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We'll trust you recall our earlier dispatch converning work underway at West Virginia University, and reports made, by Stiller, Zondlo, et. al., on the liquefaction of agricultural wastes, as with coal, using the Hydrogen-donor solvent, key to the West Virginia Process of direct coal liquefaction, tetralin.
Other researchers, in China, especially, have indicated that sawdust, cellulose in general, could also be liquefied into the raw materials for liquid fuel synthesis using variations of the tetralin-based West Virginia Process.
We suggested such processes might make a suitable end to previously-loved Intel's and News-Register's.
Others among your readership might, we're certain, think tetralin dissolution to be a suitable end to them before they have had a chance to be loved.
Regardless, we have also reported on coal-to-liquid research underway at Southern Illinois University, and they, too, see both the value in using tetralin for coal liquefaction, and the potential for using it to convert cellulose, including newsprint, pre- or post-reading, into liquid fuels.
Comment follows the excerpt:
"Liquefaction of newsprint and cellulose in tetralin under moderate reaction conditions"
LALVANI S.; RAJAGOPAL P. ; AKASH B.; KOROPCHAK J.; MUCHMORE C.
Southern Illinois Univ. Carbondale, Dep. Mechanical Eng. Energy Processes, Carbondale IL 62901
Abstract
Liquefaction of newsprint and cellulose in tetralin at 350 °C and pressure of 1.07-2.51 MPa for 1 h resulted in their 37% and 40% by weight conversion to organic liquids, respectively. A significant amount of water was also formed. The gases produced consisted of mainly CH4 and CO. The total amount of gases produced was about 3-5% of the original amount of solid charged to the reactor. A first order kinetic model was proposed for the conversion of newsprint and cellulose. Rate constants and Arrhenius parameters were also calculated. Material balance for the process showed a good correlation between the carbon and oxygen contents of the reactant solid and products. Data indicate that most of the hydrogen supplied to the products is supplied by the solvent (tetralin)... ."First, note that, in addition to organic liquids and water, a small percentage of raw material was converted into Methane and Carbon Monoxide - both reactive gases which themselves can be entrained in processes of liquid hydrocarbon synthesis.
Second, and perhaps more importantly, please make note of what should be obvious: The liquefaction of newsprint and cellulose into liquid fuel represents a recycling of Carbon Dioxide. And, it is a coal-to-liquid fuel technology - WVU's West Virginia coal-to-liquid Process - that makes the CO2 recycling possible.
Theoretically, a coal-to-liquid conversion facility utilizing the West Virginia process to convert both coal and cellulose into liquid fuels could be "Carbon Neutral". By consuming enough botanically-derived cellulose, such as newsprint or sawdust, etc., in addition to coal, it might even be possible for such a dual-feed liquid fuel manufacturing facility to earn Carbon credits - which could then be sold to other emitters, such as cement kilns, to subsidize operations and increase CTL profitability.
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One potential environmental contaminant produced by both coal coking and indirect coal-to-liquid conversion processes is a class of organic chemicals referred to generically as phenols, or, just "Phenol".
Phenol is present in wastes left behind by older, unregulated coke works, and is among the contaminants that are addressed by cleanup plans and efforts at those sites.
Like the other coal-use "pollutants" we have addressed in our dispatches, Phenol did not have to be, and does not have to be, simply "dumped", or disposed of. It does have industrial uses, such as raw material for some types of epoxy, and other useful, resins.
It's value, in fact, was recognized early in the last century, and some efforts were applied towards recovering it from coal processing installations. As in:
Robert M. Crawford; Ind. Eng. Chem., 1927, 19 (9), pp 966–968
Publication Date: September 1927
Abstract available only through the link."
Keep in mind that coke plant liquid effluents would be similar to those potentially generated by a coal-to-liquid facility employing indirect processes of coal conversion.
However, even though Phenol can be used in industry, it's inherent value and it's concentrations in coal processing effluents are both low enough that most efforts have been directed towards it's straightforward destruction and elimination from the environment. Such Phenol elimination, it seems, can be readily and efficiently accomplished by a wide variety of micro-organisms. That fact has been realized, basically, around the word, as the following references attest:
EL-SAYED Wael S. ; IBRAHIM Mohamed K.; ABU-SHADY Mohamed; EL-BEIH Fawkia; OHMURA Naoya; SAIKI Hiroshi; ANDO Akikazu
Microbiology Department, Faculty of Science, Ain Shams University, Cairo, EGYPTE
Department of Bio-Science, Central Research Institute of Electric Power Industry, 1646 Abiko, Abiko-city, Chiba 270-1194, JAPON
Department of Science and Technology, Chiba University, 648 Matsudo, Chiba 271-8510, JAPON
Abstract
New phenol degrading bacteria with high biodegradation activity and high tolerance were isolated as Burkholderia cepacia PW3 and Pseudomonas aeruginosa AT2. Both isolates could grow aerobically on phenol as a sole carbon source even at 3 g/l. The whole-cell kinetic properties for phenol degradation by strains PW3 and AT2 showed a Vmax of 0.321 and 0.253 mg/l/min/(mg protein), respectively. "and:
School of Chemical Engineering, Nanjing University of Science & Technology, Nanjing 210094, PR China
Abstract
A white rot fungus Phanerochaete chrysosporium, immobilized with the wood chips of Italian poplar, was employed for biodegradation of phenolic compounds in coking wastewater. The immobilized fungus, dried by vacuum freeze desiccator, was kept high activity after a 9-month preservation and easy to be activated and domesticated. The removal rates of phenolic compounds and COD by immobilized fungus were 87.05% and 72.09% in 6 days, which were obviously higher than that by free fungus. For phenolic compounds biodegradation, a pH ranging from 4.0 to 6.0 and a temperature ranging from 28 °C to 37 °C create suitable conditions, and optimum 5.0 and 35 °C, respectively. The optimum removal rate of phenolic compounds was over 84% and COD was 80% in 3 days. And the biodegradation of phenolic compounds followed the first-order kinetics. It is an efficient and convenient method for coking wastewater treatment."
and:
Increasing the purification ability of a tank for the biochemical purification of phenol waters and flushing liquors
Prokof'ev, V.I. and Kharitonova, N.D,
Moscow Metallurgical Works
Coke Journal, USSR, 1984
Abstract
A biochemical device for purifying flushing liquors and phenol water in operation since 1980 at the by-product coke industry of the Moscow Metallurgical Works is described. Two-stage biochemical purification is realized when water from the recovery house, which goes through mechanical cleaning, is directed into a neutralizer and then into 10 stage-I air tanks where decomposition of the phenols takes place by means of phenol-disintegrating bacteria. The purified water is supplied to a sludge neutralizer. The removal of phenols and rhodanides is ensured up to a concentration of less than or equal to mg/1 and less than or equal to 1 mg/1, respectively."
Even though Phenol emissions can thus be effectively eliminated using "Green" technology, our primary interest is in finding ways in which coal use by-products can be harvested and employed, or recycled. Towards that end, the Indians, perhaps, have presented the most elegant, esthetically-pleasing solution, as follows:
Application and use of water hyacinth for phenol removal and biogas production.
Vaidyanathan, S. - Indian Institute of Technology, Bombay, 1985
Against the background of grave industrial pollution its high cost conventional treatments and energy shortage, different researches, during the past one decade, carried out, extensive exploratory research and began investigating the potential of water hyacinth (Eichhornia crassipes) as a low cost biological system for waste water treatment and for renewable sources of energy. After reviewing the literature available on water hyacinth, research work is planned on the application of water hyacinth for removal of phenol in a continuous unit and use water hyacinth for production of biogas by anaerobic digestion in batch and continuous digesters."
So, we can produce bio-fuel from water hyacinths which consume the phenol by-product of coal processing facilities. And, the hyacinths are lovely floating flowers, by the way. Does this mean that coal plants, by producing this water hyacinth nutrient, can help to beautify Walden Pond?
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We have reported that, as been known for hundreds, perhaps thousands, of years, coal can be "reduced" by heat in a low-oxygen environment to produce both coke, for steel making and other uses, and, a flammable "coke oven gas". The gas in early days was most often vented and flared, but was sometimes collected, and piped into the steel furnaces for additional heating.
We have also reported on facilities in some major cities, Boston and Seattle, for instance, where coal was processed in "Gas Works", which were essentially just large coke ovens, and the gas produced from the coal, the coke oven gas, was then distributed for residential and industrial heating and lighting use as "town" or "producer" gas.
Coke oven gas was also known as "manufactured gas", and, as it happens, it's use was very widespread. It was made commercially in Manufactured Gas Plants, "MGP's".
Herein an excerpt from the enclosed link to New York State's Department of Environmental Conservation, with some commentary following:
"General Information About MGPs
MGP is an abbreviation for Manufactured Gas Plant. A manufactured gas plant was an industrial facility at which gas was produced from coal, oil and other feedstocks. The gas was stored, and then piped to the surrounding area, where it was used for lighting, cooking, and heating homes and businesses. The first MGPs in New York were constructed in the early 1800s, prior to the Civil War. Most were closed during the early-to-middle 1900s, and the last one ceased operations in 1972.
Gas from MGPs was used for all the same purposes that natural gas is used for today. In addition, in the late 1800s, gas was used for lighting prior to the introduction of electricity.
When and Where Did MGPs Operate?
For a period of over 100 years, manufactured gas plants (MGPs) were an important part of life in cities and towns throughout New York State and the United States as a whole. They had their beginnings in the early 1800s, providing small amounts of gas for street lighting systems. By 1900, production had greatly increased, and gas was being widely used for heating and cooking. Most towns in New York with populations of over 5000 had at least one gas plant, and larger towns often had more than one. New York City had several dozen.
Small-town facilities began to close in the 1920s and 1930s as the industry consolidated production at larger facilities and connected smaller systems together with new pipeline networks. As World War II approached, interstate pipelines were built, making natural gas from the Midwest more widely available, and cheaper than manufactured gas. Most New York State MGPs closed by 1950, but a few remained in operation in remote areas, or on standby status in areas where the interstate pipelines could not meet peak demand. The last MGP in New York State ceased operations in 1972.
How Was the Gas Produced?
Two main processes were used to produce the gas. The older and simpler process was coal carbonization. In this process, coal was heated in closed retorts or beehive ovens. Inside these ovens, the coal was kept from burning by limiting its contact with outside air. Volatile constituents of the coal would be driven off as a gas, which was collected, cooled, and purified prior to being piped into the surrounding areas for use. The solid portion of the coal would become a black, granular material called coke. Coke was a valuable fuel for many industrial uses and for home heating, because it burned hotter and more cleanly than ordinary coal. Sometimes, the coke was the primary product, and the gas was a by-product, and the facility was called a coke plant."
Mike, another synonym for Manufactured Gas is, of course, as you be able to guess from all our earlier dispatches, Syngas; so named because, once it's produced, it can be catalyzed and condensed, synthesized, into more complex hydrocarbons - liquid fuels and organic chemical manufacturing raw materials.
Moreover, coke itself is not, given the changes in the steel industry, the valuable commodity it once was. But, once you have it, you can liquefy and reform it with steam or supercritical water or hydrogen-donor catalysts, and get - liquid fuels and organic chemical manufacturing raw materials.
The contaminants New York is concerned with in this report should not be a concern of modern Manufactured Gas Plants. They consist primarily of coal tars and could themselves be collected and converted, by steam reforming or hydrogen-donor catalysis into - liquid fuels and organic chemical manufacturing raw materials.
We'll document further, in some future dispatches, the breadth of public knowledge that once existed in the US about coal-based syngas, as it was produced and used under it's various synonyms. But, one thing is clear: The knowledge and technologies required to convert our coal into more versatile liquid and gaseous fuels has been around for a very long time.
We could have been free of gas station lines, oil embargoes, unemployment, some foreign wars, and oil cartel and oil company extortion long ago. There can be no good reason why we're not employing coal conversion technology on a broad scale to break the economic chains with which foreign petroleum powers hold us in subservient, royalty-paying bondage.
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There are two things we find interesting about this study on combining coal and waste plastics together to form a raw material for liquid fuel manufacture.
First, the inclusion of plastic actually provides at least some of the needed Hydrogen to convert the primarily carbonaceous coal into liquid hydrocarbons, as in: "The waste plastics having high H/C ratio are expected to play the role of hydrogen source".
Second, the process can be refined, especially in terms of coal-to-plastic combination ratios, so that the non-organic minerals in the coal can capture and immobilize, as various salts, the chlorine which might be present in the plastics.
Excerpt as follows:
"The Influence of PVC on the Coprocessing of Coal and Plastics
Author(s): Koyano Koji, et. al., Nihon University College of Science and Technology
Journal Title: Journal of the Japan Institute of Energy
Abstract;The coprocessing with coal is one of the beneficial technologies to convert waste plastics into alternative liquid hydrocarbon for fuel oil and chemical feedstock. The waste plastics having high H/C ratio are expected to play the role of hydrogen source. On the other hand, the waste plastics include chlorine-containing plastic such as polyvinyl chloride (PVC). Hydrogen chloride generated from pyrolysis of PVC causes the problems such as the corrosion of equipment. In the coprocessing reaction, it is expected that the hydrogen chloride is captured by the minerals in coal. In this paper, the influence of PVC on the coprocessing with Wyoming subbituminous coal and the mixture of high density polyethylene, polypropylene, polystyrene, and PVC was investigated under decalin solvent. A part of hydrogen chloride generated from PVC was fixed as chlorides by the minerals in coal, but the rest formed chlorinated organic compounds. These reactions occurred competitively. When a sufficient amount of hydrogen chloride was not captured, the chain reactions of polymer radicals were inhibited by chlorine radical. This inhibitation resulted in the increase of heavy oil yield. To avoid it, the optimization of the ratio of coal and plastics was desired."
In other words, not only can coal and waste plastics be combined to produce liquid fuels, but, the ratio of coal and plastics can be optimized, both for maximum liquid fuel output based on the hydrogen content of the plastic and for immobilization of the chlorine contained by the plastic, based on the inorganic mineral content of the coal. The two raw materials can be synergistic. Combing coal and plastics to synthesize liquid fuels can be done, and we know it can be done. People are at work on fine-tuning the process.
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We have reported on environmental cleanups underway at hazardous waste sites left behind by both coke oven batteries and early coal-to-liquid conversion facilities.
Those wastes didn't have to be dumped and left behind, but they unfortunately were.
We have reported that coke oven by-products, once treated as wastes, can be collected and utilized. Coke oven gas, as we've detailed, can be harvested and used, either directly as an auxiliary fuel for steel furnaces, or converted and condensed, synthesized, into liquid fuels.
Coke itself can be reformed with steam or super critical water, as we've documented, into liquid fuels, or fuel precursors that can even be fed as a co-stream into some conventional petroleum refineries.
Various "coal tars" are another residuum of coking operations that were frequently "dumped" into the environment, and they now, at many sites, present what are perceived to be great environmental hazards.
Those coal tars, where they are still contained at the older coal processing facilities in high-enough volumes and concentrations, are carbonaceous enough that they, too, could be harvested as part of a clean up, and transformed into liquid fuels - just, as we've earlier documented, some older coal mine waste accumulations can be processed, as is planned in Schuykill, PA, into liquid fuels and valuable organic chemicals.
We submit that, even at smaller facilities where the tar accumulations aren't great enough to enable profitable harvesting and conversion, any return realized by sales of fuel or chemicals produced from the waste would at least subsidize the costs of it's remediation.
And, in such a scenario, the waste coal tar would actually be cleaned up and removed from the environment. Most of the clean up plans being executed today only lead to the, hopefully, long-term stabilization of the wastes in-place. The current clean-ups don't actually "clean up"; and, the efforts represent only sunken cost. There is zero return on the sometimes massive investment.
If we were to focus our efforts on actually reclaiming the coal tar wastes with the intent of converting them into liquid fuels and chemicals, then we would get at least some return on the cost, and, perhaps more importantly, the objectionable wastes would actually be removed from the environment. It would be a true "clean-up", not just an expensive "containment".
The enclosed report indicates one avenue of approacht. An excerpt:
"Refined chemical oil (RCO), a coal tar by-product from metallurgical coke production, was blended with light cycle oil (LCO) from United Refinery, in a 1:1 ratio. The feeds were hydrotreated in the first stage to remove sulfur and nitrogen, then hydrogenated in a second stage to saturate the ring compounds, with fractionation taking place at various stages. The main variation in the process has been the location of the fractionation units, either before hydrotreatment, after the first stage, or after the second stage. When fractionating the product after both hydrotreatments, the co-processed material yields a product distribution of 6% gasoline, 80% jet fuel, 10% diesel and 4% fuel oil. The fuels produced are being tested in real systems."
Again, it's unlikely that such a recycling focus would actually make the clean up of old coke ovens and other coal processing facilities a profitable endeavor. But, if we had a coal-to-liquid conversion industry in place in the United States, then the collection and conversion of coke oven tar wastes would help at least to defray the costs of clean-up. And, an actual clean up, as opposed to an expensive containment in place, would be effected. We would be better off both economically and environmentally.
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