PYROLYSIS OF SUNNYSIDE (UTAH) TAR SAND: CHARACTERIZATION OF VOLATILE COMPOUND EVOLUTION

Sunnyside (Utah) tar sand was subjected to programmed temperature pyrolysis and the volatile products were detected by tandem on-line mass spectrometry (MS/MS) in real time analyses. A heating rate of 4°C/min from room temperature to 900°C was employed.

Evolution of hydrogen, light hydrocarbons, nitrogen-, sulfur-, and oxygen-containing compounds was monitored by MS or MS/MS detection. Evolution of volatile organic compounds occurred in two regimes: 1) low temperature (maximum evolution at 150 to 175°C), corresponding to entrained organics, and 2) high temperature (maximum evolution at 440 to 460°C), corresponding to cracking of large organic components. Alkanes and alkenes of two carbons and higher had temperatures of maximum evolution at approximately 440°C, and methane at approximately 474°C. Aromatic hydrocarbons had temperatures of maximum evolution slightly higher, at approximately 450° C. Some nitrogen-, sulfur-, and oxygen-'ccntaining compounds were also detected in the volatile products.

Comparing the Sunnyside pyrolysis to the pyrolysis of other domestic tar sands indicated the following for hydrocarbon evolution: 1) the evolution of entrained organics relative to the total evolution was much less for Sunnyside tar sand, 2) the temperatures of maximum evolution of hydrocarbons due t o cracking reactions were slightly lower, and 3) the temperatures of maximum evolution for benzene and toluene are slightly higher than observed for other tar sands.

In general, the noncondensible gases, H₂, CO, and CO₂, exhibited evolution associated with hydrocarbon cracking reactions, and high temperature evolution associated with mineral decomposition, the water-gas shift reaction, and gasification reactions. Pyrolysis yields were dominated by the evolution of carbon oxides and water. The CO₂ primarily appeared t o cane from the decomposition of carbonate minerals. Compared t o other domestic tar sands, the gas evolution reflected more mineral decomposition character for Sunnyside tar sand.     

CHARACTERIZATION AND POTENTIAL UTILIZATION OF WHITEROCKS (UTAH) TAR SAND BITUMEN

ABSTRACT

The native Whiterocks (Utah) tar sand bitumen was separated into several boiling range fractions for detailed analysis and characterization. The lighter fraction (477-617 K) was evaluated for use as a transportation fuel and the residues (>617 K and >728 K) were evaluated for use as road asphalts. The 617 K plus residue from the Whiterocks bitumen can be classified as a viscosity grade AC-10 asphalt whereas the 728 K plus residue failed to meet asphalt specifications. Apart from the asphalt specification tests, several sophisticated techniques were used to characterize these fractions. The detailed structure of the low molecular weight portions of Whiterocks bitumen (477-617 K and 617-728 K) was determined by combined GC-MS. Several physical properties were also measured to evaluate the potential of the 477-617 K fraction as a high density/energy aviation turbine fuel. This lower molecular weight fraction of the bitumen contained predominantly naphthenic hydrocarbons and lesser concentrations of aromatic hydrocarbons. This was confirmed by the FTIR spectra and by the GC-MS analyses. As a result, the 477-617 K fraction appeared to be an excellent candidate as a feedstock for the production of high density, aviation turbine fuels following mild hydro treating. The heat of combustion, 135,500 BTU/gal., exceeded the specification for the high density/energy JP -11 aviation turbine fuel. The naphthenic hydrocarbons included alkylcyclohexanes, alkyldecalins, tricyclic terpanes, steranes, tetracyclic terpanes, and pentacyclic terpanes. The aromatic constituents were determined to be alkylbenzenes, benzomono-cycloparaffins, phenyl(cyclohexyl) alkanes, alkylnaphthalenes, benzodicycloparaffins, benzotricycloparaffins. alkylacenaphthenes, and naphthalene monocycloparaffins. These compounds were similar in nature to those found in the Green River shale oil.     

CHARACTERIZATION AMD POTENTIAL UTILIZATION OF WHITEROCKS (DTAB) TAR SAND BITUMEN II. PYROLYSIS MASS SPECTROMETRY AND NUCLEAR MAGNETIC RESONANCE ANALYSES

ABSTRACT

The proton and carbon-13 nuclear magnetic resonance characteristics of the native Whiterocks bitumen were determined by comparing the spectra of the samples to literature assignments. The tentative structural assignments of pyrolysis products were also obtained from the spectra of Curie-point low voltage mass spectrometric analysis. The results obtained from proton and carbon-13 nuclear magnetic resonance and pyrolysis-mass spectrometry analysis suggested that the native bitumen consists mostly of short- and long-chain (i.e., normal and isoprenoid chains) alkylsubstituents attached to polycyclic naphthenic, naphtheno-aromatic and/or aromatic moieties.     

CHARACTERIZATION AMD POTENTIAL UTILIZATION OF WHITEROCKS (DTAB) TAR SAND BITUMEN II. PYROLYSIS MASS SPECTROMETRY AND NUCLEAR MAGNETIC RESONANCE ANALYSES

The proton and carbon-13 nuclear magnetic resonance characteristics of the native Whiterocks bitumen were determined by comparing the spectra of the samples to literature assignments. The tentative structural assignments of pyrolysis products were also obtained from the spectra of Curie-point low voltage mass spectrometric analysis. The results obtained from proton and carbon-13 nuclear magnetic resonance and pyrolysis-mass spectrometry analysis suggested that the native bitumen consists mostly of short- and long-chain (i.e., normal and isoprenoid chains) alkylsubstituents attached to polycyclic naphthenic, naphtheno-aromatic and/or aromatic moieties.     

A DIMENSIONAL ANALYSIS OF DISSOLUTIONS OF A BITUMEN CONCENTRATE DERIVED FROM UTAH TAR SAND

ABSTRACT

Dissolution of bitumen concentrate derived from Utah tar sand by hot-water separation was studied in a stirred-tank reactor. The dissolution constitutes an important step in the bitumen concentrate clean-up process. A dimensional analysis was performed for the system which was utilized to construct a number of bitumen concentrate dissolution maps from the experimental data.     

A DIMENSIONAL ANALYSIS OF DISSOLUTIONS OF A BITUMEN CONCENTRATE DERIVED FROM UTAH TAR SAND

Dissolution of bitumen concentrate derived from Utah tar sand by hot-water separation was studied in a stirred-tank reactor. The dissolution constitutes an important step in the bitumen concentrate clean-up process. A dimensional analysis was performed for the system which was utilized to construct a number of bitumen concentrate dissolution maps from the experimental data.     

CONTINUOUS HYDROGENATION OF FLASH PYROLYSIS COAL TAR

High melting tars from the flash pyrolysis of Millmerran coal have been upgraded to mobile liquid products by continuous hydrogenation over a fluidized nickel molybdate catalyst. The hydrogenation unit developed specifically for this purpose la described and changes In properties of the tar during hydrogenation are discussed.     

CONTINUOUS HYDROGENATION OF FLASH PYROLYSIS COAL TAR

ABSTRACT

High melting tars from the flash pyrolysis of Millmerran coal have been upgraded to mobile liquid products by continuous hydrogenation over a fluidized nickel molybdate catalyst. The hydrogenation unit developed specifically for this purpose la described and changes In properties of the tar during hydrogenation are discussed.     

内蒙古油砂油的综合评价

对内蒙古油砂油性质进行了综合评价。结果表明，该油砂油密度大（20℃密度为0．9996g／cm^3），粘度较大，水含量高（16．0％），胶质、沥青质含量高，硫质量分数为2．64％，属高硫环烷基原油。油砂油各馏分的密度、粘度均较大。根据该油砂油的特性，建议该油砂油经加工后用作低凝点柴油和润滑油的调合组分，并用于重交通道路沥青的生产。     

STUDY OF COMPOSITION OF NIGERIAN TAR SAND BITUMEN

Abstract

Compositional characterization techniques developed for high-boiling heavy ends of petroleum have been applied to Nigerian tar sand bitumen. The bitumen was subjected to ion-exchange and ferric chloride coordination chromatography to separate acids, bases and neutral nitrogen compounds. The remaining Hydrocarbon plus fraction was separated into saturates, monoarmatics, diaromatics and polyaromatic plus polar compounds on dual packed column of silica - alumina gels. Simulated distillation data were also obtained for the bitumen and were used to plot a boiling point distribution curve.

Results of the characterization are compared with results in literature for tar sand bitumens and petroleum. Comparison of the results with the Utah and the Athabasca bitumens provides a basis for the evaluation of the Nigerian bitumen because considerable information about the processing characteristics of the Athabasca bitumen have been reported by many researchers.

Simulated distillation and chromatographic separation data indicate that the bitumen used in this present study closely resembles the Athabasca and the Utah tar sand bitumens with respect to hydrocarbon/non-hydrocarbon distribution, and the high-boiling petroleum fraction with respect to non-distilling portion. Information about the composition of bitumens and heavy oils is needed because of the prospect of using heavy oils including bitumens as energy sources.     

STUDY OF COMPOSITION OF NIGERIAN TAR SAND BITUMEN

Compositional characterization techniques developed for high-boiling heavy ends of petroleum have been applied to Nigerian tar sand bitumen. The bitumen was subjected to ion-exchange and ferric chloride coordination chromatography to separate acids, bases and neutral nitrogen compounds. The remaining Hydrocarbon plus fraction was separated into saturates, monoarmatics, diaromatics and polyaromatic plus polar compounds on dual packed column of silica - alumina gels. Simulated distillation data were also obtained for the bitumen and were used to plot a boiling point distribution curve.

Results of the characterization are compared with results in literature for tar sand bitumens and petroleum. Comparison of the results with the Utah and the Athabasca bitumens provides a basis for the evaluation of the Nigerian bitumen because considerable information about the processing characteristics of the Athabasca bitumen have been reported by many researchers.

Simulated distillation and chromatographic separation data indicate that the bitumen used in this present study closely resembles the Athabasca and the Utah tar sand bitumens with respect to hydrocarbon/non-hydrocarbon distribution, and the high-boiling petroleum fraction with respect to non-distilling portion. Information about the composition of bitumens and heavy oils is needed because of the prospect of using heavy oils including bitumens as energy sources.     

新疆油砂稠油制特种沥青

以新疆小西沟、风城两种油砂为原料，利用甲苯抽提制取的油砂稠油研制开发高价值的特种沥青产品。实验室的研究结果表明，小西沟油砂稠油可用作管道防腐沥青；风城油砂稠油分别与克拉玛依减压渣油和孤岛减压渣油调合后可制取油漆沥青和抛光沥青。     

NITROGEN COMPOUND DISTRIBUTION AND FUEL INCOMPATIBILITY REACTIONS IN A TAR SAND DERIVED MIDDLE DISTILLATE FUEL

A high paraffin, high nitrogen, low sulfur jet fuel derived from Athabasca tar sands was studied. The organo-nitrogen compounds in the fuel were isolated by mild acid extraction followed by silica-gel adsorption. Three extracts were derived from this fuel: a basic nitrogen compounds extract, BNC, in methylene chloride, a non-basic nitrogen compounds extract, NBNC, in methyl alcohol and an NBNC extract in methylene chloride. The major constituents of each extract were identified and quantitated by combined capillary column GC/MS. Alkyl substituted pyrroles, pyridines, indoles, tetrahydro-quinolines, carbazoles, and quinolines were the prevalent organo-nitrogen compounds present. Incompatibility tests were conducted on this fuel using the oxygen overpressure method with both doped and undoped fuel systems. The dopant of choice was cumene hydroperoxide. Practically no sediment formation was observed for the undoped fuel (0.1 mg/100mL fuel). The doped fuel matrix induced incompatibility behavior in proportion to the quantity of dopant present.     

CHARACTERIZATION OF VARIOUS BITUMEN SAMPLES FROM TAR SANDS

We have investigated twenty three bitumen samples obtained using different separation methods such as: ultracentrifugation, Dean-Stark extraction, solvent extraction employing vigorous agitation, hot water separation and the Solvent Extraction Spherical Agglomeration technique. These samples were extracted from oil sand feedstocks of different grades, Suncor sludge pond tailings and mineral agglomerates obtained from the Solvent Extraction Spherical Agglomeration process. All of the bitumen samples were examined on a comparative basis using various analytical techniques. These included: fractionation into asphaltenes and maltenes; elemental analyses; molecular weight determination using vapour pressure osmometry and gel permeation chromatography, infrared, proton and 13C nuclear magnetic resonance spectroscopy. Proton and ¹³C n.m.r. spectroscopic data were used to determine the distribution of various types of hydrogens and carbons in the samples. These data were also used to derive various molecular parameters in order to investigate average molecular structures of different bitumen samples and some of their asphaltene fractions.     

CHARACTERIZATION OF VARIOUS BITUMEN SAMPLES FROM TAR SANDS

ABSTRACT

We have investigated twenty three bitumen samples obtained using different separation methods such as: ultracentrifugation, Dean-Stark extraction, solvent extraction employing vigorous agitation, hot water separation and the Solvent Extraction Spherical Agglomeration technique. These samples were extracted from oil sand feedstocks of different grades, Suncor sludge pond tailings and mineral agglomerates obtained from the Solvent Extraction Spherical Agglomeration process. All of the bitumen samples were examined on a comparative basis using various analytical techniques. These included: fractionation into asphaltenes and maltenes; elemental analyses; molecular weight determination using vapour pressure osmometry and gel permeation chromatography, infrared, proton and 13C nuclear magnetic resonance spectroscopy. Proton and ¹³C n.m.r. spectroscopic data were used to determine the distribution of various types of hydrogens and carbons in the samples. These data were also used to derive various molecular parameters in order to investigate average molecular structures of different bitumen samples and some of their asphaltene fractions.     

THE POTENTIAL USE OF TAR SAND BITUMEN AS PAVING ASPHALT

ABSTRACT

In this paper several research reports describing the preparation of potential paving asphalts from tar sand Bitumen are reviewed and the results of the studies compared. The tar sand asphalts described in the studies were prepared from 1) hot water-recovered bitumen from deposits near San Luis Obispo, California (Edna deposits), and deposits near Vernal and Sunny-side, Utah; and 2) bitumen recovered from the Northwest Asphalt Ridge deposits near Vernal, Utah, by both in situ steamflood and in situ combustion recovery processes. Important properties of the tar sand asphalts compare favorably with those of specification petroleum asphalts. Laboratory data suggest that some tar sand asphalts may have superior aging characteristics and produce more water-resistant paving mixtures than typical petroleum asphalts.     

THE POTENTIAL USE OF TAR SAND BITUMEN AS PAVING ASPHALT

In this paper several research reports describing the preparation of potential paving asphalts from tar sand Bitumen are reviewed and the results of the studies compared. The tar sand asphalts described in the studies were prepared from 1) hot water-recovered bitumen from deposits near San Luis Obispo, California (Edna deposits), and deposits near Vernal and Sunny-side, Utah; and 2) bitumen recovered from the Northwest Asphalt Ridge deposits near Vernal, Utah, by both in situ steamflood and in situ combustion recovery processes. Important properties of the tar sand asphalts compare favorably with those of specification petroleum asphalts. Laboratory data suggest that some tar sand asphalts may have superior aging characteristics and produce more water-resistant paving mixtures than typical petroleum asphalts.     

RECOVERY OF ASPHALTENES FROM TAR SAND BY SUPERCRITICAL FLUID EXTRACTION

ABSTRACT

Many non-oil producing countries are enriched with other sources of energy, for example tar sand, oil shale, coal, biomass, and uranium, that are not fully utilized. Supercritical fluid extraction (SFE) of tar sand was carried out in a batch autoclave at different temperatures. Extracts recovered from SFE were fractionated into oils, asphaltenes, preasphaltenes and gases by solvent extraction. The highest yield) of SFE (24.3 wt % dry basis) from tar sand was obtained with n-pentane/benzene (1/1, v/v’) mixture at 655 K. Comparison of the amount of n-alkanes (C1–C4) evolved at 585 K and 685 K shows that the amount of methane is significantly increased at 685 K whereas the amount of C4 alkane is reduced. At 685 K, hydrogen and methane represent 45·1 vol % of the gases evolved from the SFE. The yields of C1–C3 alkane hydrocarbons were higher for supercritical fluid extracts at 685 K as compared to those obtained at 585 K. The quantity of olefines (C₂H₄ + C₃H₆) was found between 5·1 and 10·1 vol %.     

RECOVERY OF ASPHALTENES FROM TAR SAND BY SUPERCRITICAL FLUID EXTRACTION

Many non-oil producing countries are enriched with other sources of energy, for example tar sand, oil shale, coal, biomass, and uranium, that are not fully utilized. Supercritical fluid extraction (SFE) of tar sand was carried out in a batch autoclave at different temperatures. Extracts recovered from SFE were fractionated into oils, asphaltenes, preasphaltenes and gases by solvent extraction. The highest yield) of SFE (24.3 wt % dry basis) from tar sand was obtained with n-pentane/benzene (1/1, v/v') mixture at 655 K. Comparison of the amount of n-alkanes (C1-C4) evolved at 585 K and 685 K shows that the amount of methane is significantly increased at 685 K whereas the amount of C4 alkane is reduced. At 685 K, hydrogen and methane represent 45·1 vol % of the gases evolved from the SFE. The yields of C1-C3 alkane hydrocarbons were higher for supercritical fluid extracts at 685 K as compared to those obtained at 585 K. The quantity of olefines (C₂H₄ + C₃H₆) was found between 5·1 and 10·1 vol %.     

DETERMINATION OF OPTIMUM RATE CONSTANTS FOR AUTOCATALYTIC REACTION OF TAR SAND RECOVERV PROCESS

ABSTRACT

In this paper a parameter optimization technique is introduced involving a minimization algorithm. The technique is applicable to a wide range of problems involving data analysis. In particular, it is applied to the first-order initial-value problem describing the autocatalytic reaction of tar sand recovery process, as a result of which, the optimal reaction rate constants for a given set of experimental data are obtained. The analytical solution to the governing differential equation corresponding to these optimal parameter values is then shown to fit the experimental data. Numerical results are presented in graphical form for three different sets of data, and discussion and conclusions are provided subsequently.