Synthesis gas technology large-scale applications

CATEGORY: SYNGAS
Synthesis gas technology large-scale applications

Type	Journal Article
Author	Ib Dybkjær
Author	Kim Aasberg-Petersen
URL	http://onlinelibrary.wiley.com/doi/10.1002/cjce.22453/abstract
Volume	94
Issue	4
Pages	607-612
Publication	The Canadian Journal of Chemical Engineering
Date	April 1, 2016
Abstract	Natural gas is an important feedstock for large-scale production of many chemicals, including methanol and synthetic fuels, using either the TIGAS process to produce gasoline or Fischer-Tropsch synthesis to produce diesel. Significant research has been conducted into the development of processes that convert natural gas directly into the end product. However, the most economical route, is a process in two stages with synthesis gas production as the first step. The most capital- and energy-intensive aspect of producing synthetic fuels and chemicals is synthesis gas production. Authors review key technologies for large-scale production of synthesis gas. They find auto-thermal reforming at a low steam-to-carbon ratio to be the most economic and efficient technology for synthesis gas production in plants both for producing methanol and synthetic fuels.

Hydrocarbon Reforming on Transition Metal/Rare Earth Oxide Catalysts: Experimental and DFT Studies

CATEGORY: SYNGAS
Hydrocarbon Reforming on Transition Metal/Rare Earth Oxide Catalysts: Experimental and DFT Studies
NAM24-24th North American Catalysis Society Meeting, Pittsburgh, PA, June 14-19, 2015
Kerry Dooley 1, Rui Li 1, Michael Janik 2, Matthew Krcha 2, Jaren Lee 1 and Naidu Seetala 3
(1) Louisiana State University, USA, (2) Pennsylvania State University, USA, (3) Grambling State University, USA.
Introduction
We designed REO/transition metal (TM) oxide systems using computation, synthesis and characterization to catalytically reform/crack tars in model syngas effluents. Naphthalene was the model “tar” compound, but we also studied propane reforming, because propane was more amenable to computational (DFT) reaction study. We set as targets catalysts stable for at least a week, with the primary reforming products as CO and H2.
Materials and Methods
Materials were synthesized by adapting templated sol-gel methods [1]. They were characterized by before- and after XRD, BET, and TPO, and select materials by XANES/XAFS. Feeds for reaction studies were (typical) 9-21% H2O, 45-55% CO (in some cases CO used), 0.6-4% CH4, 26-31% H2, 1-4% N2, 0.3-3% hydrocarbon, 0-40 ppmv H2S, at 110 kPa, GHSV = 6000-40000, temperatures 903-1073 K.
Results and Discussion
We adapted the DFT + U method to model adsorption of sulfur compounds and reaction of hydrocarbons on TM-REO systems. For example, DFT+U showed oxidation states for Mn-doped ceria that agreed with XANES spectra [2,3], and DFT+U results agreed that Ce atoms are more easily reduced to Ce3+ in the mixed oxide. Relationships between the distribution of dopants (nearest neighbor, next nearest neighbor, surface-surface, surfacesubsurface) and reducibility were established (Fig. 1), and their impact on oxidation determined [4]. An example is shown in Figure 1. We therefore predicted ease of oxygen vacancy formation and established a relationship between vacancies and reforming reaction rates. Catalysts based on these predictions, such as Mn0.4/Ce/Zr/Al and Fe/Ce3/La/Al (molar ratios, except for Al) proved active for tar reforming, with good sulfur tolerance, reasonable tolerance for coke, and without excessive CH4 or CO2 production [1]. By all these measures, these materials proved superior to typical Ni-based high temperature reforming catalysts. We also are examining reforming with simpler single phase TM-REOs using propane as a model hydrocarbon. Propane was chosen because it was facile for consideration in DFT studies. Carbon are were estimated online (Table 1). Small negative yields over short time periods are possible, because the materials were “used” (for tar reforming) to begin with. catalysts are more active than the typical Ni-based high temperature reforming catalyst (which also accumulates 2.4 times more coke by TPO). The absence of a transition metal dopant leads to higher C2 (less CO + H2) yield. Note that it is possible to find a practical temperature where even these simpler materials are somewhat sulfur tolerant, showing that the doped REO oxysulfides can retain reforming activity.
Significance: It is therefore possible to design a syngas cleanup system operating solely at temperatures between the gasifier and the high temperature water-gas shift reactor. This could greatly improve heat integration (and so, operating costs) of syngas cleanup processes. For a typical syngas process (e.g., to ethanol), the gasifier effluent cleanup costs represent at least 60% of the total costs, including the collection and transport of the biomass source.
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Conversion of Syngas to LPG and Aromatics Over Commercial Fischer-Tropsch Catalyst and HZSM-5 in a Dual Bed Reactor

CATEGORY: SYNGAS 
Conversion of Syngas to LPG and Aromatics Over Commercial Fischer-Tropsch Catalyst and HZSM-5 in a Dual Bed Reactor

Type	Journal Article
Author	A. Corsaro
Author	T. Wiltowski
URL	http://dx.doi.org/10.1080/10916466.2013.845574
Volume	32
Issue	20
Pages	2497-2505
Publication	Petroleum Science and Technology
Date	October 18, 2014
Abstract	Researchers tested the commercial Co-based Fischer-Tropsch catalyst and HZSM-5 in a single reactor process. They examined the FT catalyst at 463 K, and HZSM-5 at various temperatures (523, 573, and 623 K). They studied the effect of syngas flow rate, HZSM-5 temperature and loading on liquefied petroleum gas (LPG) and aromatics selectivities. HZSM-5 addition suppressed the formation of CO2 and CH4, and remarkably enhanced the simultaneous formation of LPG and aromatics. They determined optimal operating conditions to be: THZM-5 = 623 K, HZSM-5 loading = 2.5 g, and GHSV = 4.8 Lsyngas/(gcat h).

Elemental mercury removal from syngas by nano-ZnO sorbent

CATEGORY: MERCURY
Journal of Fuel Chemistry and Technology, Volume 41, Issue 11, November 2013, Pages 1371–1377
Elemental mercury removal from syngas by nano-ZnO sorbent
Jin-song ZHOU, Pan QI, Wen-hui HOU, Shu-lin YOU, Xiang GAO, Zhong-yang LUO
State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, China
Abstract
Nano-ZnO sorbents synthesized by a homogeneous precipitation method were characterized by BET (Brunauer-Emmett-Teller), XRD (X-ray diffraction) as well as XPS (X-ray photoelectron spectroscopy) analysis.
Researchers studied the adsorption of elemental mercury by nano-ZnO under nitrogen and simulated gas atmosphere on a bench-scale fixed-bed apparatus.
They studied the effect of various gases on Hg⁰ removal performance by nano-ZnO. Results reveal that the mercury removal efficiency of the nano-ZnO is relatively poor in nitrogen atmosphere. The presence of H₂S promotes the Hg⁰ removal by nano-ZnO observably and the mercury removal efficiency can be maintained for a long time even after stopping pass into H₂S. The presence of CO and H₂ promote the Hg⁰ removal by promotion of nano-ZnO desulfurization. As the temperature increases, the formation of elemental sulfur in the surface of the nano-ZnO gradually reduces, leading to suppress the removal of Hg⁰.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S1872581314600049

Coproduction of Syngas during Regeneration of Coked Catalyst for Upgrading Heavy Petroleum Feeds

Ind. Eng. Chem. Res., Just Accepted Manuscript, DOI: 10.1021/ie402527t, Publication Date (Web): November 4, 2013
Coproduction of Syngas during Regeneration of Coked Catalyst for Upgrading Heavy Petroleum Feeds
Abstract
Gang Tian , Gang Wang , Chunming Xu , and Jinsen Gao
Abstract
Examines the gasification reactivity of coke, deposited on catalyst during upgrading heavy petroleum feeds in a FCC-like process, with steam and CO2 at 800–900 °C. There is a major difference between the performances of catalyst regeneration under steam and CO2 atmospheres.
For example, the reactivity of coke-on-catalyst during steam gasification is about 3–5 times that during CO2 gasification. Furthermore, the removal rate decreases significantly when conversion is greater than 0.5 during CO2 gasification. Using selecting steam as gasifying agent, authors have constructed a conceptual process of regeneration of coked-catalyst. The technique produces syngas by removing the coke deposited on catalyst by a combination of coke combustion with oxygen and gasification with steam.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie402527t

Water and Energy Issues in Gas-to-Liquid Processes: Assessment and Integration of Different Gas-Reforming Alternatives

CATEGORY: SYNGAS
ACS Sustainable Chem. Eng., Article ASAP, DOI: 10.1021/sc4002643, Publication Date (Web): October 24, 2013
Water and Energy Issues in Gas-to-Liquid Processes: Assessment and Integration of Different Gas-Reforming Alternatives
Abstract
Diana Yered Martínez †, Arturo Jiménez-Gutiérrez *†, Patrick Linke ‡, Kerron J. Gabriel §, Mohamed M. B. Noureldin §, and Mahmoud M. El-Halwagi §
arturo@iqcelaya.itc.mx
† Departamento de Ingeniería Química, Instituto Tecnológico de Celaya, Celaya, Gto 38010, Mexico
‡ Department of Chemical Engineering, Texas A&M University at Qatar, P.O. Box 23874, Doha, Qatar
§ Chemical Engineering Department, Texas A&M University, College Station, Texas 77843, United States
Department of Chemical and Materials Engineering, King Abdulaziz University, Jeddah, Saudi Arabia
Synopsis
Authors analyze the energy and water management effects for the development of syngas processes under the integration of three gas reforming alternatives. Recent exploitation of shale gas has led to increased interest in gas-to-liquid processes using Fischer–Tropsch chemistry.
The conventional approach is to focus on the reaction schemes, leaving major issues such as energy and water Sustainability issues such as energy and water usage require analysis of the impact of selected reforming technology. Authors discuss energy and water generation and management options for three primary alternatives for the production of syngas, including: steam reforming, partial oxidation, and autothermal reforming. They use a combination of thermodynamic models and computer-aided simulation to quantify those aspects.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/sc4002643

An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures

CATEGORY: HYDROGEN
Combustion and Flame, Volume 160, Issue 6, June 2013, Pages 995–1011
An experimental and detailed chemical kinetic modeling study of hydrogen and syngas mixture oxidation at elevated pressures
Alan Kéromnès (a), Wayne K. Metcalfe (a), Karl A. Heufer (a), Nicola Donohoe (a), Apurba K. Das (b),  (c), Chih-Jen Sung (c), Jürgen Herzler (d), Clemens Naumann (d), Peter Griebel (d), Olivier Mathieu (e), Michael C. Krejci (e), Eric L. Petersen (e), William J. Pitz (f), Henry J. Curran (a)
a Combustion Chemistry Centre, National University of Ireland, Galway, University Rd., Galway, Ireland
b Case Western Reserve University, Department of Mechanical & Aerospace Engineering, Cleveland, OH 44106, USA
c University of Connecticut, Department of Mechanical Engineering, Storrs, CT 06269, USA
d German Aerospace Center (DLR), Institute of Combustion Technology, Stuttgart, Germany
e Texas A & M University, Department of Mechanical Engineering, College Station, TX 77843, USA
f Lawrence Livermore National Laboratory, Livermore, CA 94551, USA
Abstract
Authors report examination and simulation of the oxidation of syngas mixtures using an updated chemical kinetic model. Ignition delay times for H₂/CO/O₂/N₂/Ar mixtures were measured using two rapid compression machines and shock tubes at pressures from 1 to 70 bar. Results show a strong dependence of ignition times on temperature and pressure at the end of the compression. Ignition delays decrease with increasing temperature, pressure, and equivalence ratio.
Researchers observed that the reactivity of the syngas mixtures was determined by hydrogen chemistry for CO concentrations lower than 50% in the fuel mixture. For higher CO concentrations, they noted an inhibiting effect of CO. They measured flame speeds in helium for syngas mixtures with a high CO content and at elevated pressures of 5 and 10 atm using the spherically expanding flame method. The reaction sequence H₂+HO₂↔H+H₂O₂ followed by H₂O₂(+M)↔OH+OH(+M) was found to play a key role in hydrogen ignition under high-pressure and intermediate-temperature conditions. The rate constant for H₂+HO₂ showed strong sensitivity to high-pressure ignition times and has considerable uncertainty, based on literature values. Authors conclude with a recommended  rate constant for the reaction based on available literature values and on their mechanism validation
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0010218013000023

Toward bifunctional catalysts for the direct conversion of syngas to gasoline range hydrocarbons: H-ZSM-5 coated Co versus H-ZSM-5 supported Co

CATEGORY: GASOLINE
Applied Catalysis A: General, Volume 456, 10 April 2013, Pages 11–22
Toward bifunctional catalysts for the direct conversion of syngas to gasoline range hydrocarbons: H-ZSM-5 coated Co versus H-ZSM-5 supported Co
Sina Sartipi, Johannes E. van Dijk, Jorge Gascon, Freek Kapteijn
Catalysis Engineering, Department of Chemical Engineering, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
Abstract
Researchers achieved one step production of gasoline range hydrocarbons from syngas using a combination of Fischer–Tropsch synthesis (FTS) and acid functionalities in a single bifunctional catalyst particle. They investigated two distinct catalyst configurations in which the acid functionality of H-ZSM-5 zeolite conjoins the cobalt FTS active phase: (i) H-ZSM-5 as catalytic coating on Co and (ii) H-ZSM-5 as catalytic support for Co.
They selected spherical shaped Co/SiO2 as a conventional FTS catalyst for comparison. It was used as precursor to synthesize the H-ZSM-5 coated Co catalyst. Various Silicalite-1 and H-ZSM-5 coated reference samples were prepared by subjecting Co/SiO2 to a direct hydrothermal procedure. Characterization and catalytic performance tests showed that direct hydrothermal synthesis results in transformation of SiO2 from the Co/SiO2 particles into an MFI coating of Co agglomerates. The silica support acts not only as precursor, but also as nano-mold during the preparation of the zeolite coated catalysts as the original Co/SiO2 particle shape is preserved. Co supported on mesoporous H-ZSM-5 is significantly more effective as a catalyst for the direct production of gasoline range hydrocarbons than the H-ZSM-5 coated Co catalyst.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0926860X13000914

Preliminary Studies of CO2 Removal from Precombustion Syngas through Pressure Swing Membrane Absorption Process with Ionic Liquid as Absorbent

CATEGORY: CARBON CAPTURE
Preliminary Studies of CO2 Removal from Precombustion Syngas through Pressure Swing Membrane Absorption Process with Ionic Liquid as Absorbent
Xingming Jie , John Chau , Gordana Obuskovic , and Kamalesh K. Sirkar *
sirkar@njit.edu
Otto H. York Department of Chemical, Biological and Pharmaceutical Engineering, Center for Membrane Technologies, New Jersey Institute of Technology, Newark, New Jersey 07102, United States
Ind. Eng. Chem. Res., 2013, 52 (26), pp 8783–8799, DOI: 10.1021/ie302122s
Abstract
Researchers employed 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]) as the absorbent and either hydrophobized porous ceramic tubule or hydrophobized polyether ether ketone (PEEK)-based porous hollow fiber membranes to conduct a preliminary investigation of CO₂ removal from simulated precombustion syngas by a pressure swing membrane absorption process.
He was used as a surrogate for H₂. Researchers constructed an innovative 5-valve system to improve product quality. They determined the optimal duration for the key absorption step and studied the influence of helium-rich product withdrawal time. Increases in temperature degrade product quality. The addition of polyamidoamine dendrimer of generation 0 to [bmim][DCA] mitigates the temperature effect. Increases in feed pressure degrade helium product quality.  At the same time, it is beneficial for CO₂ product quality, because more CO₂ is absorbed at higher feed pressure. Using a simulated two-stage large PEEK module system, with a 14.0% CO₂ balance helium gas mixture, helium product with CO₂ concentration as low as 4.2–5.8% could be achieved at different temperatures. Researchers conclude with an explanation as to why a PEEK membrane module shows much better performance than the ceramic tubule.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ie302122s

Production of synthetic natural gas by means of a catalytic nickel membrane

CATEGORY: SYNGAS
Fuel, Volume 94, April 2012, Pages 64–69
Production of synthetic natural gas by means of a catalytic nickel membrane
Shin-Kun Ryi, Sung-Wook Lee, Kyung-Ran Hwang, Jong-Soo Park
Energy Materials Center, Korea Institute of Energy Research (KIER), 102 Gajeong-ro, Yuseong-gu, Daejeon 305-343, South Korea
Abstract
Authors describe a novel method of methanation using a catalytic nickel membrane for synthetic natural gas (SNG) production. The methanation reaction is exothermic, so heat that is generated is removed from the reactor to prevent the methane yield from being reduced and to minimize deactivation of the catalyst due to thermal stress at hot spots.
Because the catalytic nickel membrane was fabricated by uniaxial-pressing and thermal treatment of nickel powder, it could readily remove heat from the reactor. Methanation tests conducted at various temperatures, residence times and pressures revealed that the CO and H2 conversions increased with increasing temperature and pressure and reached a maximum value of 99 and 80% at a temperature, residence time and pressure of 350 °C, 94 ms and 280 kPa, respectively. Using the methanation test results, a new reactor could be designed for high exothermic reactions.
Full Text Source (Subscription or Fee): http://www.sciencedirect.com/science/article/pii/S0016236111007551

Application of a new dataset selection procedure for the prediction of the Syngas composition of a gasification plant

CATEGORY: SYNGAS
Preprints of the 8th IFAC Symposium on Advanced Control of Chemical Processes, The International Federation of Automatic Control, Furama Riverfront, Singapore, July 10-13, 2012
Application of a new dataset selection procedure for the prediction of the Syngas composition of a gasification plant
S. M. Zanoli*, G. Astolfi* and L. Barboni **
s.zanoli@univpm.it
g.astolfi@univpm.it
l.barboni@gruppoapi.com
*D.I.I., Università Politecnica delle Marche, Ancona, Italy
** affidabilità automazioni- I&C,api raffineria di Ancona, Italy
Abstract:
Describes a model identification of a gasification process for the estimation of the Syngas composition, as well as a proposed new procedure for the selection of the identification dataset. Estimations are needed to integrate the gascromathographic measurements of the Syngas composition.  These are often not available because of periodic calibrations. The work described here is part of a broader project for the development of a supervisory controller for process optimization and for fault detection and isolation scope.
Improvements in the identification process from standard procedures were obtained by means of a suitable selection of the input data set. The proposed input data selection procedure is based on the application of the Fuzzy C-means (FCM) algorithm for the generation of the main clusters. Results on a gasification process of a refinery plant show the effectiveness of the proposed FCM method in filtering a large dataset and the reliability of the model in the prediction of the Syngas composition.
Free Full Text Source: http://scholar.google.com/scholar?start=130&q=automation+refinery&hl=en&as_sdt=0,11&as_ylo=2012

Syngas Chemical Looping Process: Design and Construction of a 25 kWth Subpilot Unit

Energy Fuels, Article ASAP, Publication Date (Web): March 15, 2012
Syngas Chemical Looping Process: Design and Construction of a 25 kWth Subpilot Unit
Deepak Sridhar, Andrew Tong, Hyung Kim, Liang Zeng, Fanxing Li, and Liang-Shih Fan*
fan.1@osu.edu
William. G. Lowrie Department of Chemical and Biomolecular Engineering 140 W 19th Avenue, 125 A Koffolt Laboratories, The Ohio State University, Columbus, Ohio 43210
Abstract
The syngas chemical looping (SCL) process employing the gas–solid counter-current flow pattern demonstrates an innovative approach to generate hydrogen and/or electricity from syngas accompanied with in situ carbon capture.
Iron-based oxygen carriers donate oxygen for complete syngas conversion in the reducer. The reduced oxygen carriers are then oxidized by steam and/or air to generate hydrogen and/or heat in the oxidizer and/or the combustor, respectively. Researchers designed a 25 kW_th subpilot SCL unit based on the simulated criteria and constructed to demonstrate the feasibility of generating high purity hydrogen with in situ carbon capture. Two test runs were presented using 4.5 mm × 2.5–4.5 mm cylindrical oxygen carriers comprising of 60 wt % iron oxide (Fe₂O₃). Initial test results support the concept of continuous hydrogen generation with in situ carbon capture using the SCL process and also highlight the advantage of adopting the counter-current moving bed reactor design.
Full Text Source (Subscription or Fee): http://pubs.acs.org/doi/abs/10.1021/ef202039y

The Production of Synthesis Gas by a Combination of Steam and Dry Reforming Using GHR

Petroleum Science and Technology, Volume 30, Issue 6, 2012, pages 594-604
The Production of Synthesis Gas by a Combination of Steam and Dry Reforming Using GHR
A. Shamkhali^a, M. R. Omidkhah^a, J. Towfighi^a & M. R. Jafari Nasr^b
Abstract
Each process for synthesis gas production has advantages and disadvantages. Authors describe a process for producing synthesis gas based on a gas-heated reformer (GHR). By burning part of the input natural gas in a pressurized furnace and conducting the produced hot gases to the GHR shell, the heat of reactions taking place in the GHR tubes can be supplied.
The remaining portion of natural gas is converted to synthesis gas in the GHR tubes. Exit carbon dioxide from the furnace can be separated and left to react in the reformer as a feed. The process features include compactness, low environmental pollution, flexibility in H₂/CO ratio of product gases, and no need for O₂.
Full Text Source (Subscription or Fee): http://www.tandfonline.com/doi/abs/10.1080/10916466.2010.489094