γ-Al2O3负载Ni、Fe催化剂同时脱硫脱硝

采用浸渍法制备了不同负载量的Ni(x)Fe(y)/γ-AL2O3催化剂,通过XRD、H2-TPR、BET和SEM对催化剂进行表征,使用微型催化反应装置考察催化剂在以CO作为还原气时,同时脱硫脱硝的催化活性。结果表明,NiO和Fe2O3做为活性组分可以很好地分散在γ-Al2O3载体上,并且不破坏其结构;Ni(8)Fe(2)/γ-Al2O3催化剂有最佳的脱硫脱硝活性,脱硫率达到96.55%,脱硝率达到97.92%。     

Fe添加对Mn/γ-Al2O3催化剂低温选择性催化还原NO的性能影响

为考察Fe添加量对锰基催化剂低温选择性催化还原(SCR)烟气中NO的性能,采用湿式浸渍法制备以γ-Al_2O_3为载体,以MnOx、FeOx为活性组分的系列催化剂,通过X射线衍射(XRD)、扫描电镜(SEM)、X射线光电子能谱(XPS)分析等手段对其进行表征。结果表明:Fe的引入对提高催化剂的SCR活性具有明显的促进作用。Fe添加量为0.04 mmol/g时制备的Mn(0.8)-Fe(0.04)/γ-Al_2O_3催化剂脱硝效率在150℃条件下即可以达到93.1%。Fe添加量为0.04mmol/g时催化剂中形成的球状结晶β-MnO_2分散最为均匀,最有利于催化反应的进行。比表面积不是影响催化剂SCR活性的决定性因素。Mn(0.8)-Fe(0.04)/γ-Al_2O_3催化剂孔径分布以2～50nm的中孔为主,活性组分也主要负载到较大的中孔中,有利于催化反应的进行。Fe的加入可以提高催化剂的抗硫性能。     

Fe-Mn/γ-Al2O3催化O3-H2O2协同氧化间甲酚

为提高臭氧氧化法对难降解有机污染物的降解效率,采用在催化臭氧氧化体系中引入H_2O_2的方法,建立催化O_3-H_2O_2联合氧化体系,使O_3与H_2O_2在体系中起协同作用。采用等体积浸渍法筛选制备了具有高催化性能的Fe-Mn/γ-Al_2O_3催化剂,应用于O_3/Fe-Mn/γ-Al_2O_3/H_2O_2复合体系协同催化臭氧氧化处理间甲酚模型废水。通过扫描电子显微镜(SEM)、物理吸附、X射线衍射(XRD)、X射线荧光光谱(XRF)、X射线光电子波谱(XPS)对催化剂的物理化学性质进行表征。考察了O_3投加量、H_2O_2投加量、初始pH、空速等因素对Fe-Mn/γ-Al_2O_3催化O_3-H_2O_2氧化间甲酚处理效果的影响,并采用GC-MS和LC-OCD,对Fe-Mn/γ-Al_2O_3催化O_3-H_2O_2氧化间甲酚的中间产物的类型及相对分子质量进行分析。结果表明,当以Fe-Mn/γ-Al_2O_3为催化剂时,协同催化氧化体系的最优处理参数为:间甲酚浓度100 mg·L~(-1),O_3投加量481 mg·L~(-1),反应时间10 min,空速6 h~(-1),H_2O_2投加量211 mg·L~(-1),进水pH 6.7。在此条件下,TOC去除率可达68.37%,间甲酚转化率可达100%。以上研究结果可为2种技术联用降解煤化工废水提供参考。     

Al2O3/β-40催化剂同时脱硫脱硝性能

以溶胶凝胶法制备的30% Al2O3/β-40为载体,采用浸渍法制备出负载不同金属氧化物的催化剂。采用XRD、H2-TPR、BET对催化剂结构和性质进行表征,以CO为还原剂考察催化剂的脱硫脱硝活性。结果显示12% NiO/30% Al2O3/β-40脱硫脱硝活性最佳,500℃时NO、SO2转化率均可达到90%以上。     

铁修饰铝柱撑黏土催化剂(Fe/Al-PILC)的制备及其对C_3H_6-SCR活性的影响

制备了铝离子柱撑蒙脱土负载铁离子的催化剂,采用XRD、H_2-TPR、Py-IR、UV-vis光谱、ICP、N_2吸附-脱附等多种分析方法,对催化剂的基础物理化学性质进行了系统地表征。在固定床微反应器内,对丙烯在该催化剂表面选择性还原NO的特性进行了研究,考察了柱撑Al~(3+)与黏土比例以及焙烧温度对催化剂的物化性质以及脱硝效果的影响。结果表明:9Fe/Al-PILC样品具有较高的C_3H_6-SCR脱硝性能,Al~(3+)/蒙脱土的比值对脱硝性能的影响较大,而载体的焙烧温度的影响相对较小;按照Al~(3+)/蒙脱土比值的大小,催化剂活性高低排序为9Fe/Al-PILC-109Fe/Al-PILC-209Fe/Al-PILC-59Fe/蒙脱土9Fe/Al-PILC-40;柱撑离子Al~(3+)使蒙脱土的比表面积急剧增大,催化剂具有微孔和介孔结构,Al~(3+)/蒙脱土比为10 mmol·g~(-1)时载体柱撑效果最佳;在负载铁离子后的Fe/Al-PILC催化剂中,铁氧化物高度分散在载体表面。H_2-TPR表明催化剂的氧化还原性能可影响催化剂的SCR活性。UV-vis结果表明,低聚态Fe_xO_y物种的形成有助于提升催化剂的反应性能。Py-IR实验结果表明,Lewis酸和Br(?)nsted酸均有利于选择性催化还原NO,9Fe/Al-PILC-10催化剂活性最好,与其Bronsted酸含量较多有关。以上结果对于进一步优化柱撑黏土催化剂的合成工艺具有参考价值。     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni（NO3）2和Fe（NO3）3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO＋NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

SiO2掺杂对V2O5-WO3/TiO2脱硝催化性能的影响

采用溶胶凝胶法制备TiO2-SiO2载体,浸渍法制备出V2O5-WO3/TiO2-SiO2催化剂,利用BET、FESEM、XRD、TGA和激光拉曼对催化剂进行表征,研究催化剂的理化性质。以NH3为还原剂,考察反应温度、SiO2掺杂量、焙烧温度、空速和使用时间对SCR催化还原NO的性能影响。结果表明,V2O5-WO3/TiO2-SiO2催化剂最佳反应温度在250~350℃。SiO2掺杂能提高活性组分V2O5和WO3在载体表面的分散性,制备出的催化剂具有更大的比表面积和更宽的温度区间,提高脱硝活性及稳定性。SiO2掺杂量对催化剂性能影响较大,制备的催化剂中,TiO2/SiO2=2显示了最大催化活性,脱硝率均在60%以上,TiO2/SiO2=0.5制备的催化剂稳定性最差。焙烧温度对催化剂性能也有影响,焙烧温度在500和600℃时,最低脱硝率为58%和23%,最佳焙烧温度为400℃,脱硝率均在80%以上,具有优越的脱硝性能。实验结果还表明,空速对V2O5-WO3/TiO2-SiO2催化剂的影响不大,在20 000 h-1空速下催化剂的使用时间对脱硝率的影响也不大,48 h内能保持在99%左右,非常稳定。     

多孔TiO2为载体的V2O5-WO3脱硝催化剂制备和表征

以硫酸氧钛为钛源,氨水为沉淀剂,制备得到大比表面积(60m2/g)的锐钛矿TiO2载体.TiO2载体具有多孔结构,孔径集中在5～12nm,孔体积达到0.24cm3/g.以多孔TiO2为载体,采用浸渍法制备不同V2O5负载量的V2O5-WO3催化剂,利用拉曼(Raman)光谱、X射线衍射(XRD)对催化剂进行表征,并研究了不同V2O5负载量催化剂的脱硝活性,以及NO浓度和NH3/NO摩尔比对催化剂活性的影响.结果表明,V2O5在TiO2表面高度分散,当V2O5负载量在3%(质量分数)以下时,载体表面钒物种为单体钒,表现出最好的脱硝活性,在280～450℃内NO转化率均能达到90%以上.该催化剂对不同进口NO浓度有较强的适应能力.采用该催化剂的脱硝工艺,NH3/NO摩尔比宜保持在0.8～1.0.     

不同晶型MnOx催化还原NO活性研究

为研究低温烟气脱硝的高效选择性催化还原(SCR)催化剂的催化活性,采用湿式浸渍法制备了以γ-Al_2O_3为载体、以MnO_x为活性组分的系列MnO_x/γ-Al_2O_3催化剂。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、BET多分子层吸附模型等测试方法对催化剂进行表征,分析Mn负载量对MnO_x晶型、形貌及催化剂比表面积的影响,并进行催化还原NO实验,通过脱硝效率反映不同MnO_x晶型时催化剂的脱硝特性。结果表明,Mn负载量对MnO_x的晶型和形貌产生明显影响。Mn负载量低于0.4mmol/g时,无法形成明显晶核;Mn负载量为0.8mmol/g时,形成球状_β-MnO_2;Mn负载量为1.2mmol/g时,形成棒状α-MnO_2。球状_β-MnO_2提高了MnO_x/γ-Al_2O_3比表面积,含球状_β-MnO_2的MnO_x/γ-Al_2O_3催化剂具有最优的催化还原NO活性,175℃条件下达到84%左右的脱硝效率。H_2O(气态,下同)和SO~3 _2的存在对催化剂脱硝性能产生影响,分别持续通入600mg/mSO_2、6.000%(体积分数)H_2O 480min,脱硝效率分别下降约14百分点和10百分点。     

H2O和SO2对V2O5-WO3/TiO2催化剂催化氧化NO的影响

研究了在120℃的反应温度下,H2O和SO2对V2O5-WO3TiO2催化剂选择性催化氧化(SCO)NO的影响.结果表明,在H2O和SO2存在的情况下催化剂失活很快,停止通入H2O和SO2后活性不能恢复,但在加热到250℃后催化活性基本恢复.FT-IR分析表明,催化剂表面形成了金属硝酸盐和Ti的硫酸盐,对催化活性有一定...     

O3、H2O2／O3及UV／O3在焦化废水深度处理中的应用

采用O3、H2O2／O3及UV／O3等高级氧化技术（AOPs）对某焦化公司的生化出水进行深度处理,考察了O3与废水的接触时间、溶液pH、反应温度等因素对废水COD去除率的影响,确定出O3氧化反应的最佳工艺参数为：接触时间40min,溶液pH8．5,反应温度25℃,此条件下废水COD及UV254的去除率最高可达47．14％和73．47％;H2O2／O3及UV／O3两种组合工艺对焦化废水COD及UV254的去除率均有一定程度的提高,但H2O2／O3系统的运行效果取决于H2O2的投加量。研究结论表明,单纯采用COD作为评价指标,并不能准确反映出O3系列AOPs对焦化废水中有机污染物的降解作用。     

Treatment of pharmaceutical wastewater containing antibiotics by O3 and O3/H2O2 processes

Ozonation of three different synthetic pharmaceutical formulation wastewater containing two human antibiotics and a veterinary antibiotic has been studied to enhance the their biodegradability. The effects of pH and initial chemical oxygen demand (COD) value as well as addition of hydrogen peroxide on ozonation process were investigated. Total organic carbon (TOC), COD, biochemical oxygen demand (BOD), and aromatic content (UV254) were the parameters followed to evaluate the performance of ozonation process. Comparison of the biodegradability of selected wastewaters containing different antibiotics confirmed that the variation of biodegradability was associated with the target compound. While BOD5/COD ratio of veterinary antibiotic formulation wastewater was increased from 0.077 to 0.38 with an applied ozone dosage of 2.96 g/l, this ratio for human antibiotic I and human antibiotic II was increased from 0 to 0.1 and 0.27 respectively. Moreover the results of this investigation showed that the ozonation process is capable of achieving high levels of COD and aromaticity removals at about their natural pH values.     

SIMAZINE REMOVAL FROM WATER IN A CONTINUOUS BUBBLE COLUMN BY O3 AND O3/H2O2

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide found in surface and ground water has been ozonized in continuous flow mode. Typical operating variables in ozonation processes have been investigated. Thus, the ozone dose fed to the system exerted a positive effect, while the gas flow rate did not influence the efficiency of the process provided ozone mass flow rate was kept constant. Increasing the pH led to a higher extension of the free radical degradation of simazine and, therefore, to a higher efficiency of the process. Also, addition of free radical promoters, i.e. hydrogen peroxide, did result in a significant improvement of the simazine removal rate. A first approach to process economy showed the system ozone/hydrogen peroxide as the most advantageous in terms of electrical energy requirements.     

The catalytic incineration of styrene over an Mn2O3/Fe2O3 catalyst

In this study, styrene monomer (SM) was treated by a commercial catalyst, Mn2O3/Fe2O3, in a fixed-bed reactor. The study can be classified into two major parts. First, the effects of operating factors, such as temperature, SM concentration, space velocity, and O2 concentration, on the performance of the catalyst were investigated. Second, two catalyst life tests were carried out to characterize the deactivation effect of SM. The results show that the catalyst results in higher conversion of SM at a higher inlet temperature and higher O2 concentrations. The conversion of SM decreases with increasing SM concentration and space velocity. From the statistical analysis of the data, we find that temperature is the most important factor on the catalytic incineration. Oxygen concentration, SM concentration, and space velocity are significant parameters as well. This paper also provides information on the deactivation effect of SM. The catalysts were characterized by surface and pore-size analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron spectroscopy for chemical analysis (ESCA) before and after the tests. The results show that the catalytic deactivation may be caused by carbon coating, and the pore size and surface area of the catalyst are smaller after deactivation.     

Simazine removal from water in a continuous bubble column by O3 and O3/H2O2.

Simazine, [2-chloro, 4,6-bis(ethylamino)-1,3,5-s-triazine], a common herbicide found in surface and ground water has been ozonized in continuous flow mode. Typical operating variables in ozonation processes have been investigated. Thus, the ozone dose fed to the system exerted a positive effect, while the gas flow rate did not influence the efficiency of the process provided ozone mass flow rate was kept constant. Increasing the pH led to a higher extension of the free radical degradation of simazine and, therefore, to a higher efficiency of the process. Also, addition of free radical promoters, i.e. hydrogen peroxide, did result in a significant improvement of the simazine removal rate. A first approach to process economy showed the system ozone/hydrogen peroxide as the most advantageous in terms of electrical energy requirements.     

Catalytic destruction of 1,2-dichlorobenzene on V2O5-WO3/Al2O3-TiO2 catalyst

Studies on the catalytic destruction of 1,2-dichlorobenzene were carried out on a specially constructed semi-technical equipment whose most important element was a catalytic reactor with a monolithic catalyst in the form of 150 x 150 x 100 mm cubes. A catalyst made from cordierite with an active layer composed of Al2O3 - 64 wt%, TiO2 - 26 wt%, V2O5 - 6.6 wt% and WO3 - 3.4 wt% was used. The reactor made it possible to carry out the process in the temperature range 150-350 degrees C, at variable catalyst loading and different velocities of gas flow through the reactor. The content of 1,2-dichlorobenzene in the air was analysed by a chromatographic method. A significant effect of catalyst loading and temperature on 1,2-dichlorobenzene destruction efficiency was observed and no effect of the linear flow velocity through the catalyst on o-dichlorobenzene destruction efficiency was reported. The applied vanadium-tungsten catalyst on a monolithic carrier made from TiO2/gamma-Al2O3 revealed very good activity that resulted in an over 80% efficiency of 1,2-dichlorobenzene destruction at the temperature around 250 degrees C at a very high catalyst loading reaching ca. 8200 h(-1). Additionally, in this study the kinetics of 1,2-dichlorobenzene decomposition was determined, specifying the order of reaction and dependence of the decomposition rate constant on temperature, using a simple power-rate law model.     

O3/H2O2法去除浮选药剂丁基黄药

采用O3/H2O2法去除水中丁基黄药,考察了H2O2/O3摩尔比、pH值、丁基黄药初始浓度、温度和自由基抑制剂对丁基黄药的去除效果的影响。结果表明,在相同O3投加量下,H2O2量越大,丁基黄药去除率越高。pH值为7～9,温度在293～303 K的范围内,O3/H2O2对丁基黄药都有很高的去除率。碳酸氢根和叔丁醇能在一定程度上降低丁基黄药的降解效率。研究还发现,在O3和H2O2投加量相同的条件下,H2O2多次投加对水中丁基黄药的处理效果明显优于一次性投加。GC/MS分析表明,O3/H2O2氧化丁基黄药氧化产物为羧酸类物质。     

O3/H2O2深度处理印染废水二级出水

采用O3/H2O2高级氧化工艺深度处理印染废水二级出水,考察了不同反应条件对O3/H2O2工艺的影响,并且对污水二级出水有机物(EfOM)的性质和去除行为进行了表征分析。结果表明,在pH=9,臭氧进气流量0.2 L/min,臭氧浓度116 mg/L,反应时间100 min,H2O2投加量9.79 mmol/L时,COD和色度去除率分别为82.2%、96.9%,B/C(BOD5/COD)由初始的0.10提升到0.32。此外,三维荧光光谱(3DEEM)、相对分子质量分布(MWD)以及亲疏水性分布分析表明,处理后EfOM的荧光特性发生变化,低分子量物质大量增加,亲疏水性分布也有所改变。     

O3／H2O2高级氧化技术H2O2加入量的简易控制方法

对与臭氧有着不同反应活性的3类有机污染物，探讨并建立了O3／H2O2高级氧化技术H2O2较优投加量的简易控制方法。结果表明，水中存在溶解臭氧是H2O2与臭氧降解效率具有协同作用的必要条件，另外，H2O2的较优加入量直接依赖于目标有机污染物与臭氧的反应活性。对于不同的有机物及在常规的臭氧化水处理时间内，H2O2加入量控制在单独臭氧化处理时水中溶解臭氧的20-30倍（质量比）之间为宜。这种简易控制H2O2加入量的方法对推广O3／H2O2技术在实际废水处理中的应用具有重要的意义。