Psychrophilic hydrogen production from petrochemical wastewater via anaerobic sequencing batch reactor: techno-economic assessment and kinetic modelling

Independent hydrogen production from petrochemical wastewater containing mono-ethylene glycol (MEG) via anaerobic sequencing batch reactor (ASBR) was extensively assessed under psychrophilic conditions (15–25 °C). A lab-scale ASBR was operated at pH of 5.50, and different organic loading rates (OLR) of 1.00, 1.67, 2.67, and 4.00 gCOD/L/d. The hydrogen yield (HY) progressed from 134.32 ± 10.79 to 189.09 ± 22.35 mL/gMEG_initial at increasing OLR from 1.00 to 4.00 gCOD/L/d. The maximum hydrogen content of 47.44 ± 3.60% was achieved at OLR of 4.0 gCOD/L/d, while methane content remained low (17.76 ± 1.27% at OLR of 1.0 gCOD/L/d). Kinetic studies using four different mathematical models were conducted to describe the ASBR performance. Furthermore, two batch-mode experiments were performed to optimize the nitrogen supplementation as a nutrient (C/N ratio), and assess the impact of salinity (as gNaCl/L) on hydrogen production. HY substantially dropped from 62.77 ± 4.09 to 6.02 ± 0.39 mL/gMEG_initial when C/N ratio was increased from 28.5 to 114.0. Besides, the results revealed that salinity up to 10.0 gNaCl/L has a relatively low inhibitory impact on hydrogen production. Eventually, the cost/benefit analysis showed that environmental and energy recovery revenues from ASBR were optimized at OLR of 4.0 gCOD/L/d (payback period of 7.13 yrs).     

Hydrocarbon-based electrode ionomer for proton exchange membrane fuel cells

The electrode ionomer is a key factor that significantly affects the catalyst layer morphology and fuel cell performance. Herein, sulfonated poly(arylene ether sulfone)-based electrode ionomers with polymers of various molecular weights and alcohol/water mixtures were prepared, and those comprising the alcohol/water mixture showed a higher performance than the ones prepared using higher boiling solvents, such as dimethylacetamide; this is owing to the formation of the uniformly dispersed ionomer catalyst layer. The relation between ionomer molecular weight for the same polymer structure and the sulfonation degree was investigated. Because the chain length of polymer varies with molecular weight and chain entanglement degree, its molecular weight affects the electrode morphology. As the ionomer covered the catalyst, the agglomerates formed were of different morphologies according to their molecular weight, which could be deduced indirectly through dynamic light scattering and scanning electron microscopy. Additionally, the fuel cell performance was confirmed in the current-voltage curve.     

The Interplay of Modulus,Strength, and Ductility in Adhesive Design Using Biomimetic Polymer Chemistry

High‐performance adhesives require mechanical properties tuned to demands of the surroundings. A mismatch in stiffness between substrate and adhesive leads to stress concentrations and fracture when the bonding is subjected to mechanical load. Balancing material strength versus ductility, as well as considering the relationship between adhesive modulus and substrate modulus, creates stronger joints. However, a detailed understanding of how these properties interplay is lacking. Here, a biomimetic terpolymer is altered systematically to identify regions of optimal bonding. Mechanical properties of these terpolymers are tailored by controlling the amount of a methyl methacrylate stiff monomer versus a similar monomer containing flexible poly(ethylene glycol) chains. Dopamine methacrylamide, the cross‐linking monomer, is a catechol moiety analogous to 3,4‐dihydroxyphenylalanine, a key component in the adhesive proteins of marine mussels. Bulk adhesion of this family of terpolymers is tested on metal and plastic substrates. Incorporating higher amounts of poly(ethylene glycol) into the terpolymer introduces flexibility and ductility. By taking a systematic approach to polymer design, the region in which material strength and ductility are balanced in relation to the substrate modulus is found, thereby yielding the most robust joints.     

Effect of hyperbranched poly(citric polyethylene glycol) with various polyethylene glycol chain lengths on starch plasticization and retrogradation

A series of hyperbranched poly(citric polyethylene glycol) (PCPEG) materials with varied polyethylene glycol (PEG) chain lengths as plasticizers were mixed with maize starch (MS) via cooking and film‐forming. The structure, pasting property, plasticization, aging property, moisture absorption and compatibility of plasticized starches were studied by means of Fourier transform infrared spectroscopy, X‐ray diffraction, rapid viscosity analysis, tension testing, moisture absorption measurements and scanning electron microscopy. Compared with PEG and citric acid, PCPEG was more effective in promoting starch chain movement and inhibiting the retrogradation of starch film. Also, PCPEG/MS had smaller moisture content. The longer the plasticizer chain, the better were the aging resistance and moisture resistance of starch. But with an increase of PEG chain length, mechanical properties of PCPEG/MS deteriorated and the compatibility between PCPEG and MS decreased. The hyperbranched derivative of PEG with longer chain exhibited improved plasticization and compatibility with starch. © 2019 Society of Chemical Industry     

Investigation on sulphonated zinc oxide nanorod incorporated sulphonated poly (1,4-phenylene ether ether sulfone) nanocomposite membranes for improved performance of microbial fuel cell

Hydrothermally prepared zinc oxide nanorods are sulphonated (S–ZnO NR) and incorporated into 15% Sulphonated Poly (1,4-Phenylene Ether Ether Sulfone) (SPEES) to improve the hydrophilicity, water uptake and ion transfer capacity. Water uptake and ion transfer capacity increased to 34.6 ± 0.6% and 2.0 ± 0.05 meq g^?1 from 29.8 ± 0.3% and 1.4 ± 0.04 meq g^?1 by adding 7.5 wt% S–ZnO NR to SPEES. Morphological studies show the prepared S–ZnO NR is well dispersed in the polymer matrix. SPEES +7.5 wt% S–ZnO NR membrane exhibits optimum performance after three-weeks of continual operation in a fabricated microbial fuel cell (MFC) to produce a maximum power density of 142 ± 1.2 mW m^?2 with a reduced biofilm compared to plain SPEES (59 ± 0.8 mW m^?2), unsulphonated filler incorporated SPEES (SPEES + 7.5 wt% ZnO, 68 ± 1.1 mW m^?2) and Nafion (130 ± 1.5 mW m^?2) thereby suggesting its suitability as a sustainable and improved cation exchange membrane (CEM) for MFCs.     

二氧化碳加氢直接合成二甲醚催化剂的研究——沉淀次序对复合催化剂结构和性能的影响

以草酸乙醇溶液为沉淀剂,采用不同的沉淀次序(并流、反加和正加)制备了CuO-ZnO-Al2O3/HZSM-5复合型催化剂,对CO2加氢直接合成二甲醚反应的催化活性顺序为:并流法催化剂>反加法催化剂>正加法催化剂。3种复合催化剂的还原温度由低到高的顺序为:并流法催化剂<反加法催化剂<正加法催化剂。在沉淀过程中,反加法和正加法均形成类胶体沉淀,相应催化剂的比表面积也较大。IR研究发现,催化剂在1101cm-1处表现Cu/Zn/Al氧化物与HZSM-5分子筛之间相互作用的IR吸收峰强度与其催化活性间存在对应关系。XRD结果表明,并流法得到的催化剂前驱体中有铜锌同形取代现象,有利于催化剂活性的发挥。     

分子筛绿色化合成技术的开发

对现有分子筛合成废液中氨氮及还原性物质的来源进行分析，确定降低排放废水中氨氮浓度及COD的方案。对现有ZRP-5分子筛制备流程进行优化，增加母液及赶胺水回用工序；建立母液浓缩装置，将钛硅分子筛及Β分子筛的合成母液及重排母液应用于ZSM-5分子筛的合成，实现废液的梯级利用。上述措施既解决了因分子筛生产废液的排放造成的环境污染，亦因废物资源化降低了ZSM-5分子筛的生产成本。     

载体比表面积及孔径对Nb_2O_5/α-Al_2O_3催化剂酸性及反应性能的影响

采用浸渍法制备了Nb2O5/α-A l2O3催化剂(简称催化剂)并用于环氧乙烷水合制乙二醇的反应,通过控制α-A l2O3载体中致孔剂的含量来调变载体的孔径、孔分布及比表面积;采用吡啶吸附红外光谱、氨程序升温脱附法研究了载体的比表面积及孔径对催化剂酸性及反应性能的影响。实验结果表明,产物的选择性受扩散因素及催化剂酸性的影响,而催化剂的酸量、酸密度可以通过载体的孔径及比表面积的变化加以调控。比表面积较小及孔径较大的载体对催化剂催化环氧乙烷水合制乙二醇的反应较为有利。当载体的比表面积小于0.80m2/g、孔径为4.00~8.00μm时,在反应温度160℃、反应压力1.5M Pa、n(H2O)∶n(EO)=22、液态空速25h-1的条件下,环氧乙烷的转化率大于99.8%,乙二醇的选择性超过89.9%。