C3H6和C3H8的性质差异对Pt-Rh型汽车排气催化剂起燃特性的影响

在实验室模拟研究中,丙烷和丙烯在Pt-Rh型汽车尾气催化剂表面的催化氧化性能的差异,会对催化剂的起燃特性表现造成影响.由于丙烯在催化剂表面存在较严重的自中毒作用,使得CO和NOx的低温起燃特性变差.在低温下,由于丙烷相对丙烯催化燃烧速率较慢,剩余的氧气和NOx发生竞争反应,导致NOx的温度-转化率曲线出现S型的起伏.     

老化对钴铈基催化剂催化氧化丙烷的影响

采用柠檬酸络合法合成Co-CeO_x多活性中心催化剂,在不同温度进行加速老化处理,测试新鲜和老化后催化剂对丙烷的催化氧化性能,同时对其结构和性质进行表征.结果表明,当加速老化温度低于650℃时,丙烷转化率达50%的温度变化幅度小于10℃;加速老化温度高于750℃时,催化剂氧化丙烷的性能快速下降.表征结果显示,Co-CeO_x催化剂主要表现为尖晶石结构,老化后晶粒尺寸显著增大,Co³⁺的含量减少,氢还原峰温度升高.加速老化处理对Co-CeO_x催化剂物理结构的影响进而抑制了其化学特性及催化活性.测试Co-CeO_x催化剂对丙酮和甲苯的催化氧化性能,分别在179和244℃达到90%的脱除效率.因此,Co-CeO_x多活性中心催化剂具有良好的氧化性能,且表现出一定的稳定性.     

用于乙醇水蒸气重整的负载型金属催化剂失活的研究进展

负载型金属催化剂的发展直接影响着乙醇水蒸气重整的研究,而造成负载型金属催化剂失活的原因有很多。重点论述了催化剂活性金属烧结和催化剂表面积碳的问题,并对目前所采用的解决办法进行阐述。同时对今后制备抗积碳性能强的负载型金属催化剂的研究方向进行展望。     

汽爆预处理对互花米草厌氧发酵产气特性的影响

针对互花米草厌氧发酵过程存在的结构抑制问题,采用高速汽爆设备,在1.5,2.0,3.0MPa条件下分别对其进行蒸汽爆破预处理试验,并采用揉搓处理作为对照.厌氧发酵试验结果表明,随汽爆压力的增加,累积产气率呈下降趋势,1.5,2.0,3.0MPa处理原料的单位挥发性固体(VS)累积产气量分别为293.6,176.1,145.4mL/g,对照为238.7mL/g.经2.0,3.0MPa处理的原料在发酵过程中存在酸积累现象,挥发性有机酸(VFA)中乙酸最高达10599.42mg/L,丙酸浓度高于1000mg/L,这是导致这2组原料累积产气量低于对照的主要原因.     

热喷处理污泥及其复混肥的养分效率与生物效应

采用室内分析和田间生物试验，研究了热喷处理污泥及其复混肥的养分供应能力及它们在农地上施用对土壤肥力、青菜产量及其品质的影响。结果表明：热喷处理能有效杀灭污泥中病原物，除自，并可使污泥中水溶性有机碳和速效氮含量分别提高87％，19％和35％，施用热喷污泥制成的复混肥不但比等养分的无机复合肥多增产38％，而且青菜体内Vc和水溶性总糖等营养品质也有明显的提高，NO3^-却只有无机复合肥处理的一半左右，污泥经势喷处理有利于提高污泥中养分的生物有效性，特别是热喷污泥制成的复混肥氮磷养分利用率显著高于无机复合肥，施用污泥和污泥复混肥还能提高土壤肥力，比单纯大量施用污泥要安全得多，土地使用年限可延长40倍。     

Minimizing energy losses in steam systems for potato starch production

This paper proposes improvements to the energy management of a steam system used for potato starch production. The system consists of a steam boiler plant (fired with natural gas), and steam and condensate pipelines with a hot air heat exchanger for drying potato starch (the steam consumer). In the existing system, the boiler cooperates with two open tanks that are responsible for energy losses due to secondary evaporation. Therefore, a closed tank system is proposed to eliminate these energy losses. The coefficients of thermal efficiency and the energy losses are compared between the open and closed tank cases. This study shows that the losses of the closed steam system are consistently lower than those of the open system, improving the coefficient of efficiency by about 6%.     

Feasibility of husk-fuelled steam engines as prime mover of grid-connected generators under the Thai very small renewable energy power producer (VSPP) program

Rice husk generated as a by-product of rice mill processes can be utilized as an energy source for husk-fuelled rice mills. The economic evaluation of the investment of husk-fuelled steam engine rice mills, which generate mechanical energy for the direct driving of milling equipments, has previously been presented in literature. It was reported that for some particular conditions of rice mill, the investment of husk-fuelled steam engine as energy-saving technology is financially feasible. Since May 2002, electricity distributors in Thailand have allowed renewable energy producers up to 1 MW to connect their generators to the grid in order to sell surplus electricity to the grid. This arrangement creates more income opportunities for husk-fuelled steam engine owners to generate not only mechanical power for rice milling processes, but also surplus electricity for feeding onto the grid. The objective of this study is to investigate the financial feasibility of the investment in a husk-fuelled steam engine system which drives grid-connected electrical generators, reduces rice mill demand and electricity and sells surplus electricity to the grid. The technical and economic data for rice mill sizes 35, 45, 60, 95 and 120 t/d presented in this study show that the husk-fuelled steam engine system with grid-connected generators improves the economic performance of applying the system solely for the largest 120 t/d rice mills. However, the conventional husk-fuelled steam engine without electric generator gives a better economic performance of the rice mills sizes from 45 to 95 t/d.     

双金属有机骨架材料衍生CuO-Cu1.5Mn1.5O4复合氧化物的丙烷催化燃烧性能

采用气相辅助的离子置换法,合成了Cu、Mn双金属有机骨架(MOF)材料,通过控制煅烧条件制备了一系列CuO-Cu_1.5Mn_1.5O₄复合氧化物,研究了不同n(Mn)/n(Cu)对丙烷催化燃烧性能的影响。结果表明:随着n(Mn)/n(Cu)提高,CuO-Cu_1.5Mn_1.5O₄催化丙烷燃烧能力增强,当n(Mn)/n(Cu)为31∶69时,催化剂对丙烷的完全燃烧温度(T₉₀)仅为309.8 ℃,催化活性远高于CuO和Mn₂O₃。表征和密度泛函理论(DFT)计算结果表明,由于Mn和Cu的相互作用,复合氧化物表面具有更高的n(Mn4+)/n(Mn3+)和n(Cu+)/n(Cu2+),从而增强了催化剂的低温还原性能。并且n(Cu+)/n(Cu2+)提高导致催化剂中氧空位浓度升高,更容易吸附活化O₂、丙烷分子,增强了催化剂的丙烷燃烧性能。     

城市生活垃圾催化气化制取富氢气体的研究

采用下吸式固定床气化炉,以煅烧白云石为催化剂水蒸气气化城市生活垃圾(MSW)有机组分,在气化温度为750~950℃,S/M(水蒸气和垃圾物料进料质量比)为0.57~1.28时,探讨了催化剂种类、气化温度和S/M等因素对富氢气体成分、产氢率、潜在产氢率、低位热值和碳转化率等的影响。较高气化温度有利于富氢气体的生成,增加碳转化率和产气率,但会降低富氢气体的热值;在实验条件下,富氢气体中H2体积分数最高达53.29%,产氢率达到7.13~46.52mol/kg,潜在产氢率为55.48~90.11mol/kg;镍基催化剂催化效果优于煅烧白云石,能大幅增加H2含量,使焦油在850℃以上完全分解。     

A steam dried municipal solid waste gasification and melting process

Considering high-moisture municipal solid waste (MSW) of China, a steam dried MSW gasification and melting process was proposed, the feasibility was tested, and the mass and energy balance was analyzed. Preliminary experiments were conducted using a fixed-bed drying apparatus, a 200 kg per day fluidized-bed gasifier, and a swirl melting furnace. Moisture percentage was reduced from 50% to 20% roughly when MSW was dried by slightly superheated steam of 150°C–350°C within 40 min. When the temperature was less than 250°C, no incondensable gas was produced during the drying process. The gasifier ran at 550°C–700°Cwith an air equivalence ratio (ER) of 0.2–0.4. The temperature of the swirl melting furnace reached about 1240°C when the gasification ER was 0.3 and the total ER was 1.1. At these conditions, the fly ash concentration in the flue gas was 1.7 g·(Nm³)⁻¹, which meant over 95% fly ash was trapped in the furnace and discharged as slag. 85% of Ni and Cr were bound in the slag, as well as 60% of Cu. The mass and energy balance analysis indicates that the boiler heat efficiency of an industrial MSW incineration plant reaches 86.97% when MSW is dried by steam of 200°C. The boiler heat efficiency is sensitive to three important parameters, including the temperature of preheated MSW, the moisture percentage of dried MS Wand the fly ash percentage in the total ash.     

电化学氧化与生物法联合降解木质素

为开发经济和环境安全的木质素降解技术,采用ECO-BD(electrochemical oxidation and biodegradation, 电化学氧化与生物降解)工艺联合降解木质素,以Ti/Sn-SbO₂电极为阳极,无水Na₂SO₄为电解质,在恒电流条件下,应用响应面法得到ECO-BD联合降解木质素的最佳电化学条件:电流密度为8.64 mA/cm2,电量为20.00 kC,c(Na₂SO₄)为0.15 mol/L. 在该条件下,ECO-BD对1 g/L木质素溶液的COD_Cr去除率为59.31%,单位能耗为28.87 kW·h/kg. 采用傅里叶变换红外光谱及气相色谱-质谱对ECO-BD联合降解木质素过程中的降解产物进行分析发现,ECO能有效地破坏木质素的酚羟基结构及发色基团,木质素多聚体的醚键先被断裂形成单体,随后芳环结构被氧化生成醌类化合物,再进一步开环和裂解生成小分子酸类或被矿化成CO₂和H₂O;电解后溶液生化可降解性由0.20~0.25升至0.31~0.37,缩短了后续生物降解时间. 研究显示,ECO能先行打断抵御微生物攻击的木质素顽固键合结构,有利于后续BD消除残余碎片,实现木质素的ECO-BD高效低成本降解.      

Migration and transformation of Sb are affected by Mn(III/IV) associated with lepidocrocite originating from Fe(II) oxidation

Antimony (Sb) is a recognized priority pollutant with toxicity that is influenced by its migration and transformation processes. Oxidation of Fe(II) to Fe(III) oxides, which is a common phenomenon in the environment, is often accompanied by the formation of Mn(III/IV) and might affect the fate of Sb. In this study, incorporated Mn(III) and sorbed/precipitated Mn(III/IV) associated with lepidocrocite were prepared by adding Mn(II) during and after Fe(II) oxidation, respectively, and the effects of these Mn species on Sb fate were investigated. Our results indicated that the association of these Mn species with lepidocrocite obviously enhanced Sb(III) oxidation to Sb(V), while concomitantly inhibiting Sb sorption due to the lower sorption capacity of lepidocrocite for Sb(V) than Sb(III). Additionally, Mn oxide equivalents increased in the presence of Sb, indicating that Sb oxidation by Mn(III/IV) associated with lepidocrocite was a continuous recycling process in which Mn(II) released from Mn(III/IV) reduction by Sb(III) could be oxidized to Mn(III/IV) again. This recycling process was favorable for effective Sb(III) oxidation. Moreover, Sb(V) generated from Sb(III) oxidation by Mn(III/IV) enhanced Mn(II) sorption at the beginning of the process, and thus favored Mn(III/IV) formation, which could further promote Sb(III) oxidation to Sb(V). Overall, this study elucidated the effects of Mn(III/IV) associated with lepidocrocite arisen from Fe(II) oxidation on Sb migration and transformation and revealed the underlying reaction mechanisms, contributing to a better understanding of the geochemical dynamics of Sb.     

Pt负载暴露(001)晶面Bi2WO6催化剂合成及光催化性能

通过水热法制备了暴露（001）晶面的Bi₂WO₆纳米片,利用光还原法将Pt纳米颗粒负载于其表面.选择苯甲醇氧化和罗丹明B（RhB）降解为探针反应,评价了催化剂的光催化性能.在苯甲醇氧化实验中,Pt负载暴露001晶面的Bi₂WO₆样品的苯甲醇转化率为20.7%,约为未负载样品的2倍.在RhB降解实验中,Pt负载样品在光照40min后对RhB的矿化率可达81.1%,而未负载样品RhB矿化率仅为55.8%,表明Pt负载样品具有更优的降解速率和矿化能力.催化剂性能的提升归因于高能晶面暴露和Pt负载的协同作用.Pt纳米颗粒的负载作为助催化剂增加了催化剂表面的活性位点,同时提高了晶面光生电子空穴对的分离和迁移效率.     

Pt负载暴露(001)晶面Bi2WO6催化剂合成及光催化性能

通过水热法制备了暴露（001）晶面的Bi₂WO₆纳米片,利用光还原法将Pt纳米颗粒负载于其表面.选择苯甲醇氧化和罗丹明B（RhB）降解为探针反应,评价了催化剂的光催化性能.在苯甲醇氧化实验中,Pt负载暴露001晶面的Bi₂WO₆样品的苯甲醇转化率为20.7%,约为未负载样品的2倍.在RhB降解实验中,Pt负载样品在光照40min后对RhB的矿化率可达81.1%,而未负载样品RhB矿化率仅为55.8%,表明Pt负载样品具有更优的降解速率和矿化能力.催化剂性能的提升归因于高能晶面暴露和Pt负载的协同作用.Pt纳米颗粒的负载作为助催化剂增加了催化剂表面的活性位点,同时提高了晶面光生电子空穴对的分离和迁移效率.     

锰铈脱硝催化剂的制备及其再生性能研究

采用等体积浸渍法制备了一系列Mn-Ce-Ox复合氧化物脱硝催化剂用于NH3选择性催化还原(NH3-SCR)NO。考察了Mn/Ce摩尔比、焙烧温度、H2O和SO2对Mn-Ce-Ox复合氧化物脱硝催化剂活性的影响及催化剂中毒再生性能。结果表明:当NH3:NO=1:1,空速为5 000 h-1,550℃焙烧制得的Mn/Ce摩尔比为5∶1的Mn-Ce-Ox复合脱硝催化剂活性最佳,活性温度窗口为100~260℃,在此温度区间内催化剂活性大于90%。200℃时,Mn-Ce-Ox复合催化剂活性最高为97.84%;在10%(V/V)H2O蒸汽和300×10-6SO2共存条件下,200℃时,催化剂活性在开始反应2.5 h内迅速下降至53%左右,并在之后的6 h内没有明显变化;中毒催化剂经常温水洗再生处理、质量分数为3%的硝酸溶液再生处理和550℃焙烧2 h再生处理后200℃活性均能恢复到90%以上,其中中毒催化剂经质量分数为3%硝酸处理后活性恢复率最高。     

Simulation and life cycle assessment of process design alternatives for biodiesel production from waste vegetable oils

This study uses the process simulator ASPEN Plus^® and Life Cycle Assessment (LCA) to compare three process design alternatives for biodiesel production from waste vegetable oils that are: the conventional alkali-catalyzed process including a free fatty acids (FFAs) pre-treatment, the acid-catalyzed process, and the supercritical methanol process using propane as co-solvent. Results show that the supercritical methanol process using propane as co-solvent is the most environmentally favorable alternative. Its smaller steam consumption in comparison with the other process design alternatives leads to a lower contribution to the potential environmental impacts (PEI’s). The acid-catalyzed process generally shows the highest PEI’s, in particular due to the high energy requirements associated with methanol recovery operations.     

Ru(III) catalyzed permanganate oxidation of aniline at environmentally relevant pH

Ru（Ⅲ） was employed as catalyst for aniline oxidation by permanganate at environmentally relevant pH for the first time. Ru（Ⅲ） could significantly improve the oxidation rate of aniline by 5-24 times with its concentration increasing from 2.5 to 15 μmol/L. The reaction of Ru（Ⅲ） catalyzed permanganate oxidation of aniline was first-order with respect to aniline, permanganate and Ru（Ⅲ）, respectively. Thus the oxidation kinetics can be described by a third-order rate law. Aniline degradation by Ru（Ⅲ） catalyzed permanganate oxidation was markedly influenced by pH, and the second-order rate constant （ktapp） decreased from 643.20 to 2.67 （mol/L）^-1 sec^-1 with increasing pH from 4.0 to 9.0, which was possibly due to the decrease of permanganate oxidation potential with increasing pH. In both the uncatalytic and catalytic permanganate oxidation, six byproducts of aniline were identified in UPLC-MS/MS analysis. Ru（Ⅲ）, as an electron shuttle, was oxidized by permanganate to Ru（Ⅵ） and Ru（Ⅶ）, which acted the co-oxidants for decomposition of aniline. Although Ru（Ⅲ） could catalyze permanganate oxidation of aniline effectively, dosing homogeneous Ru（Ⅲ） into water would lead to a second pollution. Therefore, efforts would be made to investigate the catalytic performance of supported Ru（Ⅲ） toward permanganate oxidation in our future study.     

Effects of tungsten oxide on the activity and thermal stability of a sulfate-derived titania supported platinum catalyst for propane oxidation

A Pt/WO₃/TiO₂ catalyst for propane oxidation was prepared by a stepwise wet impregnation method, and was aged at 800℃ for 5 hr. Compared to the sulfate-derived titania supported catalyst, the introduction of tungsten oxide as stable Bronsted acid sites led to the formation of more metallic platinum active sites at the Pt/WO₃ interface. The dissociation of surface intermediates for propane oxidation was promoted on the WO₃-modified catalyst. This, as well as the inhibition effects of tungsten oxide on the sintering of anatase and the phase transformation to rutile, resulting in a high activity and thermal stability for the Pt/WO₃/TiO₂ catalyst.     

天然气制甲醇项目工艺改造对环境的影响

节能减排在十一五期间被纳入规划纲要列为约束性指标。文章对新疆某甲醇厂工艺改造前后能耗和污染物排放量进行了对比分析,结果表明:在甲醇产量翻一翻的情况下,从一段蒸汽转化工艺到自热式二段炉联合转化工艺,天然气的消耗量节省了约63%,脱盐水节省了约87%;SO2排放量减少0.9 t/a,CODcr仅增加了约4 t/a。因此,对于甲醇生产来说,工艺改造能够在提高产量的同时减少能耗和污染物的排放,有利于环境的可持续发展。     

Life cycle inventory analysis of biological hydrogen production by thermophilic and photo fermentation of potato steam peels (PSP)

The environmental impact of hydrogen production in a 2-step fermentation process from potato steam peels was identified. Based on the ISO 14040, ISO 14044, ecoinvent data base and SimaPro 7.1 software, a life cycle inventory analysis was performed. Reflecting the current state of process development, the LCA shows an impact of 4.3 points (pts) which is at least 5.7 times higher than the selected reference technologies regarded as state-of-the-art. Over half (53.5%) of the environmental impact is generated by the use of phosphate in the fermentation processes. A sensitivity analysis shows a potential impact reduction of 65.8% due to recirculation of sewage or reduction of buffer concentration. The analysis also demonstrates that the production of the process ingredients cause 98.3% of the environmental impact. The impact of the process itself is 0.07 pts which is up to 10 times lower than the reference technologies.