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     

Cu基络合物催化甲醇液相氧化羰化反应

针对甲醇液相氧化羰基化法合成碳酸二甲酯(DMC)工艺,开发了新型Cu基络合催化剂(CuB rnLm)。对CuB rnLm催化剂的活性及其稳定性进行了研究。实验结果表明,采用该催化剂,甲醇转化率和DMC选择性较高;元素价态和物质结构分析表明,CuB rnLm催化剂循环使用5次后仍保持较好的稳定性。采用正交设计和中心响应曲面法设计实验,并使用S tatistica软件进行统计分析,寻求出反应的主要影响因素,并得到优化的工艺条件:反应温度100~110℃、反应压力3.0~3.5M Pa、反应时间4~6h、CuB rnLm催化剂质量浓度(以甲醇的体积计)0.15~0.20g/mL。在此工艺条件下,甲醇转化率可达23%以上,DMC的选择性为96%~98%。     

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。     

十二酰胺丙基二甲基羟乙基氯化铵与十二烷基硫酸钠水溶液的表面吸附和胶束形成

利用十二酰胺丙基二甲胺和氯乙醇反应 ,合成了十二酰胺丙基二甲基羟乙基氯化铵 (DDHA)阳离子表面活性剂 ,将其与十二烷基硫酸钠 (SDS)以不同摩尔比进行混合 ,测定了混合系统的表面张力 ,计算了单一系统和混合系统的饱和吸附量、分子最小截面积 ,表面层和胶束中 DDHA的摩尔分率及分子间相互作用参数 ,目视观察了混合系统的浑浊情况。结果表明 :在降低γcmc和 cmc方面 ,DDHA SDS混合系统有协同效应 ,表面层和胶束的组成与二组分配比有关 ,但是非对称的 ,等物质的量混合物中 ,DDHA在胶束和表面层中具有较大的摩尔分数。DDHA与 SDS在实验测定的各混合系统中都不出现混浊     

PEG20000中试放大的工艺研究

在一定温度和催化剂作用下 ,分别利用本体聚合和溶剂聚合的方法 ,在 1L、10 0L不锈钢高压反应釜中合成了相对分子质量为 2 0 0 0 0的聚乙二醇 ,并讨论了聚合反应机理 ,研究了催化剂用量、反应温度、反应时间对聚合反应的影响。经过红外、核磁共振、凝胶色谱、化学分析等方法对产物进行了表征。     

Fluorescence and IR characterization of epoxy cured with aliphatic amines

Cure reactions of the stoichiometric mixtures of diglycidyl ether of bisphenol A (DGEBA) and two very low molecular weight aliphatic polyether diamines (PED) were studied by using fluorescence and mid- and near-IR spectroscopic techniques. As the cure proceeded, the primary amine groups in PED are converted to the secondary and the tertiary amines. Near-IR spectral analysis was used to calculate the concentration of the three amine groups as a function of cure time. The decrease in the fluorescence intensity of DGEBA at about 307 nm was observed due to more effective quenching of the tertiary amine groups in PED, in comparison to the primary and the secondary amine groups. A large decrease in fluorescence intensity at 75 and 95 °C cure was observed. The amount of all the amine species was estimated from NIR spectra to shed light on the cure kinetics of PPO (polypropylene oxide) in comparison with PEO (polyethylene oxide) epoxy, as well as to explain their fluorescence behavior.The fluorescence intensity changes were correlated to the extent of epoxy reaction obtained by mid- and near-IR spectroscopy.