Delignification of disposable wooden chopsticks waste for fermentative hydrogen production by an enriched culture from a hot spring

Hydrogen(H2) production from lignocellulosic materials may be enhanced by removing lignin and increasing the porosity of the material prior to enzymatic hydrolysis. Alkaline pretreatment conditions,used to delignify disposable wooden chopsticks(DWC) waste, were investigated. The effects of NaOH concentration, temperature and retention time were examined and it was found that retention time had no effect on lignin removal or carbohydrate released in enzymatic hydrolysate. The highest percentage of lignin removal(41%) was obtained with 2% NaOH at 100℃, correlated with the highest carbohydrate released(67 mg/gpretreated DWC) in the hydrolysate. An enriched culture from a hot spring was used as inoculum for fermentative H2 production, and its optimum initial pH and temperature were determined to be 7.0 and 50℃, respectively. Furthermore, enzymatic hydrolysate from pretreated DWC was successfully demonstrated as a substrate for fermentative H2 production by the enriched culture. The maximum H2 yield and production rate were achieved at 195 mL H2/g total sugarsconsumedand 116 mL H2/(L·day), respectively.     

Ce-Mn/Al2O3-H2O2催化氧化皮革废水的研究

以浸渍法制备了Ce-Mn/Al_2O_3催化剂,研究该催化剂在H_2O_2非均相类Fenton体系中对皮革废水污染物的催化降解性能.在单因素试验的基础上,以COD去除率为响应值,采用Box-Behnken响应曲面法考察了催化剂投加量、H_2O_2投加量、初始pH、反应时间等4个因素之间的单独作用及交互作用,实验数据用Design-Expert 8.0.6软件进行处理,得到二次响应曲面模型.结果表明,4个独立变量对响应值的影响顺序如下:初始pHH_2O_2投加量催化剂投加量反应时间,数学模型拟合度高(R_(adj)~2=0.9349),利用该模型预测的最大COD去除率为78.86%,最佳反应条件为:催化剂投加量56.63 g·L~(-1),H_2O_2投加量315.15 mg·L~(-1),初始pH3.51,反应时间2 h,经实验验证COD去除率为80.94%,与模型预测值偏差2.08%.     

Removal of phosphorus and sulfur from yellow phosphorus off-gas by metal-modified activated carbon

In order to provide comprehensive utilization of high concentration CO for mono-carbon (C1) chemical industry, the purification of yellow phosphorus off-gas is of great concern. In this research, activated carbon (AC) modified by different impregnants were used for removal of PH₃, H₂S, SO₂, COS, and CS₂ in yellow phosphorus off-gas. For the removal of PH₃, AC impregnated with 0.10 mol L⁻¹ CuAc₂ was proved to be the best adsorbent. And removal efficiency of H₂S could be significantly enhanced by AC impregnated with 7% Na₂CO₃. The results of plant experiments suggested that the total concentration of the impurities in yellow phosphorus off-gas was less than 1 mg Nm⁻³ after purification operation. The metal-modified activated carbon (MMAC) was systematically characterized in terms of XPS, TGA, and DTA. The adsorption reaction mechanism was also investigated. As a result, the yellow phosphorus off-gas purified in this study can be used as a raw material gas in the C1 chemical industry.     

Identical full-scale biogas-lift reactors (BLRs) with anaerobic granular sludge and residual activated sludge for brewery wastewater treatment and kinetic modeling

Two identical full-scale biogas-lift reactors treating brewery wastewater were inoculated with different types of sludge to compare their operational conditions, sludge characteristics, and kinetic models at a mesophilic temperature. One reactor （R1） started up with anaerobic granular sludge in 12 weeks and obtained a continuously average organic loading rate （OLR） of 7.4 kg chemical oxygen demand （COD）/（m3.day）, COD removal efficiency of 80%, and effluent COD of 450 mg/L. The other reactor （R2） started up with residual activated sludge in 30 weeks and granulation accomplished when the reactor reached an average OLR of 8.3 kg COD/（m^3·day）, COD removal efficiency of 90%, and effluent COD of 240 mg/L. Differences in sludge characteristics,biogas compositions, and biogas- lift processes may be accounted for the superior efficiency of the treatment performance of R2 over R1. Grau second-order and modified StoverKincannon models based on influent and effluent concentrations as well as hydraulic retention time were successfully used to develop kinetic parameters of the experimental data with high correlation coefficients （R2 〉 0.95）, which further showed that R2 had higher treatment performance than R1. These results demonstrated that residual activated sludge could be used effectively instead of anaerobic granular sludge despite the need for a longer time.     

曝气生物滤池(Fe2+)-臭氧组合工艺强化处理石化二级出水

为了强化曝气生物滤池(BAF)-臭氧组合工艺的处理效果,以石化二级出水为处理对象,研究了投加Fe SO_4·7H_2O对组合工艺处理COD和TP效果的影响,同时采用分子量分级、三维荧光扫描、气相色谱-质谱联用仪(GC-MS)等手段对工艺处理前后水质进行了系统分析.结果表明,在二级出水COD平均浓度82.91 mg·L~(-1),TP平均浓度1.37 mg·L~(-1),Fe SO_4·7H_2O投加浓度为9 mg·L~(-1)时,组合工艺COD平均去除率为52.20%,TP平均去除率为71.50%,相比不加Fe SO_4·7H_2O的对照组,COD去除率提高17.15%,除磷效率提高51.81%.原水中相对分子质量小于1×103的有机物占52%,铁盐强化组合工艺处理后该部分比例增加至75.39%;同时各区间分子量的有机物去除效率提高.三维荧光分析结果表明,Fe SO_4·7H_2O可以提高BAF-臭氧对水中荧光类物质的去除效果.GC-MS结果表明,与对照组相比,Fe SO_4·7H_2O的投加使得出水中有机物的种类减少,浓度降低.铁盐可以强化BAF-臭氧组合工艺处理石化二级出水的能力.     

Fe2+-H2O2法处理DSD酸生产氧化母液的研究

为改善DSD酸氧化母液的可生化降解性,将废液先用有机絮凝剂TS-1(一种季胺盐)处理,TS-1的投加量为3g/L,其后用Fe²⁺-H₂O₂法氧化,Fe²⁺和H₂O₂的量分别为150mg/L,7g/L,废液COD和色度的去除率分别可达64%和62%。经处理后的废水,其BOD₅/COD≈0.3,可以认为已达到生化处理的要求。当H₂O₂的投量为2g/L,经Fe²⁺-H₂O₂氧化处理后的废液,再用FeCl₃进行两级混凝处理(FeCl₃的投加量分别为5g/L和2g/L),则COD和色度的去除率可达90%和95%。     

基质COD浓度对单室微生物电解池产甲烷的影响

单室微生物电解池(microbial electrolysis cells,MEC)产甲烷过程中,底物COD浓度可同时影响阳极和阴极微生物的活性.为了探究COD浓度的影响,构建生物阴极型单室MEC,比较COD为700、1 000、1 350 mg·L-1情形下产甲烷速率和COD去除量随外加电压的变化规律,并计算MEC的能量效益.结果表明,随着COD的增加,产甲烷速率和COD去除量均呈增大趋势.随着外加电压的升高(0.3~0.7 V),低COD条件下MEC的产甲烷速率呈增大趋势,而在中、高COD条件下,产甲烷速率随着外加电压的升高先增大后减小;COD去除量的变化规律与产甲烷速率一致.当外加电压为0.5 V时,阴极电势降至最低值(-0.694±0.001)V,有利于产甲烷菌的富集,从而获得最高的产甲烷速率和能量回收率(约42.8%).COD浓度1 000mg·L-1和外加电压0.5 V时,MEC可获得最大的能量收益0.44 k J±0.09 k J(约1 450 k J·m-3).最终结果表明,MEC可利用低浓度COD废水生产甲烷,并且可获得正的能量效益,这为废水中化学能量的回收利用提供了新的研究思路.     

石墨烯掺杂分子筛负载氧化铁芬顿催化降解苯酚影响因素的研究

通过水热晶化法制备了石墨烯掺杂介孔分子筛MCM-41复合载体,利用该载体浸渍负载氧化铁制备了非均相芬顿催化剂gh-MCM-41-Fe.以苯酚为模拟有机废水,考察了催化剂和H2O2投加量、水质因素(苯酚初始浓度、反应温度和水中腐殖酸和草酸)等对gh-MCM-41-Fe芬顿催化降解苯酚效能的影响.结果表明,当苯酚初始浓度为100 mg·L-1,催化剂在60 min催化降解苯酚去除率高达97.6%,COD去除率为65.9%,反应符合准一级反应动力学模型;苯酚降解速率随着催化剂和H2O2投加量的增加而增加,但投加过多会消耗·OH自由基从而不利苯酚降解过程;苯酚初始浓度从10 mg·L-1增至100 mg·L-1,苯酚降解速率相应降低,但体系中H2O2及·OH自由基的有效利用率反而增加;反应温度对于苯酚废水降解率和COD去除率影响不大,反应表观频率因子为105.68 min-1,表观活化能为18.43 k J·mol-1;腐殖酸和草酸对苯酚废水降解和COD去除均有抑制作用.     

改性活性碳纤维电芬顿降解苯酚废水性能研究

采用微波改性、硝酸改性、磷酸改性及氨水改性等方法改性活性碳纤维(ACF-0),依次标记为ACF-1、ACF-2、ACF-3和ACF-4.以改性前后的活性碳纤维为阴极,电芬顿催化处理苯酚模拟废水,考察不同的改性方法对H2O2生成量、COD去除率、苯酚去除率及其中间产物的影响.结果表明,微波改性活性碳纤维的吸附性能及电催化活性最优,相比未改性活性碳纤维,经微波或酸碱改性后的活性碳纤维反应体系中,H2O2生成量均有所增加.苯酚在各电芬顿催化体系中的去除率大小依次是:ACF-1>ACF-3>ACF-4>ACF-2>ACF-0;COD去除率大小依次是:ACF-1>ACF-4>ACF-3>ACF-2>ACF-0,说明微波及酸碱改性有利于提高活性碳纤维的催化性能.此外,苯酚降解中间产物的生成也会受到改性方法的影响.     

介质阻挡放电等离子协同TiO_2-GAC降解甲基橙的研究

采用介质阻挡放电(DBD)等离子协同颗粒活性炭负载TiO2(TiO2-GAC)对甲基橙进行降解,研究了该体系的协同处理效果,探讨了放电电压、初始pH、初始电导率、初始浓度和TiO2-GAC投加量等操作参数的影响,并建立了协同体系的表观反应动力学模型.实验结果表明,DBD与TiO2-GAC联合处理表现出明显的协同效应,处理25min后,协同体系对甲基橙的降解率和COD去除率分别为96.2%和90%,与单独DBD体系相比,分别提高了52.7%和50.4%;协同体系降解甲基橙的过程符合表观反应动力学模型,模型值与实验值吻合良好,总级数为2.352;体系中H2O2、O3浓度测定结果表明,与单独DBD体系对比,协同体系的H2O2浓度增高,而O3浓度降低,说明TiO2-GAC起到了催化作用;TiO2-GAC在DBD体系中获得了原位再生,五次再生循环后再生率达80%.     

厌氧膜生物反应器耦联部分亚硝化/厌氧氨氧化用于污水处理研究

本研究构建了厌氧膜生物反应器（AnMBR）-部分亚硝化/厌氧氨氧化（PN/Anammox）污水处理工艺,以探究AnMBR-PN/A工艺处理效果最佳的水力停留时间（HRT）.AnMBR将厌氧生物处理与膜分离技术相结合实现有机物去除,AnMBR出水NH₄⁺-N通过PN部分转化为NO₂^--N,最终通过NO₂^--N氧化剩余NH₄⁺-N去除.实验结果表明：在HRT=11.2 h时,AnMBR-PN/A工艺化学需氧量（COD）去除率稳定在97%以上,COD转化为CH₄效率超过77.5%,总氮（TN）去除率为78%,出水COD和TN浓度分别低于14和11 mg·L^-1.AnMBR段COD去除率达到95%,平均甲烷产率为0.39 L·L^-1·d^-1.PN段实现了NO₂^--N的高效积累,其出水中NO₂^-/NH₄⁺为0.91±0.11.Anammox段出水中的NO₂^--N、NH₄⁺-N和NO₃^--N浓度分别低于1.0、4.9和5.1 mg·L^-1.高通量测序结果表明PN段氨氧化菌主要为Nitrosomonas,丰度为7.09%,Anammox段主要微生物为Candidatus Brocadia,丰度高达21.01%.本研究构建的AnMBR-PN/A工艺实现了污水处理过程的高效能源回收和深度自养脱氮,研究成果为工程应用提供了理论支撑.     

响应面法分析卫生填埋渗滤液的Fenton处理过程

利用响应面法研究了Fenton试剂处理卫生填埋渗滤液过程中诸因素对COD去除率的影响,如渗滤液中高分子量有机物(HMWOM)与低分子量有机物(LMWOM)的TOC比例、LMWOM浓度以及双氧水和亚铁离子的摩尔比(H₂O₂/Fe²⁺).其中HMWOM/LMWOM值、LMWOM浓度和H₂O₂/Fe²⁺摩尔比值的高、低水平分别为14～38,975～3000 mg/L,1.75～4.00.由实验数据得到了1个2次响应曲面模型,该模型显示COD的去除率随着HMWOM/LMWOM值的增加而增加,但随着LMWOM浓度的增加而降低.Fenton试剂处理卫生填埋渗滤液存在着一个最佳的H₂O₂/Fe²⁺摩尔比值,COD去除率在该点能达到最高.     

UV/TiO2/H2O2体系对制药废水二级出水的处理特性研究

以某制药企业的二级出水为研究对象,对比了UV/TiO₂、UV/H₂O₂、UV/TiO₂/H₂O₂ 3种高级氧化工艺的处理效果,利用自主设计的一体化光催化装置进行了连续动态试验,并通过凝胶渗透色谱（GPC）、傅里叶变换红外光谱（FT-IR）、三维荧光光谱（EEM）、斑马鱼急性毒性试验等方法研究了处理前后有机物特性和生物毒性的变化.结果表明,与UV/TiO₂和UV/H₂O₂体系相比,UV/TiO₂/H₂O₂光芬顿体系对有机物的去除效果更好,当TiO₂投加量为1 g·L^-1,H₂O₂投加量为100 mg·L^-1时,处理效果达到最佳.一体化光催化装置能够利用UV/TiO₂/H₂O₂光芬顿技术快速高效地降解二级出水中的有机污染物,反应30 min时COD去除率达到50%以上.经UV/TiO₂/H₂O₂深度处理后,废水中的大分子有机物分解转换为小分子,有机物中的不饱和结构明显减少,腐殖质等溶解性有机物基本降解完全.毒性试验结果表明,该二级出水的生物毒性经深度处理后显著降低,对斑马鱼胚胎不存在致畸致死效应.     

微膨胀对好氧颗粒污泥脱氮过程中N2O产生量的研究

采用控制低溶解氧(DO)在SBR反应器内,研究了好氧颗粒污泥微膨胀的实现;考察了微膨胀颗粒污泥对COD和氨氮去除效能以及温室气体N2O产生量.结果表明,在低DO条件下可以获得微膨胀颗粒污泥,污泥容积指数(SVI)大都在150～250 mL.g-1之间.微膨胀颗粒污泥对COD和氨氮去除量影响不大,COD去除率从89.45%上升到90.99%;氨氮去除率从77.29%降至68.29%;硝化速率从38.95×10-3 mg.(g.min)-1降至33.46×10-3 mg.(g.min)-1.微膨胀颗粒污泥对N2O产生量影响很大,微膨胀颗粒污泥N2O产生量为2.42 mg.m-3是没有发生微膨胀颗粒污泥N2O产生量的1.26倍.微膨胀颗粒污泥N2O释放速率由3.63×10-3mg.(L.min)-1上升到4.72×10-3mg.(L.min)-1.     

改性污泥基吸附剂深度处理出水有机物的研究

本研究通过对污泥热解碳化,并负载传统的混凝剂制成改性污泥基吸附剂（Modified Sludge-Based Adsorbents, MSBAs）,用来深度处理超短污泥龄活性污泥工艺出水有机物（COD）.同时,以总有机物（TCOD）和溶解性有机物（SCOD）去除率及处理前后各类有机物组分特征变化为指标,评价MSBAs深度处理出水中有机物的效果及处理后污水中有机物的潜在风险.结果表明,改性后的污泥基吸附剂均有较好的有机物吸附效果,TCOD的去除效率可达到32.6%以上,其中,Fe₂（SO₄）₃改性制备的污泥基吸附剂对有机物的去除能力最大,TCOD最大的去除效率为42.5%,其中,SCOD最大的去除效率为44.1%.有机物特征分析结果显示,4种MSBAs对污水中疏水酸性有机物（HPO-A）有较好的去除效果,且处理后污水中有机物芳香构造化程度增加,稳定性增加,污水消毒副产物的产生可能性大大降低.     

预处理方法对玉米芯作为反硝化固体碳源的影响

分别用1.5%NaOH、1%H2SO4、1.5%H2O2和碱性双氧水(含有1.5%H2O2的NaOH溶液)并联合紫外照射对玉米芯进行预处理,将预处理后玉米芯作为反硝化固体碳源和微生物载体进行静态释碳和静态反硝化实验,考察预处理后玉米芯释碳、反硝化性能及微生物附着情况.结果表明,经过碱和碱性双氧水预处理后的玉米芯碳源可利用性和反硝化效率均有显著的改善,尤其是碱预处理方法,静态反硝化反应至41 d时,仍能保持90%以上的硝酸盐去除率.因此,碱预处理方法可以改善玉米芯释碳性能,有利于微生物的附着和碳源的利用.     

臭氧/活性炭/紫外光联用处理几种高浓度有机废水影响因素

以对硝基苯甲酸废水、鸟嘌呤废水、乙醛废水和乙醇胺废水为例,对臭氧/活性炭氧化去除废水中有机物的效果进行了初步研究,考察了臭氧投加量、pH值和紫外光等因素对臭氧/活性炭催化氧化高浓度有机废水的影响,并在最优条件下,验证了该工艺作为高浓度有机废水预处理手段,在去除废水中COD和提高可生化性(BOD5/COD)等方面的综合效果.结果表明,活性炭作为催化剂与臭氧共同作用,对对硝基苯甲酸废水COD的去除率明显高于单独臭氧氧化和活性炭吸附;臭氧/活性炭氧化对乙醛废水和乙醇胺废水这类短链类有机物降解作用不大,但对硝基苯甲酸废水、鸟嘌呤废水这些含有苯环类、长链类的有机物,去除效率较高;在中性偏碱时,pH的提高有利于COD的去除,但过高pH对COD的降解效果反而有所减弱,pH=9.0是比较合适的;在紫外光催化的条件下,采用臭氧/活性炭氧化工艺处理对硝基苯甲酸废水,COD去除率可达到52%,废水的生化性(BOD5/COD)由原来的0.10提高到0.32,大大提高了废水的可生化性.     

Fenton氧化法预处理并提高垃圾渗沥液可生化性的研究

采用Fenton氧化法对垃圾渗沥液进行预处理.基于响应面法研究了Fenton氧化法对垃圾渗沥液的处理效能,考察了初始pH值、H_2O_2投加量和[H_2O_2]/[Fe~(2+)]摩尔比对TOC去除率的影响,并拟合了TOC去除率与三因素之间的回归方程.同时,通过三维荧光和凝胶色谱比较了Fenton处理前后渗沥液的可生化性.结果发现,渗沥液中类富里酸等难降解有机物得到有效去除,B/C比从0.1左右升至0.25.研究表明,Fenton氧化法可有效改善垃圾渗沥液的可生化性,为后续生物处理创造了条件.     

非均相催化臭氧处理高浓度制药废水的研究

非均相催化臭氧是一种对高浓度制药废水进行预处理的有效方法.本研究采用单一活性炭吸附、单一臭氧氧化和臭氧/活性炭联用3种体系对实际制药废水进行预处理,并对处理过程中的工艺参数进行优化.结果表明,相比单一活性炭吸附和单一臭氧降解体系,臭氧/活性炭联用体系能显著提高COD、TOC的去除率及BOD5/COD值,并显示出良好的协...     

Photo-catalytic CO2 reduction using sol–gel derived titania-supported zinc-phthalocyanine

Carbon dioxide was photo-catalytically reduced to produce formic acid in an aqueous solution using visible light irradiation. Titania and zinc-phthalocyanine (ZnPc)-loaded titania were synthesized by a sol–gel method and in situ chemical synthesis technique. The photo-catalytic reactions were conducted in a Pyrex reactor with a visible light irradiating. XRD and DRS revealed that ZnPc was on the TiO₂ surface. The optimum technique was in situ chemical synthesis and the optimum amount of ZnPc loading was 1.0 wt.% for the highest dispersion among catalysts. The formic acid yield of 1.0 wt.% in situ ZnPc/TiO₂ was 978.6 μmol/g catalyst following 10 h of visible light illumination and the conversion was 0.37%. The yield was higher than those of sol–gel TiO₂ and ZnPc/BH-1, whose yields were 321.0 and 756.2 μmol/g catalyst, respectively. Experimental results indicated that the formic acid yield was significantly increased by loading ZnPc. ZnPc has a higher selectivity than metal catalysts for the reduction of CO₂. The photo-catalytic efficiency of ZnPc/TiO₂ was markedly increased because of the lowering re-combination probability for hole–electron pairs.