CPC/CaO2氧缓释复合材料的制备及其释氧性能探讨

利用过氧化钙（CaO2）遇水释放氧气的特性,采用混合法将CaO2载入到磷酸钙骨水泥（CPC）中,并通过挤出-滚圆造粒方法制备出CPC/CaO2氧缓释复合材料,旨在为污染地下水的好氧生物修复技术提供一种长期、高效的供氧源。由X射线衍射（XRD）分析可知,通过固相反应制取的CPC主要成分为Ca5（PO4）3（OH）和Ca10（PO4）6（OH）2,具有较快的固化时间和固化效果;CPC/CaO2氧缓释复合材料分3个阶段进行释氧,其中2、3阶段分别符合一级和零级释氧动力学特征,且其释氧速率和释氧周期得到明显改善。本研究成果可用于实际地下水修复工程,解决污染地下水原位生物修复过程中溶解氧（DO）的输送问题。     

地下水修复系统中释氧材料的改进及pH调控

在采用释氧材料的地下水污染修复系统中,释氧材料提供溶解氧的同时,往往造成体系pH的升高。针对这一问题,将过氧化钙(CaO2)、水泥、河沙、膨润土和KH2PO4按一定比例混合在一起制作了3种释氧材料,并在柱实验中观测了不同释氧材料对水体溶解氧(DO)及pH值的影响。实验数据表明,水泥对释氧材料的缓释作用明显,有助于保证释氧速率平稳,避免由于释氧材料反应过快所带来的高pH问题;在释氧材料中添加一定量KH2PO4(质量分数小于10%),可以起到缓冲体系pH值的作用,并且不会造成修复系统磷污染;电气石具有降低溶液高pH值的作用,以粒径为1～2 mm的电气石作缓冲介质可以将体系pH值由11.3降至10.2。     

聚乙烯/CaO复合材料在堆肥条件下的降解性能初探

以光钙型环境友好塑料——聚乙烯(PE)/CaO复合材料作为研究对象,通过自制的污泥堆肥与材料老化综合反应器,利用扫描电镜(SEM)与傅立叶红外光谱(FTIR)分析仪对比研究了其在高温好氧堆肥条件下的降解情况。结果表明,PE/CaO复合材料在受控高温好氧堆肥条件下,具有比纯PE材料更优的可堆肥性能。PE/CaO复合材料的CaO颗粒能吸收堆肥环境中的H2O和CO2而生成相应的产物Ca(OH)2或CaCO3,发生涨大与脱落,从而使复合材料的表面产生孔洞,而这些孔洞不仅增大了材料与环境的接触面积,同时更为降解细菌进入材料内部提供了通道,大大加速了材料的降解速度。     

地下水PRB原位生物修复中一种释氧材料的改进技术及效果分析

释氧材料经济有效的释氧是地下水原位生物修复的关键因素。实验通过在释氧材料中加入膨润土、磷酸二氢钾和硫酸铵等,改进释氧材料的性能。柱实验结果显示,该释氧材料释氧速率缓慢,释氧时间长,可以使溶液中DO长期保持在5 mg/L以上;另外,释氧材料中添加的缓冲剂及天然含水层介质对pH值有较好的缓冲作用,可以使pH值达到后续生物修复的要求。     

改性剂协同热脱附多环芳烃污染土壤效率提升研究

通过对多环芳烃(PAHs)污染土壤的异位热脱附实验，探究了碱基类(Ca(OH)₂、CaO、NaOH)、氧化类(过硫酸钠、过氧化苯甲酰、过碳酸钠)和其他类(FeCl₃、CuCl₂、颗粒活性炭)改性剂对PAHs热脱附效率的提升作用，优选最佳改性剂及配比。3类改性剂的优选结果为2.0%(质量分数，下同)Ca(OH)₂、5.0%过氧化苯甲酰和5.0%FeCl₃。添加2.0%Ca(OH)₂在300℃下脱附10 min、添加5.0%过氧化苯甲酰在200℃下脱附60 min或添加5.0%的FeCl₃在150℃下脱附60 min均可使各PAHs组分残留量达到《场地土壤环境风险评价筛选值》(DB11/T 811—2011)的修复标准。添加2.0%Ca(OH)₂对土壤PAHs热脱附去除效果最好，300℃下PAHs热脱附去除率最高，可达96.31%,而5.0%过氧化苯甲酰对PAHs热脱附去除率提升更明显。     

不同Ca/P比下碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟污水处理厂污泥厌氧消化液为处理对象,进行磷酸钙沉淀除磷小试实验,考察了不同Ca/P物质的量比下碳酸根(CO2-3)对磷酸钙沉淀反应回收磷的影响;利用扫描电镜(SEM)、X射线衍射仪(XRD)和傅里叶变换红外光谱(FTIR)对沉淀产物进行表征。结果表明,磷酸钙沉淀反应是一个快速过程,CO2-3的存在并未改变这一显著特征。磷酸钙沉淀反应过程中,CO2-3的存在降低了磷的去除率,改变了沉淀物形貌、结构和组分;实验设定范围内,磷酸钙的过饱和度越高,越难形成晶体态羟基磷灰石((Ca5(PO4)3OH,HAP);当pH值为9.0,Ca/P比为1.67时,CO2-3取代HAP晶格中的PO3-4,形成碳磷灰石(CHAP);当pH值为9.0,Ca/P比为3.33和5.01时,CO2-3和PO3-4之间竞争,形成碳酸钙(CaCO3);增大Ca/P能有效提高磷的去除率,降低CO2-3对磷酸钙沉淀反应的抑制作用,但综合考虑实际效果,选择Ca/P比为3.33作为适宜的反应条件。     

污泥回流比对厌氧/好氧工艺除磷效果影响的研究

以长距离输送的合流制污水为进水,考察不同污泥回流比下厌氧/好氧(A/O)工艺对COD、N、P的去除效果,深入研究污泥回流比对生物除P代谢过程的影响.结果表明,污泥回流比对COD及NH+4-N的去除没有明显影响,但对TN、TP、PO3-4-P的去除影响较大.随着污泥回流比的增大,聚磷菌(PAO)的厌氧释P量逐渐减小,P的去除率逐渐降低.减小污泥回流比,可延长A/O工艺厌氧池实际HRT,增加PAO在厌氧池可有效利用的碳源,使PAO在厌氧池充分释P,从而提高除P效率.     

复合介质渗透反应格栅去除地下水中的氨氮

针对受低浓度氨氮污染的地下水,实验筛选组合了不同的反应介质,利用串联的多介质填充柱模拟渗透反应格栅,通过物理吸附及生物硝化-反硝化作用来实现氮的去除。结果表明,在进水氨氮浓度为10 mg/L、流速为0.5 m/d的条件下,模拟柱对氨氮的去除率达到98%以上,且不会出现亚硝酸盐及硝酸盐浓度的升高。水体经过释氧柱后溶解氧由2mg/L升高至10 mg/L以上,表明释氧材料可提供硝化细菌所需的好氧环境。好氧柱中填充易于生物挂膜的生物陶粒及对氨氮有较强吸附能力的沸石,二者联用通过生物硝化-物理吸附协同作用实现对氨氮的去除,其中生物作用实现的氨氮去除量占总去除量的50%左右。后续厌氧反应柱填充海绵铁除氧并利用松树皮颗粒作为碳源,创造反硝化菌生长条件,硝酸盐氮浓度可由10 mg/L降低至5 mg/L以下,实现对好氧反应阶段所产生的硝酸盐的去除,避免了地下水的二次污染。     

电厂脱硫灰烧成硫铝酸盐水泥的试验研究

电厂脱硫灰由于成分复杂和高硫高钙的特点,为其综合利用造成了很多困难.试验证明,只需添加部分CaO或CaCO2,用脱硫灰作生料即可在1 300℃左右烧成硫铝酸盐水泥.这种方式可以完全利用脱硫灰中的游离CaO,CaCO3,Ca(OH)2和含硫矿物CaSO3与CaSO4,使其转化为水泥熟料矿物,如硫铝酸钙(Ca4Al6O12SO4)、硅酸二钙(Ca2SiO4)等,还能完全利用脱硫灰中的未燃烬碳,因而能达到物尽其用,是一种全新高效的利用方式,具有广阔的应用前景.     

曝气与投加NaOH对养猪废水厌氧消化液磷回收的影响

以养猪废水厌氧消化液为对象,通过批次实验比较曝气与投加Na OH 2种方式调节废水p H值对磷回收效率的影响,并进一步采用流化床反应器探讨Na OH调节条件下进水流量对氮磷回收的影响。实验结果表明:采用曝气可促使p H值在1 h内迅速升高至8.6;随着曝气时间不断延长,p H值缓慢增长,至12 h达9.1~9.2,此时正磷酸盐(PO3-4-P)回收率达87.25%。投加Na OH调节最佳p H值为9.5,PO3-4-P回收率为85.67%。容积为100 L的搅拌-上向流反应器实验结果表明,当进水流量分别为50、100和150 L/h,在100 L/h流量条件下达到最优,PO3-4-P回收率为80.22%。利用X射线衍射仪(XRD)和扫描电镜及能谱仪(SEM-EDS)对沉淀产物进行表征,可知沉淀产物中含有磷酸铵镁(MAP)和Ca CO3。     

无机抗菌剂在建筑涂料中的应用研究

研究了5种无机抗菌剂:锌型沸石抗菌剂、银型沸石抗菌剂、氧化锌晶须复合抗菌剂、纳米TiO2光催化抗菌剂和Ca10-x-yTixZny(PO4)6(OH)2复合抗菌剂在涂料中的应用。以对大肠杆菌(E.coli)的灭菌效果评价抗菌性能。结果表明:锌型抗菌涂料的抗菌效果较差,后4种类型抗菌涂料具有很好抗菌效果。但是,银型抗菌剂和氧化锌晶须复合抗菌剂在涂料中存在易引起涂料变色和难分散问题;纳米TiO2光催化型抗菌剂在涂料中易加快涂料老化;而Ca10-x-yTixZny(PO4)6(OH)2复合抗菌剂既具有良好的抗菌性能,又对涂料的基本性能没有影响,它能够应用到抗菌涂料中。     

Laboratory column studies for evaluating a barrier system for providing oxygen and substrate for TCE biodegradation

The industrial solvent trichloroethylene (TCE) is among the most ubiquitous chlorinated compounds found in groundwater contamination. The objective of this study was to develop a biobarrier system containing oxygen-organic releasing material to enhance the aerobic cometabolism of TCE in situ. The oxygen-organic material, which contains calcium peroxide and peat, is able to release oxygen and primary substrates continuously upon contact with water. Batch experiments were conducted to design and identify the components of the oxygen-organic releasing material, and evaluate the oxygen and organic substrate (presented as COD equivalent) release from the designed oxygen-organic material. The observed oxygen and chemical oxygen demand (COD) release rates were approximately 0.0246 and 0.052 mg/d/g of material, respectively. A laboratory-scale column experiment was then conducted to evaluate the feasibility of this proposed system for the bioremediation of TCE-contaminated groundwater. This system was performed using a series of continuous-flow glass columns including a soil column, an oxygen-organic material column, followed by two consecutive soil columns. Aerobic acclimated sludges were inoculated in all three soil columns to provide microbial consortia for TCE biodegradation. Simulated TCE-contaminated groundwater with a flow rate of 0.25 l/day was pumped into this system. Effluent samples from each column were analyzed for TCE and other indicating parameters (e.g., pH, dissolved oxygen). Results show that the decreases in TCE concentrations were observed over a 4-month operating period. Up to 99% of TCE removal efficiency was obtained in this passive system. Results indicate that the continuously released oxygen and organic substrates from the oxygen-organic materials enhanced TCE biotransformation. Thus, the biobarrier treatment scheme has the potential to be developed into an environmentally and economically acceptable remediation technology.     

Numerical modeling of oxygen exclusion experiments of anaerobic bioventing

A numerical and experimental study of transport phenomena underlying anaerobic bioventing (ABV) is presented. Understanding oxygen exclusion patterns in vadose zone environments is important in designing an ABV process for bioremediation of soil contaminated with chlorinated solvents. In particular, the establishment of an anaerobic zone of influence by nitrogen injection in the vadose zone is investigated. Oxygen exclusion experiments are performed in a pilot scale flow cell (2 x 1.1 x 0.1 m) using different venting flows and two different outflow boundary conditions (open and partially covered). Injection gas velocities are varied from 0.25 x 10(-3) to 1.0 x 10(-3) cm/s and are correlated with the ABV radius of influence. Numerical simulations are used to predict the collected experimental data. In general, reasonable agreement is found between observed and predicted oxygen concentrations. Use of impervious covers can significantly reduce the volume of forcing gas used, where an increase in oxygen exclusion efficiency is consistent with a decrease in the outflow area above the injection well.     

Degradation of 2,4,6-trinitrotoluene in water and soil slurry utilizing a calcium peroxide compound

The degradation of 2,4,6-trinitrotoluene was examined in pure water and contaminated soil slurry using calcium peroxide as a source of solid hydrogen peroxide and oxygen. The extent of TNT oxidation was compared with that obtained by using hydrated lime, which is normally generated by slurrying CaO2 in water and contained in CaO2 technical formulation (approximately 50%, w/w). Complete TNT degradation occurred between 280 min, 0.1% CaO2/Ca(OH)2 and 20 min, 1% CaO2/Ca(OH)2. A large part of the generated oxidation products, 80-90%, were absorbed on the solid calcium hydroxide, whereas the remaining 10-20% was detected in solution until 48 h. Removal of nitro groups was extremely effective in CaO2 slurry, where all the nitrogen (3 mol per mol of TNT) was removed from TNT within 240 min. Respect to calcium hydroxide, the peroxy compound liberated H2O2 in solution, 370 mg l-1 at 0.2% CaO2, w/v, which then decomposed within 480 min. Most of the 14C-TNT was retained more strongly on the calcium hydroxide generated by slurrying CaO2. This pool remained adsorbed on the solid until pH dropped below 5.8. The treatment of a contaminated soil slurry, 700 mg TNT kg-1, reduced CH3CN extractable TNT below 20 mg kg-1 at very low concentration of CaO2/Ca(OH)2, approximately 0.2%, w/w. Both oxidants do not lead to soil sterilization as the phosphorus added to neutralize the pH serves as a source of nutrient for the soil biomass.     

复合赤泥在高浓度含磷废水处理中的应用

赤泥与石灰粉（CaO和Ca（OH）₂）按不同比例混合制成复合赤泥,通过投加实验考察了复合赤泥的除磷效果。结果证明,对于磷酸盐浓度为45 000 mg/L左右（以P计）的酸性工业废水,复合赤泥（赤泥与Ca（OH）₂按质量比1：1混合）投加量为240 g/L,去除率为99.97%;对于10 mg/L左右的含磷废水,赤泥的最佳投加浓度为15 g/L,上清液磷浓度可降至0.30 mg/L,出水低于0.5 mg/L的排放标准。根据以上研究结果,提出了对高浓度酸性磷酸盐废水的处理宜采用复合赤泥再加原状赤泥的二级处理方法。     

The fate of hydrogen peroxide as an oxygen source for bioremediation activities within saturated aquifer systems

In situ bioremediation is an innovative technique for the remediation of contaminated aquifers that involves the use of microorganisms to remediate soils and groundwaters polluted by hazardous substances. During its application, this process may require the addition of nutrients and/or electron acceptors to stimulate appropriate biological activity. Hydrogen peroxide has been commonly used as an oxygen source because of the limited concentrations of oxygen that can be transferred into the groundwater using above-ground aeration followed by reinjection of the oxygenated groundwater into the aquifer or subsurface air sparging of the aquifer. Because of several potential interactions of H2O2 with various aquifer material constituents, its decomposition may be too rapid, making effective introduction of the H2O2 into targeted treatment zones extremely difficult and costly. Therefore, a bench-scale study was conducted to determine the fate of H2O2 within subsurface aquifer environments. The purpose of this investigation was to identify those aquifer constituents, both biotic and abiotic, that are most active in controlling the fate of H2O2. The decomposition rates of H2O2 were determined using both equilibrated water samples and soil slurries. Results showed H2O2 decomposition to be effected by several commonly found inorganic soil components; however, biologically mediated catalytic reactions were determined to be the most substantial.     

Phosphate removal and recovery with a synthetic hydrotalcite as an adsorbent

Phosphate removal is important to control eutrophication and an ion exchange process is one of several treatment processes for this purpose. Hydrotalcite compounds (HTALs) are useful as adsorbents for phosphate removal because of their ion exchange properties. In this study, the adsorption properties of a granular synthetic HTAL for phosphate and the method of regeneration of the granular HTAL were examined. The adsorption isotherm of the granular HTAL was approximated by a modified Langmuir type, and the maximum adsorption capacity was 47.3 mg P g(-1), which corresponded to the content of HTAL in the granular one. Phosphate adsorbed on the HTAL was effectively desorbed with alkaline NaCl solutions and the HTAL was regenerated with 25 w/v% MgCl(2) solution. The regenerated HTAL could be reused repeatedly for the phosphate removal. Phosphate in the exhausted desorption solution was recovered as a precipitate of calcium phosphate by addition of CaCl(2), and the residual exhausted desorption solution could be also reused after supplying NaOH. The results suggest the possibility of an effective system for phosphate removal and recovery, which includes the following processes: adsorption, desorption, recovery of phosphate, and regeneration of the HTAL and the desorption solution.