Electroreductive dechlorination of chlorophenols with Pd catalyst supported on solid electrode

Electroreductive dechlorination of chlorophenols with Pd catalyst supported on solidelectrode was studied. As solid electrodes, carbon cloth (CC), carbon felt (CF) and titanium mesh were used, and palladium was plated on solid electrodes by either electrolytic or electroless method. On each electrode with Pd, chlorophenols were qualitatively dechlorinated to phenol, while they were entirely intact on electrodes without Pd. Moreover, neither base electrode nor plating method significantly affected the activity of Pd as far as it was sufficiently loaded on the electrode. Based on the results in the experiments using one electrode repeatedly, Pd catalyst proved to possess a satisfactory duarability under the present condition. It was suggested that the reactive species responsinble for the dechlorination of chlorophenols could be formed during preliminary electrolysis. Thus, (Pd)_x-H resulting from the adsorption of electrogenerated hydrogen on metallic Pd might be assumed most probable.     

商用V/W/Ti系脱硝催化剂表面SO3生成的反应机理

基于燃煤烟气SO₃生成与排放给电厂运行及大气环境带来的严重影响,研究了一种在役典型商用蜂窝型V/W/Ti系脱硝催化剂表面的SO₃生成反应动力学及反应机理.结果表明,反应温度与SO₂浓度是影响催化剂表面SO₃生成的关键因素.在SO₂浓度为400×10^-6时,当反应温度从300℃升至360℃,SO₂-SO₃转化率从0.2%提高至0.65%,温度达到400℃后,催化剂表面V₂O₅活性增加更为显著,SO₂-SO₃转化率从0.65%增2.3%,SO₃生成反应的表观速率常数增加近3倍.SO₃在催化剂表面的生成路径为：SO₂与V⁵⁺-OH反应生成中间产物VOSO₄与HSO₄^-,随后进一步反应生成SO₃.SO₂主要通过其在催化剂表面的吸附、转化过程影响SO₃的生成,其本征动力学反应级数为0.52.O₂的本征动力学反应级数为0,SO₃生成反应可以在无O₂条件下进行,O₂存在会促进反应进行,但不会改变反应路径.     

重铬酸钾法测定化学需氧量的实验条件优化

以降低成本、减少二次污染、提供多元化实验条件为主要出发点,开展GB 11914-89中氯离子掩蔽剂加入量和催化剂种类等优化实验研究。结果表明:采用按比例加入的方式可以降低硫酸汞使用量,m[HgSO4]:m[Cl-]=10∶1即可达到有效掩蔽效果;在标准样品、地表水和一般废水的COD测定中,硫酸镍、硫酸铝钾和磷酸二氢锰作为硫酸银的替代物具有一定的可行性,建议最低加入量为4g/L。     

燃煤机组SCR脱硝催化剂的研究进展

选择性催化还原(SCR)是目前控制氮氧化物排放的主要技术。本文介绍了锅炉炉后脱硝系统的布置位置及工艺条件、已经工业化的氨选择性高温还原钒催化剂的特点,以及近年来低温脱硝催化剂的研究现状。指出我国脱硝催化剂应提高还原剂的选择性,开发新型低温催化剂应重点考察烟气中的水、二氧化硫及硫酸氢铵等对催化剂的影响。     

共沉淀法制备铜系催化剂及其稳定性的研究

主要介绍了利用共沉淀方法制备铜系催化剂,并考察了制备过程中各个工艺参数对铜系催化剂稳定性的影响。通过优化催化剂的设计和制备方法,可有效地改善Cu2+的溶出问题,使该类催化剂具有广阔的应用前景。     

Pyrolysis of low-density polyethylene using synthetic catalysts produced from fly ash

Catalytic pyrolysis of low-density polyethylene (LDPE) was investigated using various fly ash-derived silica–alumina catalysts (FSAs). FSAs were prepared by a simple activation method that basically includes NaOH treatment of fly ash by a fusion method, followed by an aging process. A series of LDPE pyrolysis experiments was conducted and the catalytic performance of FSAs was assessed in terms of the degradation temperature and the simulated boiling point distribution of the liquid products. The effects of synthesis conditions such as NaOH/fly ash weight ratio and aging time were examined by X-ray diffractometer (XRD), Brunauer-Emmett-Teller (BET) surface area analyzer, and scanning electron microscope to clarify the controlling factors affecting the catalytic activity. To obtain catalyst with high activity, it is necessary to produce sufficient silica and alumina species that can be easily co-precipitated into solid acid catalyst by destruction of the fly ash structure and to optimize the activation time for catalyst synthesis to prevent the transformation into inactive phases. The catalytic performance of FSA obtained from optimal conditions was equivalent to that of commercial catalysts, demonstrating the effectiveness of the catalyst.     

均相/异相催化剂光降解垃圾渗滤液效果的研究

垃圾渗滤液是一种复杂有毒的、生化降解性差的高浓度有机废水,高级氧化技术具有氧化能力强和无二次污染等特点,被认为是处理难降解有机污染物最有应用前景的方法.本研究在500 W汞灯、25℃、2.5 h反应条件下,对比了TiO_2、K2S2O_8、K2S2O_8/Fe2+、施氏矿物、施氏矿物/H2O_2、Fe2+/H2O_26种催化剂组合光化学处理垃圾渗滤液的效果.结果表明,施氏矿物/H2O_2和Fe2+/H2O_2光催化降解垃圾渗滤液中有机污染物的效果优于其它催化剂组合,渗滤液中CO_D去除率分别为41.6%和46.5%,TO_C去除率分别为76.0%和78.1%.然而,Fe2+/H2O_2组合在光催化处理垃圾渗滤液后会产生大量难以沉降的Fe(O_H)3絮状物,且渗滤液色度明显增加,由初始的40倍上升到175倍.而施氏矿物/H2O_2组合则避免了上述问题,色度去除率达100%,被认为是一种具有应用前景的光化学降解垃圾渗滤液的催化剂组合.     

我国电石法生产聚氯乙烯行业汞排放清单

提出了我国电石法聚氯乙烯(PVC)生产全生命周期汞排放清单的计算方法。采用低汞触媒有盐酸脱吸工艺、高汞触媒有盐酸脱吸工艺、高汞触媒无盐酸脱吸工艺的汞输入因子分别为0.045 g/kt、0.091 g/kt和0.122 g/kt,回收产品的汞输出分布因子分别为95.37%、81.97%和97.18%。估算得到:2010年我国电石法PVC生产汞输入量792.8~814.8 t;回收的产品汞705.9~724.4 t,通过大气无组织排放、管道残留以及其他未知途径汞排放79.6~82.8 t;废水汞排放1.3 t;固体废物汞排放3.6~3.7 t;废酸汞排放2.5~2.6 t。回收的产品汞是汞输出的主要途径。     

MTO废催化剂SAPO-34的再生

采用干凝胶转化法对甲醇制烯烃(MTO)废催化剂SAPO-34进行再生,将SAPO-34分子筛晶化所需的硅、铝、磷原料同时作为黏结剂使用,经干凝胶转化制备出再生催化剂,并对催化剂进行了表征及MTO反应活性评价。表征结果显示,再生催化剂的晶体结构、微观形貌、粒径分布、孔结构、耐磨性及酸中心均得到了恢复与改善,磨损指数可达0.35%/h。实验结果表明:在催化剂加入量为1.0 g、进气中甲醇质量分数为95%、甲醇质量空速为3 h-1、反应温度为450℃、反应压力为常压的条件下,再生催化剂的甲醇转化率接近100%,双烯(乙烯和丙烯)选择性较废催化剂提高了约3百分点,可达87%以上;同时,再生催化剂的寿命也较废催化剂有了明显改善。     

Ni,Co掺杂对Mn-Ce/TiO_2催化剂脱硝活性的影响

以Ti O_2为载体,采用浸渍法制备Ni或Co掺杂的Mn-Ce/Ti O_2催化剂,用于烟气的选择性催化还原法低温脱硝。考察Ni或Co的掺加对Mn-Ce/Ti O_2催化剂活性的影响,并对各催化剂进行了BET,XRD,H_2-TPR,XPS表征。实验结果表明:在NO,NH_3,O_2的体积分数分别为6×10~(-4),6×10~(-4),6×10~(-2),空速为16 000 h~(-1)的条件下,Mn-Ce/Ti O_2、Mn-Ce-Ni_(0.4)/Ti O_2和Mn-Ce-Co_(0.2)/Ti O_2催化剂的NO去除率在120℃时分别为38%,68%,74%,在150℃时分别为64%,92%,近100%,这表明掺加Ni或Co后Mn-Ce/Ti O_2催化剂的脱硝活性明显提高;在进气中加入体积分数为1×10~(-4)的SO_2后,Mn-Ce/Ti O_2催化剂的NO去除率在300 min内从98.2%下降至57.2%,而Mn-CeCo_(0.2)/Ti O_2和Mn-Ce-Ni_(0.4)/Ti O_2催化剂的NO去除率分别为73.9%和69.8%,这表明Ni或Co的掺加有助于提高催化剂的抗硫性能。表征结果表明:Ni或Co的掺加基本不影响Mn和Ce在载体Ti O_2上的分散;Ce元素以Ce~(3+)和Ce~(4+)价态存在,且主要为Ce~(4+);催化剂的比表面积变化不大;Mn O_x与Ce O_x的结晶度降低,催化剂的氧化还原能力增强。