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).     

Synthesis of Ionic Ultramicroporous Polymers for Selective Separation of Acetylene from Ethylene

The design of highly stable and efficient porous materials is essential for developing breakthrough hydrocarbon separation methods based on physisorption to replace currently used energy-intensive distillation/absorption technologies. Efforts to develop advanced porous materials such as zeolites, coordination frameworks, and organic polymers have met with limited success. Here, a new class of ionic ultramicroporous polymers (IUPs) with high-density inorganic anions and narrowly distributed ultramicroporosity is reported, which are synthesized by a facile free-radical polymerization using branched and amphiphilic ionic compounds as reactive monomers. A covalent and ionic dual-crosslinking strategy is proposed to manipulate the pore structure of amorphous polymers at the ultramicroporous scale. The IUPs exhibit exceptional selectivity (286.1–474.4) for separating acetylene from ethylene along with high thermal and water stability, collaboratively demonstrated by gas adsorption isotherms and experimental breakthrough curves. Modeling studies unveil the specific binding sites for acetylene capture as well as the interconnected ultramicroporosity for size sieving. The porosity-engineering protocol used in this work can also be extended to the design of other ultramicroporous materials for the challenging separation of other key gas constituents.     

乙烯、丙烯中微量水含量的分析

采用便携式微量水分析仪和库仑法微量水分析仪测定了乙烯、丙烯试样中的微量水含量,对试样的传输系统、进样量的控制、液体试样的气化和水标准气体的制备方法进行了改进,优化了测试条件。以低吸附惰性管线和小死体积单进单出的不锈钢减压器为试样传输系统,缩短了测试时间。采用液态烃闪蒸气化取样进样器气化液体试样并准确控制试样的进样量,可避免液体试样渐次气化对水含量测定结果的影响及对采样钢瓶大小的限制。采用渗透管发生器制备水标准气体,可验证分析结果的准确度。采用库仑法微量水分析仪测定水含量时,试样流量选择600 m L/min较适宜,开封保存15 d之内的卡尔·费休试剂对测定结果无影响。采用便携式微量水分析仪测定水含量时,选择试样流量在400~800 m L/min之间较适宜。两种仪器的测量结果相近,稳定性好,准确度高,回收率在102%~107%之间,相对偏差小于10%。     

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     

Electrocatalytic Reduction of CO2 to Ethylene by Molecular Cu‐Complex Immobilized on Graphitized Mesoporous Carbon

The electrochemical reduction of carbon dioxide (CO₂) to hydrocarbons is a challenging task because of the issues in controlling the efficiency and selectivity of the products. Among the various transition metals, copper has attracted attention as it yields more reduced and C2 products even while using mononuclear copper center as catalysts. In addition, it is found that reversible formation of copper nanoparticle acts as the real catalytically active site for the conversion of CO₂ to reduced products. Here, it is demonstrated that the dinuclear molecular copper complex immobilized over graphitized mesoporous carbon can act as catalysts for the conversion of CO₂ to hydrocarbons (methane and ethylene) up to 60%. Interestingly, high selectivity toward C2 product (40% faradaic efficiency) is achieved by a molecular complex based hybrid material from CO₂ in 0.1 m KCl. In addition, the role of local pH, porous structure, and carbon support in limiting the mass transport to achieve the highly reduced products is demonstrated. Although the spectroscopic analysis of the catalysts exhibits molecular nature of the complex after 2 h bulk electrolysis, morphological study reveals that the newly generated copper cluster is the real active site during the catalytic reactions.     

外源乙烯对黄瓜幼苗根系生长及内源多胺含量的影响

精确控制营养液溶氧浓度和外源乙烯浓度,研究了黄瓜幼苗根系在低氧水培时的生长情况以及PAs含量的变化。结果表明,外源乙烯对根际低氧逆境下黄瓜幼苗根系的生长有抑制作用,虽然根径增粗,含水量增加,但根系的总根数、总表面积、总体积、干重和鲜重都有所减少,随着乙烯浓度的增加,抑制作用增强;外源乙烯对根际低氧逆境下黄瓜幼苗根系PAs含量有着明显的拮抗作用,外源乙烯使根际低氧逆境下黄瓜幼苗根系的伤害症状加重。     

Staining of poly(ethylene terephthalate) by ruthenium tetroxide

The staining of poly(ethylene terephthalate) (PET) by ruthenium tetroxide (RuO₄) is used to obtain a contrast at the crystalline lamellar scale in transmission electron microscopy. This paper demonstrates the efficiency of this technique conducted in vapor phase on ultracut bulk samples. Advantages of this method against other contrast enhancing techniques and the parameters of staining are discussed. The depth of attack is measured and is shown to be limited by a crosslinking process. The chemical mechanisms are investigated by grazing infrared spectroscopy and involve the oxidation of the aliphatic moeities of PET.