The measurement and significance of ATP pools in activated sludge treating coke oven liquors

Coke oven liquor is a toxic wastewater produced in large quantities by the Iron and Steel, and Coking Industries, and gives rise to major effluent treatment problems in those industries. Conscious of the potentially serious environmental impact of the discharge of such wastes, pollution control agencies in many countries have made progressively more stringent quality requirements for the discharge of the treated waste. The most common means of treating the waste is the activated sludge process. Problems with achieving consistently satisfactory treatment by this process have been experienced in the past. The need to improve the quality of the discharge of the treated waste prompted attempts by TOMLINS to model the process using Adenosine Triphosophnte (ATP) as a measure of biomass, but these were unsuccessful. This thesis describes work that was carried out to determine the significance of ATP in the activated sludge treatment of the waste. The use of ATP measurements in wastewater treatment were reviewed. Investigations were conducted into the ATP behaviour of the batch activated sludge treatment of two major components of the waste, phenol, and thiocyanate, and the continuous activated sludge treatment of the liquor itself, using laboratory scale apparatus. On the basis of these results equations were formulated to describe the significance of ATP as a measured activity and biomass in the treatment system. These were used as the basis for proposals to use ATP as a control parameter in the activated sludge treatment of coke oven liquor, and wastewaters in general. These had relevance both to the treatment of the waste in the reactor and to the settlement of the sludge produced in the secondary settlement stage of the treatment process.

A comparative study on the pyrolysis of metal- and ash-enriched wood and the combustion properties of the gained char

This study aims to investigate the pyrolysis behaviour of metal-contaminated wood and the combustion properties of char derived from wood pyrolysis. Seven metals (Na, Mg, Ca, Zn, Cd, Pb and Fe(III)) were introduced to willow in cation form by ion-exchange and the thermal behaviour of demineralised samples and samples with additional ash were also investigated. The results show that the char yield increased from 21% to 24-28% and levoglucosan yield in vapour phase decreased from 88% to 62-29% after the addition of inorganic compounds, even though the metal binding capacity of wood varied from one metal ion to another. While char yield seems to be effected mainly by the concentration of the metal ions, levoglucosan yield was more dependent on the ionic species especially when sodium ions were present. When combustion experiments were carried out with char made of the metal enriched wood, two consecutive steps were observed, both effected by the presence of inorganic compounds. The first step was identified as the release and combustion of volatiles, while the second peak of the burning profile is the actual combustion of the fixed carbon. The burnout temperatures, estimated ignition indices and the conversion indicate that the type and not the amount of metal ions were the determining factors during the second step of combustion. © 2012 Published by Elsevier B.V.

Characteristics of the upper phase of bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw

Sewage sludge was pyrolysed with 40% mixed wood, 40% rapeseed and 40% straw. The reason for the mixture of different biomass is to investigate the impact of co-pyrolysis on the upper phase of bio-oil in terms of changes to composition, elemental analysis, viscosity, water content, pH, higher heating value and acid number that could impact on their applications. The biomass was pyrolysed in a laboratory at 450 °C and bio-oil was collected from two cooling traps. The bio-oil obtained from co-pyrolysis of sewage sludge with wood, rapeseed and straw was analysed for composition using the gas chromatography mass spectrometry. The upper phase from the co-pyrolysis process was also characterised for ultimate analysis, higher heating values, water content, viscosity, pH and acid number. There was an increase in the amount of upper phase produced with co-pyrolysis of 40% rapeseed. It was also found that the upper phase from sewage sludge with mixed wood has the highest viscosity, acid number and lowest pH. The bio-oil containing 40% straw was found to have a pH of 6.5 with a very low acid number while the 40% rapeseed was found to have no acid number. Sewage sludge with 40% rapeseed was found to have the highest energy content of 34.8 MJ/kg, 40% straw has 32.5 MJ/kg while the 40% mixed wood pyrolysis oil has the lowest energy content of 31.3 MJ/kg. The 40% rapeseed fraction was found to have the highest water content of 8.2% compared to other fractions.

Characterisation of waste derived intermediate pyrolysis oils for use as diesel engine fuels

This paper studies the characteristics of intermediate pyrolysis oils derived from sewage sludge and de-inking sludge (a paper industry residue), with a view to their use as fuels in a diesel engine. The feedstocks were dried and pelletised, then pyrolysed in the Pyroformer intermediate pyrolysis system. The organic fraction of the oils was separated from the aqueous phase and characterised. This included elemental and compositional analysis, heating value, cetane index, density, viscosity, surface tension, flash point, total acid number, lubricity, copper corrosion, water, carbon residue and ash content. Most of these results are compared with commercial diesel and biodiesel. Both pyrolysis oils have high carbon and hydrogen contents and their higher heating values compare well with biodiesel. The water content of the pyrolysis oils is reasonable and the flash point is found to be high. Both pyrolysis oils have good lubricity, but show some corrosiveness. Cetane index is reduced, which may influence ignition. Also viscosity is increased, which may influence atomisation quality. Carbon residue and ash content are both high, indicating potential deposition problems. Compared with de-inking sludge pyrolysis oil (DSPO), sewage sludge pyrolysis oil (SSPO) has a higher heating value, but higher corrosiveness and viscosity. The conclusions are that both intermediate pyrolysis oils will be able to provide sufficient heat when used in diesel engine; however poor combustion and carbon deposition may be encountered. Blending of these pyrolysis oils with diesel or biodiesel could overcome these problems and is recommended for further investigation.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

Experimental investigation of performance, emission and combustion characteristics of an indirect injection multi-cylinder CI engine fuelled by blends of de-inking sludge pyrolysis oil with biodiesel

De-inking sludge can be converted into useful forms of energy to provide economic and environmental benefits. In this study, pyrolysis oil produced from de-inking sludge through an intermediate pyrolysis technique was blended with biodiesel derived from waste cooking oil, and tested in a multi-cylinder indirect injection type CI engine. The physical and chemical properties of pyrolysis oil and its blends (20 and 30 vol.%) were measured and compared with those of fossil diesel and pure biodiesel (B100). Full engine power was achieved with both blends, and very little difference in engine performance and emission results were observed between 20% and 30% blends. At full engine load, the brake specific fuel consumption on a volume basis was around 6% higher for the blends when compared to fossil diesel. The brake thermal efficiencies were about 3-6% lower than biodiesel and were similar to fossil diesel. Exhaust gas emissions of the blends contained 4% higher CO2 and 6-12% lower NOx, as compared to fossil diesel. At full load, CO emissions of the blends were decreased by 5-10 times. The cylinder gas pressure diagram showed stable engine operation with the 20% blend, but indicated minor knocking with 30% blend. Peak cylinder pressure of the 30% blend was about 5-6% higher compared to fossil diesel. At full load, the peak burn rate of combustion from the 30% blend was about 26% and 12% higher than fossil diesel and biodiesel respectively. In comparison to fossil diesel the combustion duration was decreased for both blends; for 30% blend at full load, the duration was almost 12% lower. The study concludes that up to 20% blend of de-inking sludge pyrolysis oil with biodiesel can be used in an indirect injection CI engine without adding any ignition additives or surfactants.

Increase of energy recovery from sewage sludge

The use of the pyrolysis process to obtain valuable products from biomass is amongst the technologies being investigated as a source for renewable energy. The pyrolysis process yields products such as biochar, bio-oil and non condensable gases. The main objective of this project is to increase energy recovery from sewage sludge by utilising the intermediate pyrolysis process. The intermediate pyrolysis has a residence time ranging from 5 to 10 minutes. The main product yields from sewage sludge pyrolysis are 50 wt% biochar, 40 wt% bio-oil and 10 wt% non condensable gases. The project was carried out on a pilot plant scale reactor with a load capacity of 20 kg/h. This enabled a high yield of biochar and bio-oil. The characterisation of the products indicated that the organic phase of the bio-oil had good fuel properties such as having high energy content of 39 MJ/kg, low acid number of 21.5, high flash point of 150 and viscosity of 35 cSt. An increase in pyrolysis experiments enabled large quantities of pyrolysis oil production. Co-pyrolysis of sewage sludge was carried out on laboratory scale with mixed wood, rapeseed and straw. It found that there was an increase in bio-oil quantity with rapeseed while co-pyrolysis with wood helped to mask the smell of the sludge pyrolysis oil. Engine test were successfully carried out in an old Lister engine with pyrolysis oil fractions of 30% and 50% blended with biodiesel. This indicates that these pyrolysis oil fractions can be used in similar engine types without any problems however long term effects in ordinary engines are unknown. An economic evaluation was carried out about the implementation of the intermediate pyrolysis process for electricity production in a CHP using the pyrolysis oil. The prices of electricity per kWh were found to be very high.

Investigation into the performance and emissions of a stationary diesel engine fuelled by sewage sludge intermediate pyrolysis oil and biodiesel blends

This paper studies the characteristics of blends of biodiesel and a new type of SSPO (sewage sludge derived intermediate pyrolysis oil) in various ratios, and evaluates the application of such blends in an unmodified Lister diesel engine. The engine performance and exhaust emissions were investigated and compared to those of diesel and biodiesel. The engine injectors were inspected and tested after the experiment. The SSPO-biodiesel blends were found to have comparable heating values to biodiesel, but relatively high acidity and carbon residue. The diesel engine has operated with a 30/70 SSPO-biodiesel blend and a 50/50 blend for up to 10h and there was no apparent deterioration in operation observed. It is concluded that with 30% SSPO, the engine gives better overall performance and fuel consumption than with 50% SSPO. The exhaust temperatures of 30% SSPO and 50% SSPO are similar, but 30% SSPO gives relatively lower NO emission than 50% SSPO. The CO and smoke emissions are lower with 50% SSPO than with 30% SSPO. The injectors of the engine operated with SSPO blends were found to have heavy carbon deposition and noticeably reduced opening pressure, which may lead to deteriorated engine performance and exhaust emissions in extended operation. © 2013 Elsevier Ltd.

Abrasion resistance of concrete with pulverised fuel ash

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Ash control methods to limit biomass inorganic content and its effect on fast pyrolysis bio-oil stability

This research investigates specific ash control methods to limit inorganic content within biomass prior to fast pyrolysis and effect of specific ash components on fast pyrolysis processing, mass balance yields and bio-oil quality and stability. Inorganic content in miscanthus was naturally reduced over the winter period from June (7.36 wt. %) to February (2.80 wt. %) due to a combination of senescence and natural leaching from rain water. September harvest produced similar mass balance yields, bio-oil quality and stability compared to February harvest (conventional harvest), but nitrogen content in above ground crop was to high (208 kg ha.-1) to maintain sustainable crop production. Deionised water, 1.00% HCl and 0.10% Triton X-100 washes were used to reduce inorganic content of miscanthus. Miscanthus washed with 0.10% Triton X-100 resulted in the highest total liquid yield (76.21 wt. %) and lowest char and reaction water yields (9.77 wt. % and 8.25 wt. % respectively). Concentrations of Triton X-100 were varied to study further effects on mass balance yields and bio-oil stability. All concentrations of Triton X-100 increased total liquid yield and decreased char and reaction water yields compared to untreated miscanthus. In terms of bio-oil stability 1.00% Triton X-100 produced the most stable bio-oil with lowest viscosity index (2.43) and lowest water content index (1.01). Beech wood was impregnated with potassium and phosphorus resulting in lower liquid yields and increased char and gas yields due to their catalytic effect on fast pyrolysis product distribution. Increased potassium and phosphorus concentrations produced less stable bio-oils with viscosity and water content indexes increasing. Fast pyrolysis processing of phosphorus impregnated beech wood was problematic as the reactor bed material agglomerated into large clumps due to char formation within the reactor, affecting fluidisation and heat transfer.

The intermediate pyrolysis of de-inking sludge to produce a sustainable liquid fuel

De-inking sludge is a waste product generated from secondary fibre paper mills who manufacture recycled paper into new paper sheets; it refers directly to the solid residues which evolve during the de-inking stage of the paper pulping process. The current practice for the disposal of this waste is either by land-spreading, land-filling or incineration which are unsustainable. This work has explored the intermediate pyrolysis of pre-conditioned de-inking sludge pellets in a recently patented 20 kg/h intermediate pyrolysis reactor (The Pyroformer). The reactor is essentially two co-axial screws which are configured in such a way as to circulate solids within the reactor and thus facilitate in the cracking of tars. The potential application of using the volatile organic vapours and permanent gases evolved would be to generate both combined heat and power (CHP) located at paper making sites. The results show that de-inking sludge could be successfully pyrolysed and the organic vapours produced were composed of a mixture of aromatic hydrocarbons, phenolic compounds and some fatty acid methyl esters as detected by liquid GC-MS. The calorific value of the oil after condensing was between 36 and 37 MJ/kg and the liquid fuel properties were also determined, permanent gases were detected by a GC-TCD and were composed of approximately 24% CO, 6% CH and 70% CO (v/v%). The solid residue from pyrolysis also contained a small residual calorific value, and was largely composed of mainly calcium based inert metal oxides. The application of applying intermediate pyrolysis to de-inking sludge for both CHP production and waste reduction is in principle a feasible technology which could be applied at secondary fibre paper mills. © 2013 Elsevier B.V. All rights reserved.

Predicting the effect of mixing on oxygen transfer and nutrient removal in activated sludge basins

Activated sludge basins (ASBs) are a key-step in wastewater treatment processes that are used to eliminate biodegradable pollution from the water discharged to the natural environment. Bacteria found in the activated sludge consume and assimilate nutrients such as carbon, nitrogen and phosphorous under specific environmental conditions. However, applying the appropriate agitation and aeration regimes to supply the environmental conditions to promote the growth of the bacteria is not easy. The agitation and aeration regimes that are applied to activated sludge basins have a strong influence on the efficacy of wastewater treatment processes. The major aims of agitation by submersible mixers are to improve the contact between biomass and wastewater and the prevention of biomass settling. They induce a horizontal flow in the oxidation ditch, which can be quantified by the mean horizontal velocity. Mean values of 0.3-0.35 m s-1 are recommended as a design criteria to ensure best conditions for mixing and aeration (Da Silva, 1994). To give circulation velocities of this order of magnitude, the positioning and types of mixers are chosen from the plant constructors' experience and the suppliers' data for the impellers. Some case studies of existing plants have shown that measured velocities were not in the range that was specified in the plant design. This illustrates that there is still a need for design and diagnosis approach to improve process reliability by eliminating or reducing the number of short circuits, dead zones, zones of inefficient mixing and poor aeration. The objective of the aeration is to facilitate the quick degradation of pollutants by bacterial growth. To achieve these objectives a wastewater treatment plant must be adequately aerated; thus resulting in 60-80% of all energetic consummation being dedicated to the aeration alone (Juspin and Vasel, 2000). An earlier study (Gillot et al., 1997) has illustrated the influence that hydrodynamics have on the aeration performance as measure by the oxygen transfer coefficient. Therefore, optimising the agitation and aeration systems can enhance the oxygen transfer coefficient and consequently reduce the operating costs of the wastewater treatment plant. It is critically important to correctly estimate the mass transfer coefficient as any errors could result in the simulations of biological activity not being physically representative. Therefore, the transfer process was rigorously examined in several different types of process equipment to determine the impact that different hydrodynamic regimes and liquid-side film transfer coefficients have on the gas phase and the mass transfer of oxygen. To model the biological activity occurring in ASBs, several generic biochemical reaction models have been developed to characterise different biochemical reaction processes that are known as Activated Sludge Models, ASM (Henze et al., 2000). The ASM1 protocol was selected to characterise the impact of aeration on the bacteria consuming and assimilating ammonia and nitrate in the wastewater. However, one drawback of ASM protocols is that the hydrodynamics are assumed to be uniform by the use of perfectly mixed, plug flow reactors or as a number of perfectly mixed reactors in series. This makes it very difficult to identify the influence of mixing and aeration on oxygen mass transfer and biological activity. Therefore, to account for the impact of local gas-liquid mixing regime on the biochemical activity Computational Fluid Dynamics (CFD) was used by applying the individual ASM1 reaction equations as the source terms to a number of scalar equations. Thus, the application of ASM1 to CFD (FLUENT) enabled the investigation of the oxygen transfer efficiency and the carbon & nitrogen biological removal in pilot (7.5 cubic metres) and plant scale (6000 cubic metres) ASBs. Both studies have been used to validate the effect that the hydrodynamic regime has on oxygen mass transfer (the circulation velocity and mass transfer coefficient) and the effect that this had on the biological activity on pollutants such as ammonia and nitrate (Cartland Glover et al., 2005). The work presented here is one part to of an overall approach for improving the understanding of ASBs and the impact that they have in terms of the hydraulic and biological performance on the overall wastewater treatment process. References CARTLAND GLOVER G., PRINTEMPS C., ESSEMIANI K., MEINHOLD J., (2005) Modelling of wastewater treatment plants ? How far shall we go with sophisticated modelling tools? 3rd IWA Leading-Edge Conference & Exhibition on Water and Wastewater Treatment Technologies, 6-8 June 2005, Sapporo, Japan DA SILVA G. (1994). Eléments d'optimisation du transfert d'oxygène par fines bulles et agitateur séparé en chenal d'oxydation. PhD Thesis. CEMAGREF Antony ? France. GILLOT S., DERONZIER G., HEDUIT A. (1997). Oxygen transfer under process conditions in an oxidation ditch equipped with fine bubble diffusers and slow speed mixers. WEFTEC, Chicago, USA. HENZE M., GUJER W., MINO T., van LOOSDRECHT M., (2000). Activated Sludge Models ASM1, ASM2, ASM2D and ASM3, Scientific and Technical Report No. 9. IWA Publishing, London, UK. JUSPIN H., VASEL J.-L. (2000). Influence of hydrodynamics on oxygen transfer in the activated sludge process. IWA, Paris - France.

Thermal stability of sewage sludge pyrolysis oil

The stability of the oil phase obtained from intermediate pyrolysis process was used for this investigation. The analysis was based on standard methods of determining kinematic viscosity, gas - chromatography / mass - spectrometry for compositional changes, FT-IR for functional group, Karl Fischer titration for water content and bomb calorimeter for higher heaating values. The methods were used to determine changes that occurred during ageing. The temperatures used for thermal testing were 60 °C and 80 °C for the periods of 72 and 168 h. Methanol and biodiesel were used as solvents for the analysis. The bio-oil samples contained 10 % methanol, 10 % Biodiesel, 20 % Biodiesel and unstabilised pyrolysis oil. The tests carried out at 80 °C showed drastic changes compared to those at 60 °C. The bio-oil samples containing 20 % biodiesel proved to be more stable than those with 10 % methanol. The unstabilised pyrolysis oil showed the greatest changes in viscosity, composition change and highest increase in water content. The measurement of kinematic viscosity and gas chromatograph mass spectrometry were found to be more reliable for predicting the ageing process.