添加剂升温烧蚀法在制备新型介孔水环境净化材料中的应用

首次探索了一种破坏式造孔与有机复合相结合的新方法以制备介孔复合水环境净化材料，使最终产品成为一种具有广谱孔结构分布的复合环境材料。详细介绍了该方法的第二步工艺即添加剂升温烧蚀法，在优化后的最佳条件下，产品的孔径得到了进一步扩大，其中部分孔道直径可达至介孔级，同时材料的表面得到了进一步活化。经此步工艺后，所制备的中间产品染料吸附量是原材料的19．4倍，是酸洗刻蚀后产品的12．2倍；24h吸湿率是原材料的3．8倍，是酸洗刻蚀后产品的1．9倍。     

镧改性介孔材料对砷、磷的吸附

为探究在复合污染条件下介孔吸附材料对砷、磷的去除效果,通过水热合成法制备镧金属改性介孔吸附材料(La-MCM-41),采用X-射线衍射(XRD)、比表面积测定(BET)、扫描电镜(SEM)等分析方法对改性前后的介孔吸附剂进行了表征;研究了介孔吸附剂在不同吸附体系中对砷、磷的降解效果、等温线及动力学。结果表明:La-MCM-41仍具有长程有序的六方相介孔结构,BET比表面积、总孔容均减小,平均孔径有所增加;介孔吸附剂在单独吸附体系下对砷、磷的吸附量大于同步吸附体系,且均符合二级反应动力学。通过分析可知,在2种体系下,改性后的介孔吸附剂极大地提高了对砷、磷的吸附量,是一种经济高效的吸附材料。     

金纳米颗粒的掺杂蛋白介孔硅原位合成及其对p-硝基苯酚的催化

基于介孔硅材料,在其表面掺杂牛血清白蛋白,构建了一种可实现贵金属纳米材料原位制备的蛋白掺杂介孔材料MCM-BSA。通过紫外、红外、吸脱附、透射电镜等表征手段,表明掺杂后的材料兼有蛋白和介孔硅2种特性。以MCMBSA为载体,即可原位还原氯金酸制备金纳米粒,获得负载金纳米粒的复合材料GNPs@MCM-BSA。以对硝基苯酚的催化还原为模型反应,考察了掺杂蛋白介孔硅负载的金纳米粒的催化性能,发现其具有很好的对硝基苯酚催化能力。更为重要的是,该复合材料可回收循环利用6次以上,对硝基苯酚的转化率都接近100%,表明掺杂蛋白介孔硅是一类性能优异的新型纳米晶载体,可应用于环境污染物的催化还原。     

介孔TiO2的制备及光催化降解有机染料的研究

以十六烷基三甲基溴化胺为模板剂,用溶胶-凝胶法制备了介孔TiO2,用x射线衍射、透射电子显微镜、热重/差热分析及氮气吸附等方法对其进行了分析表征,并用偶氮染料阳离子红X-GRL为目标污染物分析了它的光催化活性.实验结果表明,450℃热处理后的介孔TiO2是锐钛矿型的,平均孔径为18 nm.氮气吸附曲线呈典型的介孔材料Ⅳ型吸附等温线特征.由于介孔TiO2具有较大的比表面积,因此表现出比非介孔TiO2高的光催化活性.     

介孔铁锆复合氧化物的制备及其对Cr(Ⅵ)的吸附性能

以十六烷基三甲基溴化铵(CTAB)为模板剂,以铁(Fe)和锆(Zr)为原料,采用不同Fe/Zr摩尔比例,制备出Fe/Zr复合氧化物吸附剂,对吸附剂的比表面积、孔径分布、晶型结构和零点电位(PH2pc)进行了表征.筛选吸附容量最佳的Fe/Zr吸附剂,考察了吸附条件对其去除水中Cr(Ⅵ)效果的影响,探讨了吸附动力学和等温线规律.结果表明:最佳吸附剂的Fe/Zr摩尔比为5/1,具有典型的介孔材料结构特征;该吸附剂在pH为2～8范围内均有良好的除Cr(Ⅵ)效率;30min内即可达到吸附平衡,最大吸附容量为60.90 mg/g.介孔Fe/Zr复合氧化物与现有除Cr(Ⅵ)吸附剂相比具有更高的吸附能力,是一种具有较好应用潜力的水处理除Cr(Ⅵ)吸附剂.     

PVA-I修饰介孔TiO2光催化剂对盐酸四环素的光降解

水热法制备了PVA-I修饰的介孔TiO2催化剂,利用XRD、UV-Vis、BET和Zeta电位等手段对所制备的催化剂进行了表征。研究了改性的介孔TiO2在模拟太阳光下对盐酸四环素的光催化降解,考察了盐酸四环素的初始浓度、溶液的初始pH、共存离子对盐酸四环素光催化降解去除率的影响。实验结果表明,PVA-I修饰的TiO2催化剂为锐钛矿的介孔TiO2,比表面积190.22 m2/g,催化剂的等电点为3.92。PVA-I修饰的介孔TiO2催化剂在模拟太阳光下对TC光催化降解效率可达96.7%,比P25的催化效率提高1.23倍。NO3-、SO2-4和PO3-4对盐酸四环素的光降解有明显的抑制作用。     

基于蛋黄-蛋壳结构的Fe/FeS@SiO2材料去除水中三氯乙烯

针对硫化纳米零价铁(Fe/FeS)颗粒间的团聚以及环境适应性差的问题,用正硅酸乙酯(TEOS)为原料制备中空介孔氧化硅球,再通过化学反应在壳内形成大尺寸核的方法制备具有蛋黄-蛋壳结构的Fe/FeS@SiO_2材料以防止Fe/FeS的团聚并提高其活性,并将该材料用于三氯乙烯(TCE)的去除中;采用SEM和TEM观察、红外线光谱分析(FTIR)、X射线衍射分析(XRD)、X射线光电子能谱分析(XPS)等分析方法对材料进行了表征。结果表明,在Fe/FeS@SiO_2材料还原降解TCE的实验中,Fe/FeS@SiO_2去除TCE的最佳铁与硫的摩尔比(铁硫比)为30,并且在TCE初始浓度10 mg·L~(-1)溶液中投加含有0.1 g Fe~0、铁硫比为30的Fe/FeS@SiO_2材料下,反应180 min后,TCE的去除率为90.75%,与未包裹氧化硅壳时的去除率(66.06%)相比,去除效果明显提高。介孔氧化硅壳阻止了Fe/FeS的团聚,其表面上的孔道使得材料具有更大的比表面积,加强了对TCE的吸附,同时材料中的空腔使得核与污染物的接触增加,提高了TCE的去除率。表征结果表明,Fe/FeS@SiO_2材料具有特殊的结构,包括中心核、空腔以及介孔壳,可以防止Fe/FeS的团聚。     

废弃轮胎制备中孔炭吸附材料工艺及性能研究

为了解决废弃轮胎造成的资源浪费和环境污染的问题,对以废弃轮胎橡胶为碳的前驱体原料,制备具有高吸附性能中孔炭材料工艺进行了系统的研究。通过XRD、扫描电镜以及比表面积分析,对制备的中孔炭微观结构和性能进行表征,讨论了炭化温度、碱炭比,以及活化温度和活化时间等工艺条件对制备中孔炭的产率、结构和性能的影响。结果表明,通过改变工艺条件制备的中孔炭的孔径分布可以在2~80 nm范围内进行调控。在500℃炭化温度,碱炭比为4∶1,900℃活化1 h的工艺条件下,制备的中孔炭的比表面积为473 m2/g,对甲基橙的最大吸附量达到254 mg/g。     

基于IRMOF-1的介孔ZnO/C制备、表征及催化降解3种四环素类抗生素

以Zn(NO_3)_2·6H_2O与对苯二甲酸制备的网状金属有机骨架材料IRMOF-1为前驱体,在500、600、700℃下的N_2氛围中焙烧得到不同焙烧温度制备的介孔ZnO/C,分别记为ZnO/C-500、ZnO/C-600、ZnO/C-700,利用X-射线衍射、扫描电子显微镜、紫外—可见漫反射光谱、傅立叶变换红外光谱、比表面积分析等手段对其进行表征,并用于降解四环素(TC)、强力霉素(DC)和土霉素(OTC)。结果表明,制备的介孔ZnO/C为六方纤锌矿结构,纯度高。C的复合可以降低ZnO的禁带宽度,从而拓宽了ZnO的光谱吸收范围,提高ZnO对光的利用率。焙烧产物表面随焙烧温度的升高而变粗糙,—OH含量减少,但ZnO/C-700出现碎裂现象。因此,ZnO/C-600具有最大的BET比表面积(254.9m~2/g)和孔径(2.49nm)。ZnO/C-600对TC、DC和OTC的降解效果也是最好的,120min降解率分别达到98.2%、91.1%、80.7%,重复使用4次,其光催化降解性能基本保持不变,稳定性良好。     

单质硫改性介孔炭对水溶液中汞的吸附性能研究

对介孔炭CMK-3进行单质硫改性得到OMC-S，并通过静态吸附实验研究了该材料对水溶液中汞的吸附性能。研究结果表明：单质硫改性可以在介孔炭上负载12.33%的硫，从而使得介孔炭对汞的吸附容量从185 mg/g提高到476 mg/g；OMC-S具有较广的适用pH值范围，在pH 3～11.5范围内其对汞的吸附去除率均达到92%以上；氯离子对OMC-S的吸附性能具有一定的抑制作用，原因在于它能和汞离子络合形成一系列吸附性能较差的Hg-Cl络合物，而腐殖酸在所研究的范围内对OMC-S的吸附性能无明显影响。     

脱水污泥制备聚合物合成"木材"的研究

以污水处理厂脱水污泥和废塑料为主要原料 ,通过污泥处理、聚合物改性 ,采用热塑复合法可以制备出聚合物复合材料及对应的微孔材料 ,影响材料性能的主要因素有污泥形态、废塑料种类以及它们之间的质量比等参数。最终材料表现出木材的很多性能 ,是一种使污泥高附加值利用的有效方法。     

烟草下脚料发酵制取乙醇

通过单因素实验考察了硫酸浓度、固液比和水解时间对硫酸水解的影响。结果显示最优条件为：硫酸浓度为50%（w/w）,固液比为10%（w/v）,时间为100 min。烟草下脚料在最佳硫酸水解条件下,经5倍稀释,中和pH值至5～6。取经过滤后的水解液（FH）用酿酒酵母（Sacchharomyces cerevisiae）发酵产生乙醇,最大的乙醇浓度和乙醇产量分别为1.09g/L和54.5 g/kg。未过滤水解液（UFH,包括水解残渣）加入纤维素酶（70 U/100 mL）和酿酒酵母（Sacchharomyces cerevisiae）进行发酵,最大的乙醇浓度和乙醇产量分别为1.23 g/L和61.5 g/kg。     

烟草下脚料发酵制取乙醇

通过单因素实验考察了硫酸浓度、固液比和水解时间对硫酸水解的影响。结果显示最优条件为:硫酸浓度为50%(w/w),固液比为10%(w/v),时间为100 min。烟草下脚料在最佳硫酸水解条件下,经5倍稀释,中和pH值至5～6。取经过滤后的水解液(FH)用酿酒酵母(Sacchharomyces cerevisiae)发酵产生乙醇,最大的乙醇浓度和乙醇产量分别为1.09g/L和54.5 g/kg。未过滤水解液(UFH,包括水解残渣)加入纤维素酶(70 U/100 mL)和酿酒酵母(Sacchharomyces cerevisiae)进行发酵,最大的乙醇浓度和乙醇产量分别为1.23 g/L和61.5 g/kg。     

Synthesis of high-purity Na-A and Na-X zeolite from coal fly ash

Coal fly ash (CFA) was used as a raw material for the synthesis of zeolite molecular sieve. The synthesis began with the pretreatment of CFA to remove impurities (e.g., Fe₂O₃, CaO, etc.) under various acid types (HCl, H₂SO₄, and HNO₃) and acid/CFA ratios (5–25 mL_acid/g_CFA). High product purity (up to 97%) was achieved with HCl (20%wt), and acid/CFA ratio of 20 mL_HCl/g_CFA. The treated CFA was then converted to zeolite by the fusion reaction under various Si/Al molar ratios (0.54–1.84). Zeolite type A was synthesized when the Si/Al molar ratios were lower than 1, whereas sodium aluminum silicate hydrate was formed when the Si/Al molar ratio were higher than 1. The highest water adsorption performance of the zeolite product, i.e., the outlet ethanol concentration of 99.9%wt and the specific adsorption capacity of 2.31 × 10^?2 g_water/g_zeolite, was observed with the Si/Al molar ratio of 0.82. The zeolite was tested for its water adsorption capacity repeatedly 10 times without deactivation.

Implications: This work evaluated the technical feasibility in the conversion of CFA to zeolite, which would help reduce the quantity of waste needed to be landfilled. This adds value to the unwanted material by converting it into something that can be further used. The synthesized products were shown to be quite stable as water adsorbent for the dehydration of ethanol solution.     

A TiO2/crosslinked carboxymethyl starch composite for high-efficiency adsorption and photodegradation of cationic golden yellow X-GL dye

In this paper, a crosslinked carboxymethyl starch (CCMS) was prepared with corn starch as the raw material, epichlorohydrin as the crosslinking agent, and chloroacetic acid as the etherifying agent through a series of crosslinking, alkalization, and etherification reactions, respectively. Nano-TiO₂ was loaded onto the surface of the CCMS by the sol-gel method to obtain a TiO₂/CCMS composite. The TiO₂/CCMS composite was characterized by XPS, XRD, SEM, and BET. XPS showed that the surface chemical composition of the TiO₂/CCMS composite material contained titanium; XRD diffraction patterns indicated that the crystal form of the TiO₂/CCMS composite was a combination of the CCMS and anatase TiO₂. The surface morphology obtained by SEM showed that there were nano-TiO₂ particles on the surface of the CCMS. The specific surface area of the TiO₂/CCMS composite was larger than that of CCMS. The adsorption-photodegradation performance of the TiO₂/CCMS composite was also studied under UV irradiation, and the results showed that significant adsorption-photodegradation synergies occurred.

     

环境友好型金属切削液的性能研究

以油酸、二乙醇胺、硼酸、苯并三氮唑为主要原料,采用酯交换法制得油酸二乙醇酰胺硼酸酯、相转移法制得苯并三氮唑衍生物,合成一种复合有机硼酸酯,采用傅立叶红外光谱仪对合成产物进行表征。对由复合有机硼酸酯配制的水基切削液进行防锈、润滑及清洗性能的测试。结果表明:(1)以油酸、二乙醇胺、硼酸和苯并三氮唑为主要原料制备出的复合有机硼酸酯,经红外光谱仪的表征,证实合成工艺可行。(2)水基切削液的防腐蚀和防锈性能随着复合有机硼酸酯添加量的增加而改善,在较高温较长时间的持续工作环境下同样能保持良好的防锈性能。(3)当复合有机硼酸酯添加量为0.25%(质量分数)时,水基切削液在60℃、24h的缓蚀率达到了70%左右,35℃时的单片及叠片防锈试验合格,25℃下的表面张力为33.13×10-4 N/dm,润滑性能良好。     

酸洗废液制取复合亚铁的研制及应用

介绍了利用酸洗废液为原料制备复合亚铁型混凝剂的新方法 ,并用制得的产品应用于电镀和印染废水治理工程。工程应用及实验结果表明 ,对含Ni2 + 、Cu2 + 和Cr6+ 的电镀废水 ,能使Ni2 + 、Cu2 + 出水浓度 <0 .1mg/L ,Cr6+ 未检出 ,还能处理数种化学镀废液。对印染废水 ,COD去除率和脱色率可分别达到 84 %和 98%以上 ,值得进一步研究和推广     

新型填料特性及其在生物脱硫中的应用

为解决生物脱硫反应器酸化问题,研制出一种具有pH缓冲能力的生物填料。填料主要由碳酸钙﹑纯丙乳液和羟丙基纤维素制得。填料在水中浸泡6个月不会分解,吸水率大于20%。考察填料pH缓冲能力,结果表明,填料能将pH=5.0水溶液调节至pH=6.5以上。选取缓冲能力较稳定的BT50填料填充于反应器,以排硫硫杆菌(Thiobacillus thio-parus)挂膜,5个循环后反应器有效体积内的最大固定化菌体数量约为5.86×108cells/mL,并且硫代硫酸钠的消耗速率基本稳定,表明该填料可用于生物挂膜。在长达50 d脱硫实验中,H2S脱除率均在95%以上,整个脱硫阶段不再加入任何pH调节剂,反应器内pH仍能维持在6.7～7.1之间。     

Adsorption kinetics and modeling of H2S by treated waste oil fly ash

Waste oil fly ash (OFA) collected from disposal of power generation plants was treated by physicochemical activation technique to improve the surface properties of OFA. This synthesized material was further used for potential hydrogen sulfide (H₂S) adsorption from synthetic natural gas. The raw OFA was basically modified with a mixture of acids (20% nitric acid [HNO₃] and 80% phosphoric acid [H₃PO₄]), and it was further treated with 2 M potassium hydroxide (KOH) to enhance the surface affinity as well as surface area of synthesized activated carbon. Correspondingly, it enhanced the adsorption of H₂S. Crystallinity, surface morphology, and pore volume distribution of prepared activated carbon were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller (BET) analyses. Fourier transform infrared (FTIR) study was also performed to identify the functional groups during different synthesis stages of modified activated carbon. The Langmuir, Freundlich, Sips, and dual-site Langmuir (DSL) models were used to study the kinetic and breakthrough behavior of H₂S adsorption over alkali-modified activated carbon. Modeling results of isotherms indicated that OFA has dual sites with high and low affinity for H₂S adsorption. The Clark model, Thomas model, and Yoon-Nelson model were used to examine the effects of flow rate and inlet concentration on the adsorption of H₂S. Maximum uptake capacity of 8.5 mg/g was achieved at 100 ppm inlet concentration and flow rate of 0.2 L/min.

Implications: Utilization of worthless oil fly ash from power plant is important not only for cleaning the environment but also for solid waste minimization. This research scope is to eradicate one pollutant by using another pollutant (waste ash) as a raw material. Chemical functionalization of synthesized activated carbon from oil fly ash would lead to attachment of functional groups of basic nature to attract the acidic H₂S. Such type of treatment can enhance the uptake capacity of sorbent several times.     

The fermentative production of L-lysine as an animal feed additive

A new and innovative process for the biotechnological production of L-lysine is presented, exemplified here by the fermentative production of the feed additive Biolys60. The novel feature of this product is that the entire manufacturing concept, i.e. the production strain, the raw materials, all process stages and the product specifications have been systematically tailored for optimal environmental compatibility and for minimum resource depletion and waste. The process completely dispenses with the need to discharge residual and waste material and reduces the handling of hazardous materials to a minimum. Since only a few process stages are involved, the method is economical to use and investment outlay is reduced. The process, which also leads to a higher grade product, is thus highly attractive in both ecological and economical terms. By boosting the nutrient value of the plant-based feedstuffs, the product itself makes an cost-effective contribution towards a more sustainable form of animal feeding and by reducing nitrogen emission levels promotes a more environmentally compatible form of animal husbandry.