Crude Oil and Total Petroleum Imports Top 15 Countries
February 2008 Import Highlights: April 14, 2008Preliminary monthly data on the origins of crude oil imports in February 2008 has been released and it shows that two countries exported more than 1.50 million barrels per day to the United States. Including those countries, a total of three countries exported over 1.20 million barrels per day of crude oil to the United States (see table below). The top five exporting countries accounted for 70 percent of United States crude oil imports in February while the top ten sources accounted for approximately 88 percent of all U.S. crude oil imports. The top sources of US crude oil imports for February were Canada (1.888 million barrels per day), Saudi Arabia (1.614 million barrels per day), Mexico (1.231 million barrels per day), Nigeria (0.982 million barrels per day), and Venezuela (0.927 million barrels per day). The rest of the top ten sources, in order, were Iraq (0.780 million barrels per day), Angola (0.341 million barrels per day), Kuwait (0.261 million barrels per day), Colombia (0.220 million barrels per day), and Ecuador (0.169 million barrels per day). Total crude oil imports averaged 9.514 million barrels per day in February, which is a decrease of (0.486) million barrels per day from January 2008. Canada remained the largest exporter of total petroleum in February, exporting 2.419 million barrels per day to the United States, which is a decrease from last month (2.586 thousand barrels per day). The second largest exporter of total petroleum was Saudi Arabia with 1.627 million barrels per day.
Crude Oil Imports (Top 15 Countries)(Thousand Barrels per Day)
Country
Feb-08
Jan-08
YTD 2008
Feb-07
YTD 2007
CANADA
1,888
1,944
1,917
1,840
1,848
SAUDI ARABIA
1,614
1,479
1,544
1,185
1,382
MEXICO
1,231
1,198
1,214
1,358
1,398
NIGERIA
982
1,163
1,075
1,061
1,085
VENEZUELA
927
1,135
1,034
1,115
1,031
IRAQ
780
543
658
325
433
ANGOLA
341
566
458
451
504
KUWAIT
261
239
249
158
165
COLOMBIA
220
171
194
73
106
ECUADOR
169
247
209
178
226
BRAZIL
169
169
169
103
156
ALGERIA
149
366
261
392
474
CONGO (BRAZZAVILLE)
97
91
94
41
48
CHAD
89
117
103
87
78
RUSSIA
80
16
47
49
40
Total Imports of Petroleum (Top 15 Countries)(Thousand Barrels per Day)
Country
Feb-08
Jan-08
YTD 2008
Feb-07
YTD 2007
CANADA
2,419
2,586
2,505
2,448
2,460
SAUDI ARABIA
1,627
1,503
1,563
1,207
1,394
MEXICO
1,324
1,307
1,315
1,507
1,538
VENEZUELA
1,112
1,290
1,204
1,359
1,273
NIGERIA
1,025
1,191
1,110
1,102
1,120
IRAQ
780
543
658
325
433
RUSSIA
451
392
421
241
297
VIRGIN ISLANDS
351
380
366
312
371
ANGOLA
350
578
468
464
522
ALGERIA
343
636
494
555
672
KUWAIT
261
239
249
168
170
COLOMBIA
240
198
218
85
118
ECUADOR
186
260
224
185
231
BRAZIL
172
225
200
151
203
BELGIUM
164
115
139
53
60
Monday, April 14, 2008
Monday, February 18, 2008
Top petroleum non-producing and consuming countries
Top petroleum non-producing and consuming countries
1 Japan
2 Germany
3 India
4 South Korea
5 France
6 Italy
7 Spain
8 Netherlands
1 Japan
2 Germany
3 India
4 South Korea
5 France
6 Italy
7 Spain
8 Netherlands
Dismissal of the Claims of a Biological Connection for Natural Petroleum
Dismissal of the Claims of a Biological Connection for Natural Petroleum.
1. Introduction.
With recognition that the laws of thermodynamics prohibit spontaneous evolution of liquid hydrocarbons in the regime of temperature and pressure characteristic of the crust of the Earth, one should not expect there to exist legitimate scientific evidence that might suggest that such could occur. Indeed, and correctly, there exists no such evidence.Nonetheless, and surprisingly, there continue to be often promulgated diverse claims purporting to constitute "evidence" that natural petroleum somehow evolves (miraculously) from biological matter. In this short article, such claims are briefly subjected to scientific scrutiny, demonstrated to be without merit, and dismissed.The claims which purport to argue for some connection between natural petroleum and biological matter fall into roughly two classes: the "look-like/come-from" claims; and the "similar(recondite)-properties/come-from" claims.The "look-like/come-from" claims apply a line of unreason exactly as designated: Such argue that, because certain molecules found in natural petroleum "look like" certain other molecules found in biological systems, then the former must "come-from" the latter. Such notion is, of course, equivalent to asserting that elephant tusks evolve because those animals must eat piano keys.In some instances, the "look-like/come-from" claims assert that certain molecules found in natural petroleum actually are biological molecules, and evolve only in biological systems. These molecules have often been given the spurious name "biomarkers."The scientific correction must be stated unequivocally: There have never been observed any specifically biological molecules in natural petroleum, except as contaminants. Petroleum is an excellent solvent for carbon compounds; and, in the sedimentary strata from which petroleum is often produced, natural petroleum takes into solution much carbon material, including biological detritus. However, such contaminants are unrelated to the petroleum solvent.The claims about "biomarkers" have been thoroughly discredited by observations of those molecules in the interiors of ancient, abiotic meteorites, and also in many cases by laboratory synthesis under imposed conditions mimicking the natural environment. In the discussion below, the claims put forth about porphyrin and isoprenoid molecules are addressed particularly, because many "look-like/come-from" claims have been put forth for those compounds.The "similar(recondite)-properties/come-from" claims involve diverse, odd phenomena with which persons not working directly in a scientific profession would be unfamiliar. These include the "odd-even abundance imbalance" claims, the "carbon isotope" claims, and the "optical-activity" claims. The first, the "odd-even abundance imbalance" claims, are demonstrated to be utterly unrelated to any biological property. The second, "carbon isotope" claims, are shown to depend upon measurement of an obscure property of carbon fluids which cannot reliably be considered a measure of origin. The third, the "optical-activity" claims, deserve particular note; for the observations of optical activity in natural petroleum have been trumpeted loudly for years as a "proof" of some "biological origin" of petroleum. Those claims have been thoroughly discredited decades ago by observation of optical activity in the petroleum material extracted from the interiors of carbonaceous meteorites. More significantly, recent analysis, which has resolved the previously-outstanding problem of the genesis of optical activity in abiotic fluids, has established that the phenomenon of optical activity is an inevitable thermodynamic consequence of the phase stability of multicomponent fluids at high pressures. Thereby, the observation of optical activity in natural petroleum is entirely consistent with the results of the thermodynamic analysis of the stability of the hydrogen-carbon [H-C] system, which establish that hydrocarbon molecules heavier than methane, and particularly liquid hydrocarbons, evolve spontaneously only at high pressures, comparable to those necessary for diamond formation.There are two subjects which are particularly relevant for destroying the diverse, spurious claims concerning a putative connection of petroleum and biological matter: the investigations of the carbon material from carbonaceous meteorites; and the reaction products of the Fischer-Tropsch process. Because of their importance, a brief discussion of both is in order.1.1 The carbonaceous meteorites.The carbonaceous meteorites, including particularly the carbonaceous chondrites, are meteorites whose chemical composition includes carbon in quantities ranging from a few tenths of a percent to approximately six percent, by mass.1-5 The age of the carbonaceous meteorites is typically 3-4.5 billion years; and their origins clearly abiotic. The mineral structures in these rocks establish that the carbonaceous meteorites have existed at very low temperatures, much below the freezing point of water, effectively since the time of their original formation. Such thermal history of the carbonaceous meteorites eliminates any probability that there ever existed on them life, or biological matter.6 The evidence obtained from scientific investigations of the carbon material in carbonaceous meteorites has destroyed many claims which assert a biological connection between natural petroleum and biological matter.Significantly, much of the carbon material of the carbonaceous meteorites consists of hydrocarbons, as both solids and in liquid form.1, 5, 7, 8 However, the petroleum material contained in carbonaceous meteorites cannot be considered to be the origin of the natural petroleum found in the near-surface crust of the Earth. The heating which inevitably accompanied the impact process during the accretion of meteorites into the Earth at the time of its formation would almost certainly have caused decomposition of most of their contained hydrocarbon molecules. The carbonaceous meteorites provided the Earth with its carbon (albeit much of it delivered in the form of hydrocarbons) but not its hydrocarbons or natural petroleum. (The processes by which hydrocarbons evolve from the native materials of the Earth are described, and demonstrated, in the following article.)1.2 The Fischer-Tropsch process.The Fischer-Tropsch process is the best-known industrial technique for the synthesis of hydrocarbons, and has been used for more than seventy-five years. The Fischer-Tropsch process reacts carbon monoxide and hydrogen at synthesis conditions of approximately 150 bar and 700 K, in the presence of ThO2, MgO, Al2O3, MnO, clays, and the catalysts Ni, Co, and Fe. The reactions are as follow:When a Ni-Co catalyst is used, the Fischer-Tropsch synthesis proceeds according to the reaction:When a Fe catalyst is used, the Fischer-Tropsch synthesis proceeds according to the reaction:The yield of the Fischer-Tropsch process is approximately 200 g of hydrocarbons from 1 m3 of CO and H2 mixture. During World War II, the production of liquid fuels by the Fischer-Tropsch process was used extensively in Germany; approximately 600,000 t of synthetic gasoline were synthesized in 1943.The reaction products of the Fischer-Tropsch process are only metastable in the thermodynamic conditions of their synthesis; at pressures of approximately only 150 bar and 700 K, the destruction of liquid hydrocarbons is inevitable. During the industrial Fischer-Tropsch process, the reaction products are promptly cooled and moved to conditions of lower pressure. The natural environment does not mimic the highly-controlled, and highly-regulated, industrial, Fischer-Tropsch process. The Fischer-Tropsch process cannot be considered for the generation of natural petroleum.
2. The specious "biomarker" claims:
The irrelevancy of the presence in petroleum of porphyrins, - and similarly of isoprenoids, pristane, phytane, clorins, terpines, cholestane, etc.One may read, in almost every textbook published in the English language purporting to deal with the subject of petroleum geology, diverse claims made that the presence of certain molecules found in natural petroleum constitute "evidence," or even "proof," that the petroleum evolved from biological matter. Such molecules, claimed as evidence of a biological connection, include such as porphyrins, isoprenoids, pristane, phytane, cholestane, terpines, and clorins. Closer investigations have proven such claims to be groundless. Pristane and phytane are simply branched alkanes of the isoprenoid class. Cholestane, C27H48, is a true, highly-reduced hydrocarbon, but is not to be confused with the oxidized, biotic, molecule cholesterol. Cholestane and cholesterol have similar geometric structures, and share similar carbon skeletons; there the similarity ends. Cholestane is a constituent of natural petroleum; cholesterol is not. Significantly, the Fischer-Tropsch synthesis produces isoprenoids, including phytane and pristine.Material of truly biogenic origin, such as fossil spores or pollen, is indeed often observed in petroleum, - and too often mislabeled as "biomarkers," supposedly indicating a connection between the natural petroleum and biological material. Careful investigation has established that such material has been leached into solution by the crude oil from buried organic matter in the (typically sedimentary) reservoir rocks from which the oil has been taken.9, 10Contrarily, the indisputably biological material, such as spores and pollen, found in petroleum can be considered as "abiomarkers" of petroleum origin. For examples, crude oil found in reservoir rocks of the Permian age always contain not only spores and pollen of the Permian age but also spores and pollen of older ages, such as, for example, the Carboniferous, Devonian and Precambrian in petroleum investigated in Tatarstan, Russia. In the same region and in other portions of the Volga-Urals geological province, crude oils in the Carbonaceous sediments are characterized with concentrations of spores of Carbonaceous-through-Precambrian ages, and crudes in the Devonian sandstones with spores of Devonian-through-Precambrian ages.9, 11 The types of porphyrins, isoprenoids, terpines, and clorins found in natural petroleum have been observed in material extracted from the interiors of no fewer than fifty-four meteorites, including amphoteric meteorites (Chainpur, Ngavi, Semarkona), bronze chondrites (Charis, Ghubara, Kulp, Tieschitz), carbonaceous chondrites of all four petrological classes (Alais, Bali, Bells, Cold Bockeveld, Eracot, Felix, Groznaia, Haripura, Ivuna, Kaba, Kainsaz, Karoonda, Lance, Mighei, Mokoia, Murchison, Murrey, Orgueil, Ornans, Pseudo, Renazzo, Santa Cruz, St.Capraix, Staroye Boriskino, Tonk, Vigarano, Warrenton), enstatite meteorites (Abee, Hvittis, Indarkh), hypersthene chondrites (Bishunpur, Bruderheim, Gallingebirge, Holbrook, Homestead, Krymka), iron meteorites (Arus (Yardymli), Burgavli, Canyon Diabolo, Odessa, Toluca), aubrite meteorites (Norton County), and ureilite meteorites (Dyalpur, Goalpara, Novo Urei).9, 12, 13The observations of such molecules in meteorites thoroughly discredited the claims that their presence in natural petroleum might somehow constitute evidence of a biological connection. Because especially strenuous (and especially erroneous) claims are often made particularly about the porphyrins observed in natural petroleum, those molecules will be discussed in modest detail.Porphyrins comprise a class of molecules designated cyclic ionopheres, a special class of polydentate ligands for metals. Porphyrins are heavy, approximately planar, chelating molecules, found in both biotic and abiotic systems. Several porphyrin molecules are of special biological significance: vitamin B12; chlorophyll, the porphyrin which is the agent of the photosynthesis process in plants; and the heme molecule, the porphyrin component of the protein hemoglobin which is responsible for the transport of oxygen in mammalian blood. As an example of the high molecular weight of porphyrins, hemoglobin has the empirical chemical formula, [C738H1166O208N203S2Fe]4. Neither vitamin B12, nor chlorophyll, nor heme (nor hemoglobin), nor any biotic porphyrin has ever been observed as a component of natural petroleum.The porphyrin molecules found in natural petroleum possess different side-groups than do those of chlorophyll or heme. The central chelated metal element in chlorophyll is always magnesium; in heme, it is iron. In porphyrin molecules found in natural petroleum, the central chelated metal element is typically vanadium or nickel.As stated, porphyrin molecules evolve both biologically and abiologically. During the 1960’s and 1970’s, porphyrin molecules, which are the same as those found in terrestrial natural petroleum, were observed in the hydrocarbon fluids extracted from the interiors of carbonaceous meteorites.The observations of petroleum-type porphyrins in the hydrocarbon fluids extracted from the interiors of carbonaceous meteorites destroyed, a fortiori, the claims that such molecules constitute "evidence" for a connection of petroleum with biological matter. Additionally, after the observations of porphyrins in carbonaceous meteorites, those petroleum-type porphyrins were synthesized abiologically in the laboratory under chemical and thermodynamic conditions specially set to mimic the abiotic conditions in meteorites.8, 14The "porphyrin evidence" claims were destroyed by the investigations of carbonaceous meteorites approximately thirty years ago, and are well known throughout the community of scientists working in the field of petroleum. Every compound designated as a "biomarker," and not otherwise identified as a contaminant, has been either observed in the fluids extracted from the interiors of meteorites, or synthesized in laboratories under conditions comparable to the crust of the Earth, - or both.Such scientific facts, and the general knowledge of same, not withstanding, every textbook published in the English language purportedly dealing with the subject of petroleum geology, including the ones cited above, continues to repeat the old discredited claims that the presence of (abiotic) porphyrins in natural petroleum provide evidence for its origin from biological matter.15-17 Such assertions, thirty years after having been demonstrated scientifically insupportable, must be acknowledged to be intellectual fraud, pure and simple.
3. The "odd-even" abundance claims, - involving the small imbalance of the relative abundances of linear hydrocarbon molecules containing an odd number of carbon atoms, compared to homologous ones containing an even number.The claims concerning the imbalance of linear molecules containing odd and even numbers, respectively, of carbon atoms is another of the genre of "the constituents of natural petroleum ‘have the same properties as’ the constituents of biological systems, in such-or-so a way, and therefore petroleum must have evolved from biological matter." No intelligent teenage student at, for examples, a Russian, German, Dutch, or Swiss gymnasium, would accept such reasoning. Nonetheless, such claims are commonly put forth in English-language textbooks purporting to deal with petroleum geology. Such claims are herewith shown to be without merit and insupportable.Fig. 1 Symbolic representation of a molecule of normal octane, n-C8H18.Natural petroleum is a mixture of hydrocarbon molecules of several classes. The most common class of molecules in petroleum is that of the normal alkanes, or n-alkanes, which have the chemical formula CnH2n+2 and a chain-like structure (as noted in the first article). For example, n-octane, C8H18, has the structure shown schematically in Fig. 1. Correctly, the carbon atoms do not lie exactly along a straight line; a picture of n-octane which more accurately represents its geometric properties is shown in Fig. 2, where n-C8H18 is drawn as a "stick-&-ball" model. Nonetheless, in both figures, the linear chain-like aspect of the n-alkane molecule is shown clearly.Similarly as for cyclohexane as described in the first article, the hydrocarbon n-C8H18 is geometrically related to one or more biological molecules by substitution of some of the hydrogen atoms by OH radicals. Specifically, if one of the hydrogen atoms on each carbon atom in n-C8H18 were replaced by an OH radical, the resulting molecule, n-C8H18O8, would be a carbohydrate, as shown in Fig. 3, a simple sugar related to fructose (and whose chemical potential is approximately 2,500 cal lower than that of n-octane).In a distribution of linear hydrocarbon molecules which comprise natural petroleum, the chain-like n-alkanes manifest a slight imbalance of abundances which favors molecules possessing an odd number of carbon atoms, as compared to those with an even number. Similarly, a distribution of linear biological molecules, such as the chain-like carbohydrates, manifests also a similar slight imbalance of molecules possessing an odd number of carbon atoms, again as compared to those with an even number. From this modest, and somewhat arcane, similarity of odd-to-even abundances, assertions have been made that hydrocarbons evolve from biological matter. Of course, the second law of thermodynamics prohibits such, which fact should obviate any such assertion.Simple investigation of hydrocarbons generated from abiotic matter manifest also such odd-to-even imbalance of molecular abundances for the linear molecules. The reaction products of the Fischer-Tropsch process manifest the same odd-to-even abundance imbalances of linear molecules as do both natural petroleum, as well as biological molecules.A specific example of the inevitable genesis of hydrocarbon molecules which manifest such odd-to-even abundance imbalances of linear molecules was demonstrated by Zemanian, Streett, and Zollweg more than fifteen years ago. Zemanian et al. demonstrated the genesis of heavy and liquid hydrocarbons at high pressures and temperatures from a mixture of methane and propane. Particularly, Zemanian et al. measured the relative abundances of the linear chain hydrocarbon molecules. Their observations, of the imbalance of abundances, and slight excess, of chain molecules with odd numbers of carbon atoms are quoted here (pp. 63-64):18"These results are also notable when one considers the even-to-odd carbon number ratio of petroleum.One of the arguments for a biological origin of petroleum has been that these fluids generally show a small marked prevalence of odd numbered hydrocarbons. It is also well known that living organisms produce primarily odd numbered carbon [or carbohydrate] chains. Abiological processes have been presumed to produce even and odd numbered hydrocarbons in roughly equal concentrations. The results of this work demonstrate that presumption to be false. Both biological and abiological hydrocarbon chemistries favor reactions involving two carbons over single carbon reactions [leading to preferred reactants of odd-numbered chain molecules]."It deserves note that the "odd-even abundance-imbalance" claim, as "evidence"[sic] of a biological origin of hydrocarbon molecules, was rejected by competent physicists and statistical mechanicians, almost immediately when it was introduced. The odd-even abundance imbalance is simply a result of the directional property of the covalent bond together with the geometry of linear molecules.
4. The phenomenon of optical activity in natural petroleum: Evidence of an abiotic, high-pressure genesis.Perhaps for reason of its historical provenance in fermented wine, the phenomenon of optical activity in fluids was for some time believed to have some intrinsic connection with biological processes or materials.20, 21 Such error persisted until the phenomenon of optical activity was observed in material extracted from the interiors of meteorites; some of which material had been believed previously to be uniquely of biotic origin.From the interiors of carbonaceous meteorites have been extracted the common amino-acid molecules alanine, aspartic acid, glutamic acid, glycine, leusine, proline, serine, threonine, as well as the unusual ones α-aminoisobutyric acid, isovaline, pseudoleucine.22-24 At one time, all had been considered to be solely of biotic origin. The ages of the carbonaceous meteorites were determined to be 3-4.5 billion years, and their origins clearly abiotic. Therefore, those amino acids had to be recognized as compounds of both biological and abiological genesis. Furthermore, solutions of amino acid molecules from carbonaceous meteorites were observed to manifest optical activity. Thus was thoroughly discredited the notion that the phenomenon of optical activity in fluids (particularly those of carbon compounds) might have any intrinsic connection with biotic matter. Significantly, the optical activity observed in the amino acids extracted from carbonaceous meteorites has not the characteristics of such of common biotic origin, with only one enantiomer present; instead, it manifests the characteristics observed in natural petroleum, with unbalanced, so-called scalemic, abundances of chiral molecules.25The optical activity commonly observed in natural petroleum has been for years speciously claimed as "proof" of some connection with biological detritus, - albeit one requiring both a willing disregard of the considerable differences between the optical activity observed in natural petroleum and that in materials of truly biotic origin, such as wine, as well as desuetude of the dictates of the laws of thermodynamics.Optical activity is observed in minerals such as quartz or Iceland spar, as well as in oil, and among biological molecules. The optical activity observed in petroleum is more characteristic of the same in abiotic minerals, such as naturally occurring quartz, which are polycrystalline minerals, with a scalemic distribution of domains of left- and right-rotational properties. The chiral molecules in petroleum manifest scalemic distributions, and significantly lack the homochiral distribution which characterize biotic optically active matter. The optical activity in natural petroleum is characterized by either a right (positive, or dextrorotary) or left (negative, or levorotary) rotation of the plane of polarization. By contrast, in biological material left (levorotary) rotation dominates.The observation of optical activity in hydrocarbon material extracted from the interiors of carbonaceous meteorites, and typical of such in natural petroleum, discredited those claims.2, 26 Nonetheless, the scientific conundrum as to why the hydrocarbons manifest optical activity, in both carbonaceous meteorites and terrestrial crude oil remained unresolved until recently.The chiral molecules in natural petroleum originate from three distinct sources: contamination by biological detritus in the near-surface strata from which the oil has been taken; the biological alteration and degradation of the original oil by microbes which consume and metabolize oil; and the chiral hydrocarbon molecules which are intrinsic to the petroleum and generated with it. Only the last concerns the origin of petroleum.The genesis of the scalemic distribution of chiral molecules of natural petroleum has recently been shown to be a direct consequence of the chiral geometry of the system particles acting according to the laws of classical thermodynamics. The resolution of the problem of the origin of the scalemic distributions of chiral molecules in natural petroleum has been shown to be an inevitable consequence of their high-pressure genesis.19 Thus, the phenomenon of optical activity in natural petroleum, contrary to supporting any assertion of a biological connection, strongly confirms the high-pressure genesis of natural petroleum, and thereby the modern Russian-Ukrainian theory of deep, abiotic petroleum origins.
5. The carbon isotope ratios, and their inadequacy as indicators of origin.The claims made concerning the carbon isotope ratios, and specifically such as purport to identify the origin of the material, particularly the hydrocarbons, are especially recondite and outside the experience of most persons not knowledgeable in the physics of hydrogen-carbon [H-C] systems. Furthermore, the claims concerning the carbon isotope ratios most often involve methane, the only hydrocarbon which is thermodynamically stable in the regime of temperatures and pressures of the Earth’s crust, and the only one which spontaneously evolves there.The carbon nucleus has two stable isotopes, 12C and 13C. The overwhelmingly most abundance stable isotope of carbon is 12C, which possesses six protons and six neutrons; 13C possesses an extra neutron. (There is another, unstable isotope, 14C, which possesses two extra neutrons; 14C results from a high-energy reaction of the nitrogen nucleus, 14N, with a high-energy cosmic ray particle. The isotope 14C is not involved in the claims about the isotope ratios of carbon.) The carbon isotope ratio, designated δ13C, is simply the ratio of the abundance of carbon isotopes 13C/12C, normalized to the standard of the marine carbonate named Pee Dee Belemnite. The values of the measured δ13C ratio is expressed as a percentage (compared to the standard).During the 1950’s, increasingly numerous measurements of the carbon isotope ratios of hydrocarbon gases were taken, particularly of methane; and too often assertions were made that such ratios could unambiguously determine the origin of the hydrocarbons. The validity of such assertions were tested, independently by Colombo, Gazzarini, and Gonfiantini in Italy and by Galimov in Russia. Both sets of workers established that the carbon isotope ratios cannot be used reliably to determine the origin of the carbon compound tested.Colombo, Gazzarini, and Gonfiantini demonstrated conclusively, by a simple experiment the results of which admitted no ambiguity, that the carbon isotope ratios of methane change continuously along its transport path, becoming progressively lighter with distance traveled. Colombo et al. took a sample of natural gas and passed it through a column of crushed rock, chosen to resemble as closely as possible the terrestrial environment.27 Their results were definitive: The greater the distance of rock through which the sample of methane passes, the lighter becomes its carbon isotope ratio.The reason for the result observed by Colombo et al. is straightforward: there is a slight preference for the heavier isotope of carbon to react chemically with the rock through which the gas passes. Therefore, the greater the transit distance through the rock, the lighter becomes the carbon isotope ratio, as the heavier is preferentially removed by chemical reaction along the transport path. This result is not surprising; contrarily, such is entirely consistent with the fundamental requirements of quantum mechanics and kinetic theory.Pertinent to the matter of any claim that a light carbon isotope ratio might be indicative of a biological origin, the results demonstrated by Colombo et al. establish that such a claim is insupportable. Methane which might have originated from carbon material from the remains of a carbonaceous meteorite in the mantle of the Earth, and possessing initially a heavy carbon isotope ratio, could easily have that ratio diminished, along the path of its transit into the crust of the Earth, to a value comparable to common biological material.Galimov demonstrated that the carbon isotope ratio of methane can become progressively heavier while at rest in a reservoir in the crust of the Earth, through the action of methane-consuming microbes.28 The city of Moscow stores methane in water-wet reservoirs on the outskirts of that city, into which natural gas is injected throughout the year. During summers, the quantity of methane in the reservoirs increases because of less use (primarily by heating), and during winters the quantity is drawn down. By calibrating the reservoir volumes and the distance from the injection facilities, the residency time of the methane in the reservoir is determined. Galimov established that the longer the methane remains in the reservoir, the heavier becomes its carbon isotope ratio.The reason for the result observed by Galimov is also straightforward: In the water of the reservoir, there live microbes of the common, methane-metabolizing type. There is a slight preference for the lighter isotope of carbon to enter the microbe cell and to be metabolized. The longer the methane remains in the reservoir, the more of it is consumed by the methane-metabolizing microbes, with the molecules possessing lighter isotope being consumed more. Therefore, the longer its residency time in the reservoir, the heavier becomes the carbon isotope ratio, as the lighter is preferentially removed by methane-metabolizing microbes. This result is entirely consistent with the fundamental requirements of kinetic theory.Furthermore, the carbon isotope ratios in hydrocarbon systems are also strongly influenced by the temperature of reaction. For hydrocarbons produced by the Fischer-Tropsch process, the δ13C varies from -65% at 127 C to -20% at 177 C.29, 30 No material parameter, the measurement of which varies by almost 70% with a variation of temperature of only approximately 10%, can be used as a reliable determinant of any property of that material.The δ13C carbon isotope ratio cannot be considered to determine reliably the origin of a sample of methane, - or any other compound.6. Conclusion.The claims which have traditionally been put forward to argue a connection between natural petroleum and biological matter have been subjected to scientific scrutiny and have been established to be baseless. The outcome of such scrutiny comes hardly as a surprise, given recognition of the constraints of thermodynamics upon the genesis of hydrocarbons.If liquid hydrocarbons might evolve from biological detritus in the thermodynamic regime of the crust of the Earth, we could all expect to go to bed at night in our dotage, with white hair (or, at least, whatever might remain of same), a spreading waistline, and all the undesirable decrepitude of age, and to awake in the morning, clear eyed, with our hair returned of the color of our youth, with a slim waistline, a strong, flexible body, and with our sexual vigor restored. Alas, such is not to be. The merciless laws of thermodynamics do not accommodate folklore fables. Natural petroleum has no connection with biological matter.However, recognition of such fact leaves unanswered the conundrums which eluded the scientific community for more than a century: How does natural petroleum evolve ? And from where does natural petroleum come ?The theoretical resolution of these questions had to await development of the most modern techniques of quantum statistical mechanics. The experimental demonstration of the required equipment has been only recently available.
1. Introduction.
With recognition that the laws of thermodynamics prohibit spontaneous evolution of liquid hydrocarbons in the regime of temperature and pressure characteristic of the crust of the Earth, one should not expect there to exist legitimate scientific evidence that might suggest that such could occur. Indeed, and correctly, there exists no such evidence.Nonetheless, and surprisingly, there continue to be often promulgated diverse claims purporting to constitute "evidence" that natural petroleum somehow evolves (miraculously) from biological matter. In this short article, such claims are briefly subjected to scientific scrutiny, demonstrated to be without merit, and dismissed.The claims which purport to argue for some connection between natural petroleum and biological matter fall into roughly two classes: the "look-like/come-from" claims; and the "similar(recondite)-properties/come-from" claims.The "look-like/come-from" claims apply a line of unreason exactly as designated: Such argue that, because certain molecules found in natural petroleum "look like" certain other molecules found in biological systems, then the former must "come-from" the latter. Such notion is, of course, equivalent to asserting that elephant tusks evolve because those animals must eat piano keys.In some instances, the "look-like/come-from" claims assert that certain molecules found in natural petroleum actually are biological molecules, and evolve only in biological systems. These molecules have often been given the spurious name "biomarkers."The scientific correction must be stated unequivocally: There have never been observed any specifically biological molecules in natural petroleum, except as contaminants. Petroleum is an excellent solvent for carbon compounds; and, in the sedimentary strata from which petroleum is often produced, natural petroleum takes into solution much carbon material, including biological detritus. However, such contaminants are unrelated to the petroleum solvent.The claims about "biomarkers" have been thoroughly discredited by observations of those molecules in the interiors of ancient, abiotic meteorites, and also in many cases by laboratory synthesis under imposed conditions mimicking the natural environment. In the discussion below, the claims put forth about porphyrin and isoprenoid molecules are addressed particularly, because many "look-like/come-from" claims have been put forth for those compounds.The "similar(recondite)-properties/come-from" claims involve diverse, odd phenomena with which persons not working directly in a scientific profession would be unfamiliar. These include the "odd-even abundance imbalance" claims, the "carbon isotope" claims, and the "optical-activity" claims. The first, the "odd-even abundance imbalance" claims, are demonstrated to be utterly unrelated to any biological property. The second, "carbon isotope" claims, are shown to depend upon measurement of an obscure property of carbon fluids which cannot reliably be considered a measure of origin. The third, the "optical-activity" claims, deserve particular note; for the observations of optical activity in natural petroleum have been trumpeted loudly for years as a "proof" of some "biological origin" of petroleum. Those claims have been thoroughly discredited decades ago by observation of optical activity in the petroleum material extracted from the interiors of carbonaceous meteorites. More significantly, recent analysis, which has resolved the previously-outstanding problem of the genesis of optical activity in abiotic fluids, has established that the phenomenon of optical activity is an inevitable thermodynamic consequence of the phase stability of multicomponent fluids at high pressures. Thereby, the observation of optical activity in natural petroleum is entirely consistent with the results of the thermodynamic analysis of the stability of the hydrogen-carbon [H-C] system, which establish that hydrocarbon molecules heavier than methane, and particularly liquid hydrocarbons, evolve spontaneously only at high pressures, comparable to those necessary for diamond formation.There are two subjects which are particularly relevant for destroying the diverse, spurious claims concerning a putative connection of petroleum and biological matter: the investigations of the carbon material from carbonaceous meteorites; and the reaction products of the Fischer-Tropsch process. Because of their importance, a brief discussion of both is in order.1.1 The carbonaceous meteorites.The carbonaceous meteorites, including particularly the carbonaceous chondrites, are meteorites whose chemical composition includes carbon in quantities ranging from a few tenths of a percent to approximately six percent, by mass.1-5 The age of the carbonaceous meteorites is typically 3-4.5 billion years; and their origins clearly abiotic. The mineral structures in these rocks establish that the carbonaceous meteorites have existed at very low temperatures, much below the freezing point of water, effectively since the time of their original formation. Such thermal history of the carbonaceous meteorites eliminates any probability that there ever existed on them life, or biological matter.6 The evidence obtained from scientific investigations of the carbon material in carbonaceous meteorites has destroyed many claims which assert a biological connection between natural petroleum and biological matter.Significantly, much of the carbon material of the carbonaceous meteorites consists of hydrocarbons, as both solids and in liquid form.1, 5, 7, 8 However, the petroleum material contained in carbonaceous meteorites cannot be considered to be the origin of the natural petroleum found in the near-surface crust of the Earth. The heating which inevitably accompanied the impact process during the accretion of meteorites into the Earth at the time of its formation would almost certainly have caused decomposition of most of their contained hydrocarbon molecules. The carbonaceous meteorites provided the Earth with its carbon (albeit much of it delivered in the form of hydrocarbons) but not its hydrocarbons or natural petroleum. (The processes by which hydrocarbons evolve from the native materials of the Earth are described, and demonstrated, in the following article.)1.2 The Fischer-Tropsch process.The Fischer-Tropsch process is the best-known industrial technique for the synthesis of hydrocarbons, and has been used for more than seventy-five years. The Fischer-Tropsch process reacts carbon monoxide and hydrogen at synthesis conditions of approximately 150 bar and 700 K, in the presence of ThO2, MgO, Al2O3, MnO, clays, and the catalysts Ni, Co, and Fe. The reactions are as follow:When a Ni-Co catalyst is used, the Fischer-Tropsch synthesis proceeds according to the reaction:When a Fe catalyst is used, the Fischer-Tropsch synthesis proceeds according to the reaction:The yield of the Fischer-Tropsch process is approximately 200 g of hydrocarbons from 1 m3 of CO and H2 mixture. During World War II, the production of liquid fuels by the Fischer-Tropsch process was used extensively in Germany; approximately 600,000 t of synthetic gasoline were synthesized in 1943.The reaction products of the Fischer-Tropsch process are only metastable in the thermodynamic conditions of their synthesis; at pressures of approximately only 150 bar and 700 K, the destruction of liquid hydrocarbons is inevitable. During the industrial Fischer-Tropsch process, the reaction products are promptly cooled and moved to conditions of lower pressure. The natural environment does not mimic the highly-controlled, and highly-regulated, industrial, Fischer-Tropsch process. The Fischer-Tropsch process cannot be considered for the generation of natural petroleum.
2. The specious "biomarker" claims:
The irrelevancy of the presence in petroleum of porphyrins, - and similarly of isoprenoids, pristane, phytane, clorins, terpines, cholestane, etc.One may read, in almost every textbook published in the English language purporting to deal with the subject of petroleum geology, diverse claims made that the presence of certain molecules found in natural petroleum constitute "evidence," or even "proof," that the petroleum evolved from biological matter. Such molecules, claimed as evidence of a biological connection, include such as porphyrins, isoprenoids, pristane, phytane, cholestane, terpines, and clorins. Closer investigations have proven such claims to be groundless. Pristane and phytane are simply branched alkanes of the isoprenoid class. Cholestane, C27H48, is a true, highly-reduced hydrocarbon, but is not to be confused with the oxidized, biotic, molecule cholesterol. Cholestane and cholesterol have similar geometric structures, and share similar carbon skeletons; there the similarity ends. Cholestane is a constituent of natural petroleum; cholesterol is not. Significantly, the Fischer-Tropsch synthesis produces isoprenoids, including phytane and pristine.Material of truly biogenic origin, such as fossil spores or pollen, is indeed often observed in petroleum, - and too often mislabeled as "biomarkers," supposedly indicating a connection between the natural petroleum and biological material. Careful investigation has established that such material has been leached into solution by the crude oil from buried organic matter in the (typically sedimentary) reservoir rocks from which the oil has been taken.9, 10Contrarily, the indisputably biological material, such as spores and pollen, found in petroleum can be considered as "abiomarkers" of petroleum origin. For examples, crude oil found in reservoir rocks of the Permian age always contain not only spores and pollen of the Permian age but also spores and pollen of older ages, such as, for example, the Carboniferous, Devonian and Precambrian in petroleum investigated in Tatarstan, Russia. In the same region and in other portions of the Volga-Urals geological province, crude oils in the Carbonaceous sediments are characterized with concentrations of spores of Carbonaceous-through-Precambrian ages, and crudes in the Devonian sandstones with spores of Devonian-through-Precambrian ages.9, 11 The types of porphyrins, isoprenoids, terpines, and clorins found in natural petroleum have been observed in material extracted from the interiors of no fewer than fifty-four meteorites, including amphoteric meteorites (Chainpur, Ngavi, Semarkona), bronze chondrites (Charis, Ghubara, Kulp, Tieschitz), carbonaceous chondrites of all four petrological classes (Alais, Bali, Bells, Cold Bockeveld, Eracot, Felix, Groznaia, Haripura, Ivuna, Kaba, Kainsaz, Karoonda, Lance, Mighei, Mokoia, Murchison, Murrey, Orgueil, Ornans, Pseudo, Renazzo, Santa Cruz, St.Capraix, Staroye Boriskino, Tonk, Vigarano, Warrenton), enstatite meteorites (Abee, Hvittis, Indarkh), hypersthene chondrites (Bishunpur, Bruderheim, Gallingebirge, Holbrook, Homestead, Krymka), iron meteorites (Arus (Yardymli), Burgavli, Canyon Diabolo, Odessa, Toluca), aubrite meteorites (Norton County), and ureilite meteorites (Dyalpur, Goalpara, Novo Urei).9, 12, 13The observations of such molecules in meteorites thoroughly discredited the claims that their presence in natural petroleum might somehow constitute evidence of a biological connection. Because especially strenuous (and especially erroneous) claims are often made particularly about the porphyrins observed in natural petroleum, those molecules will be discussed in modest detail.Porphyrins comprise a class of molecules designated cyclic ionopheres, a special class of polydentate ligands for metals. Porphyrins are heavy, approximately planar, chelating molecules, found in both biotic and abiotic systems. Several porphyrin molecules are of special biological significance: vitamin B12; chlorophyll, the porphyrin which is the agent of the photosynthesis process in plants; and the heme molecule, the porphyrin component of the protein hemoglobin which is responsible for the transport of oxygen in mammalian blood. As an example of the high molecular weight of porphyrins, hemoglobin has the empirical chemical formula, [C738H1166O208N203S2Fe]4. Neither vitamin B12, nor chlorophyll, nor heme (nor hemoglobin), nor any biotic porphyrin has ever been observed as a component of natural petroleum.The porphyrin molecules found in natural petroleum possess different side-groups than do those of chlorophyll or heme. The central chelated metal element in chlorophyll is always magnesium; in heme, it is iron. In porphyrin molecules found in natural petroleum, the central chelated metal element is typically vanadium or nickel.As stated, porphyrin molecules evolve both biologically and abiologically. During the 1960’s and 1970’s, porphyrin molecules, which are the same as those found in terrestrial natural petroleum, were observed in the hydrocarbon fluids extracted from the interiors of carbonaceous meteorites.The observations of petroleum-type porphyrins in the hydrocarbon fluids extracted from the interiors of carbonaceous meteorites destroyed, a fortiori, the claims that such molecules constitute "evidence" for a connection of petroleum with biological matter. Additionally, after the observations of porphyrins in carbonaceous meteorites, those petroleum-type porphyrins were synthesized abiologically in the laboratory under chemical and thermodynamic conditions specially set to mimic the abiotic conditions in meteorites.8, 14The "porphyrin evidence" claims were destroyed by the investigations of carbonaceous meteorites approximately thirty years ago, and are well known throughout the community of scientists working in the field of petroleum. Every compound designated as a "biomarker," and not otherwise identified as a contaminant, has been either observed in the fluids extracted from the interiors of meteorites, or synthesized in laboratories under conditions comparable to the crust of the Earth, - or both.Such scientific facts, and the general knowledge of same, not withstanding, every textbook published in the English language purportedly dealing with the subject of petroleum geology, including the ones cited above, continues to repeat the old discredited claims that the presence of (abiotic) porphyrins in natural petroleum provide evidence for its origin from biological matter.15-17 Such assertions, thirty years after having been demonstrated scientifically insupportable, must be acknowledged to be intellectual fraud, pure and simple.
3. The "odd-even" abundance claims, - involving the small imbalance of the relative abundances of linear hydrocarbon molecules containing an odd number of carbon atoms, compared to homologous ones containing an even number.The claims concerning the imbalance of linear molecules containing odd and even numbers, respectively, of carbon atoms is another of the genre of "the constituents of natural petroleum ‘have the same properties as’ the constituents of biological systems, in such-or-so a way, and therefore petroleum must have evolved from biological matter." No intelligent teenage student at, for examples, a Russian, German, Dutch, or Swiss gymnasium, would accept such reasoning. Nonetheless, such claims are commonly put forth in English-language textbooks purporting to deal with petroleum geology. Such claims are herewith shown to be without merit and insupportable.Fig. 1 Symbolic representation of a molecule of normal octane, n-C8H18.Natural petroleum is a mixture of hydrocarbon molecules of several classes. The most common class of molecules in petroleum is that of the normal alkanes, or n-alkanes, which have the chemical formula CnH2n+2 and a chain-like structure (as noted in the first article). For example, n-octane, C8H18, has the structure shown schematically in Fig. 1. Correctly, the carbon atoms do not lie exactly along a straight line; a picture of n-octane which more accurately represents its geometric properties is shown in Fig. 2, where n-C8H18 is drawn as a "stick-&-ball" model. Nonetheless, in both figures, the linear chain-like aspect of the n-alkane molecule is shown clearly.Similarly as for cyclohexane as described in the first article, the hydrocarbon n-C8H18 is geometrically related to one or more biological molecules by substitution of some of the hydrogen atoms by OH radicals. Specifically, if one of the hydrogen atoms on each carbon atom in n-C8H18 were replaced by an OH radical, the resulting molecule, n-C8H18O8, would be a carbohydrate, as shown in Fig. 3, a simple sugar related to fructose (and whose chemical potential is approximately 2,500 cal lower than that of n-octane).In a distribution of linear hydrocarbon molecules which comprise natural petroleum, the chain-like n-alkanes manifest a slight imbalance of abundances which favors molecules possessing an odd number of carbon atoms, as compared to those with an even number. Similarly, a distribution of linear biological molecules, such as the chain-like carbohydrates, manifests also a similar slight imbalance of molecules possessing an odd number of carbon atoms, again as compared to those with an even number. From this modest, and somewhat arcane, similarity of odd-to-even abundances, assertions have been made that hydrocarbons evolve from biological matter. Of course, the second law of thermodynamics prohibits such, which fact should obviate any such assertion.Simple investigation of hydrocarbons generated from abiotic matter manifest also such odd-to-even imbalance of molecular abundances for the linear molecules. The reaction products of the Fischer-Tropsch process manifest the same odd-to-even abundance imbalances of linear molecules as do both natural petroleum, as well as biological molecules.A specific example of the inevitable genesis of hydrocarbon molecules which manifest such odd-to-even abundance imbalances of linear molecules was demonstrated by Zemanian, Streett, and Zollweg more than fifteen years ago. Zemanian et al. demonstrated the genesis of heavy and liquid hydrocarbons at high pressures and temperatures from a mixture of methane and propane. Particularly, Zemanian et al. measured the relative abundances of the linear chain hydrocarbon molecules. Their observations, of the imbalance of abundances, and slight excess, of chain molecules with odd numbers of carbon atoms are quoted here (pp. 63-64):18"These results are also notable when one considers the even-to-odd carbon number ratio of petroleum.One of the arguments for a biological origin of petroleum has been that these fluids generally show a small marked prevalence of odd numbered hydrocarbons. It is also well known that living organisms produce primarily odd numbered carbon [or carbohydrate] chains. Abiological processes have been presumed to produce even and odd numbered hydrocarbons in roughly equal concentrations. The results of this work demonstrate that presumption to be false. Both biological and abiological hydrocarbon chemistries favor reactions involving two carbons over single carbon reactions [leading to preferred reactants of odd-numbered chain molecules]."It deserves note that the "odd-even abundance-imbalance" claim, as "evidence"[sic] of a biological origin of hydrocarbon molecules, was rejected by competent physicists and statistical mechanicians, almost immediately when it was introduced. The odd-even abundance imbalance is simply a result of the directional property of the covalent bond together with the geometry of linear molecules.
4. The phenomenon of optical activity in natural petroleum: Evidence of an abiotic, high-pressure genesis.Perhaps for reason of its historical provenance in fermented wine, the phenomenon of optical activity in fluids was for some time believed to have some intrinsic connection with biological processes or materials.20, 21 Such error persisted until the phenomenon of optical activity was observed in material extracted from the interiors of meteorites; some of which material had been believed previously to be uniquely of biotic origin.From the interiors of carbonaceous meteorites have been extracted the common amino-acid molecules alanine, aspartic acid, glutamic acid, glycine, leusine, proline, serine, threonine, as well as the unusual ones α-aminoisobutyric acid, isovaline, pseudoleucine.22-24 At one time, all had been considered to be solely of biotic origin. The ages of the carbonaceous meteorites were determined to be 3-4.5 billion years, and their origins clearly abiotic. Therefore, those amino acids had to be recognized as compounds of both biological and abiological genesis. Furthermore, solutions of amino acid molecules from carbonaceous meteorites were observed to manifest optical activity. Thus was thoroughly discredited the notion that the phenomenon of optical activity in fluids (particularly those of carbon compounds) might have any intrinsic connection with biotic matter. Significantly, the optical activity observed in the amino acids extracted from carbonaceous meteorites has not the characteristics of such of common biotic origin, with only one enantiomer present; instead, it manifests the characteristics observed in natural petroleum, with unbalanced, so-called scalemic, abundances of chiral molecules.25The optical activity commonly observed in natural petroleum has been for years speciously claimed as "proof" of some connection with biological detritus, - albeit one requiring both a willing disregard of the considerable differences between the optical activity observed in natural petroleum and that in materials of truly biotic origin, such as wine, as well as desuetude of the dictates of the laws of thermodynamics.Optical activity is observed in minerals such as quartz or Iceland spar, as well as in oil, and among biological molecules. The optical activity observed in petroleum is more characteristic of the same in abiotic minerals, such as naturally occurring quartz, which are polycrystalline minerals, with a scalemic distribution of domains of left- and right-rotational properties. The chiral molecules in petroleum manifest scalemic distributions, and significantly lack the homochiral distribution which characterize biotic optically active matter. The optical activity in natural petroleum is characterized by either a right (positive, or dextrorotary) or left (negative, or levorotary) rotation of the plane of polarization. By contrast, in biological material left (levorotary) rotation dominates.The observation of optical activity in hydrocarbon material extracted from the interiors of carbonaceous meteorites, and typical of such in natural petroleum, discredited those claims.2, 26 Nonetheless, the scientific conundrum as to why the hydrocarbons manifest optical activity, in both carbonaceous meteorites and terrestrial crude oil remained unresolved until recently.The chiral molecules in natural petroleum originate from three distinct sources: contamination by biological detritus in the near-surface strata from which the oil has been taken; the biological alteration and degradation of the original oil by microbes which consume and metabolize oil; and the chiral hydrocarbon molecules which are intrinsic to the petroleum and generated with it. Only the last concerns the origin of petroleum.The genesis of the scalemic distribution of chiral molecules of natural petroleum has recently been shown to be a direct consequence of the chiral geometry of the system particles acting according to the laws of classical thermodynamics. The resolution of the problem of the origin of the scalemic distributions of chiral molecules in natural petroleum has been shown to be an inevitable consequence of their high-pressure genesis.19 Thus, the phenomenon of optical activity in natural petroleum, contrary to supporting any assertion of a biological connection, strongly confirms the high-pressure genesis of natural petroleum, and thereby the modern Russian-Ukrainian theory of deep, abiotic petroleum origins.
5. The carbon isotope ratios, and their inadequacy as indicators of origin.The claims made concerning the carbon isotope ratios, and specifically such as purport to identify the origin of the material, particularly the hydrocarbons, are especially recondite and outside the experience of most persons not knowledgeable in the physics of hydrogen-carbon [H-C] systems. Furthermore, the claims concerning the carbon isotope ratios most often involve methane, the only hydrocarbon which is thermodynamically stable in the regime of temperatures and pressures of the Earth’s crust, and the only one which spontaneously evolves there.The carbon nucleus has two stable isotopes, 12C and 13C. The overwhelmingly most abundance stable isotope of carbon is 12C, which possesses six protons and six neutrons; 13C possesses an extra neutron. (There is another, unstable isotope, 14C, which possesses two extra neutrons; 14C results from a high-energy reaction of the nitrogen nucleus, 14N, with a high-energy cosmic ray particle. The isotope 14C is not involved in the claims about the isotope ratios of carbon.) The carbon isotope ratio, designated δ13C, is simply the ratio of the abundance of carbon isotopes 13C/12C, normalized to the standard of the marine carbonate named Pee Dee Belemnite. The values of the measured δ13C ratio is expressed as a percentage (compared to the standard).During the 1950’s, increasingly numerous measurements of the carbon isotope ratios of hydrocarbon gases were taken, particularly of methane; and too often assertions were made that such ratios could unambiguously determine the origin of the hydrocarbons. The validity of such assertions were tested, independently by Colombo, Gazzarini, and Gonfiantini in Italy and by Galimov in Russia. Both sets of workers established that the carbon isotope ratios cannot be used reliably to determine the origin of the carbon compound tested.Colombo, Gazzarini, and Gonfiantini demonstrated conclusively, by a simple experiment the results of which admitted no ambiguity, that the carbon isotope ratios of methane change continuously along its transport path, becoming progressively lighter with distance traveled. Colombo et al. took a sample of natural gas and passed it through a column of crushed rock, chosen to resemble as closely as possible the terrestrial environment.27 Their results were definitive: The greater the distance of rock through which the sample of methane passes, the lighter becomes its carbon isotope ratio.The reason for the result observed by Colombo et al. is straightforward: there is a slight preference for the heavier isotope of carbon to react chemically with the rock through which the gas passes. Therefore, the greater the transit distance through the rock, the lighter becomes the carbon isotope ratio, as the heavier is preferentially removed by chemical reaction along the transport path. This result is not surprising; contrarily, such is entirely consistent with the fundamental requirements of quantum mechanics and kinetic theory.Pertinent to the matter of any claim that a light carbon isotope ratio might be indicative of a biological origin, the results demonstrated by Colombo et al. establish that such a claim is insupportable. Methane which might have originated from carbon material from the remains of a carbonaceous meteorite in the mantle of the Earth, and possessing initially a heavy carbon isotope ratio, could easily have that ratio diminished, along the path of its transit into the crust of the Earth, to a value comparable to common biological material.Galimov demonstrated that the carbon isotope ratio of methane can become progressively heavier while at rest in a reservoir in the crust of the Earth, through the action of methane-consuming microbes.28 The city of Moscow stores methane in water-wet reservoirs on the outskirts of that city, into which natural gas is injected throughout the year. During summers, the quantity of methane in the reservoirs increases because of less use (primarily by heating), and during winters the quantity is drawn down. By calibrating the reservoir volumes and the distance from the injection facilities, the residency time of the methane in the reservoir is determined. Galimov established that the longer the methane remains in the reservoir, the heavier becomes its carbon isotope ratio.The reason for the result observed by Galimov is also straightforward: In the water of the reservoir, there live microbes of the common, methane-metabolizing type. There is a slight preference for the lighter isotope of carbon to enter the microbe cell and to be metabolized. The longer the methane remains in the reservoir, the more of it is consumed by the methane-metabolizing microbes, with the molecules possessing lighter isotope being consumed more. Therefore, the longer its residency time in the reservoir, the heavier becomes the carbon isotope ratio, as the lighter is preferentially removed by methane-metabolizing microbes. This result is entirely consistent with the fundamental requirements of kinetic theory.Furthermore, the carbon isotope ratios in hydrocarbon systems are also strongly influenced by the temperature of reaction. For hydrocarbons produced by the Fischer-Tropsch process, the δ13C varies from -65% at 127 C to -20% at 177 C.29, 30 No material parameter, the measurement of which varies by almost 70% with a variation of temperature of only approximately 10%, can be used as a reliable determinant of any property of that material.The δ13C carbon isotope ratio cannot be considered to determine reliably the origin of a sample of methane, - or any other compound.6. Conclusion.The claims which have traditionally been put forward to argue a connection between natural petroleum and biological matter have been subjected to scientific scrutiny and have been established to be baseless. The outcome of such scrutiny comes hardly as a surprise, given recognition of the constraints of thermodynamics upon the genesis of hydrocarbons.If liquid hydrocarbons might evolve from biological detritus in the thermodynamic regime of the crust of the Earth, we could all expect to go to bed at night in our dotage, with white hair (or, at least, whatever might remain of same), a spreading waistline, and all the undesirable decrepitude of age, and to awake in the morning, clear eyed, with our hair returned of the color of our youth, with a slim waistline, a strong, flexible body, and with our sexual vigor restored. Alas, such is not to be. The merciless laws of thermodynamics do not accommodate folklore fables. Natural petroleum has no connection with biological matter.However, recognition of such fact leaves unanswered the conundrums which eluded the scientific community for more than a century: How does natural petroleum evolve ? And from where does natural petroleum come ?The theoretical resolution of these questions had to await development of the most modern techniques of quantum statistical mechanics. The experimental demonstration of the required equipment has been only recently available.
Mineral oil
Mineral oil
Mineral oil or liquid petrolatum is a by-product in the distillation of petroleum to produce gasoline. It is a transparent, colorless oil composed mainly of alkanes (typically 15 to 40 carbons) [1] and cyclic paraffins, related to white petrolatum. Mineral oil is a substance of relatively low value, and it is produced in very large quantities. Mineral oil is available in light and heavy grades, and can often be found in drug stores.Applications.Refined mineral oil is used as transformer oil.Alkali metals are often submerged in mineral oil for storage or transportation. The oil prevents the metals from reacting with atmospheric moisture.Mineral oil is sometimes taken orally as a laxative. It lubricates feces and intestinal mucous membranes, and limits the amount of water removed from feces. Typically, mineral oil is effective within six hours. While it has been reported that mineral oil may be absorbed when emulsified, most information shows that it passes harmlessly through the gastrointestinal system.If used at all, mineral oil should never be given internally to young children, pets, or anyone with a cough, hiatus hernia, or nocturnal reflux, and should be swallowed with care. Due to its low density, it is easily aspirated into the lungs, where it cannot be removed by the body and can cause serious complications such as lipoid pneumonia.[2] While popular as a folk remedy, there are many safer alternatives available. In children, if aspirated, the oil can work to prevent normal breathing, resulting in death of brain cells and permanent paralysis and/or retardation.Mineral oil with added fragrance is marketed as baby oil in the US, UK and Canada.Used as an ingredient in baby lotions, cold creams, ointments and other pharmaceuticals and low-grade cosmetics.Certain mineral oils are used in livestock vaccines, as an adjuvant to stimulate a cell-mediated immune response to the vaccinating agent.Used on eyelashes to prevent brittleness and/or breaking.Used as suspending and lavigating agent in sulphur ointments.Used in small quantities (2–3 drops daily) to clean ears. Over a couple of weeks, the mineral oil softens dried or hardened earwax so that a gentle flush of water can remove it. In the case of a damaged or perforated eardrum, however, mineral oil should not be used, as oil in the middle ear can lead to ear infections.LubricationFuel, for items such as oil lamps.Electric mineral-oil–filled space heatersCoolantHYPERLINK "http://en.wikipedia.org/wiki/Fog_machine"Fog machinesUsed in some guitar string cleanersAutomotive and aviation brake fluid that does not absorb water molecules by osmosisLow viscosity mineral oil is sold as a preservative for wooden cutting boards and utensils.A coating of mineral oil protects metal surfaces from moisture and oxidation; notably, nihonto are traditionally coated in clove-scented mineral oil.Food-preparation butcher block surfaces are often conditioned periodically with mineral oil.Light mineral oil is used in textile industries and used as a jute batching oil.Mineral oil is used to darken soapstone countertops for aesthetic purposes.It works (albeit poorly) as a release agent for molds, especially in fiberglass casting.It is used as a release agent for baking pans and trays.It is occasionally used in the food industry (particularly for candy). Some studies suggest that prolonged use might be unhealthy because of low accumulation levels in organs. It has been discouraged for use in children's foods, though it is still occasionally found in candies in China and Canada.Used as a cleaner and solvent for inks in fine art printmaking as well as in oil painting, though turpentine is more often used.In the poultry industry, plain mineral oil can be swabbed onto the feet of chickens infected with scaly mites on the shank, toes, and webs. Mineral oil suffocates these tiny parasites.Some people have found success using mineral oil to remove henna used as a hair dye.Using mineral oil or baby oil to reduce a grease, oil, or asphalt stain on clothing may be counter-intuitive, but is often effective, as the mineral oil dilutes and liquefies some of the stain thereby making it easier to clean out of the clothing.Some people have used mineral oil as a cooling system for a computer, by completely submerging the computer's motherboard and system components into an aquarium tank filled with mineral oil. The oil does not have any long term effect on the components. A video and instructions on building a mineral oil cooled computer can be found here.It is commonly used to create a "wear" effect on new clay poker chips, which, without the use of mineral oil, can only be accomplished through prolonged use of the poker chips. The chips are either placed in mineral oil (and left there for a short amount of time), or the oil is applied to each chip individually, and is then rubbed off, removing any chalky residue from the new chips, also improving the look and "feel" of the chips.Used to cover gummy worms for the glossy effect it produces.Used by boxers and other combat athletes to increase sweating, reduce warm-up times and help with weight loss.Used to remove creme makeup.Other names for mineral oil.adepsine oilalbolinebaby oilbayol 55cable oilbayol fblandlubeblandol white mineral oilcarnea 21clearteckcrystol 325crystosolDiala-X, AXdrakeolelectrical insulating oilervolfiltrawhitefonolinefrigolglymolHeat-treating oilhevyteckhydraulic oilhydrocarbon oilsjute batching oilkaydolkondremulkremolLHMlignite oilliquid paraffinHYPERLINK "http://en.wikipedia.org/wiki/Lubricating"lubricating oilmaster Shimmermineral oil (saturated parrafin oil)mineral oil hydrocarbon solvent (petroleum)mineral oil mistmineral oil, aromaticmineral oil, paraffinicmineral Seal Oilmololneo-cultolnujoloil mistoil mist, mineral, severely refinedOil mist, refined mineraloil, petroleumHYPERLINK "http://en.wikipedia.org/wiki/Paraffin"paraffin oil (class)paraffin oilparolparoleinepeneteckpenrecoperfectapetrogalarpetrolatumpetroleum hydrocarbonsHYPERLINK "http://en.wikipedia.org/wiki/Petroleum"petroleum, liquidprimolprimol 355primol dprotopetsaxoltech petf triona buvasolunivolt N60, 80voltesso 35white mineral oilwhite oil
Mineral oil or liquid petrolatum is a by-product in the distillation of petroleum to produce gasoline. It is a transparent, colorless oil composed mainly of alkanes (typically 15 to 40 carbons) [1] and cyclic paraffins, related to white petrolatum. Mineral oil is a substance of relatively low value, and it is produced in very large quantities. Mineral oil is available in light and heavy grades, and can often be found in drug stores.Applications.Refined mineral oil is used as transformer oil.Alkali metals are often submerged in mineral oil for storage or transportation. The oil prevents the metals from reacting with atmospheric moisture.Mineral oil is sometimes taken orally as a laxative. It lubricates feces and intestinal mucous membranes, and limits the amount of water removed from feces. Typically, mineral oil is effective within six hours. While it has been reported that mineral oil may be absorbed when emulsified, most information shows that it passes harmlessly through the gastrointestinal system.If used at all, mineral oil should never be given internally to young children, pets, or anyone with a cough, hiatus hernia, or nocturnal reflux, and should be swallowed with care. Due to its low density, it is easily aspirated into the lungs, where it cannot be removed by the body and can cause serious complications such as lipoid pneumonia.[2] While popular as a folk remedy, there are many safer alternatives available. In children, if aspirated, the oil can work to prevent normal breathing, resulting in death of brain cells and permanent paralysis and/or retardation.Mineral oil with added fragrance is marketed as baby oil in the US, UK and Canada.Used as an ingredient in baby lotions, cold creams, ointments and other pharmaceuticals and low-grade cosmetics.Certain mineral oils are used in livestock vaccines, as an adjuvant to stimulate a cell-mediated immune response to the vaccinating agent.Used on eyelashes to prevent brittleness and/or breaking.Used as suspending and lavigating agent in sulphur ointments.Used in small quantities (2–3 drops daily) to clean ears. Over a couple of weeks, the mineral oil softens dried or hardened earwax so that a gentle flush of water can remove it. In the case of a damaged or perforated eardrum, however, mineral oil should not be used, as oil in the middle ear can lead to ear infections.LubricationFuel, for items such as oil lamps.Electric mineral-oil–filled space heatersCoolantHYPERLINK "http://en.wikipedia.org/wiki/Fog_machine"Fog machinesUsed in some guitar string cleanersAutomotive and aviation brake fluid that does not absorb water molecules by osmosisLow viscosity mineral oil is sold as a preservative for wooden cutting boards and utensils.A coating of mineral oil protects metal surfaces from moisture and oxidation; notably, nihonto are traditionally coated in clove-scented mineral oil.Food-preparation butcher block surfaces are often conditioned periodically with mineral oil.Light mineral oil is used in textile industries and used as a jute batching oil.Mineral oil is used to darken soapstone countertops for aesthetic purposes.It works (albeit poorly) as a release agent for molds, especially in fiberglass casting.It is used as a release agent for baking pans and trays.It is occasionally used in the food industry (particularly for candy). Some studies suggest that prolonged use might be unhealthy because of low accumulation levels in organs. It has been discouraged for use in children's foods, though it is still occasionally found in candies in China and Canada.Used as a cleaner and solvent for inks in fine art printmaking as well as in oil painting, though turpentine is more often used.In the poultry industry, plain mineral oil can be swabbed onto the feet of chickens infected with scaly mites on the shank, toes, and webs. Mineral oil suffocates these tiny parasites.Some people have found success using mineral oil to remove henna used as a hair dye.Using mineral oil or baby oil to reduce a grease, oil, or asphalt stain on clothing may be counter-intuitive, but is often effective, as the mineral oil dilutes and liquefies some of the stain thereby making it easier to clean out of the clothing.Some people have used mineral oil as a cooling system for a computer, by completely submerging the computer's motherboard and system components into an aquarium tank filled with mineral oil. The oil does not have any long term effect on the components. A video and instructions on building a mineral oil cooled computer can be found here.It is commonly used to create a "wear" effect on new clay poker chips, which, without the use of mineral oil, can only be accomplished through prolonged use of the poker chips. The chips are either placed in mineral oil (and left there for a short amount of time), or the oil is applied to each chip individually, and is then rubbed off, removing any chalky residue from the new chips, also improving the look and "feel" of the chips.Used to cover gummy worms for the glossy effect it produces.Used by boxers and other combat athletes to increase sweating, reduce warm-up times and help with weight loss.Used to remove creme makeup.Other names for mineral oil.adepsine oilalbolinebaby oilbayol 55cable oilbayol fblandlubeblandol white mineral oilcarnea 21clearteckcrystol 325crystosolDiala-X, AXdrakeolelectrical insulating oilervolfiltrawhitefonolinefrigolglymolHeat-treating oilhevyteckhydraulic oilhydrocarbon oilsjute batching oilkaydolkondremulkremolLHMlignite oilliquid paraffinHYPERLINK "http://en.wikipedia.org/wiki/Lubricating"lubricating oilmaster Shimmermineral oil (saturated parrafin oil)mineral oil hydrocarbon solvent (petroleum)mineral oil mistmineral oil, aromaticmineral oil, paraffinicmineral Seal Oilmololneo-cultolnujoloil mistoil mist, mineral, severely refinedOil mist, refined mineraloil, petroleumHYPERLINK "http://en.wikipedia.org/wiki/Paraffin"paraffin oil (class)paraffin oilparolparoleinepeneteckpenrecoperfectapetrogalarpetrolatumpetroleum hydrocarbonsHYPERLINK "http://en.wikipedia.org/wiki/Petroleum"petroleum, liquidprimolprimol 355primol dprotopetsaxoltech petf triona buvasolunivolt N60, 80voltesso 35white mineral oilwhite oil
Oil refinery
Oil refinery
An oil refinery is an industrial process plant where crude oil is processed and refined into more useful petroleum products, such as gasoline, diesel fuel, asphalt base, heating oil, kerosine, and liquefied petroleum gas.[1]HYPERLINK "http://en.wikipedia.org/wiki/Oil_refinery" \l "_note-Leffler"[2] Oil refineries are typically large sprawling industrial complexes with extensive piping running throughout, carrying streams of fluids between large chemical processing units.Operation.Raw oil or unprocessed ("crude") oil is not useful in the form it comes in out of the ground. Although "light, sweet" (low viscosity, low sulfur) oil has been used directly as a burner fuel for steam vessel propulsion, the lighter elements form explosive vapors in the fuel tanks and so it is quite dangerous, especially so in warships. For this and many other uses, the oil needs to be separated into parts and refined before use in fuels and lubricants, and before some of the byproducts could be used in petrochemical processes to form materials such as plastics, and foams. Petroleum fossil fuels are used in ship, automobile and aircraft engines. These different hydrocarbons have different boiling points, which means they can be separated by distillation. Since the lighter liquid elements are in great demand for use in internal combustion engines, a modern refinery will convert heavy hydrocarbons and lighter gaseous elements into these higher value products using complex and energy intensive processes.Oil can be used in so many various ways because it contains hydrocarbons of varying molecular masses, forms and lengths such as paraffins, aromatics, naphthenes (or cycloalkanes), alkenes, dienes, and alkynes. Hydrocarbons are molecules of varying length and complexity made of only hydrogen and carbon atoms. Their various structures give them their differing properties and thereby uses. The trick in the oil refinement process is separating and purifying these.Once separated and purified of any contaminants and impurities, the fuel or lubricant can be sold without any further processing. Smaller molecules such as isobutane and propylene or butylenes can be recombined to meet specific octane requirements of fuels by processes such as alkylation or less commonly, dimerization. Octane grade of gasoline can also be improved by catalytic reforming, which strips hydrogen out of hydrocarbons to produce aromatics, which have much higher octane ratings. Intermediate products such as gasoils can even be reprocessed to break a heavy, long-chained oil into a lighter short-chained one, by various forms of cracking such as Fluid Catalytic Cracking, Thermal Cracking, and Hydrocracking. The final step in gasoline production is the blending of fuels with different octane ratings, vapor pressures, and other properties to meet product specifications.Oil refineries are large scale plants, processing from about a hundred thousand to several hundred thousand barrels of crude oil per day. Because of the high capacity, many of the units are operated continuously (as opposed to processing in batches) at steady state or approximately steady state for long periods of time (months to years). This high capacity also makes process optimization and advanced process control very desirable.Major products of oil refineries.Most products of oil processing are usually grouped into three categories: light distillates (LPG, gasoline, naptha), middle distillates (kerosene, diesel), heavy distillates and residuum (fuel oil, lubricating oils, wax, tar). This classification is based on the way crude oil is distilled and separated into fractions (called distillates and residuum) as can be seen in the above drawing.[2]HYPERLINK "http://en.wikipedia.org/wiki/Liquid_petroleum_gas"Liquid petroleum gas (LPG)Gasoline (also known as petrol)NaphthaHYPERLINK "http://en.wikipedia.org/wiki/Kerosene"Kerosene and related jet aircraft fuelsHYPERLINK "http://en.wikipedia.org/wiki/Diesel"Diesel fuelHYPERLINK "http://en.wikipedia.org/wiki/Fuel_oil"Fuel oilsHYPERLINK "http://en.wikipedia.org/wiki/Lubricant"Lubricating oilsHYPERLINK "http://en.wikipedia.org/wiki/Paraffin_wax"Paraffin waxHYPERLINK "http://en.wikipedia.org/wiki/Asphalt"Asphalt and TarHYPERLINK "http://en.wikipedia.org/wiki/Petroleum_coke"Petroleum cokeCommon process units found in a refinery.Desalter unit washes out salt from the crude oil before it enters the atmospheric distillation unit.Atmospheric Distillation unit distills crude oil into fractions. See Continuous distillation.Vacuum Distillation unit further distills residual bottoms after atmospheric distillation.Naphtha Hydrotreater unit uses hydrogen to desulfurize naphtha from atmospheric distillation. Must hydrotreat the naphtha before sending to a Catalytic Reformer unit.Catalytic Reformer unit is used to convert the naphtha-boiling range molecules into higher octane reformate (reformer product). The reformate has higher content of aromatics, olefins, and cyclic hydrocarbons). An important byproduct of a reformer is hydrogen released during the catalyst reaction. The hydrogen is used either in the hydrotreaters and hydrocracker.Distillate Hydrotreater unit desulfurizes distillates (such as diesel) after atmospheric distillation.Fluid Catalytic Cracking (FCC) unit upgrades heavier fractions into lighter, more valuable products.Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter, more valuable products.Visbreaking unit upgrades heavy residual oils by thermally cracking them into lighter, more valuable reduced viscosity products.Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to organic disulfides.Coking units (either delayed or fluid coking) process very heavy residual oils into gasoline and diesel fuel, leaving petroleum coke as a residual product.Alkylation unit produces high-octane component for gasoline blending.Dimerization unit converts olefins into higher-octane gasoline blending components. For example, butenes can be dimerized into isooctene which may subsequently be hydrogenated to form isooctane. There are also other uses for dimerization.Isomerization unit converts linear molecules to higher-octane branched molecules for blending into gasoline or feed to alkylation units.Steam reforming unit produces hydrogen for the hydrotreaters or hydrocracker.Liquified gas storage units for propane and similar gaseous fuels at pressure sufficient to maintain in liquid form. These are usually spherical vessels or bullets (horizontal vessels with rounded ends.Storage tanks for crude oil and finished products, usually cylindrical, with some sort of vapor emission control and surrounded by an earthen berm to contain spills.Amine gas treater, Claus unit, and tail gas treatment for converting hydrogen sulfide from hydrodesulfurization into elemental sulfur.Utility units such as cooling towers for circulating cooling water, boiler plants for steam generation, instrument air systems for pneumatically operated control valves and an electrical substation.Wastewater collection and treating systems consisting of API separators, dissolved air flotation (DAF) units and some type of further treatment (such as an activated sludge biotreater) to make such water suitable for reuse or for disposal.Specialty end products.These will blend various feedstocks, mix appropriate additives, provide short term storage, and prepare for bulk loading to trucks, barges, product ships, and railcars.Gaseous fuels such as propane, stored and shipped in liquid form under pressure in specialized railcars to distributors.Liquid fuels blending (producing automotive and aviation grades of gasoline, kerosene, various aviation turbine fuels, and diesel fuels, adding dyes, detergents, antiknock additives, oxygenates, and anti-fungal compounds as required). Shipped by barge, rail, and tanker ship. May be shipped regionally in dedicated pipelines to point consumers, particularly aviation jet fuel to major airports, or piped to distributors in multi-product pipelines using product separators called pipeline inspection gauges ("pigs").Lubricants (produces light machine oils, motor oils, and greases, adding viscosity stabilizers as required), usually shipped in bulk to an offsite packaging plant.Wax (paraffin), used in the packaging of frozen foods, among others. May be shipped in bulk to a site to prepare as packaged blocks.Sulfur (or sulfuric acid), byproducts of sulfur removal from petroleum which may have up to a couple percent sulfur as organic sulfur-containing compounds. Sulfur and sulfuric acid are useful industrial materials. Sulfuric acid is usually prepared and shipped as the acid precursor oleum.Bulk tar shipping for offsite unit packaging for use in tar-and-gravel roofing.Asphalt unit. Prepares bulk asphalt for shipment.Petroleum coke, used in specialty carbon products or as solid fuel.Petrochemicals or petrochemical feedstocks, which are often sent to petrochemical plants for further processing in a variety of ways. The petrochemicals may be olefins or their precursors, or various types of aromatic petrochemicals.Safety and environmental concerns.The refining process releases numerous different chemicals into the atmosphere; consequently, there are substantial air pollution emissions[7] and a notable odor normally accompanies the presence of a refinery. Aside from air pollution impacts there are also wastewater concerns,[3] risks of industrial accidents such as fire and explosion, and noise health effects due to industrial noise.The public has demanded that many governments place restrictions on contaminants that refineries release, and most refineries have installed the equipment needed to comply with the requirements of the pertinent environmental protection regulatory agencies. In the United States, there is strong pressure to prevent the development of new refineries, and no major refinery has been built in the country since Marathon's Garyville, Louisiana facility in 1976. However, many existing refineries have been expanded during that time. Environmental restrictions and pressure to prevent construction of new refineries may have also contributed to rising fuel prices in the United States.[8] Additionally, many refineries (over 100 since the 1980s) have closed due to obsolescence and/or merger activity within the industry itself. This activity has been reported to Congress and in specialized studies not widely publicised.Environmental and safety concerns mean that oil refineries are sometimes located some distance away from major urban areas. Nevertheless, there are many instances where refinery operations are close to populated areas and pose health risks such as in the Campo de Gibraltar, a Spanish state owned refinery near the towns of Gibraltar, Algeciras, La Linea, San Roque and Los Barrios with a combined population of over 300,000 residents within a 5 mile radius and the CEPSA refinery in Santa Cruz on the island of Tenerife, Spain[9] which is sited in a densely-populated city center and next to the only two major evacuation routes in and out of the city. In California's Contra Costa County and Solano County, a shoreline necklace of refineries and associated chemical plants are adjacent to urban areas in Richmond, Martinez, Pacheco, Concord, Pittsburg, Vallejo and Benicia, with occasional accidental events that require "shelter in place" orders to the adjacent populations.History.The world's first oil refineries were set up by Ignacy Łukasiewicz near Jaslo, Austrian Empire (now in Poland) in the years 1854-56[10]HYPERLINK "http://en.wikipedia.org/wiki/Oil_refinery" \l "_note-7"[11] but they were initially small as there was no real demand for refined fuel. As Łukasiewicz's kerosene lamp gained popularity the refining industry grew in the area.The first large oil refinery opened at Ploieşti, Romania in 1856.[12] Several other refineries were built at that location with investment from United States companies before being taken over by Nazi Germany during World War II. Most of these refineries were heavily bombarded by US Army Air Forces in Operation Tidal Wave, August 1, 1943. Since then they have been rebuilt, and currently pose somewhat of an environmental concern.Another early example is Oljeön, now preserved as a museum at the UNESCO world heritage site Engelsberg. It started operation in 1875 and is part of the Ecomuseum Bergslagen.At one time, the world's largest oil refinery was claimed to be Ras Tanura, Saudi Arabia, owned by Saudi Aramco. For most of the 20th century, the largest refinery of the world was the Abadan refinery in Iran. This refinery suffered extensive damage during the war Iran-Iraq war. The world's largest refinery complex is the "Centro de Refinación de Paraguaná" (CRP) operated by PDVSA in Venezuela with a production capacity of 956,000 barrels per day (Amuay 635,000 bpd, Cardón 305,000 bpd and Bajo Grande 16,000 bpd). SK Corporation's Ulsan refinery in South Korea with a capacity of 840,000 bpd and Reliance Petroleum's refinery in Jamnagar, India with 660,000 bpd are the second and third largest, respectively.Early US refineries processed crude oil to recover the kerosene. Other products (like gasoline) were considered wastes and were often dumped directly into the nearest river. The invention of the automobile shifted the demand to gasoline and diesel, which remain the primary refined products today. Refineries pre-dating the EPA were very toxic to the environment. Strict legislation has mandated that refineries meet modern air and water cleanliness standards. In fact, obtaining a permit to build even a modern refinery with minimal impact on the environment (other than CO2 emissions) is so difficult and costly that no new refineries have been built (though many have been expanded) in the United States since 1976. As a result, some believe that this may be the reason that the US is becoming more and more dependent on the imports of finished gasoline, as opposed to incremental crude oil. On the other hand, studies have revealed that accelerating merger activity in the refining and production sector has reduced capacity further, resulting in tighter markets in the United States in particular
An oil refinery is an industrial process plant where crude oil is processed and refined into more useful petroleum products, such as gasoline, diesel fuel, asphalt base, heating oil, kerosine, and liquefied petroleum gas.[1]HYPERLINK "http://en.wikipedia.org/wiki/Oil_refinery" \l "_note-Leffler"[2] Oil refineries are typically large sprawling industrial complexes with extensive piping running throughout, carrying streams of fluids between large chemical processing units.Operation.Raw oil or unprocessed ("crude") oil is not useful in the form it comes in out of the ground. Although "light, sweet" (low viscosity, low sulfur) oil has been used directly as a burner fuel for steam vessel propulsion, the lighter elements form explosive vapors in the fuel tanks and so it is quite dangerous, especially so in warships. For this and many other uses, the oil needs to be separated into parts and refined before use in fuels and lubricants, and before some of the byproducts could be used in petrochemical processes to form materials such as plastics, and foams. Petroleum fossil fuels are used in ship, automobile and aircraft engines. These different hydrocarbons have different boiling points, which means they can be separated by distillation. Since the lighter liquid elements are in great demand for use in internal combustion engines, a modern refinery will convert heavy hydrocarbons and lighter gaseous elements into these higher value products using complex and energy intensive processes.Oil can be used in so many various ways because it contains hydrocarbons of varying molecular masses, forms and lengths such as paraffins, aromatics, naphthenes (or cycloalkanes), alkenes, dienes, and alkynes. Hydrocarbons are molecules of varying length and complexity made of only hydrogen and carbon atoms. Their various structures give them their differing properties and thereby uses. The trick in the oil refinement process is separating and purifying these.Once separated and purified of any contaminants and impurities, the fuel or lubricant can be sold without any further processing. Smaller molecules such as isobutane and propylene or butylenes can be recombined to meet specific octane requirements of fuels by processes such as alkylation or less commonly, dimerization. Octane grade of gasoline can also be improved by catalytic reforming, which strips hydrogen out of hydrocarbons to produce aromatics, which have much higher octane ratings. Intermediate products such as gasoils can even be reprocessed to break a heavy, long-chained oil into a lighter short-chained one, by various forms of cracking such as Fluid Catalytic Cracking, Thermal Cracking, and Hydrocracking. The final step in gasoline production is the blending of fuels with different octane ratings, vapor pressures, and other properties to meet product specifications.Oil refineries are large scale plants, processing from about a hundred thousand to several hundred thousand barrels of crude oil per day. Because of the high capacity, many of the units are operated continuously (as opposed to processing in batches) at steady state or approximately steady state for long periods of time (months to years). This high capacity also makes process optimization and advanced process control very desirable.Major products of oil refineries.Most products of oil processing are usually grouped into three categories: light distillates (LPG, gasoline, naptha), middle distillates (kerosene, diesel), heavy distillates and residuum (fuel oil, lubricating oils, wax, tar). This classification is based on the way crude oil is distilled and separated into fractions (called distillates and residuum) as can be seen in the above drawing.[2]HYPERLINK "http://en.wikipedia.org/wiki/Liquid_petroleum_gas"Liquid petroleum gas (LPG)Gasoline (also known as petrol)NaphthaHYPERLINK "http://en.wikipedia.org/wiki/Kerosene"Kerosene and related jet aircraft fuelsHYPERLINK "http://en.wikipedia.org/wiki/Diesel"Diesel fuelHYPERLINK "http://en.wikipedia.org/wiki/Fuel_oil"Fuel oilsHYPERLINK "http://en.wikipedia.org/wiki/Lubricant"Lubricating oilsHYPERLINK "http://en.wikipedia.org/wiki/Paraffin_wax"Paraffin waxHYPERLINK "http://en.wikipedia.org/wiki/Asphalt"Asphalt and TarHYPERLINK "http://en.wikipedia.org/wiki/Petroleum_coke"Petroleum cokeCommon process units found in a refinery.Desalter unit washes out salt from the crude oil before it enters the atmospheric distillation unit.Atmospheric Distillation unit distills crude oil into fractions. See Continuous distillation.Vacuum Distillation unit further distills residual bottoms after atmospheric distillation.Naphtha Hydrotreater unit uses hydrogen to desulfurize naphtha from atmospheric distillation. Must hydrotreat the naphtha before sending to a Catalytic Reformer unit.Catalytic Reformer unit is used to convert the naphtha-boiling range molecules into higher octane reformate (reformer product). The reformate has higher content of aromatics, olefins, and cyclic hydrocarbons). An important byproduct of a reformer is hydrogen released during the catalyst reaction. The hydrogen is used either in the hydrotreaters and hydrocracker.Distillate Hydrotreater unit desulfurizes distillates (such as diesel) after atmospheric distillation.Fluid Catalytic Cracking (FCC) unit upgrades heavier fractions into lighter, more valuable products.Hydrocracker unit uses hydrogen to upgrade heavier fractions into lighter, more valuable products.Visbreaking unit upgrades heavy residual oils by thermally cracking them into lighter, more valuable reduced viscosity products.Merox unit treats LPG, kerosene or jet fuel by oxidizing mercaptans to organic disulfides.Coking units (either delayed or fluid coking) process very heavy residual oils into gasoline and diesel fuel, leaving petroleum coke as a residual product.Alkylation unit produces high-octane component for gasoline blending.Dimerization unit converts olefins into higher-octane gasoline blending components. For example, butenes can be dimerized into isooctene which may subsequently be hydrogenated to form isooctane. There are also other uses for dimerization.Isomerization unit converts linear molecules to higher-octane branched molecules for blending into gasoline or feed to alkylation units.Steam reforming unit produces hydrogen for the hydrotreaters or hydrocracker.Liquified gas storage units for propane and similar gaseous fuels at pressure sufficient to maintain in liquid form. These are usually spherical vessels or bullets (horizontal vessels with rounded ends.Storage tanks for crude oil and finished products, usually cylindrical, with some sort of vapor emission control and surrounded by an earthen berm to contain spills.Amine gas treater, Claus unit, and tail gas treatment for converting hydrogen sulfide from hydrodesulfurization into elemental sulfur.Utility units such as cooling towers for circulating cooling water, boiler plants for steam generation, instrument air systems for pneumatically operated control valves and an electrical substation.Wastewater collection and treating systems consisting of API separators, dissolved air flotation (DAF) units and some type of further treatment (such as an activated sludge biotreater) to make such water suitable for reuse or for disposal.Specialty end products.These will blend various feedstocks, mix appropriate additives, provide short term storage, and prepare for bulk loading to trucks, barges, product ships, and railcars.Gaseous fuels such as propane, stored and shipped in liquid form under pressure in specialized railcars to distributors.Liquid fuels blending (producing automotive and aviation grades of gasoline, kerosene, various aviation turbine fuels, and diesel fuels, adding dyes, detergents, antiknock additives, oxygenates, and anti-fungal compounds as required). Shipped by barge, rail, and tanker ship. May be shipped regionally in dedicated pipelines to point consumers, particularly aviation jet fuel to major airports, or piped to distributors in multi-product pipelines using product separators called pipeline inspection gauges ("pigs").Lubricants (produces light machine oils, motor oils, and greases, adding viscosity stabilizers as required), usually shipped in bulk to an offsite packaging plant.Wax (paraffin), used in the packaging of frozen foods, among others. May be shipped in bulk to a site to prepare as packaged blocks.Sulfur (or sulfuric acid), byproducts of sulfur removal from petroleum which may have up to a couple percent sulfur as organic sulfur-containing compounds. Sulfur and sulfuric acid are useful industrial materials. Sulfuric acid is usually prepared and shipped as the acid precursor oleum.Bulk tar shipping for offsite unit packaging for use in tar-and-gravel roofing.Asphalt unit. Prepares bulk asphalt for shipment.Petroleum coke, used in specialty carbon products or as solid fuel.Petrochemicals or petrochemical feedstocks, which are often sent to petrochemical plants for further processing in a variety of ways. The petrochemicals may be olefins or their precursors, or various types of aromatic petrochemicals.Safety and environmental concerns.The refining process releases numerous different chemicals into the atmosphere; consequently, there are substantial air pollution emissions[7] and a notable odor normally accompanies the presence of a refinery. Aside from air pollution impacts there are also wastewater concerns,[3] risks of industrial accidents such as fire and explosion, and noise health effects due to industrial noise.The public has demanded that many governments place restrictions on contaminants that refineries release, and most refineries have installed the equipment needed to comply with the requirements of the pertinent environmental protection regulatory agencies. In the United States, there is strong pressure to prevent the development of new refineries, and no major refinery has been built in the country since Marathon's Garyville, Louisiana facility in 1976. However, many existing refineries have been expanded during that time. Environmental restrictions and pressure to prevent construction of new refineries may have also contributed to rising fuel prices in the United States.[8] Additionally, many refineries (over 100 since the 1980s) have closed due to obsolescence and/or merger activity within the industry itself. This activity has been reported to Congress and in specialized studies not widely publicised.Environmental and safety concerns mean that oil refineries are sometimes located some distance away from major urban areas. Nevertheless, there are many instances where refinery operations are close to populated areas and pose health risks such as in the Campo de Gibraltar, a Spanish state owned refinery near the towns of Gibraltar, Algeciras, La Linea, San Roque and Los Barrios with a combined population of over 300,000 residents within a 5 mile radius and the CEPSA refinery in Santa Cruz on the island of Tenerife, Spain[9] which is sited in a densely-populated city center and next to the only two major evacuation routes in and out of the city. In California's Contra Costa County and Solano County, a shoreline necklace of refineries and associated chemical plants are adjacent to urban areas in Richmond, Martinez, Pacheco, Concord, Pittsburg, Vallejo and Benicia, with occasional accidental events that require "shelter in place" orders to the adjacent populations.History.The world's first oil refineries were set up by Ignacy Łukasiewicz near Jaslo, Austrian Empire (now in Poland) in the years 1854-56[10]HYPERLINK "http://en.wikipedia.org/wiki/Oil_refinery" \l "_note-7"[11] but they were initially small as there was no real demand for refined fuel. As Łukasiewicz's kerosene lamp gained popularity the refining industry grew in the area.The first large oil refinery opened at Ploieşti, Romania in 1856.[12] Several other refineries were built at that location with investment from United States companies before being taken over by Nazi Germany during World War II. Most of these refineries were heavily bombarded by US Army Air Forces in Operation Tidal Wave, August 1, 1943. Since then they have been rebuilt, and currently pose somewhat of an environmental concern.Another early example is Oljeön, now preserved as a museum at the UNESCO world heritage site Engelsberg. It started operation in 1875 and is part of the Ecomuseum Bergslagen.At one time, the world's largest oil refinery was claimed to be Ras Tanura, Saudi Arabia, owned by Saudi Aramco. For most of the 20th century, the largest refinery of the world was the Abadan refinery in Iran. This refinery suffered extensive damage during the war Iran-Iraq war. The world's largest refinery complex is the "Centro de Refinación de Paraguaná" (CRP) operated by PDVSA in Venezuela with a production capacity of 956,000 barrels per day (Amuay 635,000 bpd, Cardón 305,000 bpd and Bajo Grande 16,000 bpd). SK Corporation's Ulsan refinery in South Korea with a capacity of 840,000 bpd and Reliance Petroleum's refinery in Jamnagar, India with 660,000 bpd are the second and third largest, respectively.Early US refineries processed crude oil to recover the kerosene. Other products (like gasoline) were considered wastes and were often dumped directly into the nearest river. The invention of the automobile shifted the demand to gasoline and diesel, which remain the primary refined products today. Refineries pre-dating the EPA were very toxic to the environment. Strict legislation has mandated that refineries meet modern air and water cleanliness standards. In fact, obtaining a permit to build even a modern refinery with minimal impact on the environment (other than CO2 emissions) is so difficult and costly that no new refineries have been built (though many have been expanded) in the United States since 1976. As a result, some believe that this may be the reason that the US is becoming more and more dependent on the imports of finished gasoline, as opposed to incremental crude oil. On the other hand, studies have revealed that accelerating merger activity in the refining and production sector has reduced capacity further, resulting in tighter markets in the United States in particular
Arctic National Wildlife Refuge
Arctic National Wildlife Refuge
The Arctic National Wildlife Refuge (ANWR) covers 19,049,236 acres (79,318 km²) in northeastern Alaska, in the North Slope region. It was originally protected in 1960 by order of Fred A. Seaton, the Secretary of the Interior under U.S. President Dwight D. Eisenhower. As part of Alaska National Interest Lands Conservation Act, the refuge was expanded by the United States Congress in 1980 through the lobbying efforts of Olaus and Margaret Murie, with The Wilderness Society.Eight million acres (32,375 km²) of the refuge are designated as U.S. Wilderness Area. The 1980 expansion of the refuge designated 1.5 million acres (6,070 km²) of the coastal plain as the 1002 area and mandated studies of the natural resources of this area, especially petroleum. Congressional authorization is required before oil drilling may proceed in this area. The remaining 10.1 million acres (40,873 km²) of the refuge are designated as "Minimal Management," a category intended to maintain existing natural conditions and resource values. These areas are suitable for wilderness designation, although there are presently no proposals to designate them as wilderness.There are presently no roads within or leading into the refuge, though there are settlements there. On the northern edge of the Refuge is the Inupiaq village of Kaktovik and on the southern boundary the Gwich'in settlement of Arctic Village. A popular wilderness route and historic passage exists between the two villages, traversing the Refuge and all its ecosystem types from boreal, interior forest to Arctic Ocean coast. Generally, visitors gain access to the land by aircraft, but it is also possible to reach the refuge by boat or by walking (the Dalton Highway passes near the western edge of the refuge). In the United States of America, the geographic location most remote from human trails, roads, or settlements is found here, at the headwaters of the Sheenjek River.Wildworld.The refuge supports a greater variety of plant and animal life than any other protected area in the circumpolar arctic. A continuum of six different ecozones spans some 200 miles (300 km) north to south.Along the northern boundary of the refuge, barrier islands, coastal lagoons, salt marshs, and shorebirds. Fish such as dolly varden and arctic cisco are found in nearshore waters. Coastal lands and sea ice are used by caribou seeking relief from biting insects during summer, and by polar bears hunting seals and giving birth in snow dens during winter.The arctic coastal plain stretches southward from the coast to the foothills of the Brooks Range. This area of rolling hills, small lakes, and north-flowing, braided rivers is dominated by tundra vegetation consisting of low shrubs, sedges, and mosses. Caribou travel to the coastal plain during June and July to give birth and raise their young. Migratory birds and insects flourish here during the brief arctic summer. Tens of thousands of snow geese stop here during September to feed before migrating south, and musk oxen live here year-round.South of the coastal plain, the mountains of the eastern Brooks Range rise to over 9,000 feet (3,000 m). This northernmost extension of the Rocky Mountains marks the continental divide, with north-flowing rivers emptying into the Arctic Ocean and south-flowing rivers joining the great Yukon River. The rugged mountains of the Brooks Range are incised by deep river valleys creating a range of elevations and aspects that support a variety of low tundra vegetation, dense shrubs, rare groves of poplar trees on the north side and spruce on the south. During summer, peregrine falcons, gyrfalcons, and golden eagles build nests on cliffs. Harlequin ducks and red-breasted mergansers are seen on swift-flowing rivers. Dall sheep and wolves are active all year, while grizzly bears and arctic ground squirrels are frequently seen during summer but hibernate in winter.The southern portion of the Arctic Refuge is within the boreal forest of interior Alaska. Beginning as predominantly treeless tundra with scattered islands of black and white spruce trees, the forest becomes progressively denser as the foothills yield to the expansive flats north of the Yukon River. Frequent forest fires ignited by lightning result in a complex mosaic of birch, aspen, and spruce forests of various ages. Wetlands and south-flowing rivers create openings in the forest canopy. Neotropical migratory birds breed here in spring and summer, attracted by plentiful food and the variety of habitats. Caribou travel here from farther north to spend the winter. Year-round residents of the boreal forest include moose, lynx, marten, wolverines, black and grizzly bears, and wolves.Each year, thousands of waterfowl and other birds nest and reproduce in areas surrounding Prudhoe Bay and Kuparuk fields and a healthy and increasing caribou herd migrates through these areas to calve and seek respite from annoying pests such as human activity. Oil field facilities have been located and designed to accommodate wildlife and utilize the least amount of tundra surface.Arctic Refuge drilling controversy.Because the Arctic National Wildlife Refuge is known to contain a large supply of crude oil, the issue of drilling for oil in roughly 2000 of the 19,600,000 acre area has been a debated topic since World War II. The controversy has been a political football for every U.S. President since Jimmy Carter
The Arctic National Wildlife Refuge (ANWR) covers 19,049,236 acres (79,318 km²) in northeastern Alaska, in the North Slope region. It was originally protected in 1960 by order of Fred A. Seaton, the Secretary of the Interior under U.S. President Dwight D. Eisenhower. As part of Alaska National Interest Lands Conservation Act, the refuge was expanded by the United States Congress in 1980 through the lobbying efforts of Olaus and Margaret Murie, with The Wilderness Society.Eight million acres (32,375 km²) of the refuge are designated as U.S. Wilderness Area. The 1980 expansion of the refuge designated 1.5 million acres (6,070 km²) of the coastal plain as the 1002 area and mandated studies of the natural resources of this area, especially petroleum. Congressional authorization is required before oil drilling may proceed in this area. The remaining 10.1 million acres (40,873 km²) of the refuge are designated as "Minimal Management," a category intended to maintain existing natural conditions and resource values. These areas are suitable for wilderness designation, although there are presently no proposals to designate them as wilderness.There are presently no roads within or leading into the refuge, though there are settlements there. On the northern edge of the Refuge is the Inupiaq village of Kaktovik and on the southern boundary the Gwich'in settlement of Arctic Village. A popular wilderness route and historic passage exists between the two villages, traversing the Refuge and all its ecosystem types from boreal, interior forest to Arctic Ocean coast. Generally, visitors gain access to the land by aircraft, but it is also possible to reach the refuge by boat or by walking (the Dalton Highway passes near the western edge of the refuge). In the United States of America, the geographic location most remote from human trails, roads, or settlements is found here, at the headwaters of the Sheenjek River.Wildworld.The refuge supports a greater variety of plant and animal life than any other protected area in the circumpolar arctic. A continuum of six different ecozones spans some 200 miles (300 km) north to south.Along the northern boundary of the refuge, barrier islands, coastal lagoons, salt marshs, and shorebirds. Fish such as dolly varden and arctic cisco are found in nearshore waters. Coastal lands and sea ice are used by caribou seeking relief from biting insects during summer, and by polar bears hunting seals and giving birth in snow dens during winter.The arctic coastal plain stretches southward from the coast to the foothills of the Brooks Range. This area of rolling hills, small lakes, and north-flowing, braided rivers is dominated by tundra vegetation consisting of low shrubs, sedges, and mosses. Caribou travel to the coastal plain during June and July to give birth and raise their young. Migratory birds and insects flourish here during the brief arctic summer. Tens of thousands of snow geese stop here during September to feed before migrating south, and musk oxen live here year-round.South of the coastal plain, the mountains of the eastern Brooks Range rise to over 9,000 feet (3,000 m). This northernmost extension of the Rocky Mountains marks the continental divide, with north-flowing rivers emptying into the Arctic Ocean and south-flowing rivers joining the great Yukon River. The rugged mountains of the Brooks Range are incised by deep river valleys creating a range of elevations and aspects that support a variety of low tundra vegetation, dense shrubs, rare groves of poplar trees on the north side and spruce on the south. During summer, peregrine falcons, gyrfalcons, and golden eagles build nests on cliffs. Harlequin ducks and red-breasted mergansers are seen on swift-flowing rivers. Dall sheep and wolves are active all year, while grizzly bears and arctic ground squirrels are frequently seen during summer but hibernate in winter.The southern portion of the Arctic Refuge is within the boreal forest of interior Alaska. Beginning as predominantly treeless tundra with scattered islands of black and white spruce trees, the forest becomes progressively denser as the foothills yield to the expansive flats north of the Yukon River. Frequent forest fires ignited by lightning result in a complex mosaic of birch, aspen, and spruce forests of various ages. Wetlands and south-flowing rivers create openings in the forest canopy. Neotropical migratory birds breed here in spring and summer, attracted by plentiful food and the variety of habitats. Caribou travel here from farther north to spend the winter. Year-round residents of the boreal forest include moose, lynx, marten, wolverines, black and grizzly bears, and wolves.Each year, thousands of waterfowl and other birds nest and reproduce in areas surrounding Prudhoe Bay and Kuparuk fields and a healthy and increasing caribou herd migrates through these areas to calve and seek respite from annoying pests such as human activity. Oil field facilities have been located and designed to accommodate wildlife and utilize the least amount of tundra surface.Arctic Refuge drilling controversy.Because the Arctic National Wildlife Refuge is known to contain a large supply of crude oil, the issue of drilling for oil in roughly 2000 of the 19,600,000 acre area has been a debated topic since World War II. The controversy has been a political football for every U.S. President since Jimmy Carter
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