Methyl chloride purification for the silicone industry

This study experimentally investigated methyl chloride (MeCl) purification method using an inhouse designed and built volumetric adsorption/desorption rig. MeCl is an essential raw material in the manufacture of silicone however all technical grades of MeCl contain concentrations (0.2 - 1.0 % wt) of dimethyl ether (DME) which poison the process. The project industrial partner had previously exhausted numerous separation methods, which all have been deemed not suitable for various reasons. Therefore, adsorption/desorption separation was proposed in this study as a potential solution with less economic and environmental impact. Pure component adsorption/desorption was carried out for DME and MeCl on six different adsorbents namely: zeolite molecular sieves (types 4 Å and 5 Å); silica gels (35-70 mesh, amorphous precipitated, and 35-60 mesh) and granular activated carbon (type 8-12 mesh). Subsequent binary gas mixture adsorption in batch and continuous mode was carried out on both zeolites and all three silica gels following thermal pre-treatment in vacuum. The adsorbents were tested as received and after being subjected to different thermal and vacuum pre-treatment conditions. The various adsorption studies were carried out at low pressure and temperature ranges of 0.5 - 3.5 atm and 20 - 100 °C. All adsorbents were characterised using Brunauer Emmett Teller (BET), thermogravimetric analysis (TGA), scanning electron microscopy (SEM) and energy dispersive x-ray analysis (EDXA) to investigate their physical and chemical properties. The well-known helium (He) expansion method was used to determine the empty manifold and adsorption cell (AC) regions and respective void volumes for the different adsorbents. The amounts adsorbed were determined using Ideal gas laws via the differential pressure method. The heat of adsorption for the various adsorbate-adsorbent (A-S) interactions was calculated using a new calorimetric method based on direct temperature measurements inside the AC. Further adsorption analysis included use of various empirical and kinetic models to determine and understand the behaviour of the respective interactions. The gas purification behaviour was investigated using gas chromatography and mass spectroscopy (GC-MC) analysis. Binary gas mixture samples were syringed from the manifold iii and AC outlet before and after adsorption/desorption analysis through manual sample injections into the GC-MS to detect and quantify the presence of DME and ultimately observe for methyl chloride purification. Convincing gas purification behaviour was confirmed using two different GC columns, thus giving more confidence on the measurement reliability. From the single pure component adsorption of DME and MeCl on the as received zeolite 4A subjected to 1 h vacuum pre-treatment, both gases exhibited pseudo second order adsorption kinetics with DME exhibiting a rate constant nearly double that of MeCl thus suggesting a faster rate of adsorption. From the adsorption isotherm classification both DME and MeCl exhibited Type II and I adsorption isotherm classifications, respectively. The strength of bonding was confirmed by the differential heat of adsorption measurement, which was found to be 23.30 and 10.21 kJ mol-1 for DME and MeCl, respectively. The former is believed to adsorb heterogeneously through hydrogen bonding whilst MeCl adsorbs homogenously via van der Waal’s (VDW) forces. Single pure component adsorption on as received zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) resulted in similar adsorption/desorption behaviour in similar quantities (mol kg-1). The adsorption isotherms for DME and MeCl on zeolite 5A, silica gels (35-70, amorphous precipitated and 35-60) and activated carbon 8-12 exhibited Type I classifications, respectively. Experiments on zeolite 5A indicated that DME adsorbed stronger, faster and with a slightly stronger strength of interaction than MeCl but in lesser quantities. On the silica gels adsorbents, DME exhibited a slightly greater adsorption capacity whilst adsorbing at a similar rate and strength of interaction compared to MeCl. On the activated carbon adsorbent, MeCl exhibited the greater adsorption capacity at a faster rate but with similar heats of adsorption. The effect of prolonged vacuum (15 h), thermal pre-treatment (150 °C) and extended equilibrium time (15 min) were investigated for the adsorption behaviour of DME and MeCl on both zeolites 4A and 5A, respectively. Compared to adsorption on as received adsorbents subjected to 1 h vacuum the adsorption capacities for DME and MeCl were found to increase by 1.95 % and 20.37 % on zeolite 4A and by 4.52 % and 6.69 % on zeolite 5A, respectively. In addition the empirical and kinetic models and differential heats of adsorption resulted in more definitive fitting curves and trends due to the true equilibrium position of the adsorbate with the adsorbent. Batch binary mixture adsorption on thermally and vacuum pre-treated zeolite 4A demonstrated purification behaviour of all adsorbents used for MeCl streams containing DME impurities, with a concentration as low as 0.66 vol. %. The GC-MS analysis showed no DME detection for the tested concentration mixtures at the AC outlet after 15 or 30 min, whereas MeCl was detectable in measurable amounts. Similar behaviour was also observed when carrying out adsorption in continuous mode. On the other hand, similar studies on the other adsorbents did not show such favourable MeCl purification behaviour. Overall this study investigated a wide range of adsorbents (zeolites, silica gels and activated carbon) and demonstrated for the first time potential to purify MeCl streams containing DME impurities using adsorption/desorption separation under different adsorbent pre-treatment and adsorption operating conditions. The study also revealed for the first time the adsorption isotherms, empirical and kinetic models and heats of adsorption for the respective adsorbentsurface (A-S) interactions. In conclusion, this study has shown strong evidence to propose zeolite 4A for adsorptive purification of MeCl. It is believed that with a technical grade MeCl stream competitive yet simultaneous co-adsorption of DME and MeCl occurs with evidence of molecular sieiving effects whereby the larger DME molecules are unable to penetrate through the adsorbent bed whereas the smaller MeCl molecules diffuse through resulting in a purified MeCl stream at the AC outlet. Ultimately, further studies are recommended for increased adsorption capacities by considering wider operating conditions, e.g. different adsorbent thermal and vacuum pre-treatment and adsorbing at temperatures closer to the boiling point of the gases and different conditions of pressure and temperature.

Better queue management in a busy public hospital of a developing country without appointment system::an application using data envelopment analysis

Queuing is a key efficiency criterion in any service industry, including Healthcare. Almost all queue management studies are dedicated to improving an existing Appointment System. In developing countries such as Pakistan, there are no Appointment Systems for outpatients, resulting in excessive wait times. Additionally, excessive overloading, limited resources and cumbersome procedures lead to over-whelming queues. Despite numerous Healthcare applications, Data Envelopment Analysis (DEA) has not been applied for queue assessment. The current study aims to extend DEA modelling and demonstrate its usefulness by evaluating the queue system of a busy public hospital in a developing country, Pakistan, where all outpatients are walk-in; along with construction of a dynamic framework dedicated towards the implementation of the model. The inadequate allocation of doctors/personnel was observed as the most critical issue for long queues. Hence, the Queuing-DEA model has been developed such that it determines the ‘required’ number of doctors/personnel. The results indicated that given extensive wait times or length of queue, or both, led to high target values for doctors/personnel. Hence, this crucial information allows the administrators to ensure optimal staff utilization and controlling the queue pre-emptively, minimizing wait times. The dynamic framework constructed, specifically targets practical implementation of the Queuing-DEA model in resource-poor public hospitals of developing countries such as Pakistan; to continuously monitor rapidly changing queue situation and display latest required personnel. Consequently, the wait times of subsequent patients can be minimized, along with dynamic staff scheduling in the absence of appointments. This dynamic framework has been designed in Excel, requiring minimal training and work for users and automatic update features, with complex technical aspects running in the background. The proposed model and the dynamic framework has the potential to be applied in similar public hospitals, even in other developing countries, where appointment systems for outpatients are non-existent.

Safety criteria for the private spaceflight industry

The Federal Aviation Administration (FAA) Office of Commercial Space Transportation (AST) has set specific rules and generic guidelines to cover experimental and operational flights by industry forerunners such as Virgin Galactic and XCOR. One such guideline Advisory Circular (AC) 437.55-1[1] contains exemplar hazard analyses for spacecraft designers and operators to follow under an experimental permit. The FAA's rules and guidelines have also been ratified in a report to the United States Congress, Analysis of Human Space Flight Safety[2] which cites that the industry is too immature and has 'insufficient data' to be proscriptive and that 'defining a minimum set of criteria for human spaceflight service providers is potentially problematic' in order not to 'stifle the emerging industry'. The authors of this paper acknowledge the immaturity of the industry and discuss the problematic issues that Design Organisations and Operators now face.

Technological capability development in China's energy service company industry

Technological capability (TC) plays a strategic role in the competitive advantage of not only individual corporate entities but also entire industries. This paper investigates the crucial factors that affect technological capability development by Energy Service Companies (ESCOs) in China. It identifies how differently sized ESCOs make progress in developing TCs. Through looking at the successes achieved by developed countries in the field of energy conservation, ESCOs are able to improve energy efficiency and reduce emissions and are deemed to provide an effective means of conserving energy in China. Existing literature indicates that limited TC levels of are one of the crucial barriers facing Chinese ESCOs. Through investigating three different sizes of Chinese ESCO - small, medium-sized and large - this paper provides a framework to present the idea that Chinese ESCOs' TC development is affected by four key internal and external capabilities: management capability, investment capability, innovation capability and linkage capability. Through comparative analysis, the paper establishes that small and medium-sized private ESCOs are mainly affected by investment and linkage capabilities. Large state-owned ESCOs are mainly affected by innovation and management capability. In addition, all three types of ESCO exhibit a strong desire to develop their technological capability, but small and medium-sized ESCOs exhibit a stronger desire to conduct research and development (R&D) than large ESCOs, whilst large ESCOs prefer to increase their technical reserves through acquisition. This paper identifies factors that affect Chinese ESCOs' TC, but it does intend to address the problem of how to reduce the negative effects of limited TC or the question of how to improve the TC development of Chinese ESCOs effectively. This paper contributes to the field of TC development in the ESCO industry.