Synthesis and characterization of catalysts produced from paper mill sludge: I. Determination of NOx removal capability

Characteristics and catalytic properties of a series of carbon-based catalysts (CBCs) produced from paper mill sludge were evaluated. The major processes involved in the production of the catalysts were chemical activation, impregnation, pyrolysis, and post pyrolysis rinsing. The porous structure, catalytic activity and thermostability of the catalysts were tailored during the production stage by introducing hetero-atoms (zinc chloride, and ferric nitrate) in the carbon structure. Characterization of the produced CBCs included determination of the surface area, pore size, and pore size distribution (PSD) from standard N₂-adsorption isotherm data. The extent of graphitization and the presence of metal crystals were identified from X-ray diffraction (XRD). The limit of the catalyst gasification was estimated from thermogravimetric analysis (TGA) conducted in an oxidized environment. The NO_x reduction capability of the produced catalysts was evaluated in the presence of carbon monoxide using a fixed bed reactor. The reaction temperature ranged from 300 to 500°C. It was shown that paper mill sludge is an excellent precursor for the production of CBCs with NO_x removal capability of 66–94%. The catalytic capability of the produced CBCs varied according to the method of production, catalyst surface properties (surface area, pore structure, PSD), metal composition and reaction temperature. The highest NO_x removal capacity was observed for the catalytic reactions carried out at 400°C. The mesoporous catalyst produced with a Zn:Fe molar ratio of 1:0.5 exhibited the maximum NO_x removal catalytic activity of 94%.     

Removal of NO from flue gas by aqueous chlorine-dioxide scrubbing solution in a lab-scale bubbling reactor

The present study attempts to clean up nitric oxide from the simulated flue gas using aqueous chlorine-dioxide solution in the bubbling reactor. Chlorine-dioxide is generated by chloride–chlorate process. Experiments are carried out to examine the effect of various operating variables like input NO concentration, presence of SO₂, pH of the solution and NaCl feeding rate on the NO_x removal efficiency at 45 °C. Complete oxidation of nitric oxide into nitrogen dioxide occurred on passing sufficient ClO₂ gas into the scrubbing solution. NO is finally converted into nitrate and ClO₂ is reduced into chloride ions. A plausible reaction mechanism concerning NO_x removal by ClO₂ is suggested. DeNO_x efficiency increased slightly with the increasing input NO concentration. The presence of SO₂ improved the NO₂ absorption but pH of solution showed marginal effect on NO₂ absorption. NO_x removal mechanism changed when medium of solution changed from acidic to alkaline. A constant NO_x removal efficiency of about 60% has been achieved in the wide pH range of 3–11 under optimized conditions.     

Removal of SO2 and NO from flue gas by wet scrubbing using an aqueous NaClO2 solution

This study used a NaClO₂/NaOH solution as the additive/absorbent to determine the extent of NO_x removal in a wet scrubbing system. A combined SO_x/NO_x removal system was also tested. The experiments were performed in a bench-scale spraying sieve tray wet scrubber in a continuous mode. The operating variables included NO and SO₂ concentrations, L/G ratio, molar ratio, and initial pH.

The results of the individual DeNO_x experiments show that the maximum DeNO_x efficiencies ranged from 3.1 to 12.6%. The results of the combined DeSO_x/DeNO_x experiments show that the maximum DeNO_x and DeSO_x efficiencies ranged from 36.6 to 71.9% and from 89.4 to 100.0%, respectively. The major parameters affecting NO_x removal efficiencies are the L/G ratio and the dosage of additive. The major parameter influencing DeSO_x efficiencies is the L/G ratio.     

SCR烟气脱硝系统出口烟道NOx测点技术改造

燃煤电站锅炉排放的氮氧化物是大气污染的一个重要来源,控制NO_x排放已成为当前电厂的重要工作。上海漕泾电厂分别于2014年和2015年实施了超低排放改造工程,在改造后的长期运行过程中发现,1号机组选择性催化还原烟气脱硝法（SCR）装置出口NO_x浓度值与烟囱出口数据有着较大偏差。通过对SCR所在烟道流场的数值模拟发现,原有SCR进出口的测点在烟道入口NO_x浓度分布不均匀时不能准确测量出NO_x的浓度值,因此对原有的NO_x出口测点进行了技术改造,变原来的2点平均测量为网格多点测量。技术改造后发现测点NO_x与烟囱出口NO_x数据变化趋势吻合,为进一步的按需喷氨提供了基础。     

六角切圆锅炉改造后NOx排放特性研究

为了研究六角切圆煤粉锅炉在超低排放改造后脱硝进出口NO_x的分布及出口逃逸氨浓度的特点,进行了现场试验测试。结果发现,脱硝系统的入口NO_x分布不均匀、喷氨量不均匀是导致出口NO_x分布不均匀、氨逃逸质量浓度超过设计值的主要原因,机组需要进行喷氨优化调整。     

Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1--<?Pub Caret?>x/TiO2

Copper--cerium--zirconium catalysts loaded on TiO₂ prepared by a wet impregnation method were investigated for NH₃-selective catalytic reduction (SCR) of NO_x. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy (DRIFT). When NH₃ is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe_0.25Zr_0.75/TiO₂ at high temperature, while Br?nsted acid sites are more important than Lewis acid sites at low temperature. For the NH₃+NO+O₂ co-adsorption, NH₃ species occupy most of activity sites on CuCe_0.25Zr_0.75/TiO₂ catalyst, and mainly exist in the forms of NH₄⁺ (at low temperature) and NH₃ coordinated (at high temperature), playing a crucial role in the NH₃-SCR process. Two different reaction routes, the L-H mechanism at low temperature (<200°C) and the E-R mechanism at high temperature (>200°C), are presented for the SCR reaction over CuCe_0.25Zr_0.75/TiO₂ catalyst.     

Kinetics of Carbon Multi-wall Nanotube Synthesis by Catalytic Pyrolysis of Methane

By method of isothermal gravimetry at 600-700°C, CH₄ concentration 32-100% in Ar and 91-100% in H₂ under atmospheric pressure the kinetics of CH₄ pyrolysis under Ni/La₂O₃ catalysts is studied. Estimated apparent activation energy of reaction is 73 kJ/mol for fresh catalyst and 71 kJ/mol for aged one. The reaction order on CH₄ changes from 1.05 at 600°C to 1.3 at 700°C. The influence of H₂ concentration on the reaction rate is more complicated. On the basis of kinetics measurements continuously working laboratory-scale reactor with gas and catalyst counter-flow is constructed and tested.     

Characterization and microstructure of highly preferred oriented lead barium titanate thin films on MgO (100) by sol-gel process

Highly preferred oriented lead barium titanate (Pb_1−x,Ba_x)TiO₃ thin film, with particular emphasis on (Pb_0.5,Ba_0.5)TiO₃, can be obtained by spin-coating on MgO (100) substrate by using the precursor sol, which was synthesized from acetylacetone chelating with titanium isopropoxide and ethylene glycol as a solvent, in the sol-gel process. Film thickness, pyrolysis temperature and heating rate were studied systemically to investigate their influences on the formation of preferred oriented thin films. The highly preferred (001)/(100) oriented thin film could be obtained by the pyrolysis of wet film at 500 °C and annealing at 600 °C at a slow heating rate of 5 °C/min. It is confirmed that the tetragonal perovskite structure of the titanate ceramic decreases with an increase of Ba content in (Pb_1−x,Ba_x)TiO₃. The (001)/(100) oriented films were synthesized from all compositions between x = 0.2 and x = 0.8, at a crystallization temperature of 600 °C. In particular, for the Ba content in the range of x = 0.50.6, highly preferred (001)/(100) planes were observed.     

Optical and electrical properties of p-type AgInSnxS2−x (x = 0–0.04) thin films prepared by spray pyrolysis

AgInSn_xS_2−x (x = 0–0.2) polycrystalline thin films were prepared by the spray pyrolysis technique. The samples were deposited on glass substrates at temperatures of 375 and 400 °C from alcoholic solutions comprising silver acetate, indium chloride, thiourea and tin chloride. All deposited films crystallized in the chalcopyrite structure of AgInS₂. A p-type conductivity was detected in the Sn-doped samples deposited at 375 °C, otherwise they are n-type. The optical properties of AgInSn_xS_2−x (x < 0.2) resemble those of chalcopyrite AgInS₂. Low-temperature PL measurements revealed that Sn occupying an S-site could be the responsible defect for the p-type conductivity observed in AgInSn_xS_2−x (x < 2) thin films.     

The preparation and gas sensitivity study of polythiophene/SnO2 composites

Nanocomposites of SnO₂ and polythiophene (PTP) were synthesized by the in situ chemical oxidative polymerization method. These nanocomposites were characterized by FTIR, transmission electron microscope (TEM), X-ray diffraction (XRD) and thermogravimetric and differential thermal analysis (TG–DTA) techniques, which proved the polymerization of thiophene monomer and the strong interaction between polythiophene and SnO₂. The composites were used for gas sensing to methanol (MeOH), ethanol (EtOH), acetone, and NO_x at different working temperature. It was found that PTP/SnO₂ materials with different PTP mass percent (1%, 5%, 10%, 20% and 30%) could detect NO_x with very higher selectivity and sensitivity at much lower working temperature than the reported SnO₂. The PTP/SnO₂ nanocomposites responded to NO_x at concentration as low as 10 ppm. PTP/SnO₂ composite containing 5 mass% PTP showed the highest sensitivity at room temperature. The sensing mechanism of PTP/SnO₂ nanocomposites to NO_x was presumed to be the effects of p–n heterojunction between PTP and SnO₂.     

基于遗传算法优化BP神经网络的SCR脱硝系统催化剂体积设计

火电厂SCR脱硝系统的设计需要在满足脱硝效率的同时,尽可能节约成本,因此需要准确预测SCR脱硝所需的催化剂体积。火电厂的烟气条件复杂多变,烟气温度、烟气流量、出入口NO_x浓度等参数都会影响SCR催化剂的体积设计,因此催化剂体积预测是一个多因素耦合的问题。针对这一特点,使用BP神经网络对催化剂体积设计进行了预测,并针对该模型结构上的缺陷,进行基于遗传算法优化的神经网络建模研究。结果表明,遗传算法优化后的BP神经网络模型预测精度和数据拟合能力均有提高,为脱硝系统的催化剂体积设计提供了新思路。     

面向灵活性发电的燃煤机组大气排放特性分析

随着可再生能源发电在电网中占比逐年增加,越来越多的燃煤机组参与灵活性发电。为了弄清灵活性发电燃煤机组的大气排放特性,以某亚临界600 MW和300 MW机组为例,通过对运行数据进行回归分析,获得了机组在启动、正常调峰和深度调峰阶段的CO₂、NO_x、SO₂和粉尘的排放特性。结果表明：正常调峰阶段,随着机组负荷下降,煤耗和CO₂排放因子逐渐增大,净烟气NO_x排放因子先减小后增大,SO₂排放因子略有下降;粉尘排放因子略有上升;深度调峰阶段,随机组负荷的进一步降低煤耗和CO₂排放因子明显增大,净烟气NO_x和粉尘排放因子迅速增大,SO₂排放因子继续下降;启动过程净烟气NO_x和粉尘排放因子明显高于调峰工况,SO₂排放因子略小于调峰工况。另外,调峰过程中较高的升降负荷率使得原烟气NO_x、SO₂排放因子明显增大,净烟气粉尘排放因子明显增大。     

Metal Oxide Nanoparticles as Novel Gate Materials for Field-Effect Gas Sensors

Oxide nanoparticle layers have shown interesting behavior as gate materials for high temperature (typically at 300-400°C) metal-insulator-silicon carbide (MISiC) capacitive sensors. Distinct shifts in the depletion region of the C-V (capacitance-voltage) characteristics could be observed while switching between different oxidizing and reducing gas ambients (air, O₂, H₂, NH₃, CO, NO_x, C₃H₆). Shifts were also noticed in the accumulation region of the C-V curves, which can be attributed to the change in resistivity of the gate material. Sensor response patterns have been found to depend on operating temperature.     

尖晶石型AFe2O4催化剂的制备及其催化燃烧甲苯的研究

通过溶胶-凝胶-自蔓延燃烧法制备尖晶石型AFe₂O₄(A=Cu, Co, Ni, Mg, Zn)催化剂, 以甲苯为VOCs模拟气, 考察AFe₂O₄催化剂对VOCs的催化燃烧活性, 并采用XRD、N₂吸附-脱附、SEM、TEM、H₂-TPR、XPS对催化剂进行表征分析。结果表明: AFe₂O₄表现出较好的催化燃烧活性, 其中CuFe₂O₄的催化燃烧活性最佳, 起燃温度(T50)和完全燃烧温度(T90)分别为188℃、239℃。AFe₂O₄具有明显的片状尖晶石晶体, 并形成以介孔为主的多级孔结构, 该特点为催化剂提供了大量表面活性位。A位元素种类对其催化燃烧活性影响较大, 当A位元素为Cu时, Cu的H₂还原峰面积远大于其他元素, H₂还原温度仅为289℃, 表面亲电子氧和氧空位浓度占氧元素总量(O_ele/O_1S)的36%。CuFe₂O₄为片状反尖晶石晶型, 晶格体积仅为0.294 nm³, 并伴有CuO和α-Fe₂O₃物种。以介孔为主的多级孔结构、特有的片状反尖晶石晶型以及该晶型与CuO和α-Fe₂O₃的协同作用是CuFe₂O₄催化燃烧活性提高的主要原因。     

污水厂脱水污泥制吸附剂及脱除H2S效能研究

采用热解炭化法制备了一系列污泥吸附剂,优化制备工艺,利用扫描电镜(SEM)、比表面积和孔径分析等技术对污泥吸附剂的结构进行了表征,并研究了脱除H2S效能。结果表明,活化温度、活化时间和固液比等因素均对污泥吸附剂的碘吸附值产生影响。当活化温度为550℃、活化时间为2.0h、固液比为1∶2时所制备材料(SA)的碘吸附值最高,为493.12mg/g;制备的SA具有较好的脱除H2S效能,能满足精脱硫的要求,当空速为4600h-1时,SA的除臭时间可达48min;此外SA中含有的多种金属元素,平均孔径为3.4nm,这些性质均有利于H2S的吸附脱除。     

Mn-doped perovskite-type oxide LaFeO3 as highly active and durable bifunctional electrocatalysts for oxygen electrode reactions

Perovskite oxides based on the alkaline earth metal lanthanum for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline electrolytes are promising catalysts, but their catalytic activity and stability remain unsatisfactory. Here, we synthesized a series of LaFe_1−xMn_xO₃ (x = 0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1) perovskite oxides by doping Mn into LaFeO₃ (LF). The results show that the doping amount of Mn has a significant effect on the catalytic performance. When x = 0.5, the catalyst LaFe_0.5Mn_0.5O₃ (LFM) exhibits the best performance. The limiting current density in 0.1 mol·L⁻¹ KOH solution is 7 mA·cm⁻², much larger than that of the commercial Pt/C catalyst (5.5 mA·cm⁻²). Meanwhile, the performance of the doped catalyst is also superior to that of commercial Pt/C in terms of the long-term durability. The excellent catalytic performance of LFM may be ascribed to its abundant O²⁻/O⁻ species and low charge transfer resistance after doping the Mn element.     

Simple method for synthesis of carbon nanotubes over Ni-Mo/Al2O3 catalyst via pyrolysis of polyethylene waste using a two-stage process

Synthesis of valuable multi-walled carbon nanotubes (MWCNTs) by thermal pyrolysis of low-density polyethylene (LDPE) waste was investigated via a two-stage process. The first stage was the thermal pyrolysis of LDPE to gaseous hydrocarbons, and the second stage was the catalytic decomposition of the pyrolysis gases over Ni-Mo/Al₂O₃ catalysts. Two catalysts with the compositions of 5.2%Ni-10.96%Mo/Al₂O₃ and 10%Ni-9.5%Mo/Al₂O₃ were tested for carbon nanotubes (CNTs) formation. The catalyst containing 10%Ni showed better activity in terms of CNTs production. Accordingly, the impact of either pyrolysis or decomposition temperatures was investigated using the 10%Ni-9.5%Mo/Al₂O₃ catalyst. TEM, XRD, Raman spectroscopy, TGA, TPR, and BET analysis tools were used to characterize the fresh catalysts as well as the obtained carbon nanomaterials. TEM images proved that MWCNTs with various morphological structures were obtained at all pyrolysis and decomposition temperatures. Moreover, cup-stacked carbon nanotubes (CS-CNTs) were observed at the decomposition temperature of 600°C. MWCNTs with the best quality were produced at decomposition temperature of 750°C. The optimum pyrolysis and decomposition temperatures in terms of CNTs production were at 700 and 650°C, respectively.     

Influence of a fiber-network microstructure of paper-structured catalyst on methanol reforming behavior

A novel microstructured catalyst that consists of Cu/ZnO catalyst powders and ceramic fibers was successfully prepared using pulp fibers as a tentative matrix by a papermaking technique. As-prepared material, called a paper-structured catalyst, possessed porous microstructure with layered ceramic fiber networks (average pore size ca. 20 μm, porosity ca. 50%). In the process of methanol autothermal reforming (ATR) to produce hydrogen, paper-structured catalysts demonstrated both high methanol conversion and low concentration of undesirable carbon monoxide as compared with catalyst powders and pellets. The catalytic performance of paper-structured catalysts depended on the use of pulp fibers, which were added in the paper-forming process and finally removed by thermal treatment before ATR performance tests. Confocal laser scanning microscopy and mercury intrusion analysis suggested that the tentative pulp fiber matrix played a significant role in regulating the fiber-network microstructure inside paper composites. Various metallic filters with different average pore sizes, used as supports for Cu/ZnO catalysts, were subjected to ATR performance tests for elucidating the pore effects. The tests indicated that the pore sizes of catalyst support had critical effects on the catalytic efficiency: the maximum hydrogen production was achieved by metallic filters with an average pore size of 20 μm. These results suggested that the paper-specific microstructures contributed to form a suitable catalytic reaction environment, possibly by promoting efficient diffusion of heat and reactants. The paper-structured catalyst with a regular pore microstructure is expected to be a promising catalytic material to provide both practical utility and high efficiency in the catalytic gas-reforming process.     

Preparation of SiO2 thin films using the Cat-CVD method

Using the catalytic chemical vapor deposition (Cat-CVD) method, a-Si and SiN_x films have been the main focus of studies. SiO₂ films have not been studied because of the limited life of catalysts such as tungsten or molybdenum in an oxidative atmosphere. In this report, we describe oxide film preparation using an iridium catalyst. We determined the most appropriate catalyst material for the oxide film process by exposing heated materials in tetraethoxysilane (TEOS) or O₂ gas. As the result, it was confirmed that the Ir catalyst works in a slow oxidative atmosphere. Using the Ir catalyst, SiO₂ films were deposited in two gas combinations: TEOS and N₂O, and SiH₄ and N₂O. Although the SiO₂ film processed with the combination of TEOS and N₂O was stoichiometric, its breakdown voltage is not sufficient. The SiO₂ film processed with the combination of SiH₄ and N₂O showed good electrical property.     

Epitaxial growth of strained Si1−yCy films by the hot-wire cell method and its application to metal oxide semiconductor devices

We succeeded in obtaining strained Si_1−yC_y films at a substrate temperature of 200 °C by the hot-wire cell method. The substitutional carbon concentration in films annealed at 700 °C was 0.9%, while it was limited to 0.13% for a sample grown by gas-source molecular beam epitaxy (MBE) at a substrate temperature of 700 °C. We investigated the thermal stability of strained Si_1−yC_y films for device application. Annealing at over 900 °C caused the formation of 3C-SiC and relaxation of the strain occurred. From this result, we found that the process temperature should be lower than 800 °C. A low-temperature MOSFET process, in which all process temperatures after deposition of Si_1−yC_y were lower than 800 °C, was developed and a strained Si_1−yC_y MOSFET was fabricated.