Waste plastic disposal and excessive use of fossil fuels have caused environment concerns in the world. Both plastics and petroleum derived fuels are hydrocarbons that contain the elements of carbon and hydrogen. The difference between them is that plastic molecules have longer carbon chains than those in LPG, petrol, and diesel fuels. Therefore, it is possible to convert waste plastic into fuels. The main objectives of this study were to understand and optimize the processes of plastic pyrolysis for maximizing the diesel range products, and to design a continuous pyrolysis apparatus as a semi-scale commercial plant. Pyrolysis of polyethylene (PE), polypropylene (PP), and polystyrene (PS) has been investigated both theoretically and experimentally in a lab-scale pyrolysis reactor. The key factors have been investigated and identified. The cracking temperature for PE and PP in the pyrolysis is at 450 ºC, but that of PS is lower, at 320 ºC. High reaction temperature and heating rate can significantly promote the production of light hydrocarbons. Long residence time also favours the yield of the light hydrocarbon products. The effects of other factors like type of reactor, catalyst, pressure and reflux rate have also been investigated in the literature review. From the literature review, the pyrolysis reaction consists of three progressive steps: initiation, propagation, and termination. Initiation reaction cracks the large polymer molecules into free radicals. The free radicals and the molecular species can be further cracked into smaller radicals and molecules during the propagation reactions. β-scission is the dominant reaction in the PE propagation reactions. At last, the radicals will combine together into stable molecules, which are termination reactions. There are three types of cracking of the polymers: random cracking, chain strip cracking, and end chain cracking. The major cracking on the polymer molecular backbone is random cracking. Some cracking occurs at the ends of the molecules or the free radicals, which is end chain cracking. Some polymers have reactive functional side group on their molecular backbones. The functional groups will break off the backbone, which is chain strip cracking. Chain strip cracking is the dominant cracking reaction during polystyrene pyrolysis. The reaction kinetics was investigated in this study. The activation energy and the energy requirement for the pyrolysis are dependent on the reaction process and the distribution of the final products. Following the equations from other literatures, the theoretical energy requirement for pyrolyze 1kg PE is 1.047 MJ. The estimated calorific value of the products is about 43.3 MJ/kg. Therefore, the energy profit is very high for this process. The PE pyrolysis products are mainly 1-alkenes, n-alkanes, and α, ω-dialkenes ranging from C1 to C45+. The 1-alkenes and the n-alkanes were identified with a special method developed in this research. It was found that secondary cracking process has a significant influence on the distribution of the product. This process converts heavy hydrocarbons into gas or light liquid product and significantly reduces 1-alkenes and α, ω-dialkenes. This secondary process can be controlled by adjusting the reflux rate of the primary product. The product of PE pyrolysis with maximized diesel range output consist of 18.3% non-condensable gases, 81.7% w/w liquid product, and less than 1% pure carbon under high reflux rate process. Some zeolite catalysts were tested to reduce the heavy molecular weight wax. It was found that NKC-5 (ZSM-5) was the most effective catalyst among zeolites tested. The proportion of the non-condensable gases was promoted from 17% w/w to 58% w/w by adding 10% w/w NKC-5 into the PE feedstock. The products of PP pyrolysis are mainly methyl- oligomers. The reflux effect on the product from pyrolysis of PP is not as great as that on PE. The PP pyrolysis product with high reflux rate consists of 15.7% non-condensable gases, 84.2% condensed liquid product, and less than 0.25% char. Cyclohexane is the dominant component, 21%w/w in the liquid product. 44%v/v of the non-condensable gases is propene. In the pyrolysis product of PS, there are 4% non-condensable gases, 93% liquid, and 3% char. Styrene accounts for 68.59%w/w in the PS liquid pyrolysis products due to the chain strip reactions. There was 19% v/v hydrogen in the gas product, which did not exist in the PE pyrolysis gas product. The composition of the char is almost pure carbon, which is similar to that from PE pyrolysis. The mixture of virgin and post-consumer PE, PP and PS have also been investigated to identify the feedstock interaction and the effect of the contamination on the product. The interaction promotes the production of non-condensable gases. However, the effect of the interaction on the distribution of total product is not significant. Contamination of paper labels on the post-consumer plastics may result in higher solid residue in the product but no significant effect on the product was found in this study. Based on the achievements, a continuous semi-scale reactor has been designed and constructed at maximum capacity of 27.11kg/hr in this research. From the experiments of pyrolysis of both virgin PE and post-consumer PE on this semi-scale pyrolysis reactor, it was found that the major components are 1-alkenes, n-alkanes, and α, ω- dialkenes. The distribution of the condensed products of PE pyrolysis from the semiscale reactor is the same as that of the products from low reflux rate process with the lab-scale reactor. However, the proportion of non-condensable gases is much higher than that from pyrolysis in the lab-scale tests with low reflux rate because the semiscale plant has higher reaction temperature and heating rate. Lower proportion of unsaturated hydrocarbons was found in the condensed product from the post-consumer PE pyrolysis than in the virgin PE product because of the contamination on the postconsumer PE. The actual energy consumption for cracking and vaporizing PE into fuels is 1.328 MJ/kg which is less than 3% of the calorific value of the pyrolysis products. Therefore, the pyrolysis technology has very high energy profit, 42.3 MJ/kg PE, and is environmental-friendly. The oil produced has very high quality and close to the commercial petroleum derived liquid fuels. The experience of design and operation of the semi-scale plant will be helpful for building a commercial scale plant in the future.

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The present work, where additional value-creating processes in existing combined heat and power (CHP) structures have been examined, is motivated by a political- and consumer-driven strive towards a bioeconomy and a stagnation for the existing business models in large parts of the CHP sector. The research is based on cases where the integration of flash pyrolysis for co-production of bio-oil, co-gasification for production of fuel gas and synthetic biofuels as well as leaching of extractable fuel components in existing CHP plants have been simulated. In particular, this work has focused on the CHP plants that utilize boilers of fluidized bed (FB) type, where the concept of coupling a separate FB reactor to the FB of the boiler forms an important basis for the analyses. In such dual fluidized bed (DFB) technology, heat is transferred from the boiler to the new rector that is operating with other fluidization media than air, thereby enabling other thermochemical processes than combustion to take place. The result of this work shows that broader operations at existing CHP plants have the potential to enable production of significant volumes of chemicals and/or fuels with high efficiency, while maintaining heat supply to external customers. Based on the insight that the technical preconditions for a broader operation are favourable, the motivation and ability among the incumbents in the Swedish CHP sector to participate in a transition of their operation towards a biorefinery was examined. The result of this assessment showed that the incumbents believe that a broader operation can create significant values for their own operations, the society and the environment, but that they lack both a strong motivation as well as important abilities to move into the new technological fields. If the concepts of broader production are widely implemented in the Swedish FB based CHP sector, this can substantially contribute in the transition towards a bioeconomy. / Bioeconomy has been identified to hold a great potential for reducing fossil fuel dependence and for maintaining and creating economic growth. Large parts of the combined heat and power (CHP) sector, which successfully have contributed in the transition towards a fossil free society, are at present facing stagnation. District heating actors are facing challenges due to warmer climate, better insulated buildings and competition from heat pumps. The forest industry where CHP plants supplies processes with heat is facing structural changes foremost in the graphic segments. The emerging bioeconomy and the stagnation for the existing business models in large parts of the CHP sector form the background for the examination of additional value-creating processes in the existing CHP structure presented in this thesis. The technical viability for integration of fast pyrolysis, gasification and leaching with existing CHP plants has been analysed as well as the motivation and ability of the CHP incumbents to participate in a transition towards the bioeconomy by developing their plants to biorefineries.

"This dissertation documents a study on parameter estimation methods for comprehensive pyrolysis modeling. There are four parts to this work, which are (1) evaluating effects of applying different kinetic models to pyrolysis modeling of fiberglass reinforced polymer composites; (2); evaluation of pyrolysis parameters for fiberglass reinforced polymer composites based on multi-objective optimization; (3) parameter estimation for comprehensive pyrolysis modeling: guidance and critical observations; and (4) engineering guide for estimating material pyrolysis properties for fire modeling. In the first section (Section 1), evaluation work is conducted to determine the effects of applying different kinetic models (KMs), developed based on thermal analysis using TGA data, when used in typical 1D pyrolysis models of fiberglass reinforced polymer (FRP) composites. The study shows that that increasing complexity of KMs to be used in pyrolysis modeling is unnecessary for the FRP samples investigated. Additionally, the findings from this research indicates that the basic assumption of considering thermal decomposition of each computational cell in comprehensive pyrolysis modeling as equivalent to that in a TGA experiment becomes inapplicable at depth and higher heating rates. The second part of this dissertation (Section 2) reports the results from a study conducted to investigate the ability of global, multi-objective and multi-variable optimization methods to estimate material parameters for comprehensive pyrolysis models. The research materials are two fiberglass reinforced polymer (FRP) composites that share the same fiberglass mats but with two different resin systems. One resin system is composed of a single component and the other system is composed of two components (resin and fire retardant additive). The results show that for a well-configured parameter estimation exercise using the optimization method described above, (1) estimated results are within ± 100% of the measurements in general; (2) increasing complexity of the kinetic modeling for a single component system has insignificant effect on estimated values; (3) increasing complexity of the kinetic modeling for a multiple component system with each element having different thermal characteristics has positive effect on estimated values; and (4) parameter estimation using an optimization method with appropriate level of complexity in kinetic model and optimization targets can find estimations that can be considered as effective material property values. The third part of this dissertation (Section 3) proposes a process for conducting parameter estimation for comprehensive pyrolysis models. The work describes the underlying concepts considered in the proposed process and gives discussions of its limitations. Additionally, example cases of parameter estimation exercise are shown to illustrate the application of the parameter estimation process. There are four materials considered in the example cases – thermoplastics (PMMA), corrugated cardboard, fiberglass reinforced polymer composites and plywood. In the last part (Section 4), the actual Guide, a standardized procedure for obtaining material parameters for input into a wide range of pyrolysis models is presented. This is a step-by-step process that provides a brief description of modeling approaches and assumptions; a typical mathematical formulation to identify model parameters in the equations; and methods of estimating the model parameters either by independent measurements or optimization in pair with the model. In the Guide, example cases are given to show how the process can be applied to different types of real-world materials. "

Typescript (photocopy). / Digitized by Kansas Correctional Industries

(¤@)FVP of (4-Methoxystyryl)pyridenes gave the corresponding phenol products 18 and tricyclic products 20, which all included indene structure. (¤G)FVP of ortho-Chlorostyrylarenes gave the cyclized prodccts 17, which eliminated chloro group. Photolytic study of ortho-Chlorostyrylarenes gave chloro-containing cyclized products 22.

Thermal gasification of biomass is being considered as one of the most promising technologies for converting biomass into gaseous fuel. Here we present results of gasification, using an adiabatic bed gasifier with air, steam as gasification medium, of mesquite and juniper. From Thermo-gravimetric analyses the pre-exponential factor (B) and activation energy of fuels for pyrolysis were obtained using single reaction models (SRM) and parallel reaction model (PRM). The single reaction model including convention Arrhenius (SRM-CA) and maximum volatile release rate model (SRM-MVR). The parallel reaction model fits the experimental data very well, followed by MVR. The CA model the least accurate model. The activation energies obtained from PRM are around 161,000 kJ/kmol and 158,000 kJ/kmol for juniper and mesquite fuels, respectively. And, the activation energies obtained from MVR are around100,000 kJ/kmol and 85,000 kJ/kmol for juniper and mesquite fuels, respectively. The effects of equivalence ratio (ER), particle size, and moisture content on the temperature profile, gas composition, tar yield, and higher heating value (HHV) were investigated. For air gasification, when moisture increased from 6% to 12% and ER decreased from 4.2 to 2.7, the mole composition of the dry product gas for mesquite varied as follow: 18-30% CO, 2-5% H2, 1-1.5% CH4, 0.4-0.6% C2H6, 52-64% N2, and 10-12% CO2. The tar yield shows peak value (150 g/Nm^3) with change in moisture content between 6-24%. The tar collected from the gasification process included light tar and heavy tar. The main composition of the light tar was moisture. The chemical properties of heavy tar were determined. For air-steam gasification, H2 rich mixture gas was produced. The HHV of the mesquite gas increased first when S: F ratio increased from 0.15 to 0.3 and when the S: F ratio increased to 0.45, HHV of the gas decreased. Mesquite was blended with the Wyoming Powder River Basin (PRB) coal with ratio of 90:10 and 80:20 in order to increase the Tpeak and HHV. It was found that the Tpeak increased with the increase of PRB coal weight percentage (0% to 20%).

Y2O3:Eu particles are phosphors that have found wide applications. Flamesynthesized Y2O3:Eu particles may have either the cubic or the monoclinic structure. The effects of particle size and Eu doping concentration on crystal structure and the surface elemental composition of the flame-synthesized Y2O3:Eu particles had not been previously reported. In this study, a flame aerosol process was used to generate polydisperse Y2O3:Eu particle. H2 was used as the fuel gas, with either air or O2 gas as the oxidizer. The precursor was aqueous solutions of the metal nitrates, atomized using a 1.7-MHz ultrasonic atomizer. The product particles were analyzed by transmission electron microscopy (TEM), X-ray diffractometer (XRD), Selected area electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), fluorescence spectrophotometer, and inductively coupled plasma mass spectrometer (ICP-MS). The Y2O3:Eu particles generated in H2/O2 flames were spherical and fully dense, with diameters in the range of 10~3000 nm. In particle samples with lower Eu doping concentrations, a critical particle diameter was found, whose value increased with increasing Eu doping concentration. Particles well below the critical diameter had the monoclinic structure; those well above the critical diameter had the cubic structure. At sufficiently high Eu doping concentrations, all Y2O3:Eu generated in H2/O2 flames had the monoclinic structure. On the other hand, all particles generated in the H2/air flames had the cubic structure. For the Y2O3:Eu particles generated in H2/O2 flames, XPS results showed that the surface Eu concentration was several times higher than the doping concentration. For Y2O3:Eu particles generated in H2/air flames, the surface Eu concentration was equal to the doping concentration. For both types of particles, the photoluminescence intensity reached a maximum corresponding to a surface Eu concentration 40~50%. The photoluminescence intensity then decreased rapidly with higher Eu doping concentration. The effect of particle size and Eu doping concentration on crystal structure may be explained by the interplay between surface energy and polymorphism. A mechanism for this surface enrichment phenomenon was proposed based on the binary Eu2O3-Y2O3 phase diagram.

The need for clean potable water and sustainable energy are two current and pressing issues with implications affecting the global population. Renewed interests in alternative energy have prompted researchers to investigate the full capacity of biofuels. These interests have led to not only the examination of current method limitations, but also to the investigation of new conversion methods. One promising method for bioenergy production is pyrolysis of lignocellulosic feedstocks. Through pyrolysis, a single crop may produce ethanol, bio-oil, and/or gaseous energy (syngas). The remaining solid phase product is a black carbon dubbed 'biochar'. In the current study, biochar was used as a both an unamended sorbent and a precursor to form powdered activated carbons (PACs) capable of removing waterborne viruses. Biochar was activated with KOH, ZnCl2, and H3PO4 and analyzed using the Brunauer, Emmett and Teller (BET) method, a combination of Kjeldahl digest and ICP-MS, and scanning electron microscopy (SEM). Sorbents were tested in batch studies using phosphate buffered saline (PBS), surface water, and groundwater. Bacteriophages MS2 and thetaX174 served as viral surrogates. All activation treatments significantly increased surface area, up to 1495.5 m2/g (KOH-activated). While the non-activated biochar was not effective in virus removal, the KOH-activated PAC had tremendous removal in the PBS/MS2 batch (mean 98.7% removal, up to 6.2 x 109 particles/mL, as compared to the Darco S-51: 82.3%). As evidenced by this study, sorption efficiency will be governed by viral species, carbon type and concentration, and water quality. The results of this study indicate that biochar can serve as a precursor for a highly porous and effective PAC, capable of removing waterborne viruses from environmental waters.

(1)Flash vaccum pyrolysis of furo[3,2-c]pyran-4-one gave starting material, but in photolytic system we gave a isomer: furo[2,3-c]pyran-5-one. (2)Flash vaccum pyrolysis of benzoic 1,2-dimethyl-3-indoly anhydride,via a ketene intermediate,gave a dimmer.