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Hybrid HEFA-HDCJ Process for the Production of Jet Fuel Blendstocks
The hydrotreatment of bio-oil derived from the pyrolysis and biocrude from hydrothermal liquefaction of lignocellulosic materials to produce hydrocarbons faces significant technological challenges, mainly due to the high reactivity and poor thermal stability of bio-oil, resulting in the formation of large quantities of coke. This problem has been addressed by existing PNNL patents with a two-step hydrotreatment technology in which the bio-oil is first stabilized with a noble hydrogenation metal (often Pt or Ru). Then, in the second step, the bio-oil is deoxygenated with a Ni-Mo or Co-Mo sulfide catalyst. The main problem with this approach is that the Pt/Ru catalysts deactivate easily in the presence of S or other impurities, which are commonly present in pyrolysis oils. In this project, we explored technological solutions to mitigate coke formation, avoiding the use of Pt/Ru catalysts. Our strategy is based on three actions: (1) Bio-oil stabilization in the presence of alcohols. In this project, we studied the stabilization with butanol. (2) the use of a cosolvent to solubilize the bio-oil. Because coke formation reactions are second-order reactions a reduction in the concentration of reactive bio-oil molecules. In this case, we used yellow greases as a co-solvent. (3) Separation of bio-oil reactive fractions. In this project, we studied the removal of water-soluble fractions. Our batch co-hydrotreatment studies confirmed that the addition of butanol and methanol and the blend with lipids effectively contributed to mitigating coke formation (reducing coke yield to about 1 wt.% %). The removal of sugars did not have a noticeable effect on the overall coke yield, suggesting that coke precursors are present in all bio-oil fractions.
Producing Jet Fuel from Biogas Using Cool GTL SM
GTI Energy advanced the development of Cool GTL SM through a multi-phase project that studied and confirmed the promising value of this technology. It optimized the process by creating an integrated pilot plant capable of producing 50 gallons of total liquid hydrocarbon fuel. It also performed testing campaigns and developed a conceptual commercial design to support technoeconomic and life-cycle analyses, resulting in data that demonstrated a greenhouse gas emissions benefit.
Hybrid HEFA-HDCJ Process for the Production of Jet Fuel Blendstocks
The hydrotreatment of bio-oil derived from the pyrolysis and biocrude from hydrothermal liquefaction of lignocellulosic materials to produce hydrocarbons faces significant technological challenges, mainly due to the high reactivity and poor thermal stability of bio-oil, resulting in the formation of large quantities of coke. This problem has been addressed by existing PNNL patents with a two-step hydrotreatment technology in which the bio-oil is first stabilized with a noble hydrogenation metal (often Pt or Ru). Then, in the second step, the bio-oil is deoxygenated with a Ni-Mo or Co-Mo sulfide catalyst. The main problem with this approach is that the Pt/Ru catalysts deactivate easily in the presence of S or other impurities, which are commonly present in pyrolysis oils. In this project, we explored technological solutions to mitigate coke formation, avoiding the use of Pt/Ru catalysts. Our strategy is based on three actions: (1) Bio-oil stabilization in the presence of alcohols. In this project, we studied the stabilization with butanol. (2) the use of a cosolvent to solubilize the bio-oil. Because coke formation reactions are second-order reactions a reduction in the concentration of reactive bio-oil molecules. In this case, we used yellow greases as a co-solvent. (3) Separation of bio-oil reactive fractions. In this project, we studied the removal of water-soluble fractions. Our batch co-hydrotreatment studies confirmed that the addition of butanol and methanol and the blend with lipids effectively contributed to mitigating coke formation (reducing coke yield to about 1 wt.% %). The removal of sugars did not have a noticeable effect on the overall coke yield, suggesting that coke precursors are present in all bio-oil fractions. Our analytical work suggests that they may be concentrated in the water-insoluble/CH 2 Cl 2 insoluble fractions of pyrolysis oils. Although the technological strategies tested resulted in significant coke reductions, the levels achieved were not sufficiently low to ensure a reliable operation in continuous, fixed-bed trickle-bed reactors. Long runs of more than 100 hours (maximum: 255 h) of co-processing time on stream were achieved in a continuous 40 mL reactor. When the same test was conducted in a larger 400 mL reactor, pressure drop increases associated with coke formation were observed. This increase in coke formation could be due to larger temperature gradients in the bed. Hydrodeoxygenation tests in moving bed reactors and using more active hydrogenation catalysts (for example Ni) could lead to more reliable operations. Unfortunately, our team did not have access to such experimental setups. The technoeconomic analysis suggests that although alcohol use is an effective means to reduce coke formation, the use of alcohol increases production cost. Thus, its use needs to be minimized. A delicate balance needs to be found between the use of technological solutions that allow the reliable operation of the system (stabilization with Ni catalysts, use of small quantities of solvents, processing in moving bed reactors) with a tolerable level of coke formation for the hydrodeoxygenation reactor used and that result in minimum production costs.
Effect of nitrogenous bases on the thermal stability of jet fuels
Fuels from naphthenic petroleums were evaluated, and it was found that they had more N bases than those paraffinic ones (0.00024 and 0.000009% N, respectively). The removal of the N bases improved significantly the thermal stability and reduced the residue formation during oxidation of the fuel. The improvement depended on both content and composition of the bases. Thus, fuels with similar content of N bases (0.00058% N) and thermal stability had oxidation residues of 17.5 and 5.6 and sol. gum of 13 and 1.5 mg/100 ml, before and after removing the N bases, respectively.
Computer model for refinery operations with emphasis on jet fuel production. Volume 2: Data and technical bases
The FORTRAN computing program predicts the flow streams and material, energy, and economic balances of a typical petroleum refinery, with particular emphasis on production of aviation turbine fuel of varying end point and hydrogen content specifications. The program has provision for shale oil and coal oil in addition to petroleum crudes. A case study feature permits dependent cases to be run for parametric or optimization studies by input of only the variables which are changed from the base case. The report has sufficient detail for the information of most readers.
Computer model for refinery operations with emphasis on jet fuel production. Volume 1: Program description
A FORTRAN computer program is described for predicting the flow streams and material, energy, and economic balances of a typical petroleum refinery, with particular emphasis on production of aviation turbine fuel of varying end point and hydrogen content specifications. The program has provision for shale oil and coal oil in addition to petroleum crudes. A case study feature permits dependent cases to be run for parametric or optimization studies by input of only the variables which are changed from the base case.
Computer model for refinery operations with emphasis on jet fuel production. Volume 3: Detailed systems and programming documentation
The FORTRAN computing program predicts flow streams and material, energy, and economic balances of a typical petroleum refinery, with particular emphasis on production of aviation turbine fuels of varying end point and hydrogen content specifications. The program has a provision for shale oil and coal oil in addition to petroleum crudes. A case study feature permits dependent cases to be run for parametric or optimization studies by input of only the variables which are changed from the base case.
Jet Fuel Thermal Stability
Various aspects of the thermal stability problem associated with the use of broadened-specification and nonpetroleum-derived turbine fuels are addressed. The state of the art is reviewed and the status of the research being conducted at various laboratories is presented. Discussions among representatives from universities, refineries, engine and airframe manufacturers, airlines, the Government, and others are presented along with conclusions and both broad and specific recommendations for future stability research and development. It is concluded that significant additional effort is required to cope with the fuel stability problems which will be associated with the potentially poorer quality fuels of the future such as broadened specification petroleum fuels or fuels produced from synthetic sources.
Military jet fuel from shale oil
Investigations leading to a specification for aviation turbine fuel produced from whole crude shale oil are described. Refining methods involving hydrocracking, hydrotreating, and extraction processes are briefly examined and their production capabilities are assessed.
Emission FTIR analyses of thin microscopic patches of jet fuel residue deposited on heated metal surface
Deposits laid down in patches on metal strips in a high pressure/high temperature fuel system simulator operated with aerated fuel at varying flow rates were analyzed by emission FTIR in terms of functional groups. Significant differences were found in the spectra and amounts of deposits derived from fuels to which small concentrations of oxygen-, nitrogen-, or sulfur-containing heterocyclics or metal naphthenates were added. The spectra of deposits generated on strips by heating fuels and air in a closed container were very different from those of the flowing fluid deposits. One such closed-container dodecane deposit on silver gave a strong surface-enhanced Raman spectrum.
Aerodynamic effect of combustor inlet-air pressure on fuel jet atomization
Mean drop diameters were measured with a recently developed scanning radiometer in a study of the atomization of liquid jets injected cross stream in high velocity and high pressure airflows. At constant inlet air pressure, reciprocal mean drop diameter, was correlated with airflow mass velocity. Over a combustor inlet-air pressure range of 1 to 21 atmospheres, the ratio of orifice to mean drop diameter, D(O)/D(M), was correlated with the product of Weber and Reynolds number, WeRe, and with the molecular scale momentum transfer ratio of gravitational to inertial forces.
Aerodynamic effect of combustor inlet-air pressure on fuel jet atomization
Mean drop diameters were measured with a recently developed scanning radiometer in a study of the atomization of liquid jets injected cross stream in high velocity and high pressure airflows. At constant inlet air pressure, reciprocal mean drop diameter was correlated with airflow mass velocity. Over a combustor inlet-air pressure range of 1 to 21 atmospheres, the ratio of orifice to mean drop diameter, D(O)/D(M), was correlated with the product of Weber and Reynolds number, WeRe, and with the molecular scale momentum transfer ratio of gravitational to inertial forces. Previously announced in STAR as N84-22910
Jet fuel instability mechanisms
The mechanisms of the formation of fuel-insoluble deposits were studied in several real fuels and in a model fuel consisting of tetralin in dodecane solution. The influence of addition to the fuels of small concentrations of various compounds on the quantities of deposits formed and on the formation and disappearance of oxygenated species in solution was assessed. The effect of temperature on deposit formation was also investigated over the range of 308-453 K.
Aerodynamic effect of combustor inlet air pressure on fuel jet atomization
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Characterization studies of deposits formed from thermally stressed jet fuels
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Application of photoacoustic techniques to the study of jet fuel residue
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Characterization of jet fuels by triple quadrupole mass spectrometry
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