Petrochemicals from oil,natural gas,coal and biomass: Production costs in 2030–2050

Methane, coal and biomass are being considered as alternatives to crude oil for the production of basic petrochemicals, such as light olefins. This paper is a study on the production costs of 24 process routes utilizing these primary energy sources. A wide range of projected energy prices in 2030–2050 found in the open literature is used. The basis for comparison is the production cost per t of high value chemicals (HVCs or light olefin-value equivalent). A Monte Carlo method was used to estimate the ranking of production costs of all 24 routes with 10,000 trials of varying energy prices and CO₂ emissions costs (assumed to be within $0–100/t CO₂; the total CO₂ emissions, or cradle-to-grave CO₂ emissions, were considered). High energy prices in the first three quarter of 2008 were tested separately. The main findings are:

• •Production costs: while the production costs of crude oil- and natural gas-based routes are within $500–900/t HVCs, those of coal- and biomass-based routes are mostly within $400–800/t HVCs. Production costs of coal- and biomass-based routes are in general quite similar while in some cases the difference is significant. Among the top seven most expensive routes, six are oil- and gas-based routes. Among the top seven least expensive routes, six are coal and biomass routes.
• •CO₂ emissions costs: the effect of CO₂ emissions costs was found to be strong on the coal-based routes and also quite significant on the biomass-based routes. However, the effect on oil- and gas-based routes is found to be small or relatively moderate.
• •Energy prices in 2008: most of the coal-based routes and biomass-based routes (particularly sugar cane) still have much lower production costs than the oil- and gas-based routes (even if international freight costs are included).

To ensure the reduction of CO₂ emissions in the long-term, we suggest that policies for the petrochemicals industry focus on stimulating the use of biomass as well as carbon capture and storage features for coal-based routes.     

Historical Analysis of SO<Subscript>2</Subscript> Pollution Control Policies in China

Coal is not only an important energy source in China but also a major source of air pollution. Because of this, China’s national sulfur dioxide (SO₂) emissions have been the highest in the world for many years, and since the 1990s, the territory of China’s south and southwest has become the third largest acid-rain-prone region in the world. In order to control SO₂ emissions, the Chinese government has formulated and promulgated a series of policies and regulations, but it faces great difficulties in putting them into practice. In this retrospective look at the history of SO₂ control in China, we found that Chinese SO₂ control policies have become increasingly strict and rigid. We also found that the environmental policies and regulations are more effective when central officials consistently give environmental protection top priority. Achieving China’s environmental goals, however, has been made difficult by China’s economic growth. Part of this is due to the practice of environmental protection appearing in the form of an ideological “campaign” or “storm” that lacks effective economic measures. More recently, better enforcement of environmental laws and regulations has been achieved by adding environmental quality to the performance assessment metrics for leaders at all levels. To continue making advances, China needs to reinforce the economic and environmental assessments for pollution control projects and work harder to integrate economic measures into environmental protection. Nonetheless, China has a long way to go before economic growth and environmental protection are balanced.     

Purification of oxyfuel-derived CO2

Oxyfuel combustion in a pulverised fuel coal-fired power station produces a raw CO₂ product containing contaminants such as water vapour plus oxygen, nitrogen and argon derived from the excess oxygen for combustion, impurities in the oxygen used, and any air leakage into the system. There are also acid gases present, such as SO₃, SO₂, HCl and NO_x produced as byproducts of combustion. At GHGT8 (White and Allam, 2006) we presented reactions that gave a path-way for SO₂ to be removed as H₂SO₄ and NO and NO₂ to be removed as HNO₃. In this paper we present initial results from the OxyCoal-UK project in which these reactions are being studied experimentally to provide the important reaction kinetic information that is so far missing from the literature. This experimental work is being carried out at Imperial College London with synthetic flue gas and then using actual flue gas via a sidestream at Doosan Babcock's 160 kW coal-fired oxyfuel rig. The results produced support the theory that SO_x and NO_x components can be removed during compression of raw oxyfuel-derived CO₂ and therefore, for emissions control and CO₂ product purity, traditional FGD and deNO_x systems should not be required in an oxyfuel-fired coal power plant.     

SO2 Dispersion and Monthly Evaluation of the Industrial Source Complex Short-Term (ISCST32) Model at Mina Al-Fahal Refinery,Sultanate of Oman

Modeling of air pollutant dispersion has been undertaken for emissions of sulfur dioxide (SO₂) at the Mina Al-Fahal refinery in the Sultanate of Oman. The study was conducted during the period of November 1999 to October 2000. The Industrial Source Complex Short-Term (ISCST32) air pollution model was adopted to predict the ground level concentration of SO₂ in and around the refinery. The modeling results were validated against measured data during the study period. The comparison, based on the monthly average measurements, showed that the model underestimates the observed SO₂ concentrations. However, the predicted ground level concentrations of SO₂ during the months of September, October, November, and June were in better agreement with the observations. The predicted SO₂ values are presented in the form of concentration contours to determine the spatial distribution of SO₂ and to assess the impact on air quality over the survey area. Predicted SO₂ concentrations were found lower than the World Health Organisation (WHO) guideline value of 365 μg/m³, with the maximum ground level concentrations being found to occur relatively close to the sources of emission. Moreover, concentration contour patterns for the modeled area vary with changes in meteorological conditions. On the basis of this study, the refinery is not likely to cause any significant deterioration in air quality, and predicted concentrations of SO₂ are well below those likely to influence health.     

Study of individual reactions of the sour compression process for the purification of oxyfuel-derived CO2

Following the feasibility study of sour compression process as a novel purification method of producing NO_x-free, SO₂-free oxyfuel-derived CO₂ using actual fluegas, in this paper, we present the study of the individual reactions taking place in the process in a controlled environment. We have previously showed that an increase of NO/NO₂ concentration in the inlet stream is beneficial for SO₂ removal as NO₂ promotes SO₂ oxidation and the further removal as liquid acid. In this study we show that the reaction SO₂ + NO₂ → SO₃ + NO does not take place significantly in the absence of liquid water at a range of conditions relevant to the sour compression process. When liquid water is present, SO₂ is oxidised by NO₂ regenerating NO with the rate of conversion of SO₂ being dependent on the acid concentration in the liquid. The formation of small liquid droplets where very low levels of pH (?0) can be reached is shown to be of great importance to the SO₂ + NO₂ conversion process.     

Kinetics of sulfur dioxide- and oxygen-induced degradation of aqueous monoethanolamine solution during CO2 absorption from power plant flue gas streams

Studies of the kinetics of sulfur dioxide (SO₂)- and oxygen (O₂)-induced degradation of aqueous monoethanolamine (MEA) during the absorption of carbon dioxide (CO₂) from flue gases derived from coal- or natural gas-fired power plants were conducted as a function of temperature and the liquid phase concentrations of MEA, O₂, SO₂ and CO₂. The kinetic data were based on the initial rate which shows the propensity for amine degradation and obtained under a range of conditions typical of the CO₂ absorption process (3–7 kmol/m³ MEA, 6% O₂, 0–196 ppm SO₂, 0–0.55 CO₂ loading, and 328–393 K temperature). The results showed that an increase in temperature and the concentrations of MEA, O₂ and SO₂ resulted in a higher MEA degradation rate. An increase in CO₂ concentration gave the opposite effect. A semi-empirical model based on the initial rate, ?r_MEA = {6.74 × 10⁹ e^?(29,403/RT)[MEA]^0.02([O]^2.91 + [SO₂]^3.52)}/{1 + 1.18[CO₂]^0.18} was developed to fit the experimental data. With the higher order of reaction, SO₂ has a higher propensity to cause MEA to degrade than O₂. Unlike previous models, this model shows an improvement in that any of the parameters (i.e. O₂, SO₂, and CO₂) can be removed without affecting the usability of the model.     

Economic and Environmental Analysis of Retrofitting a Large Office Building with Energy-Efficient Lighting Systems

An evaluation of the economic and environmental costs and benefits that would result if the Zorinsky Federal Building, located in Omaha, Nebraska, USA, converted its current lighting system to a more energy-efficient system (i.e., joined the EPA's Green Lights Program) was conducted. Lighting accounts for 20–25 percent of all electricity sold in the United States. Costs considered in the study included the cost of retrofitting the building's existing lighting system and the cost of disposal of the current lamps and ballast fixtures. Benefits included a reduction of electric utility costs and a reduction of emissions of SO₂, NO _x , CO₂, and CO from electric utility power plants. Environmental and health issues for air pollutant emissions were also addressed. The results showed that significant reductions in utility bills as well as reductions in air emissions would result from a major building converting to a more energy efficient lighting system. The results showed that conversion of this large building would reduce SO₂ emissions by 14.6 tons/yr and NO _x emissions by 6.3 tons/yr. In addition, the conversion would reduce annual energy costs by approximately $114,000.     

Limitations for brine acidification due to SO2 co-injection in geologic carbon sequestration

Co-injection of sulfur dioxide during geologic carbon sequestration can cause enhanced brine acidification. The magnitude and timescale of this acidification will depend, in part, on the reactions that control acid production and on the extent and rate of SO₂ dissolution from the injected CO₂ phase. Here, brine pH changes were predicted for three possible SO₂ reactions: hydrolysis, oxidation, or disproportionation. Also, three different model scenarios were considered, including models that account for diffusion-limited release of SO₂ from the CO₂ phase. In order to predict the most extreme acidification potential, mineral buffering reactions were not modeled. Predictions were compared to the case of CO₂ alone which would cause a brine pH of 4.6 under typical pressure, temperature, and alkalinity conditions in an injection formation. In the unrealistic model scenario of SO₂ phase equilibrium between the CO₂ and brine phases, co-injection of 1% SO₂ is predicted to lead to a pH close to 1 with SO₂ oxidation or disproportionation, and close to 2 with SO₂ hydrolysis. For a scenario in which SO₂ dissolution is diffusion-limited and SO₂ is uniformly distributed in a slowly advecting brine phase, SO₂ oxidation would lead to pH values near 2.5 but not until almost 400 years after injection. In this scenario, SO₂ hydrolysis would lead to pH values only slightly less than those due to CO₂ alone. When SO₂ transport is limited by diffusion in both phases, enhanced brine acidification occurs in a zone extending only 5 m proximal to the CO₂ plume, and the effect is even less if the only possible reaction is SO₂ hydrolysis. In conclusion, the extent to which co-injected SO₂ can impact brine acidity is limited by diffusion-limited dissolution from the CO₂ phase, and may also be limited by the availability of oxidants to produce sulfuric acid.     

Potential CO2 emission reduction for BF–BOF steelmaking based on optimised use of ferrous burden materials

Currently, the blast furnace (BF) to basic oxygen furnace (BOF) is the dominant steel production route in the steel industry. The direct CO₂ emission in this process system exceeds 1 t of CO₂/t of crude steel produced. Different ferrous burden materials, for instance iron ore and scrap, can be used in various proportions in this steelmaking route. This paper analyses how energy use, conversion costs, and CO₂ emissions can be influenced by the use of different ferrous burden materials when producing crude steel. An optimisation mixed integer linear programming (MILP) model has been applied for analysis. By the use of the optimisation model, it is possible to highlight some issues of special importance, such as best practices to increase production at low conversion cost, or best practices to increase production at low CO₂ emission. It is found out that more benefits will be gained when using the system-oriented analysis to the steelmaking process. Furthermore, a comprehensive view of the trade-offs between the objectives of Cost and CO₂ can provide useful information for decision makers to generate strategies under the future emission trading.     

Optimization of pretreatment conditions for enhanced sugar release

Present investigation was done to evaluate various algal genera found in water bodies of Varanasi city. The potential of any biomass for biofuels (bioalcohols, biohydrogen, etc.) production depends on the quantity of extractable sugar present in it. Acid (H₂SO₄) and alkali (NaOH) pretreatment were performed, and H₂SO₄ was chosen due to its nearly double yield as compared with alkaline pretreatment. Response surface methodology was utilized for the optimization of operating parameters such as treatment temperature, time, and acid concentration. Sugar yield up to 0.33 g/g of dry biomass was obtained using cyanobacterial biomass of Lyngbya limnetica, at 100°C, 59.19 min, and H₂SO₄ concentration of 1.63 M.     

CO2 capture for refineries,a practical approach

This paper evaluates the opportunities and associated costs for post-combustion capture at a world-scale complex refinery. It is concluded that it is technically feasible to apply post-combustion capture at such a refinery. The costs for capture and sequestration from a gasifier are calculated to be lowest at about 30 Euro per ton; this process currently already produces a concentrated CO₂ stream. Next, the CO₂ source most suited for capture appears to be a combined stack, but there are a number of other sources that may be targeted at comparable costs. In total these sources may form about 40% of the overall refinery emissions. Our evaluations show the costs of capture from such sources based on available amine technology will be in the range of 90–120 Euro per ton, which is about 3–4 times higher than the current carbon trading values. The capture of CO₂ from a large amount of smaller CO₂ sources will bring along even much higher costs. A high-level study of the CO₂ emissions profile of a number of Shell refineries shows that, typically, up to 50% of the emitted CO₂ may be captured at similar costs. About 10–20% of concentrated CO₂ associated with hydrogen manufacturing may be captured at lower costs. The remainder of emitted dilute CO₂ will bring along significantly higher costs. Based on this study, it is concluded for the justification of the implementation of post-combustion capture at refineries, either a significant increase in carbon trading values, mandatory regulations, or a major technological break-through is required.     

Environmental quality in India: Application of environmental Kuznets curve and Sustainable Human Development Index

This study explores the trend of selected air pollutants, carbon dioxide (CO₂), nitrogen dioxide NO₂), sulfur dioxide (SO₂) and particulate matter 10 microns in diameter (PM₁₀) in India. Environmental Kuznets curves (EKC), which show the association of the economy and pollution, are fitted for selected Indian states to understand whether EKC in India fits well with the inverted “U” shape. We observed that CO₂ and PM₁₀ are steadily increasing in India. The states of Kerala and Punjab follow the inverted “U” shape of EKC, while Bihar, Uttar Pradesh, West Bengal, and Maharashtra may take decades to reduce pollutants. A new Sustainable Human Development Index calculated in this paper indicates a diverse picture of Indian states, especially in regard to environmental parameters. The government needs to implement stringent, state‐specific laws and regulations to assist in curbing air pollutants. The time has also come to represent the rankings of states in terms of an environmentally inclusive development index.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Cold DeNOx development for oxyfuel power plants

Flue gas purification is a necessary method to avoid emission of sour gases like SO_x and NO_x into the environment. Another important aspect is the zero CO₂ emission from coal-fired power plants. Oxyfuel technology is one of the processes to reach this goal. LINDE KCA Dresden in cooperation with Vattenfall Europe is operating a pilot plant producing liquefied CO₂. Product specification and material requirements make flue gas purification for the removal of SO_x and NO_x unavoidable. The new oxyfuel technologies offer new process conditions for flue gas purification which are not available at atmospheric conditions.At Linde laboratories, catalytic and non-catalytic DeNOx and DeSOx processes have been screened for oxyfuel application. After first feasibility studies, laboratory experiments and economic evaluations, it was decided to develop a process based on wet scrubber systems to remove NO_x from flue gas, simultaneously producing ammonia nitrites which can be thermally decomposed into nitrogen in a second step. After demonstration of the single process steps on laboratory scale, a pilot scrubber was erected and commissioned in 2010 at Schwarze Pumpe Oxyfuel Pilot Plant. In September 2010, the successful completion of the pilot tests demonstrated the NO_x removal efficiency of this technology. The data from the pilot plant tests have been used to finalise a kinetic model describing the NO_x absorption behaviour regarding NO_x removal rate and nitrite selectivity for demonstration of plant scale up. This DeNOx-process is now marketed under the name “LICONOX”.     

Valorization of sodium sulfate waste to potassium sulfate fertilizer: experimental studies,process modeling,and optimization

ABSTRACT

Sodium sulfate is a common low-value industrial by-product but can be managed using the Glaserite process to convert it into high-value potassium sulfate. The aim of the study is to investigate the potential for implementing this process in an industrial application. Experimental studies were completed to determine the yield and purity of both glaserite and potassium sulfate. Process simulation using SysCAD was utilized to optimize a two-stage glaserite process to produce potassium sulfate. Comparison of experimental and simulated data was made to validate the simulator’s results, finding the AAD in solid and liquid phase for glaserite production to be 6.9% and 5.7%, respectively, and for potassium sulfate to be 5.7% and 2.3%, respectively. For a process treating seven MT/hr of Na₂SO₄, a KCl feed strategy of 3.0 MT/hr to the glaserite reactor and 4.5 MT/hr to the K₂SO₄ reactor was found to maximize yield and minimize water demand. It was also found that ambient temperatures were preferred for the K₂SO₄ reactor and that K₂SO₄ yield suffered significantly under certain conditions when the glaserite reactor operated at 50°C or above.     

Performance analysis of bioethanol (Water Hyacinth) on diesel engine

The increasing consumption and excessive extraction of conventional fuels is the matter of serious concern. Nowadays, world is looking for alternative sources of fuel which can partially replace conventional fuel dependence. The current investigation intends to provide evaluation of bio-ethanol preparation from Water Hyacinth (WH) and its influence on diesel engine performance under various operating conditions. This study explores the extraction of glucose from WH (Eichhornia crassipes) pretreated with sulfuric acid (H₂SO₄) for production of bio-ethanol. For the production of bio-ethanol different concentrations of H₂SO₄ acid hydrolysate (1%, 2%, 4%, 6%, 8%, and 10%) were prepared which was then followed by fermentation with cellulose fermenting yeasts. From results, it was observed that 4% H₂SO₄ acid hydrolysis produces higher concentrations of ethanol than other concentrations. Bio-ethanol extracted from WH was blended with diesel in different proportions (5%, 10%, 15%, 20%, and 25%) v/v and performance and emissions were experimentally investigated on single cylinder diesel engine under various load conditions. Experimental results show that 5 BED [5% bio-ethanol (WH + 95%diesel v/v) and 10BED (10% bio-ethanol (WH + 90%diesel v/v)] produces higher brake power, brake thermal efficiency and brake mean effective pressure with improved exhaust emission profiles than any other blend.     

Hollow fiber membrane separation process in the presence of gaseous and particle impurities for post-combustion CO2 capture

The membrane separation process for CO₂ capture can be interfered by the gaseous components and the fine particles in flue gas, especially in desulfurized flue gas. In this work, the pint-sized Polyimide(PI) hollow fiber membrane contactors were self-packed to investigate the membrane CO₂ separation from flue gas containing fine particles and gaseous contaminants (SO₂,SO₃,H₂O). First, the effects of SO₂, SO₃, water vapor, and gypsum particles on the CO₂ capture were studied independently and synergistically. The results showed that the effect of SO₂ on the membrane separation properties is indistinctive; however, the membrane performance was damaged seriously with the addition of SO₃. The high humidity promoted the CO₂ separation initially before inhibiting the PI membrane performance. Moreover, the decrease of the CO₂/N₂ selectivity and the permeation rate were accelerated with the coexistence of SO₂. The membrane performance showed an obvious deterioration in the presence of gypsum particles, with a 21% decrease in the CO₂/N₂ selectivity and 51% decrease in the permeation rate. Furthermore, the gypsum particles exerted dramatic damage. Under the WFGD conditions, the combined effects of SO₂, water vapor, and the gypsum particles influenced the stability of the membrane significantly. This tendency is mainly attributed to the deposition of fine particles and aerosol on the membrane surface, which occupied the effective area and enhanced the mass transfer resistance. This study of impurities’ influence could play an important role in further industrial application of membrane CO₂ capture.     

Copper smelting and refining

Detailed research by the Commodities Research Unit (CRU) reveals a wide variation in direct operating costs at copper smelters and refineries. The cost curve for smelters is almost a straight line, indicating that so far there has been no levelling of costs as there has been in the mining industry. Operating costs at smelters using reverberatory furnaces are well below costs at plants using modern technology, but this apparent paradox is shown to be a reflection of location. CRU argues that costs are an important determinant of smelter/refinery competitiveness, but that other factors such as location and tariffs are also significant. Operating margins world-wide show enormous variations, but companies' increasing interest in their processing operations, coupled with changes in tariffs, are predicted to lead to a much more competitive market.     

Characterization of a limestone in a batch fluidized bed reactor for sulfur retention under oxy-fuel operating conditions

CO₂ and SO₂ are some of the main polluting gases emitted into atmosphere in combustion processes using fossil fuel for energy production. The former is one of the major contributors to build-up the greenhouse effect implicated in global climate change and the latter produces acid rain. Oxy-fuel combustion is a technology, which consists in burning the fuel with a mix of pure O₂ and recirculated CO₂. With this technology the CO₂ concentration in the flue gas may be enriched up to 95%, becoming possible an easy CO₂ recovery. In addition, oxy-fuel combustion in fluidized beds allows in situ desulfurization of combustion gases by supplying calcium based sorbent.In this work, the effect of the principal operation variables affecting the sulfation reaction rate in fluidized bed reactors (temperature, CO₂ partial pressure, SO₂ concentration and particle size) under typical oxy-fuel combustion conditions have been analyzed in a batch fluidized bed reactor using a limestone as sorbent. It has been observed that sulfur retention can be carried out by direct sulfation of the CaCO₃ or by sulfation of the CaO (indirect sulfation) formed by CaCO₃ calcination. Direct sulfation and indirect sulfation operating conditions depended on the temperature and CO₂ partial pressure. The rate of direct sulfation rose with temperature and the rate of indirect sulfation for long reaction times decreased with temperature. An increase in the CO₂ partial pressure had a negative influence on the sulfation conversion reached by the limestone due to a higher temperature was needed to work in conditions of indirect sulfation. Thus, it is expected that the optimum temperature for sulfur retention in oxy-fuel combustion in fluidized bed reactors be about 925–950 °C. Sulfation reaction rate rose with decreasing sorbent particle size and increasing SO₂ concentration.     

Mitigation of power sector environmental emissions through energy efficiency improvements: the case of Pakistan

This paper assesses the potential of selected efficient electrical appliances for avoiding power generation and for mitigation of selected air pollutants from the power sector in Pakistan from technical as well as national, utility and user perspectives. The study shows that about 14, 21 and 35% of the total CO₂, SO₂and NO_xemissions in the business as usual (BAU) case could be avoided by the adoption of selected efficient appliances during 1997–2015 from the national perspective, while the corresponding figures from the user perspective are 12, 17 and 29%, respectively. All selected efficient appliances would be cost effective to the users if electricity prices were set at the long-run marginal cost of supply.1998 Academic Press