳的水碳比范围是1．5－2．5之间。     

水泥分解炉掺烧干污泥对NO_x排放的影响

针对水泥窑炉NOx排放问题,提出了在分解炉上采用掺烧干污泥对烟气进行脱硝的方法。通过在水泥分解炉进行实验,研究了掺烧干污泥对NOx的影响。实验表明,在保持CO浓度和含氧量在一定范围内相对不变的条件下,NOx浓度随着干污泥掺烧量增加而减少。在保持干污泥掺烧量、CO浓度在一定范围内相对不变的情况下,NOx排放浓度随着含氧量的增加而增加,表明在富氧环境下,NOx比较容易生成。在保持干污泥掺烧量、含氧量不变的情况下,NOx排放浓度随着CO浓度的增加而减少,说明在高温环境下,干污泥暴露在烟气中的碳不断与氧反应,加快了干污泥活性炭化的进程,并促使NOx不断被吸附。同时,NOx生成所需的氧被碳原子掠夺,从而使CO浓度增加,并抑制了NOx的生成。     

水淬钢渣碳酸化固定CO_2

利用HSC-Chemistry软件平台对以气-液-固三相为基础的水淬钢渣碳酸化固定二氧化碳进行了热力学分析,结果表明,温度700 K以下钢渣主要含钙相在水溶液中能够自发与CO2反应,碳酸化固定CO2是可行的;并通过实验研究了反应时间、钢渣粒径、CO2流量及液固比等主要参数对水淬钢渣碳酸化固定CO2的影响。结果显示,在初期阶段反应迅速,固碳率在3 h达到27.9%,即固定二氧化碳的能力约为279 kg/t(钢渣),随后逐渐趋于平衡。粒度越细对固碳过程越有利,液固比及CO2流量影响不明显;XRD及SEM结果也验证了水淬钢渣固定CO2是可行的。     

反胶束漆酶/纤维素酶体系中油酸酯化的优化

漆酶和纤维素酶在反胶束水核中心具有较强的催化活性。为了对反胶束酶体系中油酸酯化反应深入研究,采用生物表面活性剂鼠李糖脂构建反胶束体系作为漆酶与纤维素酶酯化油酸的催化反应场所。通过实验研究了反胶束体系的不同条件对酯化产物含量的影响。对于反胶束漆酶体系,最佳酯化条件为:含水量W040%,鼠李糖脂临界胶束浓度20mmol·L~(-1),pH值4,温度40℃;对于反胶束纤维素酶体系,最佳酯化条件为:含水量20%,鼠李糖脂临界胶束浓度80 mmol·L~(-1),pH值4,温度30℃。综合考虑几个因素,漆酶比纤维素酶更适合应用于反胶束中油酸的酯化。研究同时采用荧光光谱法对漆酶和纤维素酶在反胶束体系中结构性能的变化进行研究,结果表明,当反胶束体系处于最佳酯化反应条件时,荧光强度最高。     

废液晶显示器偏光片水热产乳酸研究

以废液晶显示面板中的偏光片为原料,对其进行水热产乳酸研究,并考察了反应温度(250～375℃)、反应时间(1～11min)以及氧化剂(体积分数为30％的H2O2)投加量(0～1.0 mL)对乳酸产率的影响.结果表明,反应温度、反应时间均会对偏光片水热产乳酸产生一定影响,乳酸产率随反应温度和反应时间的增加呈现先增加后减少的趋势,最佳水热条件为反应温度350℃,反应时间5 min,此时乳酸产率达17％左右.投加氧化剂能显著提高乳酸的产率,在最佳水热条件下,氧化剂投加量为0.6 mL时乳酸的产率可提高到21％.     

餐厨垃圾中典型组分的裂解液化特征研究

利用实验室规模的实验装置管式加热炉进行餐厨垃圾热解实验,实验分析了反应温度对餐厨垃圾热解产物分布的影响,米饭、白菜、猪肉、塑料和纸5种原料在最佳温度下可实现热解油质量产率的最大化,分别为45.02%、24.55%、61.19%、73.77%和24.86%。其中,米饭和白菜热解油含水率较高,可达到30%~40%,将含水率降到15%后,测定热值分别为25.51 MJ/kg和17.75 MJ/kg。塑料和纸混合热解时,塑料热解过程的放热效应可缩小纸的热解温度区间,增加热解油产量。红外光谱分析厨余热解油包含多种含氧有机物。通过气质联用仪(GC-MS)分析塑料热解油和塑料与纸混合热解油在180℃以下蒸馏出的液相产物,主要组分为烷烃和烯烃,从成分和热值分析,与汽油、柴油相近。     

泥磷乳浊液联合磷矿浆液相脱硝

根据当前一些湿法脱硝技术在燃煤烟气净化中的应用及研究进展,降低湿法脱硝技术的成本是研究的关键,一些价格低廉的吸收液的选择是优先考虑的对象,为此,采用泥磷乳浊液联合磷矿浆进行脱硝效率实验,通过在磷矿浆中添加泥磷,提高了磷矿浆体系的脱硝效率。实验条件主要从泥磷与磷矿的质量比、反应温度、含氧量、烟气流量方面来控制。结果表明,在实验最佳条件下,即泥磷与磷矿的质量比2:5,反应温度60℃,含氧量21%,烟气流量0.3 L·min~(-1),泥磷乳浊液联合磷矿浆液相脱硝体系,脱硝率80%以上可保持240 min以上。     

二氧化碳水合物储气特性的实验研究

利用二氧化碳水合物小型实验装置分别在恒容和恒压条件下,研究了机械搅拌对二氧化碳气体溶解的影响以及温度与水-气比对二氧化碳水合物形成和储气密度的影响。通过实验结果发现,机械搅拌对二氧化碳的溶解有非常明显的促进作用,可以在3 min内完成溶解过程,促进溶解作用好于添加剂SDS。研究还发现,反应温度越低,二氧化碳水合物的生成速率越快,总的储气量越大,而水-气比越大,储气密度越小。在实验压力3 MPa、反应温度273.55 K的条件下,1体积的水生成水合物后可储存157体积的二氧化碳。     

MIL-101前体制备多孔铁碳材料构建高效异相电芬顿体系

通过水热法合成MIL-101(Fe)材料,并在N2氛围中进行高温碳化制备多孔铁碳(N-MIL-FeC)电极材料,探究其电催化氧还原性能及阴极电芬顿降解模拟染料废水性能。将制备的N-MIL-FeC材料进行电催化氧还原反应(ORR)性能测试,结果表明,Fe/H_2BDC摩尔比为2∶1,碳化温度为900℃,N-MIL-FeC材料CV扫描所得图形峰电位最小且峰电流最高,具有最优的ORR催化活性。在此基础上,将最佳条件下制得的N-MIL-FeC负载在碳纸上制成催化阴极应用于电芬顿反应催化降解模拟染料废水RhB。在催化剂负载量为1.5 mg·cm~(-2),pH为7条件下,浓度10 mg·L~(-1)的RhB溶液经过70 min降解率达到99%以上。通过淬灭实验和电子顺磁共振(EPR)测试证明羟基自由基(·OH)是参与催化降解反应的主要活性中间体。以MIL-101(Fe)为前驱体制备的多孔铁碳材料性能较好,有一定的应用前景。     

尿素和添加剂湿法烟气同时脱硫脱氮工艺研究(Ι)

对尿素和添加剂同时吸收烟气中 SO2 和 NOx 进行了实验研究。结果表明 ,烟气中 SO2 极易脱除 ,在实验条件下 SO2 脱除率均大于 99%,操作工艺条件变化主要是影响 NOx脱除率。尿素和添加剂质量分数对 NOx 脱除率影响较小 ,NOx脱除率随尿素和添加剂质量分数的增加而缓慢增加 ;吸收剂 p H和吸收反应温度对 NOx脱除率有显著影响 ,最佳 p H为 7,最佳反应温度为 70～80℃。     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the i 13 C values were observed although the samples had isotopically distinct i -D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

The Use of Stable Isotopes to Differentiate Specific Source Markers for MTBE

The recent controversy over the use of MTBE within gasoline to boost oxygen content and decrease carbon monoxide emissions to the atmosphere has led to a proposed phase-out of this compound by 2002. This paper is a preliminary investigation into the use of gas chromatography isotope-ratio mass spectrometry (GCIRMS) to determine both carbon and hydrogen isotopic compositions of MTBE as a means of differentiating sources of MTBE. Three pure MTBE samples were purchased from chemical distributors. Little variation of the δ¹³C values were observed although the samples had isotopically distinct δ-D values. Four different methods of obtaining carbon isotope ratios of neat MTBE, MTBE in gasoline, and MTBE in water are described, and the precision and accuracy of each is discussed. The carbon isotopic compositions of MTBE within 10 gasoline samples from three different areas of the United States show a wide range of carbon isotope compositions. This novel method of MTBE analysis could be valuable in forensic investigations.     

Pyrolysis kinetics and residue characteristics of petrochemical industrial sludge

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene,ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

Pyrolysis Kinetics and Residue Characteristics of Petrochemical Industrial Sludge

ABSTRACT

This study investigated the pyrolysis characteristics of sludge from wastewater treatment plants in the petrochemical industry and focused on the pyrolysis kinetics, elemental composition of residue, and volatile organic compounds (VOCs) of exhaust gas. As pyrolysis temperature increased to 773 K, the increasing rate of crude oil production tended to a stable condition. The result indicated that the optimal temperature of crude oil and water mixed production was 773 K. When pyrolysis temperature increased from 673 to 973 K, carbon, oxygen, nitrogen, and hydrogen concentrations of residue decreased and the sulfur concentration of residue increased. The concentrations of benzene, toluene, ethylbenzene, and styrene increased by the increasing pyrolysis temperature. We found that the reaction order of sludge pyrolysis was 2.5 and the activation energy of the reaction was 11.06 kJ/mol. We believe that our pyrolysis system is transitional between devolatilization and combustion.     

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.     

Degradation of 2,4-dichlorophenol by combining photo-assisted Fenton reaction and biological treatment.

The photo-Fenton reaction effect on the biodegradability improvement of 100 mg/L solution of 2,4-dichlorophenol (DCP) has been investigated. Biochemical oxygen demand (BOD) at 5 and 21 days, BODn/ chemical oxygen demand (COD) and BODn/total organic carbon (TOC) ratios, average oxidation state, and inhibition on activated sludge were monitored. For 50 mg/L hydrogen peroxide and 10 mg/L iron(II) initial concentrations and 40 minutes of reaction time in the photo-Fenton process, the biodegradability of the pretreated solution, measured as BOD5/COD ratio, was improved from 0 for the original DCP solution up to 0.18 (BOD21/COD = 0.24). At that point, all DCP was eliminated from the solution. To study the effect of the pretreatment step, the biological oxidation of pretreated solutions was tested in two semicontinuous stirred tank reactors, one operated with activated sludge and one with biomass acclimated to phenol. Results showed that more than 80% TOC removal could be obtained by codigestion of the pretreated solution with municipal wastewater. Total organic carbon removals of approximately 60% were also obtained when the sole carbon source for the aerobic reactors was the pretreated solution. The hydraulic retention times used in the bioreactors were of the same order of magnitude as those used at domestic wastewater treatment plants (i.e., between 12 and 24 hours). Kinetic studies based on pseudo-first-order kinetics have also been carried out. Constants were found to be in range 0.67 to 1.7 L x g total volatiles suspended solids(-1) x h(-1).     

The influence of air–fuel ratio on engine performance and pollutant emission of an SI engine using ethanol–gasoline-blended fuels

Ethanol–gasoline-blended fuel was tested in a conventional engine under various air–fuel equivalence ratios (λ) for its performance and emissions. The amount of fuel injection was adjusted manually by an open-loop control system using a CONSULT controller. It was found that without changing throttle opening and injection strategy, λ could be extended to a leaner condition as ethanol content increased. The results of engine performance tests showed that torque output would increase slightly at small throttle valve opening when ethanol–gasoline-blended fuel was used. It was also shown that CO and HC emissions were reduced with the increase of ethanol content in the blended fuel, which resulted from oxygen enrichment. At an air–fuel equivalence ratio slightly larger than one, the smallest amounts of CO and HC and the largest amounts of CO₂ resulted. It was noted that under the lean combustion condition, CO₂ emission was controlled by air–fuel equivalence ratio; while under the rich combustion condition, CO₂ emission is offset by CO emission. It was also found that CO₂ emission per unit horse power output for blended fuel was similar or less than that for gasoline fuel. From the experimental data, the optimal ethanol content in the gasoline and air–fuel equivalence ratio in terms of engine performance and air pollution was found.     

Adsorption-oxidation of hydrogen sulfide on activated carbon fibers: effect of the composition and the relative humidity of the gas phase

The removal of hydrogen sulfide by oxidation-adsorption on two type carbon fibers, Actitex FC1201 and RS1301, was studied. Two kinetic steps where identified. During the first step, the degradation appears to be limited by the oxidation reaction. In the second kinetic step, the by-products inhibit the hydrogen sulfide degradation. This leads to a limitation in the carbon site's accessibility and to a lower kinetic. The Langmuir-Hinshelwood model was used to correlate the experimental results and to estimate the kinetic (k) and the Langmuir adsorption (K) constants. For FC1201 fibers, the kinetic constant (k) is five time higher and the adsorption constant is five time lower compared to the RS1301 fibers. The role of the humidity was found to be highly beneficial for the removal of hydrogen sulfide. Especially in the second kinetic step, where it removes the by-product formed and therefore delays the occurrence of this low kinetic step. The kinetic constant (k) is strongly influenced by humidity while the Langmuir adsorption constant (K) seems independent. The effect of the nature of the gas phase on the reaction kinetic was also studied. Under a dry atmosphere, we note that the oxidation-reaction occurs even if the gaseous oxygen is not present. This oxidation is due to the oxygen surface function of the carbon fibers. Moreover, the degradation kinetic is faster under a dry nitrogen atmosphere. The presence of water traces leads to the acidification of the carbon surface, under oxygen or carbon dioxide atmospheres, and hence limits the hydrogen sulfide dissociation. In a humid atmosphere, the oxygen or carbon dioxide leads to a faster reaction kinetic. The acidification of the carbon surface is largely counterbalanced by the dissolution of the by-products.     

乳化液膜体系去除电解锰废水中的Mn~（2＋）

采用乳化液膜法处理电解锰废水,考察制乳条件和提取条件对去除效果的影响。研究结果表明最佳制乳条件为：4%（V/V）span-80做表面活性剂,3%二（2-乙基己基）磷酸酯做载体,柴油做膜溶剂,用NaOH调节内水相pH为12,制乳时间为10 min,油内比2∶1;最佳提取条件：外水相pH为6～7、乳水比1∶10、提取时间10 min。制得的乳化液膜对电解锰废水中的Mn2＋去除率可高达99.99%,出水Mn2＋浓度低于2mg/L,实现水质达标排放。     

乳化液膜体系去除电解锰废水中的Mn2+

采用乳化液膜法处理电解锰废水,考察制乳条件和提取条件对去除效果的影响。研究结果表明最佳制乳条件为:4%(V/V)span-80做表面活性剂,3%二(2-乙基己基)磷酸酯做载体,柴油做膜溶剂,用NaOH调节内水相pH为12,制乳时间为10 min,油内比2∶1;最佳提取条件:外水相pH为6～7、乳水比1∶10、提取时间10 min。制得的乳化液膜对电解锰废水中的Mn2+去除率可高达99.99%,出水Mn2+浓度低于2mg/L,实现水质达标排放。