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On-line detection of sulfur species in light petroleum liquids using gas chromatography and sulfur selective detection
02
Subsurface hydrocarbon contamination associated with petroleum spills is a widespread occurrence that presents a significant threat to groundwater resources. The natural attenuation test site (NATS) at Columbus Air Force Base, MS, provided a unique opportunity to monitor changes in the molecular microbial ecology as well as stimulation of natural biodegradative processes under transient field study conditions. A large, synthetic jet fuel mixture containing BTEX compounds and naphthalene in a decane carrier was introduced into the subsurface. Over 462 days, a plume of hydrocarbon contamination developed and stabilized at a distance of ~15 m downgradient from the source area. Exposure of indigenous microorganisms to the contaminant hydrocarbons was evaluated using an array of gene probes targeting common genotypes associated with the aerobic biodegradation of BTEX and naphthalene. Each of the targeted genotypes alkB, nahA, nahH, todClC2, and xylA showed significant responses to hydrocarbon exposure. Aerobic mineralization potentials of selected contaminants were greater in sediments collected from within the plume relative to uncontaminated areas, suggesting that an aerobic contaminant-degrading community successfully developed within the plume. An increase in aerobic degradation activity coincided with the arrival of the hydrocarbon front within the well field. The Natural Attenuation Study at Columbus AFB successfully linked adaptations of indigenous microorganisms to hydrocarbon exposure during a transient field study. 02/00157 Characteristics of shale from the manturovo field and products of its processing Iorudas, K.A. Khim. Tverd. Topl. (Mosco~t~), 2000, 2, 80-87. (In Russian) Thermal processing of a high-sulphur shale under conditions similar to those of the Galoter process, with solid heat transfer agent, was studied. 02/00156 Composition for increasing the fluidity of crude oil and unplugging petroleum wells and pipes Slemcu, N. et al. Rom. RO 109,113 (Cl. E2lB43/22), 30 Nov 1994, Appl. 9,301,615, 3 Dee 1993. 3. (In Romania) The fluidity of crude oil is increased, petroleum wells and pipes are unplugged by using fluidization agents including anthracene oil from coal distillation at 270-310”, interface activating agent as ethoxylated nonylphenols and a ammonium salt. The anthracene oil can be replaced by creosot. 02/00159 History of forecast and discovery of the Dnepropetrovsk-Donetsk petroleum-gas pool region Kabyshev, B.P. Geol. Zh., 1999, 4, 89-92. (In Russian) Romenskoye oil field, first of the fields which were opened in Dnepropetrovsk-Donetsk oil-gas bearing region, and also this region was discovered in 1937 on the basis of the prognosis of N.S. Shatsky and on the results of drilling the wells drilled with the aim of search for gypsums, potassium salt, oil, carried out under the leadership of F.O. Lycenko between 1932 and 1936. Nobody had predicted presence of oil in the DDB region before 1931, since the hypotheses of the great Donbass coal bearing were dominant at that time, however they would not be proved subsequently. These hypotheses stated that the fold Carboniferous of the Donets geosynclinal type existed under the cover of the little in thickness Mesozoic deposits. More than one hundred years geologists had been searching for great coal deposits in the DDB region, however, oil and gas were found. 02/00160 Medium oils for slurry-bed reaction and methods for the manufacture of dimethyl ether Tomura, K. et al. Jpn. Kokai Tokkyo Koho JP 2000 109,437 (Cl. CO7C9/16), 18 Apr 2000, JP Appl. 1998/220,338, 4 Aug 1998. 10. (In Japanese) Medium oils contain mainly hydrocarbons with paraffin carbons consisting >70% of the total carbons. Thus, di-Me ether was prepared from 47.5:47.5:5 volume ratio CO-H-CO* in the presence of oxide catalysts using hydrogenated butene-isobutene copolymer as a medium oil. 02/00161 Method for invisibly tagging petroleum products using visible dyes Pa&, T.D. er al. Eur. Pat. Appl. EP 1,001,003 (Cl. CIOLl/OO), 17 May 2000, US Appl. 188,639, 9 Nov 1998. 17. This invention provides a method for invisibly tagging, for subsequent identification purposes, various liquid petroleum hydrocarbons, such as crude oil, diesel fuel, heating oil, kerosene, lubricating oils, waxes, jet fuel, and in particular gasoline, remarkably using visible dyes by incorporating therein one or more visible dyes at minute levels such that they cannot be visually detected by the human eye. Visible dyes which have high solubility in petroleum hydrocarbons and maximum absorption in the 550-700 nm visible wavelength range are used to impart such invisible markings. The visible dyes, although employed at non-visible levels, are still capable of detection in a relatively quick and
Liquid fuels (sources, properties, recovety)
simple manner which requires minimal instrumentation, creastes no waste products for disposal, and gives true quantitative results of dye concentrations in the field. This invention, therefore, further provides a method for so identifying the tagged petroleum hydrocarbons by exposing the tagged hydrocarbon to visible light having wavelengths in the portion of the spectrum utilized and detecting and quantifying the presence of the dyes in the tagged product from their characteristic absorption with available absorption detection equipment sensitive in this spectral region. This invention also provides visible dye compositions particularly appropriate for the invisible tagging. Offshore well floating natural gas recovery and 02/00162 methanol-manufacturing system Hoy-Petersen, A. et al. PCT Int. Appl. WO 00 23,689 (Cl. E2lB43/34), 27 Apr 2000, GB Appl. 1998/22,975, 21 Ott 1998. 15. A system for the recovery of small amounts of associated natural gas from an offshore oil field comprises a floating vessel, a means on that vessel to separate small amounts of gas from crude oil, a means on that vessel to convert the separated gas to methanol, a segregated storage space on the vessel to contain the methanol, and a provision to transfer the methanol intermittently to a products tanker or to segregated tanks in an off-take tanker for removal from the oil field and subsequent recovery. The means to convert the separated gas to methanol includes a compact reformer capable of operation at high temperature and pressure to convert gas and steam to carbon monoxide and hydrogen (i.e. synthesis gas) and a means to synthesize methanol from the carbon monoxide and hydrogen. Diagrams of the floating vessel and contained apparatus are presented. Oil shales as competitive fuel for new generation 02/00163 technologies for power engineering Volkov, E.P., Gavrilov, A.F. IZV. Akad. Nauk, Energ., 1998, I, 116127. (In Russian) World sources of oil shales were reviewed. It was she\ un that despite the low heating value of oil shale, their use based o n thermal processing to obtain highly calorific tar and fuel gas can be c ompetitive to coal as fuel for heating and power engineering. Highly efficient thermal power plant versions were discussed. On-line detection of sulfur species in light 02/00164 petroleum liquids using gas chromatography and sulfur selective detection Thind, S. Proc. Annu. ISA Anal. Div. Symp., 2000, 33, 105-114. Sulphur, one of the basic building blocks of life, can be harmful when released into the environment. Sulphur particles can cause a haze of air pollution dense enough to hinder visibility; they are a major component of acid rain, and, when they are propelled into the upper atmosphere, they are partially responsible for the destruction of the ozone layer. Intense environmental legislation has placed more emphasis on detecting and measuring sulphur levels in fuels and processes. In the efforts to have better control over the process for the sulphur removal, continuous sulphur species analysis is a very useful tool. 02/00165 Organic petrology, chemical composition, and reflectance of pyrobitumen from the El Soldado copper deposit, Chile Wilson, N.S.F. Inf. J. Coal Geol., 2000, 43, (l-4) 53-82. Detailed organic petrology of authigenic sulphide inclusions, degassing vesicles, and anisotropic pyrobitumen and graphitic carbon allowed the elucidation of a complex diagenetic history of a biodegraded reservoir in faulted volcanic and subvolcanic rocks. Due to the over-maturity of the host sequence, biomarker techniques (aliphatic and aromatic) were unsuitable to investigate the composition of the pyrobitumen. However, microprobe and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analyses, Rock-Eva1 pyrolysis, and t3C NMR techniques were used to ascertain the composition of the pyrobitumen. Spatial variations in the maturity of the pyrobitumen were assessed using both random reflectance (R,) and rotational reflectance (R,,, and Romtn). The data are consistent with the following evolution for EI Soldado. As a result of burial in the Cretaceous back-arc basin, petroleum was generated from organic-rich shales in the underlying lower Lo Prado Formation and migrated into primary and structural porosity in the host rocks, the predominantly volcanic upper Lo Prado Formation. Low-temperature (~90°C) biodegradation of petroleum developed an early assemblage (Stage I assemblage) of pyrite (fsphaleritefchalcopyrite). Geopetal structures related to pressure degassing of semisolid petroleum suggest that migration occurred while the strata were horizontal, at approximately 130 Ma. Continued basinal burial led to thermal degassing, increased maturation and contraction of the petroleum into pyrobitumen. Around 20 Ma later an influx of high-temperature (ca. 250-350°C) Cu-rich fluids induced by regional granitoid intrusion (Stage II assemblage) replaced preexisting pyrite and pyrobitumen. The mineralizing fluids altered the pyrobitumen physically and chemically: (a) increasing R, to greater than ca. 5% in the core of the orebodies Fuel and Energy Abstracts
January 2002
17
Subsurface hydrocarbon contamination associated with petroleum spills is a widespread occurrence that presents a significant threat to groundwater resources. The natural attenuation test site (NATS) at Columbus Air Force Base, MS, provided a unique opportunity to monitor changes in the molecular microbial ecology as well as stimulation of natural biodegradative processes under transient field study conditions. A large, synthetic jet fuel mixture containing BTEX compounds and naphthalene in a decane carrier was introduced into the subsurface. Over 462 days, a plume of hydrocarbon contamination developed and stabilized at a distance of ~15 m downgradient from the source area. Exposure of indigenous microorganisms to the contaminant hydrocarbons was evaluated using an array of gene probes targeting common genotypes associated with the aerobic biodegradation of BTEX and naphthalene. Each of the targeted genotypes alkB, nahA, nahH, todClC2, and xylA showed significant responses to hydrocarbon exposure. Aerobic mineralization potentials of selected contaminants were greater in sediments collected from within the plume relative to uncontaminated areas, suggesting that an aerobic contaminant-degrading community successfully developed within the plume. An increase in aerobic degradation activity coincided with the arrival of the hydrocarbon front within the well field. The Natural Attenuation Study at Columbus AFB successfully linked adaptations of indigenous microorganisms to hydrocarbon exposure during a transient field study. 02/00157 Characteristics of shale from the manturovo field and products of its processing Iorudas, K.A. Khim. Tverd. Topl. (Mosco~t~), 2000, 2, 80-87. (In Russian) Thermal processing of a high-sulphur shale under conditions similar to those of the Galoter process, with solid heat transfer agent, was studied. 02/00156 Composition for increasing the fluidity of crude oil and unplugging petroleum wells and pipes Slemcu, N. et al. Rom. RO 109,113 (Cl. E2lB43/22), 30 Nov 1994, Appl. 9,301,615, 3 Dee 1993. 3. (In Romania) The fluidity of crude oil is increased, petroleum wells and pipes are unplugged by using fluidization agents including anthracene oil from coal distillation at 270-310”, interface activating agent as ethoxylated nonylphenols and a ammonium salt. The anthracene oil can be replaced by creosot. 02/00159 History of forecast and discovery of the Dnepropetrovsk-Donetsk petroleum-gas pool region Kabyshev, B.P. Geol. Zh., 1999, 4, 89-92. (In Russian) Romenskoye oil field, first of the fields which were opened in Dnepropetrovsk-Donetsk oil-gas bearing region, and also this region was discovered in 1937 on the basis of the prognosis of N.S. Shatsky and on the results of drilling the wells drilled with the aim of search for gypsums, potassium salt, oil, carried out under the leadership of F.O. Lycenko between 1932 and 1936. Nobody had predicted presence of oil in the DDB region before 1931, since the hypotheses of the great Donbass coal bearing were dominant at that time, however they would not be proved subsequently. These hypotheses stated that the fold Carboniferous of the Donets geosynclinal type existed under the cover of the little in thickness Mesozoic deposits. More than one hundred years geologists had been searching for great coal deposits in the DDB region, however, oil and gas were found. 02/00160 Medium oils for slurry-bed reaction and methods for the manufacture of dimethyl ether Tomura, K. et al. Jpn. Kokai Tokkyo Koho JP 2000 109,437 (Cl. CO7C9/16), 18 Apr 2000, JP Appl. 1998/220,338, 4 Aug 1998. 10. (In Japanese) Medium oils contain mainly hydrocarbons with paraffin carbons consisting >70% of the total carbons. Thus, di-Me ether was prepared from 47.5:47.5:5 volume ratio CO-H-CO* in the presence of oxide catalysts using hydrogenated butene-isobutene copolymer as a medium oil. 02/00161 Method for invisibly tagging petroleum products using visible dyes Pa&, T.D. er al. Eur. Pat. Appl. EP 1,001,003 (Cl. CIOLl/OO), 17 May 2000, US Appl. 188,639, 9 Nov 1998. 17. This invention provides a method for invisibly tagging, for subsequent identification purposes, various liquid petroleum hydrocarbons, such as crude oil, diesel fuel, heating oil, kerosene, lubricating oils, waxes, jet fuel, and in particular gasoline, remarkably using visible dyes by incorporating therein one or more visible dyes at minute levels such that they cannot be visually detected by the human eye. Visible dyes which have high solubility in petroleum hydrocarbons and maximum absorption in the 550-700 nm visible wavelength range are used to impart such invisible markings. The visible dyes, although employed at non-visible levels, are still capable of detection in a relatively quick and
Liquid fuels (sources, properties, recovety)
simple manner which requires minimal instrumentation, creastes no waste products for disposal, and gives true quantitative results of dye concentrations in the field. This invention, therefore, further provides a method for so identifying the tagged petroleum hydrocarbons by exposing the tagged hydrocarbon to visible light having wavelengths in the portion of the spectrum utilized and detecting and quantifying the presence of the dyes in the tagged product from their characteristic absorption with available absorption detection equipment sensitive in this spectral region. This invention also provides visible dye compositions particularly appropriate for the invisible tagging. Offshore well floating natural gas recovery and 02/00162 methanol-manufacturing system Hoy-Petersen, A. et al. PCT Int. Appl. WO 00 23,689 (Cl. E2lB43/34), 27 Apr 2000, GB Appl. 1998/22,975, 21 Ott 1998. 15. A system for the recovery of small amounts of associated natural gas from an offshore oil field comprises a floating vessel, a means on that vessel to separate small amounts of gas from crude oil, a means on that vessel to convert the separated gas to methanol, a segregated storage space on the vessel to contain the methanol, and a provision to transfer the methanol intermittently to a products tanker or to segregated tanks in an off-take tanker for removal from the oil field and subsequent recovery. The means to convert the separated gas to methanol includes a compact reformer capable of operation at high temperature and pressure to convert gas and steam to carbon monoxide and hydrogen (i.e. synthesis gas) and a means to synthesize methanol from the carbon monoxide and hydrogen. Diagrams of the floating vessel and contained apparatus are presented. Oil shales as competitive fuel for new generation 02/00163 technologies for power engineering Volkov, E.P., Gavrilov, A.F. IZV. Akad. Nauk, Energ., 1998, I, 116127. (In Russian) World sources of oil shales were reviewed. It was she\ un that despite the low heating value of oil shale, their use based o n thermal processing to obtain highly calorific tar and fuel gas can be c ompetitive to coal as fuel for heating and power engineering. Highly efficient thermal power plant versions were discussed. On-line detection of sulfur species in light 02/00164 petroleum liquids using gas chromatography and sulfur selective detection Thind, S. Proc. Annu. ISA Anal. Div. Symp., 2000, 33, 105-114. Sulphur, one of the basic building blocks of life, can be harmful when released into the environment. Sulphur particles can cause a haze of air pollution dense enough to hinder visibility; they are a major component of acid rain, and, when they are propelled into the upper atmosphere, they are partially responsible for the destruction of the ozone layer. Intense environmental legislation has placed more emphasis on detecting and measuring sulphur levels in fuels and processes. In the efforts to have better control over the process for the sulphur removal, continuous sulphur species analysis is a very useful tool. 02/00165 Organic petrology, chemical composition, and reflectance of pyrobitumen from the El Soldado copper deposit, Chile Wilson, N.S.F. Inf. J. Coal Geol., 2000, 43, (l-4) 53-82. Detailed organic petrology of authigenic sulphide inclusions, degassing vesicles, and anisotropic pyrobitumen and graphitic carbon allowed the elucidation of a complex diagenetic history of a biodegraded reservoir in faulted volcanic and subvolcanic rocks. Due to the over-maturity of the host sequence, biomarker techniques (aliphatic and aromatic) were unsuitable to investigate the composition of the pyrobitumen. However, microprobe and laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS) analyses, Rock-Eva1 pyrolysis, and t3C NMR techniques were used to ascertain the composition of the pyrobitumen. Spatial variations in the maturity of the pyrobitumen were assessed using both random reflectance (R,) and rotational reflectance (R,,, and Romtn). The data are consistent with the following evolution for EI Soldado. As a result of burial in the Cretaceous back-arc basin, petroleum was generated from organic-rich shales in the underlying lower Lo Prado Formation and migrated into primary and structural porosity in the host rocks, the predominantly volcanic upper Lo Prado Formation. Low-temperature (~90°C) biodegradation of petroleum developed an early assemblage (Stage I assemblage) of pyrite (fsphaleritefchalcopyrite). Geopetal structures related to pressure degassing of semisolid petroleum suggest that migration occurred while the strata were horizontal, at approximately 130 Ma. Continued basinal burial led to thermal degassing, increased maturation and contraction of the petroleum into pyrobitumen. Around 20 Ma later an influx of high-temperature (ca. 250-350°C) Cu-rich fluids induced by regional granitoid intrusion (Stage II assemblage) replaced preexisting pyrite and pyrobitumen. The mineralizing fluids altered the pyrobitumen physically and chemically: (a) increasing R, to greater than ca. 5% in the core of the orebodies Fuel and Energy Abstracts
January 2002
17