Theoretical and experimental study on the emission characteristics of waste plastics incineration by modified O2/RFG combustion technology

For mitigating the emission of greenhouse gas CO₂ from general air combustion systems, a clean combustion technology O₂/RFG is in development. The O₂/RFG combustion technology can significantly enhance the CO₂ concentration in the flue gas; however, using almost pure oxygen or pure CO₂ as feed gas is uneconomic and impractical. As a result, this study proposes a modified O₂/RFG combustion technology in which the minimum pure oxygen is mixed with the recycled flue gas and air to serve as the feed gas. The effects of different feed gas compositions and ratios of recycled flue gas on the emission characteristics of CO₂, CO and NO_x during the plastics incineration are investigated by theoretical and experimental approaches.Theoretical calculations were carried out by a thermodynamic equilibrium program and the results indicated that the emissions of CO₂ were increased with the O₂ concentrations in the feed gas and the ratios of recycled flue gas increased. Experimental results did not have the same trends with theoretical calculations. The best feed gas composition of the modified O₂/RFG combustion was 40% O₂ + 60% N₂ and the best ratio of recycled flue gas was 15%. As the O₂ concentration in feed gas and the ratio of recycled flue gas increased, the total flow rates and pressures of feed gas reduced. The mixing of solid waste and feed gas was incomplete and the formation of CO₂ decreased. Moreover, the emission of CO was decreased as the O₂ concentration in feed gas and the ratio of recycled flue gas increased. The emission of NO_x gradually increased with rising the ratio of recycled flue gas at lower O₂ concentration (<40%) but decreased at higher O₂ concentration (>60%).     

Experimental investigation of NOx emissions in oxycoal combustion

This work presents the results of an experimental investigation on NO_x emissions from coal combustion in a pilot scale test facility. Three oxidiser atmospheres have been compared, namely air, CO₂/O₂, and O₂ enriched recirculated flue gas. NO_x emissions from two different combustion modes have been studied, swirl flame and flameless combustion. The influence of the burner oxygen ratio and the oxidiser O₂ concentration on NO_x formation and reduction have been analysed. With increasing burner oxygen ratio, an increase of NO_x emissions has been obtained for air and CO₂/O₂ in both, swirl flame and flameless combustion. In case of the swirl flame, flue gas recirculation leads to a reduction of NO_x emissions up to 50%, whereas in case of flameless combustion this reduction is around 40% compared to CO₂/O₂. No significant impact of the oxidiser O₂ concentration in the CO₂/O₂ mixture on NO_x emissions is observed in the range between 18 and 27 vol.% in swirl flames. An analysis of NO_x formation and reduction mechanisms showed, that the observed reduction of NO_x emissions by flue gas recirculation cannot be attributed to the reduction of recirculated NO_x alone, but also to a reduced conversion of fuel-N to NO.     

Pulverized coal combustion in air and in O2/CO2 mixtures with NOx recycle

This paper presents experimental results of a 20 kW vertical combustor equipped with a single pf-burner on pulverised coal combustion in air and O₂/CO₂ mixtures with NO_x recycle. Experimental results on combustion performance and NO_x emissions of seven international bituminous coals in air and in O₂/CO₂ mixtures confirm the previous findings of the authors that the O₂ concentration in the O₂/CO₂ mixture has to be 30% or higher to produce matching temperature profiles to those of coal-air combustion while coal combustion in 30% O₂/70% CO₂ leads to better coal burnout and less NO_x emissions than coal combustion in air. Experimental results with NO_x recycle reveal that the reduction of the recycled NO depends on the combustion media, combustion mode (staging or non-staging) and recycling location. Generally, more NO is reduced with coal combustion in 30% O₂/70% CO₂ than with coal combustion in air. Up to 88 and 92% reductions of the recycled NO can be achieved with coal combustion in air and in 30% O₂/70% CO₂ respectively. More NO is reduced with oxidant staging than without oxidant staging when NO is recycled through the burner. Much more NO is reduced when NO recycled through the burner (from 65 to 92%) than when NO is recycled through the staging tertiary oxidant ports (from 33 to 54%). The concentration of the recycled NO has little influence on the reduction efficiency of the recycled NO with both combustion media—air and 30% O₂/70% CO₂.     

Modeling of oxy-fuel combustion for a western Canadian sub-bituminous coal

The motivation of this research is to develop practical oxy-coal combustion techniques in order to facilitate the conversion of coal-fired utility power plants so as to recover a CO₂ rich flue gas stream for use and/or sequestration. The objective of this study is to ascertain the applicability and accuracy of a modeling tool to assist with future pilot scale oxy-fuel combustion experiments and burner scale-up studies. Two modes of oxy-coal combustion, O₂ enriched air (OEA) and recycled flue gas (RFG), were experimentally tested in a 0.3 MW_th pilot-scale combustor using a western Canadian sub-bituminous coal. The computational fluid dynamic tool was utilized to model the combustion, heat transfer and pollutant formation characteristics of these test cases and to examine the impact due to changes in the combustion medium, burner swirl and burner configuration. The model provided insights for the observed variation in NO_x production among the test cases: the dramatic increase in the OEA mode, the drop at higher burner swirl settings and the surprisingly small reduction in the RFG mode. Overall the model results compared well with measured data in all test cases and established confidence in using the model to explore new design concepts for oxy-coal combustion.     

CO2 capture using oxygen enhanced combustion strategies for natural gas power plants

This paper describes a series of experiments conducted with natural gas in air and in mixtures of oxygen and recycled flue gas, termed O₂/CO₂ recycle combustion. The objective is to enrich the flue gas with CO₂ to facilitate its capture and sequestration. Detailed measurements of gas composition, flame temperature and heat flux profiles were taken inside CANMET's 0.3 MWth down-fired vertical combustor fitted with a proprietary pilot scale burner. Flue gas composition was continuously monitored. The effects of burner operation, including swirling of secondary stream and air staging, on flame characteristics and NO_x emissions were also studied. The results of this work indicate that oxy-gas combustion techniques based on O₂/CO₂ combustion with flue gas recycle offer excellent potential for retrofit to conventional boilers for CO₂ emission abatement. Other benefits of the technology include considerable reduction and even elimination of NO_x emissions, improved plant efficiency due to lower gas volume and better operational flexibility.     

The effect of O2 enrichment on NOx formation in biomass co-fired pulverised coal combustion

Oxygen enrichment of the combustion air in pulverised coal combustion for power plant is seen as a possible retrofit measure to improve CO₂ scrubbing and capture. This technique produces a reduced volume of flue gas with higher CO₂ concentration than normal air combustion that will contributes to the enhancement of amine scrubbing plant efficiencies. We report in this article the results of a study at the small pilot scale into the effect of these combustion modifications on the formation of NO_x and associated carbon burnout changes. Experiments were performed using a Russian coal, typical of that used in some UK power stations with shea meal and Pakistani cotton stalk as biomass fuels co-fired at a fraction of 15%th. The down-fired pulverised coal combustor was operated at 20 kWth under air-staged conditions for NO_x control and the secondary and over-fire air flows were both enriched by up to 79% (100% O₂) for a range of splits giving a 35% overall O₂ concentration for full enrichment. When the same enrichment process was applied to biomass/coal combustion different behaviour was observed with respect to NO_x formation. We have shown that oxygen enrichment can achieve benefits of improved carbon burnout with a positive impact on NO_x emissions over and above the primary aim of increasing CO₂ concentration in the flue gas for enhanced capture efficiencies. With all other conditions of overall stoichiometry, OFA levels and O₂ enrichment levels remaining the same, NO_x levels at 22% OFA initially increased over the range of secondary air enrichment, particularly for shea meal/coal co-firing. At 31% OFA the trends were to lower NO_x at high enrichment levels. However, co-firing with shea meal initially showed an increase in NO_x emission at lower levels of enrichment (up to 40% O₂) followed by overall lower NOx emissions at 100% O₂ in the secondary air. The results show that NO_x emissions can either increase or decrease depending on the operating conditions. The differences in behaviour are attributed, not only to the effects of enrichment on the stoichiometry of the near-burner zone, but also on the flame dynamics and intensity of combustion related to the associated reductions in gas velocity and swirl intensity by the transition from air to pure O₂ in the secondary oxidant stream.     

Catalytic Conversions of Polychlorinated Benzenes and Dioxins with Low-chlorine Using V2O5/TiO2

Chlorinated benzene, especially 1,2-dichlorobenzene (1,2-DCB), has been widely used as one of surrogate compounds of dioxin to find the noble methods to control dioxin. However, the relationship between the catalytic activity of dioxin surrogate compound and dioxin has not been understood quite well. In this work, we used a vanadium based catalyst (V₂O₅/TiO₂) to compare catalytic activity of chlorinated benzenes and dibenzo-p-dioxins with low-chlorine content using the lab-scale system. We investigated the catalytic conversions of low-chlorinated dioxins, [2-monochlorodibenzo-p-dioxin (2-MCDD), 2,3-dichlorodibenzo-p-dioxin (2,3-DCDD)] and polychlorinated benzenes [1,2-DCB, 1,2,3,4-tetrachlorobenzene (1,2,3,4-TeCB), pentachlorobenzene (PeCB), hexachlorobenzene (HCB)] using a V₂O₅/TiO₂ catalyst to understand quantitative relationship between dioxin and benzene with the chlorination level. The catalytic decomposition of chlorinated aromatic compounds was following 1,2-DCB > 1,2,3,4-TeCB > 2-MCDD > PeCB ≥ 2,3-DCDD > HCB. It might be more reasonable that PeCB or HCB should be used as the dioxin surrogate compound rather than 1,2-DCB. Also, we investigated the effect of both O₂ content and space velocity (SV) on the catalytic decomposition of 1,2-DCB in the presence of V₂O₅/TiO₂ catalyst because these factors should be considered significantly in combustion facilities to control various pollutants. The decomposition of 1,2-DCB shows dependency on the SV while the effect of oxygen content on the catalytic decomposition is negligible in the range of 5–20%.     

Characteristics of polycyclic aromatic hydrocarbons emissions of diesel engine fueled with biodiesel and diesel

With mutagenic and carcinogenic potential, polycyclic aromatic hydrocarbons (PAHs) from mobile source exhaust have contributed to a substantial share of air toxics. In order to characterize the PAHs emissions of diesel engine fueled with diesel, biodiesel (B100) and its blend (B20), an experimental study has been carried out on a direct-injection turbocharged diesel engine. The particle-phase and gas-phase PAHs in engine exhaust were collected by fiberglass filters and “PUF/XAD-2/PUF” cartridges, respectively, then the PAHs were determined by a gas chromatograph/mass spectrometer (GC/MS). The experimental results indicated that comparing with diesel, using B100 and B20 can greatly reduce the total PAHs emissions of diesel engine by 19.4% and 13.1%, respectively. The Benzo[a]Pyrene (BaP) equivalent of PAHs emissions were also decreased by 15.0% with the use of B100. For the three fuels, the gas-phase PAHs emissions were higher than particle-phase PAHs emissions and the most abundant PAH compounds from engine exhaust were naphthalene and phenanthrene. The analysis showed that there was a close correlation between total PAHs emissions and particulate matter (PM) emissions for three fuels. Furthermore, the correlation became more significant when using biodiesel.     

Combustion characteristics of lignite-fired oxy-fuel flames

This experimental work describes the combustion characteristics of lignite-fired oxy-fuel flames, in terms of temperature distribution, gas composition (O₂, CO₂, CO, total hydrocarbon concentration and NO) and ignition behaviour. The aim is to evaluate the flame structure of three oxy-fuel cases (obtained by changing the flue gas recycle rate) including a comparison with an air-fired reference case. Measurements were performed in Chalmers 100 kW test unit, which facilitates oxy-fuel combustion under flue gas recycling conditions. Temperature, O₂ and CO concentration profiles and images of the flames indicate that earlier ignition and more intense combustion with higher peak temperatures follow from reduction of the recycle rate during oxy-fuel operation. This is mostly due to higher O₂ concentration in the feed gas, reduced cooling from the recycled flue gas, and change in flow patterns between the cases. The air case and the oxy-fuel case with the highest recycle rate were most sensitive to changes in overall stoichiometry. Despite significant differences in local CO concentration between the cases, the stack concentrations of CO are comparable. Hence, limiting CO emissions from oxy-fuel combustion is not more challenging than during air-firing. The NO emission, as shown previously, was significantly reduced by flue gas recycling.     

Experimental study of ash formation during pulverized coal combustion in O2/CO2 mixtures

The present paper was addressed to mineral transformations and ash formation during O₂/CO₂ combustion of pulverized coal. Four Chinese thermal coals were burned in a drop tube furnace to generate ashes under various combustion conditions. The ash samples were characterized with XRD analysis and ⁵⁷Fe Mössbauer spectroscopy. The impacts of O₂/CO₂ combustion on mineral transformation and ash formation were explored through comparisons between O₂/CO₂ combustion and O₂/N₂ combustion. It was found that, O₂/CO₂ combustion did not significantly change the mineral phases formed in the residue ashes, but did affect the relative amounts of the mineral phases. The differences observed in the ashes formed in two atmospheres were attributed to the impact of the gas atmosphere on the combustion temperatures of coal char particles, which consequently influenced the ash formation behaviors of included minerals.     

An investigation of the catalytic abatement of emissions from the combustion of diesel/bioethanol blends

In this study, we investigated the activity of pre-sulfated 1%Pt–2%Sn/γ–Al₂O₃ on the catalytic abatement of the combustion emissions of three fuels: pure diesel E(0), pure bioethanol E(100) and bioethanol blended diesel containing 10% bioethanol E(10). The emissions generated, by each blend combustion, were conducted continuously to the catalyst sample. The catalytic activity was determined by following the evolution of the outflow emissions concentrations by FTIR gas spectroscopy as a function of the catalyst temperature. Results showed that the addition of bioethanol to diesel may be necessary to enhance the catalytic oxidation of diesel unburned hydrocarbons and particulate matter on pre-sulfated 1%Pt–2%Sn/γ–Al₂O₃.     

The activity of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for PAHs removal in the waste incineration processes: Effects of particulates, heavy metals, and acid gases

This study investigated the activity of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for polycyclic aromatic hydrocarbons (PAHs) removal and the influence of particulates, heavy metals, and acid gases (SO₂ and HCl) on the performance of catalysts. The experiments were carried out in a laboratory-scale waste incineration system. Experimental results show that the destruction removal efficiency (DRE) of PAHs by Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts were 80% and 59%, respectively when the flue gas did not contain any pollutants. The concentrations of PAHs increased by using a Rh/Al₂O₃ catalyst when the flue gas contained Cd, Pb, and SO₂ and also increased by using a Rh-Na/Al₂O₃ catalyst when the flue gas contained particulates, Cd, and HCl. Adding Na to the Rh/Al₂O₃ catalyst can inhibit the increases of 3-4 ring PAHs when the flue gas contained Pb. The influence of acid gases on the performance of the Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts followed the sequence SO₂ > HCl > SO₂ + HCl. The activity of the catalysts for PAHs removal was significantly suppressed by increased concentrations in particulates and Cd, yet promoted by a high Pb concentration. The results of ESCA analysis indicated that the presence of Cd and Pb did not change the chemical states of Rh and Na, but the presence of SO₂ and HCl did.     

Photocatalytic conversion of benzene to phenol using modified TiO2 and polyoxometalates

The application of photocatalytic reactions to organic synthesis has attracted interests in view of the development of environmentally benign synthetic processes. This study investigated the effects of various parameters (electron acceptor, surface modification, and the combination of photocatalysts) on the direct synthesis of phenol from benzene using photocatalytic oxidation processes. The OH radicals generated on UV-illuminated TiO₂ photocatalyst directly hydroxylate benzene to produce phenol, hydroquinone, and catechol. The addition of Fe³⁺, H₂O₂, or Fe³⁺ + H₂O₂ highly enhanced the phenol production yield and selectivity in TiO₂ suspension. Surface modifications of TiO₂ had significant influence on the phenol synthetic reaction. Depositing Pt nanoparticles on TiO₂ (Pt/TiO₂) markedly enhanced the yield and selectivity. Surface fluorination of TiO₂ (F-TiO₂) increased the phenol yield two-fold because of the enhanced production of mobile (free) OH radicals on F-TiO₂. Polyoxometalate (POM) in phenol synthesis played the dual role both as a homogeneous photocatalyst and as a reversible electron acceptor in TiO₂ suspension. POM alone was as efficient as TiO₂ alone in the phenol production. In particular, the addition of POM to the TiO₂ suspension increased the phenol yield from 2.6% to 11% (the highest yield obtained in this study). Reaction mechanisms for each photocatalytic system were discussed in relation to the phenol synthesis.     

Simultaneous easy CO2 recovery and drastic reduction of SOx and NOx in O2/CO2 coal combustion with heat recirculation

Coal combustion with O₂/CO₂ is promising because of its easy CO₂ recovery, extremely low NO_x emission and high desulfurization efficiency. Based on our own fundamental experimental data combined with a sophisticated data analysis, its characteristics were investigated. It was revealed that the conversion ratio from fuel-N to exhausted NO in O₂/CO₂ pulverized coal combustion was only about one fourth of conventional pulverized coal combustion. To decrease exhausted NO further and realize simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x, a new scheme, i.e. O₂/CO₂ coal combustion with heat recirculation, was proposed. It was clarified that in O₂/CO₂ coal combustion, with about 40% of heat recirculation, the same coal combustion intensity as that of coal combustion in air could be realized even at an O₂ concentration of as low as 15%. Thus exhausted NO could be decreased further into only one seventh of conventional coal combustion. Simultaneous easy CO₂ recovery and drastic reduction of SO_x and NO_x could be realized with this new scheme.     

A new process for the synthesis of diphenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts

The two-step synthesis of diphenyl carbonate (DPC) from dimethyl carbonate (DMC) and phenol has been compared in liquid phase and gas phase, both over heterogeneous catalysts. In the first step, equilibrium yields of methyl phenyl carbonate (MPC) in the transesterification of DMC and phenol were very low at low temperatures in the liquid phase although reaction rates were fast. This endothermic reaction was more favorable at high temperatures in the gas-phase reaction. Titanium oxide catalysts supported on SiO₂ or activated carbon were found to be effective in a continuous gas flow reactor. In case of the second step, the disproportionation of MPC, selective formation of DPC was not feasible in the gas-phase reaction due to extensive side reactions. However, there was no by-product in the liquid-phase reaction over the TiO₂/SiO₂ catalyst. Therefore, our proposed two-step synthesis process consists of the gas-phase transesterification of DMC and phenol followed by the liquid-phase disproportionation of MPC to DPC, both over the TiO₂/SiO₂ catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Combustion characteristics of coal in a mixture of oxygen and recycled flue gas

The combustion of coal in a mixture of pure O₂ and recycled flue gas is one variant of a novel combustion approach called oxy-fuel combustion. With the absence of N₂, this approach leads to a flue gas stream highly enriched in CO₂. For many applications, this flue gas stream can then be compressed and sequestered without further separation. As a result, oxy-fuel combustion is an attractive way to capture CO₂ produced from fossil fuel combustion. When coal is burned in this O₂ and CO₂ rich environment, its combustion characteristics can be very different from conventional air-fired combustion. In CETC-O, a vertical combustor research facility has been used in the past years to investigate the combustion characteristics of several different coals with this variant of oxy-fuel combustion. This included flame stability, emissions of NO_x, SO_x and trace elements, heat transfer, in-furnace flame profiles and flue gas compositions. This paper will report some of the major findings obtained from these research activities.     

Catalytic oxidation of hydrogen over Au/TiO2 catalysts

Selective catalytic oxidation of hydrogen in the presence of hydrocarbons was studied in a fixed bed quartz reactor, over 3 wt%Au/TiO₂ and 5 wt%Au/TiO₂ catalysts. This reaction can be utilised in the production of light alkenes via catalytic dehydrogenation, providing in situ heat to the endothermic dehydrogenation reaction and simultaneously removing a fraction of the produced hydrogen. It is important to avoid the non-selective combustion of the hydrocarbons in the mixture. Both 3 wt%Au/TiO₂ and 5 wt%Au/TiO₂ are active for the combustion of hydrogen, but in a gas mixture with propane and oxygen the selectivity is dependent upon the feed ratio of hydrogen and oxygen. At 550 °C, with propane present, no carbon oxides are formed when the H₂:O₂ ratio is four, but at lower ratios some CO₂ and some CO is formed.     

One-step hydroxylation of benzene to phenol. II. Gas phase N2O oxidation over Mo/Fe/borosilicate molecular sieve

The Fe/Mo/partially deboronated borosilicate molecular sieve catalyst prepared by the chemical vapor deposition (CVD) method was active for the selective formation of phenol by gas-phase N₂O oxidation of benzene. The impregnated counterpart exhibited lower activity than the CVD catalyst. The borosilicate molecular sieve itself also was active. Two mechanistic paths are postulated based on reactive oxygen species such as O^–, which can be generated via interaction of N₂O with the iron sites in the CVD-borosilicate molecular sieve catalyst, or OH⁺, which can be generated by Brønsted sites on the borosilicate molecular sieve itself.     

Photocatalytic degradation of rhodamine B and phenol by solution combustion synthesized BiVO4 photocatalyst

Visible-light-induced BiVO₄ photocatalyst has been successfully synthesized via a solution combustion synthesis (SCS) method. The photocatalytic activities of the as-synthesized sample were evaluated by the photodegradation of rhodamine B (RhB) and phenol under visible-light irradiation (λ > 420 nm). The decolorization of high-concentrated RhB (10^− 4 M) and the variation of the chemical oxygen demand (COD), demonstrated that the BiVO₄ photocatalyst was efficient in aromatic organic compounds degradation. The reduction of total organic carbon (TOC) (about 22.0% after 4.5 h of irradiation) showed that the mineralization of RhB over the BiVO₄ photocatalyst is realized. Additionally, much enhanced photocatalytic performance for phenol degradation was also realized with the assistance of appropriate amount of H₂O₂.     

Comparisons of pulverized coal combustion in air and in mixtures of O2/CO2

Pulverized coal combustion in air and the mixtures of O₂/CO₂ has been experimentally investigated in a 20 kW down-fired combustor (190 mm id×3 m). Detailed comparisons of gas temperature profiles, gas composition profiles, char burnouts, conversions of coal–N to NO_x and coal–S to SO₂ and CO emissions have been made between coal combustion in air and coal combustion in various O₂/CO₂ mixtures. The effectiveness of air/oxidant staging on reducing NO_x emissions has also been investigated for coal combustion in air and O₂/CO₂ mixtures. The results show that simply replacing the N₂ in the combustion air with CO₂ will result in a significant decrease of combustion gas temperatures. However, coal combustion in 30% O₂/70% CO₂ can produce matching gas temperature profiles to those of coal combustion in air while having a lower coal–N to NO_x conversion, a better char burnout and a lower CO emission. The results also confirm that air/oxidant staging is very effective in reducing NO_x emissions for coal combustion in both air and a 30% O₂/70% CO₂ mixture. SO₂ emissions are proved to be almost independent of the combustion media investigated.