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Title: Autothermal reforming of natural gas to synthesis gas:reference: KBR paper #2031.

Abstract

This Project Final Report serves to document the project structure and technical results achieved during the 3-year project titled Advanced Autothermal Reformer for US Dept of Energy Office of Industrial Technology. The project was initiated in December 2001 and was completed March 2005. It was a joint effort between Sandia National Laboratories (Livermore, CA), Kellogg Brown & Root LLC (KBR) (Houston, TX) and Sued-Chemie (Louisville, KY). The purpose of the project was to develop an experimental capability that could be used to examine the propensity for soot production in an Autothermal Reformer (ATR) during the production of hydrogen-carbon monoxide synthesis gas intended for Gas-to-Liquids (GTL) applications including ammonia, methanol, and higher hydrocarbons. The project consisted of an initial phase that was focused on developing a laboratory-scale ATR capable of reproducing conditions very similar to a plant scale unit. Due to budget constraints this effort was stopped at the advanced design stages, yielding a careful and detailed design for such a system including ATR vessel design, design of ancillary feed and let down units as well as a PI&D for laboratory installation. The experimental effort was then focused on a series of measurements to evaluate rich, high-pressure burner behavior at pressuresmore » as high as 500 psi. The soot formation measurements were based on laser attenuation at a view port downstream of the burner. The results of these experiments and accompanying calculations show that soot formation is primarily dependent on oxidation stoichiometry. However, steam to carbon ratio was found to impact soot production as well as burner stability. The data also showed that raising the operating pressure while holding mass flow rates constant results in considerable soot formation at desirable feed ratios. Elementary reaction modeling designed to illuminate the role of CO{sub 2} in the burner feed showed that the conditions in the burner allow for the direct participation of CO{sub 2} in the oxidation chemistry.« less

Authors:
 [1];
  1. (KBR, Houston, TX)
Publication Date:
Research Org.:
Sandia National Laboratories
Sponsoring Org.:
USDOE
OSTI Identifier:
912649
Report Number(s):
SAND2007-2331
TRN: US200801%%1129
DOE Contract Number:
AC04-94AL85000
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
03 NATURAL GAS; 10 SYNTHETIC FUELS; AMMONIA; ATTENUATION; BURNERS; CARBON; CHEMISTRY; DESIGN; FLOW RATE; HYDROCARBONS; LASERS; METHANOL; NATURAL GAS; OXIDATION; SOOT; STABILITY; STEAM; STOICHIOMETRY; SYNTHESIS; SYNTHESIS GAS; Synthesis gas.; Soot

Citation Formats

Mann, David, and Rice, Steven, D. Autothermal reforming of natural gas to synthesis gas:reference: KBR paper #2031.. United States: N. p., 2007. Web. doi:10.2172/912649.
Mann, David, & Rice, Steven, D. Autothermal reforming of natural gas to synthesis gas:reference: KBR paper #2031.. United States. doi:10.2172/912649.
Mann, David, and Rice, Steven, D. Sun . "Autothermal reforming of natural gas to synthesis gas:reference: KBR paper #2031.". United States. doi:10.2172/912649. https://www.osti.gov/servlets/purl/912649.
@article{osti_912649,
title = {Autothermal reforming of natural gas to synthesis gas:reference: KBR paper #2031.},
author = {Mann, David and Rice, Steven, D.},
abstractNote = {This Project Final Report serves to document the project structure and technical results achieved during the 3-year project titled Advanced Autothermal Reformer for US Dept of Energy Office of Industrial Technology. The project was initiated in December 2001 and was completed March 2005. It was a joint effort between Sandia National Laboratories (Livermore, CA), Kellogg Brown & Root LLC (KBR) (Houston, TX) and Sued-Chemie (Louisville, KY). The purpose of the project was to develop an experimental capability that could be used to examine the propensity for soot production in an Autothermal Reformer (ATR) during the production of hydrogen-carbon monoxide synthesis gas intended for Gas-to-Liquids (GTL) applications including ammonia, methanol, and higher hydrocarbons. The project consisted of an initial phase that was focused on developing a laboratory-scale ATR capable of reproducing conditions very similar to a plant scale unit. Due to budget constraints this effort was stopped at the advanced design stages, yielding a careful and detailed design for such a system including ATR vessel design, design of ancillary feed and let down units as well as a PI&D for laboratory installation. The experimental effort was then focused on a series of measurements to evaluate rich, high-pressure burner behavior at pressures as high as 500 psi. The soot formation measurements were based on laser attenuation at a view port downstream of the burner. The results of these experiments and accompanying calculations show that soot formation is primarily dependent on oxidation stoichiometry. However, steam to carbon ratio was found to impact soot production as well as burner stability. The data also showed that raising the operating pressure while holding mass flow rates constant results in considerable soot formation at desirable feed ratios. Elementary reaction modeling designed to illuminate the role of CO{sub 2} in the burner feed showed that the conditions in the burner allow for the direct participation of CO{sub 2} in the oxidation chemistry.},
doi = {10.2172/912649},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Apr 01 00:00:00 EDT 2007},
month = {Sun Apr 01 00:00:00 EDT 2007}
}

Technical Report:

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  • This Project Final Report serves to document the project structure and technical results achieved during the 3-year project titled Advanced Autothermal Reformer for US Dept of Energy Office of Industrial Technology. The project was initiated in December 2001 and was completed March 2005. It was a joint effort between Sandia National Laboratories (Livermore, CA), Kellogg Brown & Root LLC (KBR) (Houston, TX) and Süd-Chemie (Louisville, KY). The purpose of the project was to develop an experimental capability that could be used to examine the propensity for soot production in an Autothermal Reformer (ATR) during the production of hydrogen-carbon monoxide synthesismore » gas intended for Gas-to-Liquids (GTL) applications including ammonia, methanol, and higher hydrocarbons. The project consisted of an initial phase that was focused on developing a laboratory-scale ATR capable of reproducing conditions very similar to a plant scale unit. Due to budget constraints this effort was stopped at the advanced design stages, yielding a careful and detailed design for such a system including ATR vessel design, design of ancillary feed and let down units as well as a PI&D for laboratory installation. The experimental effort was then focused on a series of measurements to evaluate rich, high-pressure burner behavior at pressures as high as 500 psi. The soot formation measurements were based on laser attenuation at a view port downstream of the burner. The results of these experiments and accompanying calculations show that soot formation is primarily dependent on oxidation stoichiometry. However, steam to carbon ratio was found to impact soot production as well as burner stability. The data also showed that raising the operating pressure while holding mass flow rates constant results in considerable soot formation at desirable feed ratios. Elementary reaction modeling designed to illuminate the role of CO2 in the burner feed showed that the conditions in the burner allow for the direct participation of CO2 in the oxidation chemistry.« less
  • Experimental autothermal reforming (ATR) results obtained in the previous phase of this work with sulfur-free pure hydrocarbon liquids are summarized. Catalyst types and configuration used were the same as in earlier tests with No. 2 fuel oil to facilitate comparisons. Fuel oil has been found to form carbon in ATR at conditions much milder than those predicted by equilibrium. Reactive differences between paraffins and aromatics in ATR, and thus the formation of different carbon precursors, have been shown to be responsible for the observed carbon formation characteristics (fuel-specific). From tests with both light and heavy paraffins and aromatics, it ismore » concluded that high boiling point hydrocarbons and polynuclear aromatics enhance the propensity for carbon formation in ATR. Effects of olefin (propylene) addition on the ATR performance of benzene are described. In ATR tests with mixtures of paraffins and aromatics (n-tetradecane and benzene) synergistic effects on conversion characteristics were identified. Comparisons of the No. 2 fuel oil data with the experimental results from this work with pure (and mixed) sulfur-free hydrocarbons indicate that the sulfur content of the fuel may be the limiting factor for efficient ATR operation. Steam reforming of hydrocarbons in conventional reformers is heat transfer limited. Steam reforming tasks performed have included performance comparisons between conventional pellet beds and honeycomb monolith catalysts. Metal-supported monoliths offer higher structural stability than ceramic supports, and have a higher thermal conductivity. Data from two metal monoliths of different catalyst (nickel) loading were compared to pellets under the same operating conditions.« less
  • The mechanism of carbon formation on nickel autothermal steam reforming catalysts has been studied by temperature-programming, thermogravimetric and electron microscopic techniques. Temperature-programmed surface reaction (TPSR) studies of carbon deposited on nickel reforming catalysts by the decomposition of C/sub 2/H/sub 4/ and C/sub 2/H/sub 2/ exhibit seven forms of carbon that are distinguished by their characteristic reactivity with H/sub 2/ and 3.0-vol % H/sub 2/O/He. The relative population of the different carbon states depends primarily on the temperature during deposition. C/sub 2/H/sub 2/ exposure populates the same carbon states as C/sub 2/H/sub 4/ exposure but at approximately 100/sup 0/K lower depositionmore » temperature. Similar carbon states were found on all nickel catalysts studies including Ni/..gamma..-Al/sub 2/O/sub 3/ and Ni/MgO-Al/sub 2/O/sub 3/ leading to the conclusion that the support has little effect on carbon deposit formation and reactivity. The reactivity of the carbon states is not altered by exposure to steam in C/sub 2/H/sub 4/-H/sub 2/O mixtures, but the amount of carbon deposited decreases to zero as H/sub 2/O/C increases past a critical ratio.« less
  • The fuel cell systems that are being considered for use as dispersed generators by electric utilities are, at present, limited to the use of clean light hydrocarbon fuels such as naphtha and natural gas. This report presents the results of research on a fuel processing concept, termed Autothermal Reforming, or ATR, which may expand the useful fuel range to include middle distillate fuels derived from petroleum or coal. Experiments were conducted with a 4-in.-dia by 15-in.-long catalytic reactor (nickel catalyst) to produce a hydrogen-rich gas from No. 2 Fuel Oil and steam-air mixtures, at essentially atmospheric pressure. The hydrogen yieldmore » was mapped in the carbon-free region as a function of the major operating parameters, particularly the steam-to-carbon and air-to-carbon ratios, and the preheat temperature. The results are compared with the equilibrium yield predictions. Two optimum cases were identified. The first case represents a partial oxidation process with air with just enough steam added to suppress carbon formation. In the second case, 80 percent of the hydrogen was produced by partial oxidation and 20 percent by steam reforming. A preheat temperature of 1400/sup 0/F and a catalyst bed temperature of 2000/sup 0/F was required to achieve the second case results, at an air-to-carbon molar ratio of 1.9 and a steam-to-carbon molar ratio of 3.0. This hydrogen yield translates to a 9500 Btu/kWh power plant heat rate at typical phosphoric acid fuel cell operating conditions.« less
  • The mechanisms by which various fuel component hydrocarbons related to both heavy petroleum and coal-derived liquids are converted to hydrogen without forming carbon were investigated. Reactive differences between paraffins and aromatics in autothermal reforming (ATR) were shown to be responsible for the observed fuel-specific carbon formation characteristics. The types of carbon formed in the reformer were identified by SEM and XRD analyses of catalyst samples and carbon deposits. From tests with both light and heavy paraffins and aromatics, it is concluded that high boiling point hydrocarbons and polynuclear aromatics enhance the propensity for carbon formation. The effects of propylene additionmore » on the ATR performance of benzene are described. In ATR tests with mixtures of paraffins and aromatics, synergistic effects on conversion characteristics were identified. Indications that the sulfur content of the fuel may be the limiting factor for efficient ATR operation were found. The conversion and degradation effects of the sulfur additive (thiophene) were examined.« less