Algae
Found in both marine and freshwater environment, algae have also been studied as potential sources of energy. Macroalgae - more commonly known as seaweed or kelp - are fast-growing plants that can reach a considerable size up to 60 m in length 219 . A few experimental seaweed farms were built along the coast of southern California in the 1970s, but due to difficult weather conditions and rough waters, the open-sea project was rapidly abandoned. More protected from the elements, near-shore...
Production of Methanol from SynGas to Carbon Dioxide
In 2004, the worldwide demand for methanol stood at 32 million tonnes. Although virtually any hydrocarbon source coal, petroleum, naphtha, coke, etc. can be converted to methanol via derived syn-gas, methane from natural gas accounted for some 90 of the feedstock used for methanol manufacture. Most existing plants have production capacities ranging from 100 000 to 800 000 t per year. In the past, plants were generally constructed close to large methanol-consuming centers in the United States or...
Microbial or Photochemical Conversion of Methane to Methanol
Certain bacteria, known as methanotrophs, can obtain all the energy and carbon they need for life from methane 187 . The key step for their utilization of methane is its selective conversion to methanol using oxygen. In subsequent biological processes, methanol is further oxidized to formaldehyde, which in turn can be either incorporated into biomass or oxidized to CO2, thereby providing the energy needed by the bacteria. Nature's catalyst for the conversion of methane to methanol is an enzyme...
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Loker Hydrocarbon Research Institute All books published by Wiley-VCH are carefully produced. Nevertheless, authors, editors, and publisher do not warrant the information contained in these books, including this book, to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate. Library of Congress Card No. Applied for British Library Cataloguing-in-Publication Data A catalogue record for this...
SynGas from Natural Gas Methane Steam Reforming
In methane steam reforming, methane is reacted in a highly endothermic reaction with steam over a catalyst, typically based on nickel, at high temperatures 800-1000 C, 20-30 atm 182 to form CO and H2. A part of the CO formed reacts consequently with steam in the water gas shift WGS reaction to yield more H2 and also CO2. The gas obtained is thus a mixture of H2, CO and CO2. The concentration of the various components depends on the reaction conditions temperature, pressure and H2O CH4 ratio....
Total trillion m
Figure 4.12 Distribution of world natural gas proven reserves in 2004. Based on data from BP Statistical Review of World Energy 2005. Figure 4.13 Liquid natural gas LNG tanker for transportation of natural gas across the seas. day to both the United States and the United Kingdom. In the United States, the construction of some ten new LNG regasification terminals is projected within a decade, compared to only a half-dozen operating today, all of which were built more than 20 years ago. Because...
Fossil Fuels and Climate Change
Climate change, and especially global warming, is receiving much attention and is considered as one of the most pressing and severe global environmental problems facing humanity. Its significance has been widely reported to the general public by the media, always eager to emphasize the possible catastrophic consequences of global warming and link it even to claimed extreme weather experienced in the recent years. The Hollywood film The day after tomorrow, an environmental catastrophe movie in...
Methanol from Carbon Dioxide
When hydrocarbons are burned they produce CO2 and water. The great challenge is to reverse this process and to produce - efficiently and economically - hydrocarbon fuels and materials from CO2 and water. Of course Nature, in its process of photosynthesis, captures CO2 by green plants from the air and converts it with water, using the Sun's energy and chlorophyll as the catalyst, into new plant life. Thus, plant life replenishes itself by recycling atmospheric CO2. The difficulty is that the...
Production via SynGas
Today, methanol is almost exclusively produced from syn-gas, which is a mixture of hydrogen, carbon monoxide and CO2 over a heterogeneous catalyst according to the following equations The two reactions in Eqs. 1 and 2 are exothermic, with heats of reaction equal to -21.7 kcal mol-1 and -9.8 kcal mol-1, respectively. They both result in a decrease of volume as the reaction proceeds. According to Le Chatelier's principle, the conversion to methanol is therefore favored by increasing pressure and...
Emissions from MethanolPowered Vehicles
Transportation-associated air pollution is a major problem in large metropolitan areas. CO, NOx, volatile organic compounds VOCs , SO2 and particulate matter PM emitted by automobiles, trucks and buses can have serious effects on the population's health, especially in children, elderly and other sensitive persons. As described earlier, the use of clean-burning methanol in ICEs could immediately help to reduce these emissions 173 . Included in the VOCs is formaldehyde, an air-toxic and ozone...
Methanol from Biogas
Most mammals including humans , as well as termites, produce a flammable gas termed biogas when they digest their food. Biogas is also generated in wetlands, swamps and bogs where large amounts of rotting vegetation may accumulate. Biogas is formed when anaerobic bacteria break down organic material in the absence of oxygen. Anaerobic bacteria are some of the oldest forms of life on Earth, having evolved before the photosynthetic processes of green plants were able to release large quantities...
Methanol as Fuel in Internal Combustion Engines ICE
In contrast to gasoline, which is a complex mixture containing many different hydrocarbons and some additives, methanol is a simple chemical. It contains about half the energy density of gasoline, which means that 2 L of methanol contains the same energy as 1 L of gasoline. Even though methanol's energy content is lower, it has a higher octane rating of 100 average of the research octane number RON of 107 and motor octane number MON of 92 which means that the fuel air mixture can be compressed...
Methanol from Biomass
Although reserves of methane from natural gas are still very large, they are nevertheless finite and diminishing. The exploitation of unconventional natural gas resources and methane hydrates could significantly increase the amounts of methane available to mankind. Innovative processes continue to be explored for the transformation of methane into easy-to-handle liquid fuels, primarily methanol, but this will not solve the problem of increasing CO2 concentrations in the atmosphere and its...
Nuclear Energy
In 2002, nuclear power - which is used almost exclusively to produce electricity in commercial applications - generated some 2700 TWh of electric power, representing about 17 of the world's electricity consumption Fig. 8.15 . Its share of the total primary energy supply amounted to 7 14 . Today, some 440 commercial nuclear reactors are operating in 30 countries with over 360 000 MW of total production capacity. Currently, the United States has 104 commercial nuclear power plants accounting for...
MethanolBased Proteins
Methanol can also serve as the source for single-cell protein production. Single-cell proteins SCP refers to proteins produced by a variety of microorganisms degrading hydrocarbon substrates while gaining energy 108, 113 . The protein content depends on the type of microorganism bacteria, yeast, mold, etc. The use of microorganisms in human alimentation has been practiced since ancient times, in the form of yeasts used in brewing and baking, and bacteria in cultured dairy products such as...
Methanol Production through MonoHalogenated Methanes
Another possible alternative for the selective conversion of methane to methanol proceeds through the intermediate catalytic formation of methyl chloride or bromide CH3Cl, CH3Br , which are then hydrolyzed to methanol or dimethyl ether with the byproduct HCl or HBr being reoxidized 197, 198 . The chlorination of paraffins, discovered by Dumas in 1840, is the oldest known substitution reaction and is practiced on a large scale in industry. It is usually a free radical process initiated either...
Fuel Cell Efficiency
In contrast to heat engines gasoline and diesel engines , the fuel cell does not involve conversion of heat to mechanical energy and the overall thermodynamic efficiencies can be very high. The thermodynamic derivation of the Carnot cycle of a heat engine states that all the heat supplied to it cannot be converted to mechanical energy, and that some of the heat is rejected. The heat is accepted from a source at higher temperature TH in Kelvin , part of it is converted to mechanical energy, and...
Catalytic GasPhase Oxidation of Methane
In homogeneous gas-phase oxidation, methane is generally reacted with oxygen at high pressures 30 to 200 atm and high temperatures 200 to 500 C . Optimum conditions for the selective oxidation to methanol have been extensively in vestigated. It was observed that selectivity to methanol increases with decreasing oxygen concentration in the system. The best result 75-80 selectivity in methanol formation at 8-10 conversion was achieved under cold flame conditions 450 C, 65 atm, less than 5 O2...
Fuel Cells Based on Other Fuels and Biofuel Cells
Direct oxidation fuel cells based on other fuels such as ethanol, formaldehyde, formic acid, DME, dimethoxymethane, and trimethoxymethane, have been studied in laboratories worldwide. However, none of these has shown so far the promise of either the H2-PEM fuel cell or DMFC, although application of fuel mixes is feasible. Biofuel cells use biocatalysts for the conversion of chemical energy into electrical energy. As most organic materials undergo combustion with the evolution of energy, the...
Economics of SynGas Generation
The investment in the syn-gas generation unit accounts generally for more than half of the total investment for natural gas-based plants producing methanol. For plants using coal as a feedstock, this represents even more, generally 70-80 183 . The remaining 20-50 accounts for the capital costs involved in the actual production of methanol. The price of methanol from coal is thus more dependent on the technology than the cost of the feedstock, which remains much cheaper and less fluctuating than...
Hydrogen
Romm J. J., The Hype about Hydrogen. Fact and Fiction in the Race to Save the Climate, Island Press, Washington, DC, 2004. Hoffmann P., Tomorrow's Energy. Hydrogen, Fuel Cells, and the Prospects for a Cleaner Planet, The MIT Press, Cambridge, 2002. Rifkin J., The Hydrogen Economy, Tarcher Putnam, New York, 2002. Sperling D., Cannon J., The Hydrogen Energy Transition Moving Toward the Post Petroleum Age in Transportation, Elsevier Academic Press, 2004. The Hydrogen Economy Opportunities, Costs,...
Coalbed Methane
Coalbed methane, as its name indicates, is derived from coal, which acts in both the role of source rock and reservoir for methane. During the geological formation of coal under high temperature and pressure, volatile substances such as water and methane are liberated. Some gas may escape the coal. However, if the pressure of the formation is sufficient, significant quantities of methane are retained in the pressurized coal matrix in an adsorbed form. Because of its large surface area, coal can...
Electricity from Photovoltaic Conversion
The conversion of daylight into electricity, called the photovoltaic effect, was first discovered by the French scientist Edmond Becquerel in 1839. The explanation for this effect was later provided by Albert Einstein who received for this work and not the theory of relativity the Nobel Prize in physics. However, the development of the first practical photovoltaic cell occurred only in 1954 at the Bell Telephone Laboratories, with the production of a silicon-based cell with 6 efficiency in...
Electric Power from Saline Solar Ponds
A solar saline pond is a few meters in depth and artificially maintained so that the degree of its salinity, and consequently density, is higher at the bottom than at the surface. The difference in salinity is created by dissolving large amounts of salt at the bottom of the pond and keeping the surface supplied with low-saline water, to maintain the necessary salinity gradient. Because of the difference in salinity there is minimal mixing between the layers, and convection is prevented....
Fractional Distillation
Atmospheric fractional distillation, the first and core step in the refining process, uses heat to separate the numerous different hydrocarbon components present in oil into several fractions, depending on their boiling point. The first volatile products of the crude oil are gaseous hydrocarbons of one to four carbon atoms that were dissolved in the oil. Liquid petroleum gases LPG can be used as fuel or converted to useful chemicals. With increasingly higher boiling range and number of...
Solar Thermal Power for Electricity Production
Solar thermal power systems use mirrors and optical devices to redirect, focus, and concentrate the Sun's rays onto a receiver, where heat is generated. The first application of this technique was recorded in 212 bc, when Archimedes is said to have used mirrors to burn Roman ships attacking Syracuse. Today, the thermal energy can than be used to produce steam-driven generators for electricity production, or to initiate chemical reactions. The concentration of sunlight may be achieved with...
Methanol Safety
Methanol, as mentioned earlier, is a colorless liquid with a mild alcoholic odor. It is widely used as a chemical intermediate and solvent by industries and is present in a variety of consumer products. This includes, for example, the blue windshield washer fluid that most motor car owners are familiar with, which is in fact composed in large part of methanol. The use of methanol not only as a windshield washer fluid but also as a deicing fluid, antifreeze or even fuel for camping cooking...
Methane Hydrates
Another unconventional gas source that has attracted increasing attention in recent years are methane hydrates Fig. 4.14 . Gas hydrates are naturally occurring crystalline, ice-like solids in which the gas molecules are trapped by water in cagelike structures called clathrates. Although many gases can form hydrates in nature, methane hydrate is by far the most common. Various clathrate compounds Figure 4.14 Methane hydrate. A molecule of methane is trapped in a cage made out of water molecules...
Methanol through Methyl Formate
In order to reduce the pressure and temperature needed for the current methanol production process, and also to improve its thermodynamic efficiency, alternative routes to convert CO H2 mixtures to methanol under milder conditions have been developed. Among these, the most notable is the synthesis of methanol via methyl formate, first proposed in 1919 by Christiansen 184-186 . This methanol synthesis route consists of two steps. Methanol is first carbony-lated to methyl formate, which is...
Advanced MethanolPowered Vehicles
Methanol or its derivatives DME, DMC, biodiesel can already be used as substitutes for gasoline and diesel fuel in today's ICE-powered cars, with only minor modifications to existing engines and fuel systems. ICE is a much-proven and reliable technology, which has been continuously improved and perfected since its invention over a hundred years ago. Fuel economy compared to generated power is now better, and emissions lower than ever before. Hybrid cars, combining an ICE with an electric motor...
Present Uses of Methanol
Today, methanol is mainly a primary feedstock for the chemical industry. It is manufactured in large quantities over 32 million tons per year in 2004 114 as an intermediate for the production of a variety of chemicals Fig. 11.1 . Worldwide, almost 70 of the methanol production is used to produce formaldehyde 38 , methyl-tert-butyl ether MTBE, 20 and acetic acid 11 . Methanol is also a feedstock for chloromethanes, methylamines, methyl methacrylate, and dimethyl terephthalate, etc. 108 . These...
Selective Oxidation of Methane to Methanol
A major disadvantage of the present process of producing methanol through syngas is the large energy requirement of the first highly endothermic steam reforming step. The process is also inefficient in the sense that it first transforms methane in an oxidative reaction to carbon monoxide and some CO2 which, in turn, must be reduced again to methanol. The direct selective transformation of methane to methanol is therefore a highly desirable goal, but this is difficult to accomplish in a...
Carbon Dioxide from the Atmosphere
To deal with small and dispersed CO2 emitters and to avoid the need to develop and construct a huge CO2-collecting infrastructure, CO2 could be captured from the atmosphere - an approach that has already been proposed by some in the past 224-227 . The atmosphere could thus serve as an effective means of transporting CO2 emissions to the site of capture. This would make the CO2 collection independent of CO2 sources, and CO2 could be captured from any source - small or large, static or mobile....
LiquidPhase Oxidation of Methane to Methanol
In order to minimize the formation of side products and increase the selectivity to methanol, the use of lower reaction temperatures lt 250 C is preferable. Currently used catalysts for methane oxidation are, however, not sufficiently active at lower temperatures. The development of a new generation of catalysts which could produce selectively methanol directly from methane in high yields at lower temperatures is therefore highly desirable. As discussed, gas-phase reactions have met with...
The Continuing Need for Hydrocarbons and their Products
Besides still providing the bulk of our energy needs, fossil fuels also are the sources for our hydrocarbon fuels and derived products. Hydrocarbons are the compounds of carbon and hydrogen. In methane CH4 , the simplest saturated hydrocarbon alkane and the main component of natural gas, a single carbon atom is bonded to four hydrogen atoms. The higher homologues of methane, ethane, propane, butane and so on, have the general formula CnH2n 2, displaying the tendency of carbon to form chains...
SynGas from CO Reforming Autothermal Reforming and Combination of Steam
In order to produce syn-gas without either consuming or producing much heat, modern plants are usually combining exothermic partial oxidation with endother-mic steam reforming in order to have an overall thermodynamically neutral reaction while obtaining a syn-gas with a composition suited for methanol synthesis S close to 2 . In this process, termed autothermal reforming, the heat produced by the exothermic partial oxidation is consumed by the endothermic steam reforming reaction. Partial...
Co2 Conversion To Methanol And Eu Projects
1. Olah G. A., Methanol Economy trademark No 78 692,647. 2. World Energy Outlook 2004, International Energy Agency, Paris, 2004. 3. World Energy Council WEC , 4. Smil V., Energy at the Crossroads, Global Perspectives and Uncertainties, MIT Press, Cambridge, 2003. 5. World Energy Outlook 2001 Insights, International Energy Agency, Paris, 2001. 6. Energy Technologies for the 21st Century, International Energy Agency, Paris, 1997. 7. FutureGen. Integrated Hydrogen, Electric Power Production and...
Hydrogen for Fuel Cells from Methanol Reforming
In seeking to overcome the problems associated with hydrogen storage and distribution, numerous approaches have set out to use liquids rich in hydrogen such as gasoline or methanol as a source of hydrogen via on-board reformers. In contrast to pure hydrogen-based systems, they are compact containing on a volume basis more hydrogen than even liquid hydrogen and easy to store and handle without pressurization. The possibility of generating hydrogen with more than 80 efficiency by the on-board...
Diminishing Oil and Gas Reserves
The World is entirely dependent on oil. The transportation sector in particular, so vital in our society for carrying people, goods, food and materials, relies on more than 95 of its gasoline, diesel and kerosene derived from petroleum, and consumes about 60 of the oil produced. We also depend on oil for the large variety of petrochemicals and derived products such as plastics, detergents and synthetic fabrics that today are so ubiquitous in our daily lives that we can hardly think about where...
Methanol and Dimethyl Ether as Diesel Fuels Substitute in Compression Ignition
Methanol, when combusted, does not produce smoke, soot or particulates. Parti-culate matter - whether carcinogenic compounds are absorbed onto them, or not - have been identified as a significant health hazard, especially in large cities. Diesel fuel generally produces particles during combustion. This, and the fact that methanol produces very low emissions of NOx because it burns at lower temperatures, makes methanol attractive as a substitute for diesel fuel 123 . Diesel engines are quite...
Methanol from Methane Without SynGas
As long as methane, the main component of natural gas is still quite abundant, it will inevitably be used to produce methanol, and through it synthetic hydrocarbons and their products. It should also be recognized that as discussed in Chapter 4 there are also other large methane resources such as unconventional natural gas sources as well as methane hydrates tied up in vast areas of subarctic tundras and under the seas in the areas of the continental shelves. All of these re sources will...
Tight Sands and Shales
Tight sands and shales are low-permeability geological formations which sometimes contain large accumulation of natural gas. This means that the underground rock layers holding the gas are very dense, and thus the gas does not flow easily toward wells drilled to collect it, resulting in low recovery rates. This can be enhanced by horizontal drilling and fracturing of the rocks with explosives, or with hydraulic pressure to provide pathways for the trapped gas to flow more easily to the...
Properties and Historical Background
Methanol, also called methyl alcohol or wood alcohol, is a colorless, water-soluble liquid with a mild alcoholic odor. It freezes at -97.6 C, boils at 64.6 C, and has a density of 0.791 at 20 C. Methanol in its relatively pure form was first isolated in 1661 106 by Robert Boyle, who called it spirit of the box because he produced it through the distillation of boxwood. Its chemical identity or elemental composition, CH3OH, was described in 1834 by Jean-Baptiste Dumas and Eugene Peligot. They...
Methanol to Gasoline MTG Process
The MTG process was conceived and developed in response to the energy crisis of the 1970s. It was the first major new route to synthetic hydrocarbons since the introduction of the Fischer-Tropsch process before World War II, and provided an alternative pathway for the production of high-octane gasoline from coal or natural gas. Discovered by accident by a research team at Mobil, the MTG process was actually developed before the MTO process. In fact, the MTO process can be considered as a...
Methanol to Olefin MTO Process
The methanol to olefin technology, or MTO, was developed as a two-step process, which first converts natural gas via syn-gas to methanol, followed by its transformation to light olefins. The driving force for the development of this technology was to utilize natural gas sources far from major consumer centers. The conversion of methanol to olefins proceed through the pathway The initial step is the dehydration of methanol to dimethyl ether DME , which then reacts further to form ethylene and...
Coal in the Industrial Revolution and Beyond
Coal was formed during the carboniferous period - roughly 360 to 290 million years ago - from the anaerobic decomposition of then-living plants. These plants ended up as coal because, upon their death, they failed to decompose in the usual way, by the action of oxygen to form eventually CO2 and water. As the carboniferous plants died, they often fell into oxygen-poor swamps or mud, or were covered by sediments. Because of the lack of oxygen they only partly decayed. The resulting spongy mass of...
MethanolBased Chemical Products and Materials
Today, methanol is one of the most important feedstocks for the chemical industry. Most of the 32 million tonnes of methanol produced yearly are used for the production of a large variety of chemical products and materials, including such basic chemicals as formaldehyde, acetic acid and methyl-tert-butyl ether MTBE which is, however, phased out in most of the United States , as well as various polymers, paints, adhesives, construction materials and others. In processes for the production of...
Energy from Nuclear Fission Reactions
Inside the nuclear reactor, the released energy comes from the fission of 235U atoms Fig. 8.16 . When a 235U nucleus is struck by a slow neutron, it splits, releasing two smaller atoms and two or three neutrons in a process called fission. The two new atoms may themselves undergo further radioactive decay, releasing beta or gamma radiation to achieve stability. The energy released by the fission is a result from the fact that the fission products and emitted neutrons, weigh together less than...
Methanol and the Methanol Economy
Methanol Production and Use, Eds. W.-H. Cheng, H. H. Kung , Marcel Dekker, New York, 1994. Asinger F., Methanol, Chemie- und Energierohstoff. Die Mobilisation der Kohle, Springer-Verlag, Heidelberg, 1987. Perry J. H., Perry C. P., Methanol, Bridge to a Renewable Energy Future, University Press of America, Lanham, Maryland, 1990. Bernton H., Kovarik W., Sklar S., The Forbidden Fuel. Power Alcohol in the Twentieth Century, Boyd Griffin, New York, 1982. Dovring F., Farming for Fuel, Praeger, New...
Methanol Storage and Distribution
In parallel to the development of methanol-fueled vehicles, a widespread distribution network for methanol will have to be established to make it as easily available for the consumer as are petroleum-based fuels today. While the passage from ICE to fuel cell-powered methanol vehicles represents a radical technological change, the development of a fueling infrastructure to fuel them is not. Refueling stations dispensing methanol will be almost identical to today's fueling stations, reflecting...