有机废水湿式O_3氧化降解过程的研究

采用 O3 湿式氧化降解含氯乙烯的有机废水 ,实验研究了不同 p H、不同温度以及不同初始氯乙烯浓度对反应过程的影响 ,初步探讨了在高 p H时 O3 的自分解催化产生自由基 OH·机理和污染物的氧化降解过程。通过实验研究与分析 ,获得了氯乙烯有机废水 O3 氧化过程的动力学方程     

非程序升温色谱法分析CO/CO2加氢反应混合物

在非程序升温单桩色谱仪上，采用双柱温法对ＣＯ／ＣＯ２加氢反应混合物进行在线分析，设置条件为３ｍ长的色谱柱ＧＤＸ－４０３，柱前压和检测温度固定不变，氢气为载气，ＴＣＤ为检测器，结果表明：在柱温３１３Ｋ，可以分析ＣＯ、ＣＨ４、ＣＯ２。在柱温３６８Ｋ，可以分析Ｈ２Ｏ和甲醇。通过计算反应前后２组物质浓度的变化，可以快速、准确评价催化剂的活性和选择性。     

Coupling catalytic hydrolysis and oxidation for CS2 removal

CS2 removal was Obtained by coupling catalytic hyidation on bi-functional catalyst.On the hydrolysis active sites,CS2 is hydrolyzed to H2S,while on the oxidation active sites,H2S is oxidized to elemental S or sulfuric acid deposited on the porous support.The above process can be expressed as followsCS2→H2O COS →H2O H2S→O2 S/SO2- 4.H2S oxidation eliminates its prohibition on CS2 hydrolysis so that the rate of coupling removal CS2 is 5 times higher than that of CS2 hydrolysis.The same active energy of hydrolysis and coupling reaction also indicates that H2S oxidation does not change the reaction mechanism of CS2 hydrolysis.Temperature has obvious effect on the process while the mole ratio of O2 concentration to CS2 concentration (O/S) does not,especially in excess of 2.5.The formation of sulfuric acid on the catalyst surface poisons hydrolysis active sites and causes the decrease of left OH-1 concentration on the catalysts surface.Lower temperature is suggested for this bi-functional catalyst owing to the low yield ratio of S/SO4 2-.     

Hydrogen generation from polyvinyl alcohol-contaminated wastewater by a process of supercritical water gasification

Gasification of polyvinyl alcohol(PVA)-contaminated wastewater in supercritical water(SCW)was investigated in a continuous flow reactor at 723-873 K,20-36 MPa and residence time of 20-60 s.The gas and liquid products were analyzed by GC/TCD,and TOC analyzer.The main gas products were H_2,CH_4,CO and CO_2.Pressure change had no significant influence on gasification efficiency. Higher temperature and longer residence time enhanced gasification efficiency,and lower temperature favored the production of H_2. The effects of KOH catalyst on gas product composition were studied,and gasification efficiency were analyzed.The TOC removal efficiency(R_(TOC)),carbon gasification ratio(R_(CG))and hydrogen gasification ratio(R_(HG))were up to 96.00%,95.92% and 126.40% at 873 K and 60 s,respectively,which suggests PVA can be completely gasified in SCW.The results indicate supercritical water gasification for hydrogen generation is a promising process for the treatment of PVA wastewater.     

Catalytic reduction of nitric oxide with carbon monoxide on copper-cobalt oxides supported on nano-titanium dioxide

A series of copper-cobalt oxides supported on nano-titanium dioxide were prepared for the reduction of nitric oxide with carbon monoxide and characterized using techniques such as XRD, BET and TPR. Catalyst CuCoOx/TiO2 with Cu/Co molar ratio of 1/2, Cu- Co total loading of 30% at the calcination temperature of 350°C formed CuCo2O4 spinel and had the highest activity. NO conversion reached 98.9% at 200°C. Mechanism of the reduction was also investigated, N2O was mainly yielded below 100°C, while N2 was produced instead at higher temperature. O2 was supposed to accelerate the reaction between NOx and CO for its oxidation of NO to give more easily reduced NO2, but the oxidation of CO by O2 to CO2 decreased the speed of the reaction greatly. Either SO2 or H2O had no adverse impact on the activity of NO reduction; however, in the presence of both SO2 and H2O, the catalyst deactivated quickly.     

SO2对CoH-ZSM-5催化CH4还原NO催化性能的影响

研究了富氧条件下SO₂对CoH-ZSM-5上CH₄选择还原NO(CH₄-SCR)的影响,应用SO₂-TPSR,NO+(O₂)-TPD等方法研究了产生中毒的原因并定量研究了被毒化的活性位.反应在773 K进行时,加入体积分数78×10^-6SO₂,NO的转化率由72%逐渐降低并稳定在58%,提高反应温度至823 K,NO稳定转化率上升至62%.同时加入2.5     

二氧化氯氧化法处理偏二甲肼污水工艺

利用二氧化氯氧化法处理含偏二甲肼的污水,通过实验数据分析初步确定二氧化氯氧化偏二甲肼的化学反应机理。采取二氧化氯多级串联氧化法,再通过活性炭吸附柱处理含偏二甲肼的污水。偏二甲肼与二氧化氯的摩尔之比控制在1:9~1:11,并采取多级氧化塔串联方式,可提高二氧化氯的氧化效率与利用率。对于发射场的实际污水处理工艺条件为偏二甲肼/ClO2摩尔投料比:1:9;氧化温度:15℃;陈化时间:15d;污水通过Φ25×400吸附柱(100g活性炭)流量3mL/min。处理后的污水各项指标符合GB8978-1996污水综合排放标准。     

油田含油污水Fenton氧化处理方法的研究

油田含油污水处理问题是一项难度极大的技术课题,本文采用Fenton试剂对油田含油污水进行氧化处理,实验过程中考察pH值、H2O2的初始浓度、Fe2+/H2O2(摩尔比)、H2O2/CODCr(质量比)、反应时间等因素对CODCr去除率的影响。     

Fenton试剂催化氧化法处理离子交换树脂再生废水

针对离子交换树脂再生废水中的难降解有机物利用Fenton试剂进行催化氧化处理。实验结果表明：当反应条件是H2O2与FeSO4·7H2O摩尔比为5：1、H：O2（30％）投加量为0．35mol／L（4次投加）、pH值为3．5、反应时间为2h时,废水的处理效果最佳;并采用正交实验确定了各反应因素对废水的CODcr去除效果的影响水平。     

Greenhouse gases fluxes and soil thermal properties in a pasture in central Missouri

Fluctuations of greenhouse gases emissions and soil properties occur at short spatial and temporal scales, however, results are often reported for larger scales studies. We monitored CO2, CH4, and N2O fluxes and soil temperature (T), thermal conductivity (K), resistivity (R) and thermal di usivity (D) from 2004 to 2006 in a pasture. Soil air samples for determination of CO2, CH4 and N2O concentrations were collected from static and vented chambers and analyzed within two hours of collection with a gas chromatograph. T, K, R and D were measured in-situ using a KD2 probe. Soil samples were also taken for measurements of soil chemical and physical properties. The pasture acted as a sink in 2004, a source in 2005 and again a sink of CH4 in 2006. CO2 and CH4 were highest, but N2O as well as T, K and D were lowest in 2004. Only K was correlated with CO2 in 2004 while T correlated with both N2O (r = 0.76, p = 0.0001) and CO2 (r = 0.88, p = 0.0001) in 2005. In 2006, all gases fluxes were significantly correlated with T, K and R when the data for the entire year were considered. However, an in-depth examination of the data revealed the existence of month-to-month shifts, lack of correlation and di ering spatial structures. These results stress the need for further studies on the relationship between soil properties and gases fluxes. K and R o er a promise as potential controlling factors for greenhouse gases fluxes in this pasture.     

Fe (II)活化过硫酸盐处理喹啉工艺参数优化及生物毒性

以喹啉为处理目标物,采用Fe²⁺活化K₂S₂O₈（PS）的高级氧化体系在不同环境因素下降解喹啉.结果表明：与单一PS体系和Fe²⁺体系相比,Fe²⁺/PS体系可以有效降解喹啉.在初始喹啉浓度为250mg/L,喹啉/PS物质的量比为1：10,PS/Fe²⁺物质的量比为3,初始pH3,反应温度为45℃,反应时间为80min的条件下,喹啉降解率可达100%.提高PS和Fe²⁺浓度均能有效提高喹啉降解率,但超过一定限值后对喹啉去除效果不明显.Fe²⁺/PS去除喹啉的过程符合一级反应动力学.溶液初始pH值越高,喹啉去除率越低;反应温度越高,喹啉去除率越高.自由基淬灭实验证实,Fe²⁺活化PS体系中有SO₄^-·和OH·的存在,其中由SO₄^-·产生的OH·对喹啉的降解占主导地位.通过GC/MS检测到2种中间产物8-羟基喹啉和2（1H）-喹啉酮,据此推测基于硫酸根自由基强化喹啉降解的可能路径.大肠杆菌急性毒性实验结果证实,虽然Fe²⁺/PS体系去除喹啉过程中产生了毒性更强的中间产物,但酸性条件和较高的反应温度有利于体系脱毒.     

Fe (II)活化过硫酸盐处理喹啉工艺参数优化及生物毒性

以喹啉为处理目标物,采用Fe²⁺活化K₂S₂O₈（PS）的高级氧化体系在不同环境因素下降解喹啉.结果表明：与单一PS体系和Fe²⁺体系相比,Fe²⁺/PS体系可以有效降解喹啉.在初始喹啉浓度为250mg/L,喹啉/PS物质的量比为1：10,PS/Fe²⁺物质的量比为3,初始pH3,反应温度为45℃,反应时间为80min的条件下,喹啉降解率可达100%.提高PS和Fe²⁺浓度均能有效提高喹啉降解率,但超过一定限值后对喹啉去除效果不明显.Fe²⁺/PS去除喹啉的过程符合一级反应动力学.溶液初始pH值越高,喹啉去除率越低;反应温度越高,喹啉去除率越高.自由基淬灭实验证实,Fe²⁺活化PS体系中有SO₄^-·和OH·的存在,其中由SO₄^-·产生的OH·对喹啉的降解占主导地位.通过GC/MS检测到2种中间产物8-羟基喹啉和2（1H）-喹啉酮,据此推测基于硫酸根自由基强化喹啉降解的可能路径.大肠杆菌急性毒性实验结果证实,虽然Fe²⁺/PS体系去除喹啉过程中产生了毒性更强的中间产物,但酸性条件和较高的反应温度有利于体系脱毒.     

CO2去除垃圾焚烧飞灰水洗液中Pb和Zn的工艺条件

为探明CO₂对飞灰水洗液中Pb和Zn的去除效果,研究了CO₂浓度、通入时间、流速以及体系反应温度和重金属离子初始浓度对Pb和Zn在水洗液中沉淀的影响.结果表明:水洗液中Pb和Zn的初始浓度越低,通入CO₂后Pb和Zn的残留率越低;增大CO₂浓度、延长通入时间、增大流速以及降低体系反应温度,均可有效降低Pb和Zn的残留率;CO₂沉淀处理在最佳工艺条件〔CO₂浓度为10%(φ)、通入时间为80 s、流速为2 mL/min以及体系反应温度为40~50 ℃〕下,Pb和Zn的残留率分别降至3%和0.1%以下.      

SnO2-TiO2负载CuO催化剂的CO氧化催化性能

对２种ｎ－型半导体的复合氧化物负载的氧化铜催化剂的ＣＯ氧化催化性能进行了研究,采用程序升温反应方法,得到ＣＯ转化率随反应温度的变化曲线,ＣＯ最低全转化温度越低,活性越好。考察了载体的不同制备方法如成胶方法、干燥方法,焙烧温度以及不同ＳｎＯ２：ＴｉＯ２摩尔比对ＣＯ２氧化性能的影响。     

氯离子影响热活化过硫酸盐降解苯酚的机理研究

地下水中广泛存在的氯离子(Cl?)会在自由基作用下生成氯活性物质,进而与污染物反应可能引发新的环境风险. 为研究Cl?影响过硫酸盐(PS)高级氧化技术修复苯酚污染地下水的效果及机理,采用热活化PS氧化体系考察温度、PS浓度、初始pH及Cl?浓度对苯酚降解效果的影响,结合三维荧光平行因子分析(EEM-PARAFAC)查明苯酚降解过程中体系的光谱特征,借助气相色谱-质谱联用仪识别氯代有毒副产物的数量及种类,并揭示其降解机理. 结果表明:①反应温度的升高和PS浓度的增加均可促进苯酚的降解,且降解过程符合伪一级动力学模型. ②Cl?的存在会加速热活化PS对苯酚的降解,其降解效率随Cl?浓度的增加而提高,当Cl?浓度为10、25和50 mmol/L时,反应5 h后苯酚降解率为100%. ③苯酚降解过程中反应体系的荧光特征可分为4种荧光组分(C1、C2、C3和C4),Cl?存在时,C1和C2组分的荧光强度降幅更大,C3和C4组分主要为苯酚降解产物的光谱特征,其中C3组分的荧光强度随反应时间延长呈先增强后降低趋势. ④根据质谱测试结果,推断出Cl?存在时苯酚降解的可能机理,主要包括羟基化/氧化和氯化作用,其中生成的氯代有毒副产物包括2-氯苯酚、4-氯苯酚、2,4-二氯苯酚、氯氢醌、3,5-二氯儿茶酚、2,3-二氯-2-甲基丁烷和2-氯-4-甲基-2-戊醇. 研究显示,Cl?会提升热活化PS对苯酚污染地下水的修复效率,但也会因氯化作用生成氯代有毒副产物.      

CH_4火焰中CO_2对NO行为影响的实验研究

针对CH4 火焰中CO2 浓度对于NO降解的影响进行了详细地分析研究。结果表明 :过量空气系数对于NO的降解有着很大的影响。和氧化性气氛相比 ,还原性气氛更有利于NO的降解。同时还原性气氛中CO2 的存在降低了NO的降解率 ,而氧化性气氛中CO2 的存在能够促进NO的降解。在还原性气氛中 ,随着CO2 浓度的升高 ,其继续减少NO降解率的作用也越来越不明显     

O2/CO2气氛下氮反应机理的研究

选取CH4、O2、CO2、Ar、NO、NH3，等气体，作为混合气和煤粉一起送入一维沉降炉内，以模拟O2／CO2气氛下煤中燃料氮、循环NO以及二者的相互作用对NO排放的影响，结果显示，在还原性气氛下NH3、HCN、CH4、CO与循环NO间的反应是NO排放下降的主要因素，且煤焦与NO的异相反应、吸附反应对NO的降解效果要明显高于氧化性气氛，同时，CO2体积分数的增加使得燃料中氮的氧化率升高，循环NO的降解率下降；氧化性气氛下随CO2体积分数的增加，燃料中氮的氧化率也增加，但循环NO的降解率升高．当CO2体积分数不变时，其对NO降解的作用随循环NO体积分数的增加愈加明显，在循环NO也不变且CO2体积分数较低时，随过量空气系数的增加，循环NO的降解率下降，而CO2体积分数较高时则出现相反情况。     

Oxidation of gaseous elemental mercury in a high voltage discharge reactor

Effects of the voltage waveform, discharge tooth wheel number and CO2/NO/SO2 concentration in the simulated flue gas on Hg0 oxidation were investigated using a link tooth wheel-cylinder reactor energized by di erent high voltage power supplies. Negative DC discharge induced more ozone production and a higher Hg0 oxidation e ciency than positive DC discharge and 12 kHz AC discharge. The discharge tooth wheel number had almost no e ect on the maximum Hg0 oxidation e ciency. The allowable supplied voltage decreased with the increase of discharge tooth wheel number. CO2 could stabilize the discharge process and increase the maximum voltage for a stable discharge. It has also been found that NO consumed O3 induced by high voltage discharge, thereby decreased Hg0 oxidation e ciency; while SO2 had a slight promoting e ect on Hg0 oxidation.     

UV/氯联合处理含溴溶液中溴酸根的生成

研究了UV和氯联合作用下溴酸根离子(BrO^-₃)在低浓度含溴溶液中的生成,旨在探讨pH、次氯酸钠(NaOCl)浓度、溶解氧(DO)、光强和温度等因素对其生成的影响.研究表明,暗反应条件下H₂O-NaOCl-Br^-体系较稳定,而UV照射可使游离氯浓度持续降低,同时伴有部分Br^-（6 .6%～32%）被氧化成BrO^-₃离子;pH、温度和光强恒定时余氯的分解可用拟一级反应速率方程拟合;实验条件下（I为610～1 896 μW/cm²,T为12 .2～36 .1℃）,拟一级反应速率常数分别与体系温度和光强值有线性关系;BrO^-₃的生成大致可以分为快速、慢速和平缓3个阶段;在慢速生成阶段,BrO^-₃的生成量与余氯的分解量有良好的线性关系（绝大部分相关系数在0 .96以上）;实验范围内（pH为4 .41～11 .07,DO为1 .5～9 　mg/L,Cl₂为1 .23～4 .50 　mg/L）,低pH、低DO和高初始NaOCl（以氯计）浓度有利于溴酸根的生成,提高温度与光强均不同程度提高溴酸根生成速度,但同时因加速余氯的分解而减少了溴酸根的总生成时间.     

镍基催化剂的制备及其对垃圾气化产氢的催化活性

以陶粒为载体,采用常温浸渍法制备了负载型镍基催化剂,并利用X射线衍射分析(XRD)、X射线荧光分析(XRF)、BET、环境扫描电镜-能谱仪分析(ESEM-EDX)和元素分析等对其进行了表征,该催化剂BET表面积为101.3m2/g.活性组分NiO颗粒平均粒径约为2μm,均匀分散在载体表面.并在下吸式固定床气化炉中,进行水蒸气催化气化城市生活垃圾有机组分的实验来评价镍基催化剂的催化活性.结果表明,在镍基催化剂的作用下,H2和CO含量明显增加,H2含量最高达43.22%,CO2、CH4、C2H4和C2H6.平均含量降至1%以下.催化气化过程的产氢率远远高于气化过程,最高达19.9mol H2/kg,低温段催化气化的潜在产氢率高于气化过程,但高温段低于气化过程;高温有利于气化产气中H2和CO的生成,还可以促进CH4、C2H4和C2H6的分解.催化气化过程的焦油产率、灰渣产率明显低于气化过程,特别是焦油产率降至2%以下,而产气率则高于气化过程.