Dynamic simulation of chemical processes

This thesis describes the design and implementation of an interactive dynamic simulator called DASPRII. The starting point of this research has been an existing dynamic simulation package, DASP. DASPII is written in standard FORTRAN 77 and is implemented on universally available IBM-PC or compatible machines. It provides a means for the analysis and design of chemical processes. Industrial interest in dynamic simulation has increased due to the recent increase in concern over plant operability, resiliency and safety. DASPII is an equation oriented simulation package which allows solution of dynamic and steady state equations. The steady state can be used to initialise the dynamic simulation. A robust non linear algebraic equation solver has been implemented for steady state solution. This has increased the general robustness of DASPII, compared to DASP. A graphical front end is used to generate the process flowsheet topology from a user constructed diagram of the process. A conversational interface is used to interrogate the user with the aid of a database, to complete the topological information. An original modelling strategy implemented in DASPII provides a simple mechanism for parameter switching which creates a more flexible simulation environment. The problem description generated is by a further conversational procedure using a data-base. The model format used allows the same model equations to be used for dynamic and steady state solution. All the useful features of DASPI are retained in DASPII. The program has been demonstrated and verified using a number of example problems, Significant improvements using the new NLAE solver have been shown. Topics requiring further research are described. The benefits of variable switching in models has been demonstrated with a literature problem.

Chemical studies of plasma etchants used in integrated circuit manufacture

Plasma or "dry" etching is an essential process for the production of modern microelectronic circuits. However, despite intensive research, many aspects of the etch process are not fully understood. The results of studies of the plasma etching of Si and Si02 in fluorine-containing discharges, and the complementary technique of plasma polymerisation are presented in this thesis. Optical emission spectroscopy with argon actinometry was used as the principle plasma diagnostic. Statistical experimental design was used to model and compare Si and Si02 etch rates in CF4 and SF6 discharges as a function of flow, pressure and power. Etch mechanisms m both systems, including the potential reduction of Si etch rates in CF4 due to fluorocarbon polymer formation, are discussed. Si etch rates in CF4 /SF6 mixtures were successfully accounted for by the models produced. Si etch rates in CF4/C2F6 and CHF3 as a function of the addition of oxygen-containing additives (02, N20 and CO2) are shown to be consistent with a simple competition between F, 0 and CFx species for Si surface sites. For the range of conditions studied, Si02 etch rates were not dependent on F-atom concentration, but the presence of fluorine was essential in order to achieve significant etch rates. The influence of a wide range of electrode materials on the etch rate of Si and Si02 in CF4 and CF4 /02 plasmas was studied. It was found that the Si etch rate in a CF4 plasma was considerably enhanced, relative to an anodised aluminium electrode, in the presence of soda glass or sodium or potassium "doped" quartz. The effect was even more pronounced in a CF4 /02 discharge. In the latter system lead and copper electrodes also enhanced the Si etch rate. These results could not be accounted for by a corresponding rise in atomic fluorine concentration. Three possible etch enhancement mechanisms are discussed. Fluorocarbon polymer deposition was studied, both because of its relevance to etch mechanisms and its intrinsic interest, as a function of fluorocarbon source gas (CF4, C2F6, C3F8 and CHF3), process time, RF power and percentage hydrogen addition. Gas phase concentrations of F, H and CF2 were measured by optical emission spectroscopy, and the resultant polymer structure determined by X-ray photoelectron spectroscopy and infrared spectroscopy. Thermal and electrical properties were measured also. Hydrogen additions are shown to have a dominant role in determining deposition rate and polymer composition. A qualitative description of the polymer growth mechanism is presented which accounts for both changes in growth rate and structure, and leads to an empirical deposition rate model.

Chemical modification of smectite clays

Today, speciality use organoclays are being developed for an increasingly large number of specific applications. Many of these, including use in cosmetics, polishes, greases and paints, require that the material be free from abrasive impurities so that the product retains a smooth `feel'. The traditional `wet' method preparation of organoclays inherently removes abrasives naturally present in the parent mineral clay, but it is time-consuming and expensive. The primary objective of this thesis was to explore the alternative `dry' method (which is both quicker and cheaper but which provides no refining of the parent clay) as a process, and to examine the nature of the organoclays produced, for the production of a wide range of commercially usable organophilic clays in a facile way. Natural Wyoming bentonite contains two quite different types of silicate surface (that of the clay mineral montmorillonite and that of a quartz impurity) that may interact with the cationic surfactant added in the `dry' process production of organoclays. However, it is oil shale, and not the quartz, that is chiefly responsible for the abrasive nature of the material, although air refinement in combination with the controlled milling of the bentonite as a pretreatment may offer a route to its removal. Ion exchange of Wyoming bentonite with a long chain quaternary ammonium salt using the `dry' process affords a partially exchanged, 69-78%, organoclay, with a monolayer formation of ammonium ions in the interlayer. Excess ion pairs are sorbed on the silicate surfaces of both the clay mineral and the quartz impurity phases. Such surface sorption is enhanced by the presence of very finely divided, super paramagnetic, Fe2O3 or Fe(O)(OH) contaminating the surfaces of the major mineral components. The sorbed material is labile to washing, and induces a measurable shielding of the 29Si nuclei in both clay and quartz phases in the MAS NMR experiment, due to an anisotropic magnetic susceptibility effect. XRD data for humidified samples reveal the interlamellar regions to be strongly hydrophobic, with the by-product sodium chloride being expelled to the external surfaces. Many organic cations will exchange onto a clay. The tetracationic cyclophane, and multipurpose receptor, cyclobis(paraquat-p-phenylene) undergoes ion exchange onto Wyoming bentonite to form a pillared clay with a very regular gallery height. The major plane of the cyclophane is normal to the silicate surfaces, thus allowing the cavity to remain available for complexation. A series of group VI substituted o-dimethoxybenzenes were introduced, and shown to participate in host/guest interactions with the cyclophane. Evidence is given which suggests that the binding of the host structure to a clay substrate offers advantages, not only of transportability and usability but of stability, to the charge-transfer complex which may prove useful in a variety of commercial applications. The fundamental relationship between particle size, cation exchange capacity and chemical composition of clays was also examined. For Wyoming bentonite the extent of isomorphous substitution increases with decreasing particle size, causing the CEC to similarly increase, although the isomorphous substitution site: edge site ratio remains invarient throughout the particle size range studied.

Mechanisms of chemical and physical transdermal penetration enhancement

The underlying theme of this thesis is one of exploring the processes involved in the enhancement of percutaneous absorption. The development of an attenuated total reflectance Fourier-Transform infrared (ATR-FTIR) spectroscopic method to analyse diffusion of suitable topically applied compounds in membrane is described. Diffusion coefficients (D/h2) and membrane solubility (AO) for topically applied compounds were determined using a solution to Fick's second law of diffusion. This method was employed to determine the diffusional characteristics of a model permeant, 4-cyanophenol (CP), across silicone membrane as a function of formulation applied and permeant physicochemical properties. The formulations applied were able to either affect CP diffusivity and/or its membrane solubility in the membrane; such parameters partially correlated with permeant physicochemical properties in each formulation. The interplay during the diffusion process between drug, enhancer and vehicle in stratum corneum (SC) was examined. When enhancers were added to the applied formulations, CP diffusivity and solubility were significantly enhanced when compared to the neat propylene glycol (PG) application. Enhancers did not affect PG diffusivity in SC but enhancers did affect PG solubility in SC. PG diffusion closely resembled that of CP, implying that the respective transport processes were inter-related. Additionally, a synergistic effect, which increases CP diffusivity and membrane solubility in SC, was found to occur between PG and water. Using 12-azidooleic acid (AOA) as an IR active probe for oleic acid, the simultaneous penetration of CP, AOA and PG into human stratum corneum was determined. It was found that the diffusion profiles for all three permeants were similar. This indicated that the diffusion of each species through SC was closely related and most likely occurred via the same route or SC microenvironment.

The chemical structure and mechanical properties of phenolic resins and related polymers

Paper-based phenolic laminates are used extensively in the electrical industry. Many small components are fabricated from these materials by the process known as punching. Recently an investigation was carried out to study the effect of processing variables on the punching properties. It was concluded that further work would be justified and that this should include a critical examination of the resin properties in a more controlled and systematic manner. In this investigation an attempt has been made to assess certain features of the resin structure in terms of thermomechanical properties. The number of crosslinks in the system was controlled using resins based on phenol and para-cresol formulations. Intramolecular hydrogen bonding effects were examined using substituted resins and a synthetically derived phenol based on 1,3-di-(o-hydroxyphenyl) propane.. A resin system was developed using the Friedel Crafts reaction to examine inter-molecular hydrogen bonding at the resin-paper interface. The punching properties of certain selected resins were assessed on a qualitative basis. In addition flexural and dynamic mechanical properties were determined in a general study of the structure-property relationships of these materials. It has been shown that certain features of the resin structure significantly influenced mechanical properties. :F'urther, it was noted that there is a close relationship between punching properties, mechanical damping and flexural strain. This work includes a critical examination of the curing mechanism and views are postulated in an attempt to extend knowledge in this area of the work. Finally, it is argued that future work should be based on a synthetic approach and that dynamic mechanical testing would provide a powerful tool In developing a deeper understanding of the resin fine structure.

The development of chemical exposure limits for the workplace

The thesis examines and explains the development of occupational exposure limits (OELs) as a means of preventing work related disease and ill health. The research focuses on the USA and UK and sets the work within a certain historical and social context. A subsidiary aim of the thesis is to identify any short comings in OELs and the methods by which they are set and suggest alternatives. The research framework uses Thomas Kuhn's idea of science progressing by means of paradigms which he describes at one point, `lq ... universally recognised scientific achievements that for a time provide model problems and solutions to a community of practitioners. KUHN (1970). Once learned individuals in the community, `lq ... are committed to the same rules and standards for scientific practice. Ibid. Kuhn's ideas are adapted by combining them with a view of industrial hygiene as an applied science-based profession having many of the qualities of non-scientific professions. The great advantage of this approach to OELs is that it keeps the analysis grounded in the behaviour and priorities of the groups which have forged, propounded, used, benefited from, and defended, them. The development and use of OELs on a larger scale is shown to be connected to the growth of a new profession in the USA; industrial hygiene, with the assistance of another new profession; industrial toxicology. The origins of these professions, particularly industrial hygiene, are traced. By examining the growth of the professions and the writings of key individuals it is possible to show how technical, economic and social factors became embedded in the OEL paradigm which industrial hygienists and toxicologists forged. The origin, mission and needs of these professions and their clients made such influences almost inevitable. The use of the OEL paradigm in practice is examined by an analysis of the process of the American Conference of Governmental Industrial Hygienists, Threshold Limit Value (ACGIH, TLV) Committee via the Minutes from 1962-1984. A similar approach is taken with the development of OELs in the UK. Although the form and definition of TLVs has encouraged the belief that they are health-based OELs the conclusion is that they, and most other OELs, are, and always have been, reasonably practicable limits: the degree of risk posed by a substance is weighed against the feasibility and cost of controlling exposure to that substance. The confusion over the status of TLVs and other OELs is seen to be a confusion at the heart of the OEL paradigm and the historical perspective explains why this should be. The paradigm has prevented the creation of truly health-based and, conversely, truly reasonably practicable OELs. In the final part of the thesis the analysis of the development of OELs is set in a contemporary context and a proposal for a two-stage, two-committee procedure for producing sets of OELs is put forward. This approach is set within an alternative OEL paradigm. The advantages, benefits and likely obstacles to these proposals are discussed.

Characterisation of a cavity transfer mixer as a chemical reactor

This research project examined the feasibility of using a cavity transfer mixer (CTM) as a continuous reactor to perform reactions between either solid or liquid reagents and polymer melt; reactions which have previously been typically carried out in batch reactor systems. Equipment has been developed to allow uniform and reproducible introduction of reagents into the polymer melt. Reactions have also been performed using batch processing equipment to enable comparison with the performance of the CTM. It was concluded that: a) there are certain reactions which cannot be carried out in a CTM, but which can be performed in a batch system such as a mill or a sigma blade mixer. This was found to be the case for some neutralisation reactions where the product was quasi crosslinked. b) the reactions that can be carried out in a CTM are performed more efficiently in a CTM than on a batch process. For example, when monomers were to be grafted onto polymers, this was more safely and efficiently performed in the CTM than in a mill or a sigma blade mixer. Residence time distributions (RTDs) for three CTMs were studied in order to gain an insight into the effect of CTM geometry on RTD, polymer melt flow pattern and reactor performance. A mathematical model has been developed to predict the influence of process parameters on RTD and the results compared with experimentally observed trends. The comparison was good. A programme of research has been drawn up to form the basis of an industrially based sponsored development project of the CTM reactor. This work programme was successfully marketed to companies with commercial interest in modified rubber and plastics as an integral part of the research programme of this thesis and the sponsored research programme has paralleled the work reported here.

Automation, rationalisation and concentration : a case study in the British chemical industry

This thesis is based upon a case study of the adoption of digital, electronic, microprocessor-based control systems by Albright & Wilson Limited - a UK chemical producer. It offers an explanation of the company's changing technology policy between 1978 and 1981, by examining its past development, internal features and industrial environment. Part One of the thesis gives an industry-level analysis which relates the development of process control technology to changes in the economic requirements of production . The rapid diffusion of microcomputers and other microelectronic equipment in the chemical industry is found to be a response to general need to raise the efficiency of all processes, imposed by the economic recession following 1973. Part Two examines the impaot of these technical and eoonomic ohanges upon Albright & Wilson Limited. The company's slowness in adopting new control technology is explained by its long history in which trends are identified whlich produced theconservatism of the 1970s. By contrast, a study of Tenneco Incorporated, a much more successful adoptor of automating technology, is offered with an analysis of the new technology policy of adoption of such equipment which it imposed upon Albright & Wilson, following the latter's takeover by Tenneco in 1978. Some indications of the consequences by this new policy of widespread adoptions of microprocessor-based control equipment are derived from a study of the first Albright & Wilson plant to use such equipment. The thesis concludes that companies which fail to adopt rapidly the new control technology may not survive in the recessionary environment, the long- established British companies may lack the flexibility to make such necessary changes and that multi-national companies may have an important role jn the planned transfer and adoption of new production technology through their subsidiaries in the UK.

Intermediate pyrolysis studies of aquatic biomass and potential applications in the BtVB-process

Aquatic biomass is seen as one of the major feedstocks to overcome difficulties associated with 1st generation biofuels, such as competition with food production, change of land use and further environmental issues. Although, this finding is widely accepted only little work has been carried out to investigate thermo-chemical conversion of algal specimen to produce biofuels, power and heat. This work aims at contributing fundamental knowledge for thermo-chemical processing of aquatic biomass via intermediate pyrolysis. Therefore, it was necessary to install and commission an analytical pyrolysis apparatus which facilitates intermediate pyrolysis process conditions as well as subsequent separation and detection of pyrolysates (Py- GC/MS). In addition, a methodology was established to analyse aquatic biomass under intermediate conditions by Thermo-Gravimetric Analysis (TGA). Several microalgae (e.g. Chlamydomonas reinhardtii, Chlorella vulgaris) and macroalgae specimen (e.g. Fucus vesiculosus) from main algal divisions and various natural habitats (fresh and saline water, temperate and polar climates) were chosen and their thermal degradation under intermediate pyrolysis conditions was studied. In addition, it was of interest to examine the contribution of biochemical constituents of algal biomass onto the chemical compounds contained in pyrolysates. Therefore, lipid and protein fractions were extracted from microalgae biomass and analysed separately. Furthermore, investigations of residual algal materials obtained by extraction of high valuable compounds (e.g. lipids, proteins, enzymes) were included to evaluate their potential for intermediate pyrolysis processing. On basis of these thermal degradation studies, possible applications of algal biomass and from there derived materials in the Bio-thermal Valorisation of Biomass-process (BtVB-process) are presented. It was of interest to evaluate the combination of the production of high valuable products and bioenergy generation derived by micro- and macro algal biomass.

Mass transfer and chemical reaction on a distillation plate

A multistage distillation column in which mass transfer and a reversible chemical reaction occurred simultaneously, has been investigated to formulate a technique by which this process can be analysed or predicted. A transesterification reaction between ethyl alcohol and butyl acetate, catalysed by concentrated sulphuric acid, was selected for the investigation and all the components were analysed on a gas liquid chromatograph. The transesterification reaction kinetics have been studied in a batch reactor for catalyst concentrations of 0.1 - 1.0 weight percent and temperatures between 21.4 and 85.0 °C. The reaction was found to be second order and dependent on the catalyst concentration at a given temperature. The vapour liquid equilibrium data for six binary, four ternary and one quaternary systems are measured at atmospheric pressure using a modified Cathala dynamic equilibrium still. The systems with the exception of ethyl alcohol - butyl alcohol mixtures, were found to be non-ideal. Multicomponent vapour liquid equilibrium compositions were predicted by a computer programme which utilised the Van Laar constants obtained from the binary data sets. Good agreement was obtained between the predicted and experimental quaternary equilibrium vapour compositions. Continuous transesterification experiments were carried out in a six stage sieve plate distillation column. The column was 3" in internal diameter and of unit construction in glass. The plates were 8" apart and had a free area of 7.7%. Both the liquid and vapour streams were analysed. The component conversion was dependent on the boilup rate and the reflux ratio. Because of the presence of the reaction, the concentration of one of the lighter components increased below the feed plate. In the same region a highly developed foam was formed due to the presence of the catalyst. The experimental results were analysed by the solution of a series of simultaneous enthalpy and mass equations. Good agreement was obtained between the experimental and calculated results.

Strain-facilitated process for the lift-off of a Si layer of less than 20 nm thickness

We report a process for the lift-off of an ultrathin Si layer. By plasma hydrogenation of a molecular-beam-epitaxy-grown heterostructure of SiSb-doped-SiSi, ultrashallow cracking is controlled to occur at the depth of the Sb-doped layer. Prior to hydrogenation, an oxygen plasma treatment is used to induce the formation of a thin oxide layer on the surface of the heterostructure. Chemical etching of the surface oxide layer after hydrogenation further thins the thickness of the separated Si layer to be only 15 nm. Mechanisms of hydrogen trapping and strain-facilitated cracking are discussed. © 2005 American Institute of Physics.

Pyrolysis study of halogen-containing aromatics reflecting reactions with polypropylene in a posttreatment decontamination process

Halogen-containing aromatics, mainly bromine-containing phenols, are harmful compounds contaminating pyrolysis oil from electronic boards containing halogenated flame retardants. In addition, theirformation increases the potential for evolution of polybrominated dibenzo-p-dioxins (PBDDs) and dibenzofurans (PBDFs) at relatively low temperature (up to 500 °C). As a model compound, 2,4-dibromophenol (DBP) was pyrolyzed at 290-450 °C. While its pyrolysis in a nitrogen flow reactor or in encapsulated ampules yields bromine-containing phenols, phenoxyphenols, PBDDs, and PBDFs, pyrolysis of DBP in a hydrogen-donating medium of polypropylene (PP) at 290-350 °C mainly results in the formation of phenol and HBr, indicating the occurrence of a facile hydrodebromination of DBP. The hydrodebromination efficiency depends on temperature, pressure, and the ratio of the initial components. This thermal behavior of DBP is compared to that of 2,4-dichlorophenol and decabromodiphenyl ether. A treatment of halogen-containing aromatics with PP offers a new perspective on the development of low-environmental-impact disposal processes for electronic scrap. © 2005 American Chemical Society.

Simulation process of biodiesel production over heterogeneous catalysts

Biodiesel production is a very promising area due to the relevance that it is an environmental-friendly diesel fuel alternative to fossil fuel derived diesel fuels. Nowadays, most industrial applications of biodiesel production are performed by the transesterification of renewable biological sources based on homogeneous acid catalysts, which requires downstream neutralization and separation leading to a series of technical and environmental problems. However, heterogeneous catalyst can solve these issues, and be used as a better alternative for biodiesel production. Thus, a heuristic diffusion-reaction kinetic model has been established to simulate the transesterification of alkyl ester with methanol over a series of heterogeneous Cs-doped heteropolyacid catalysts. The novelty of this framework lies in detailed modeling of surface reacting kinetic phenomena and integrating that with particle-level transport phenomena all the way through to process design and optimisation, which has been done for biodiesel production process for the first time. This multi-disciplinary research combining chemistry, chemical engineering and process integration offers better insights into catalyst design and process intensification for the industrial application of Cs-doped heteropolyacid catalysts for biodiesel production. A case study of the transesterification of tributyrin with methanol has been demonstrated to establish the effectiveness of this methodology.

Simulation process of biodiesel production over heterogeneous catalysts

Biodiesel production is a very promising area due to the relevance that it is an environmental-friendly diesel fuel alternative to fossil fuel derived diesel fuels. Nowadays, most industrial applications of biodiesel production are performed by the transesterification of renewable biological sources based on homogeneous acid catalysts, which requires downstream neutralization and separation leading to a series of technical and environmental problems. However, heterogeneous catalyst can solve these issues, and be used as a better alternative for biodiesel production. Thus, a heuristic diffusion-reaction kinetic model has been established to simulate the transesterification of alkyl ester with methanol over a series of heterogeneous Cs-doped heteropolyacid catalysts. The novelty of this framework lies in detailed modeling of surface reacting kinetic phenomena and integrating that with particle-level transport phenomena all the way through to process design and optimisation, which has been done for biodiesel production process for the first time. This multi-disciplinary research combining chemistry, chemical engineering and process integration offers better insights into catalyst design and process intensification for the industrial application of Cs-doped heteropolyacid catalysts for biodiesel production. A case study of the transesterification of tributyrin with methanol has been demonstrated to establish the effectiveness of this methodology.

Optical biochemical sensors based on long-period fibre gratings UV-inscribed in D-fibre with enhanced sensitivity by HF etching process

We report a new concept of biochemical sensor device based on long-period grating structures UV-inscribed in D-fiber. The surrounding-medium refractive index sensitivity of the devices has been enhanced significantly by a hydrofluoric acid etching process. The devices have been used to measure the sugar concentrations showing clearly an encoding relation between the chemical concentration and the grating spectral response, demonstrating their capability for potential biochemical sensing applications.