Inherently safer design of solvent processes at the conceptual stage: Practical application for substitution

The implementation of inherently safer design concepts is considered beneficial to avoid hazards during early stages of design. The application of existing process design and modeling techniques that aid ‘substitution’, ‘intensification’ and ‘attenuation’ has been shown in this work. The techniques have been applied to solvent processes because of the inherent hazards associated with them, such as large inventories, and presence of highly toxic and flammable materials. For ‘substitution’, computer aided molecular design technique has been applied to select inherently safer solvents for a solvent operation. For ‘intensification’ and ‘attenuation’, consequence models and regulatory guidance from EPA RMP have been integrated into process simulation. Combining existing techniques provides a design team with a higher level of information to make decisions based on process safety. A case study has been shown for liquid extraction of acetic acid–water mixture. Suitable solvents were identified using ICAS 11.0-ProCAMD, and consequence models were integrated into Aspen plus simulator using a calculator sheet. Solvents such as 5-nonanone, 2-nonanone and 5-methyl-2-hexanone provide inherently safer options, but conventionally-used solvent, ethyl acetate, provides higher degree of separation capability. A conclusive decision regarding feasible solvents and operating conditions would depend on design requirements, regulatory guidance, and safety criteria specified for the process. Inherent safety has always been an important consideration to be implemented during early design steps, and this paper presents a methodology to incorporate the principles and to obtain inherently safer alternatives.     

A decomposition analysis of CO2 emissions: evidence from Malaysia’s tourism industry

The most important question raised from issues of environmental degradation is how economic activities bring about changes that will result in pollution. In the pursuit of tourism economy, contrary to popular interest, the travel and tourism (T&T) industry may cause environmental damages through the emissions of carbon dioxide (CO₂) from energy consumption in areas such as transportation and delivery of amenities. Given this major concern, this paper attempts to investigate the linkage between tourism and CO₂ emissions in Malaysia between 1981 and 2011. In particular, this study fills the knowledge gap by taking a closer look at the impact of international tourist arrivals on CO₂ emissions by sector – electricity and heat generation and transport. Results from the bound test method suggest that there exists a long-run relationship among the variables under consideration when CO₂ emissions become the dependent variable. The original result is similarly robust to alternatives, which are CO₂ emissions from sectors of electricity and heat generation and transport. Furthermore, the vector error correction model causality analysis indicates a causal relationship between tourism and CO₂ emissions by transport and electricity and heat generation. Subsequently, several tourism-related policies are drawn from these findings.     

Iodide-assisted total lead measurement and determination of different lead fractions in drinking water samples

Lead and its compounds are toxic and can harm human health, especially the intelligence development in children. Accurate measurement of total lead present in drinking water is crucial in determining the extent of lead contamination and human exposure due to drinking water consumption. The USEPA method for total lead measurement (no. 200.8) is often used to analyze lead levels in drinking water. However, in the presence of high concentration of the tetravalent lead corrosion product PbO(2), the USEPA method was not able to fully recover particulate lead due to incomplete dissolution of PbO(2) particles during strong acid digestion. In this study, a new procedure that integrates membrane separation, iodometric PbO(2) measurement, strong acid digestion and ICP-MS measurement was proposed and evaluated for accurate total lead measurement and quantification of different lead fractions including soluble Pb(2+), particulate Pb(II) carbonate and PbO(2) in drinking water samples. The proposed procedure was evaluated using drinking water reconstituted with spiked Pb(2+), spiked particulate Pb(II) carbonate and in situ formed or spiked PbO(2). Recovery tests showed that the proposed procedure and the USEPA method can achieve 93-112% and 86-103% recoveries respectively for samples containing low PbO(2) concentrations (0.018-0.076 mg Pb per L). For samples containing higher concentrations of PbO(2) (0.089-1.316 mg Pb per L), the USEPA method failed to meet the recovery requirement for total lead (85-115%) while the proposed method can achieve satisfactory recoveries (91-111%) and differentiate the soluble Pb(2+), particulate Pb(II) carbonate and PbO(2).     

Effect of membrane type and material on performance of a submerged membrane bioreactor

This study evaluated the impact of membrane type and material on filtration performance in a submerged membrane bioreactor (MBR) for municipal wastewater treatment. Three types of microfiltration membranes with similar pore size of 0.1 microm but different materials and types, phase-inversed polytetrafluoroethylene (PTFE), track-etched polycarbonate (PCTE) and track-etched polyester (PETE), were used. Changes in permeability with time for the PCTE and PTFE membranes appeared similarly, whereas the PETE membrane exhibited the most rapid flux decline. Lower TOC in the permeate compared to the supernatant was probably due to a combination of biodegradation by the biofilm (cake layer) developed on the membrane surface and further filtration by cake layer and narrowed pores. The faster permeability decline and higher TOC removal rate of the PETE membrane were attributed to an initial permeate flux higher than an average design flux, which led to a faster rate of fouling and thicker cake layer. Therefore, an MBR should not be operated at a flux higher than the average design flux for a specific type of membrane. A gradual increment of biomass concentration did not significantly affect membrane permeability of each membrane investigated. Dissolved organic carbon fractionation results showed that the composition of each fraction between the supernatant and permeates did not change significantly with time, suggesting that membrane hydrophobicity was not a dominant factor affecting MBR fouling in this study. The organic foulants desorbed from the PCTE membrane contained approximately 60% of hydrophobic fraction, which was probably attributable to the extracellular polymeric substances proteins released from the biomass attached to the membrane. While the total filtration resistance of the PTFE membrane was influenced by a higher surface roughness, those of the PETE and PCTE membranes, which had a similar and lower roughness, were affected by the initial operating flux.     

A superstructure model for the synthesis of single-contaminant water networks with partitioning regenerators

This paper presents a novel superstructure-based optimization model for the synthesis of industrial water networks with partitioning regenerators. Such regenerators function by splitting a contaminated water stream into a regenerated lean stream and a low-quality reject stream. Membrane separation-based processes are examples of these types of regenerators. The optimization model presented in this work integrates a single, centralized partitioning regenerator with a source–demand superstructure under the assumption that the processes within the plant are of the fixed flow rate type. The formulation is non-linear as a result of the presence of bilinear terms in the regenerator balance equations, but global optimal solutions can be found using commercial software. The features of the model are illustrated by solving case studies from the literature. It is notable from these examples that considerable design flexibility exists in networks of this type, since potentially both the lean and reject streams from the partitioning regenerator can be reused/recycled within the plant.     

Association of arsenic and kidney dysfunction in people with diabetes and validation of its effects in rats

We studied villagers with and without diabetes from arsenic-endemic areas and a nearby control site in Xinjiang Autonomous Region, PR China. Water and urinary arsenic were assayed for exposure measurement. Urinary NAG (N-acetyl-beta-glucosaminidase), a kidney function test, blood glucose, triglyceride, cholesterol, high density lipid and low density lipid were measured. Villagers from endemic areas were found to have higher urinary arsenic concentrations. The NAG results also suggest that chronic arsenic exposure presents a significant adverse impact on the kidney function of villagers in the endemic areas. However, blood glucose levels of diabetes individuals were lower than those from the control site. These observations were validated in rats which were chronically exposed to arsenic in drinking water. The distinct relationship between chronic arsenic exposure and diabetes mellitus requires further investigation. A rodent model is a useful tool for study of this type.     

Arsenicosis status and urinary malondialdehyde (MDA) in people exposed to arsenic contaminated-coal in China

The current arsenic exposure condition, arsenicosis prevalence, urinary arsenic and MDA (malondialdehyde) concentrations in people were studied. The study area, a village in Xing Ren County in Guizhou Province, PR China, is a coal-borne arsenicosis endemic area that was identified several decades ago. The residents in Xing Ren have been using coal containing high arsenic levels all their life. Urinary arsenic levels of villagers were 192.2+/-22 microg/g creatinine (n=113) in the coal-borne endemic area (Xing Ren county) and were significantly higher than 63.6+/-5.9 microg/g creatinine (n=30) in a neighbouring control site (a village in Xing Yi county). The urinary MDA concentrations of villagers from the endemic area were also significantly higher compared to those of the control area. There was a strong correlation between age and urinary arsenic and MDA concentrations in the endemic area of Xing Ren; urinary arsenic and MDA levels decreased with age. Fifty out of 113 (44.3%) villagers in the endemic area had arsenicosis symptoms and the prevalence in villagers older than 40 y was 100% in male (92.2% overall). Urinary MDA concentration was significantly higher in people with arsenicosis symptoms in the endemic areas. Oxidative stress (urinary MDA concentration) was strongly related to arsenic exposure but not to the age and smoking habit. Higher urinary arsenic and MDA levels in younger villagers from the endemic area suggest that they are having a higher exposure to coal-borne emitted arsenic because they spend more time indoor. There is an urgent need to develop proper intervention methods in the Guizhou endemic areas in order to reduce the risk to the local communities who are still using arsenic contaminated-coal.     

Insights on the solubilization products after combined alkaline and ultrasonic pre-treatment of sewage sludge

This work provides insights on the solubilization products after a simultaneous combination of alkaline and ultrasonic(ALK + ULS) pre-treatment of sewage sludge.Soluble chemical oxygen demand(SCOD) increased from 1200 to 11,000 mg/L after such treatment. Organics with molecular weight around 5.6 k Da were solubilized because of the synergistic effect of ultrasound and alkali. Organics with molecular weight larger than300 k Da increased from 7.8% to 60%, 16% and 42.3% after ULS, ALK and ALK + ULS treatment, respectively. Excitation emission matrix fluorescence spectroscopy analysis identified soluble microbial product-like and humic acid-like matters as the main solubilization products. Sludge anaerobic biodegradability was significantly enhanced with the simultaneous application of ALK + ULS pre-treatment. ALK + ULS pre-treatment resulted in 37.8% biodegradability increase compared to the untreated sludge. This value was higher compared to the biodegradability increase induced by individual ALK pre-treatment(5.7%) or individual ULS pre-treatment(20.7%) under the same conditions applied.     

Biocompatible Polyurethane Scaffolds Prepared from Glycerol Monostearate-Derived Polyester Polyol

Biodegradable polyester polyol was synthesized from oleochemical glycerol monostearate (GMS) and glutaric acid under a non-catalyzed and solvent-free polycondensation method. The chemical structure of GMS-derived polyester polyol (GPP) was elucidated by FTIR, ¹H and ¹³C NMR, and molecular weight of GPP was characterized by GPC. The synthesized GPP with acid value of 3.03 mg KOH/g sample, hydroxyl value of 115.72 mg KOH/g sample and M_n of 1345 g/mol was incorporated with polyethylene glycol (PEG) and polycaprolactone diol (PCL diol) to produce a water-blown porous polyurethane system via one-shot foaming method. The polyurethanes were optimized by evaluating glycerol as a crosslinker, silicone surfactant and water blowing agent on tensile properties of polyurethanes. All polyurethanes underwent structural change, and crystalline hard segments of polyurethanes were shifted to higher temperature suggested that hard segments undergone re-ordering process during enzymatic treatment. In terms of biocompatibility, polyurethane scaffold produced by reacting 100% w/w of GPP with isophorone diisocyanate and additives showed the highest cells viability of 3T3 mouse fibroblast (94%, day 1), and MG63 human osteosarcoma (107%, day 1) and better cell adhesion as compared to reference polyurethane produced by only PEG and PCL diol (3T3 cell viability: 8%; MG63 cell viability: 2%). The current work demonstrated GPP synthesized from renewable and environmental friendly resources produced polyurethanes that allows improvement in physico-chemical, mechanical and biocompatibility properties. By blending with increasing content of GPP, the water-blown porous polyurethane scaffold has shown great potential as biomaterial for soft and hard tissue engineering.