Bioenergy systems for the future 7 catalysts for conversion of synthesis gas

Bioenergy systems for the future 7 catalysts for conversion of synthesis gas Bioenergy systems for the future 7 catalysts for conversion of synthesis gas Bioenergy systems for the future 7 catalysts for conversion of synthesis gas Bioenergy systems for the future 7 catalysts for conversion of synthesis gas Bioenergy systems for the future 7 catalysts for conversion of synthesis gas Bioenergy systems for the future 7 catalysts for conversion of synthesis gas

Catalysts for conversion of synthesis gas V Palma, C Ruocco, M Martino, E Meloni, A Ricca University of Salerno, Salerno, Italy Nomenclature BTL CTL CNT CSTR DME DMT FT FTS GHSV GTL GNS HTFTS HTS LTFTS LTS MMA MMT MTBE MTO MTP NCNT NP NW-FS O/P OCNT PEMFC PROX PSA RWGS biomass to liquid coal to liquid carbon nanotubes continuous stirred tank reactor dimethyl ether dimethyl terephthalate Fischer-Tropsch Fischer-Tropsch synthesis gas hourly space velocity gas to liquid graphene nanosheets high-temperature Fischer-Tropsch synthesis high-temperature shift (or high-temperature water-gas shift) low-temperature Fischer-Tropsch synthesis low-temperature shift (or low-temperature water-gas shift) methyl methacrylate million metric tons methyl tert-butyl ether methanol to olefin methanol to paraffin nitrogen-functionalized carbon nanotube narrow pore nanowires olefins/paraffins oxygen-functionalized carbon nanotube proton exchange membrane fuel cell preferential oxidation pressure swing adsorption reverse water-gas shift Bioenergy Systems for the Future http://dx.doi.org/10.1016/B978-0-08-101031-0.00007-7 © 2017 Elsevier Ltd All rights reserved 218 Bioenergy Systems for the Future SSA STP WGS WP 7.1 specific surface area standard temperature and pressure water-gas shift wide pore Introduction The synthesis gas (or simply syngas) is the reaction product of several transformation processes (Fig 7.1) such as reforming processes (Ghoneim et al., 2015), partial oxidation (Christian Enger et al., 2008) and gasification (Mahinpey and Gomez, 2016); the chemical composition of syngas depends on the raw materials and the production process used (Couto et al., 2013), however the main components are carbon oxides (CO and CO2) and hydrogen (H2) Syngas is recognized as the most suitable raw material for manufacturing a wide range of chemicals and fuels and is therefore involved in several catalytic processes (Fig 7.1) The wide use of the syngas, in recent decades, has been favored by the low cost of fossil sources; however, the increasingly severe restrictions on CO2 emissions, the growing worry of public opinion on climate changes, and the spread of alarming data on the reserves of crude oil have pushed the interest toward the use of alternative sources The best alternative to the fossil fuels are the biomass, renewable materials that contain considerable quantities of carbon, hydrogen, and oxygen, restorable by photosynthetic reaction (Maschio et al., 1994) Certainly, there are many disadvantages in using biomass with respect the fossil fuel, the presence of contaminants, a variable hydrogen to carbon ratio due to the composition of the sources, a low energy density and high costs make them uncompetitive; however, nowadays, there are no other real alternatives Theoretically, all biological materials (both animal and vegetable) represent a biomass; however, only cheap materials and wastes are conveniently converted into syngas, and wastes from wood processing, energy crops, agricultural residues, by-products from processing of biological materials, municipal and sludge wastes, and food industry wastes are normally used as raw materials for the syngas Methanol synthesis Raw materials (natural gas, coal, biomass) Ammonia synthesis, other processes Syngas Fisher Tropsch process (synthetic fuels) Fig 7.1 Syngas—production and transformation Catalysts for conversion of synthesis gas 219 production There exist two processes for converting the biomass in biofuel and biopower, the fermentation that produces mainly ethanol (biogas) and the thermochemical conversion to syngas The variability of the sources requires a flexibility in processing steps; however, the most of biomass contain a significant amount of water, so a preliminary drying process is commonly performed before going to the conversion processes; alternatively, a hydrothermal processing directly degrades the biomass (Tekin et al., 2014); similarly, the product gas stream, from thermochemical process (pyrolysis, combustion, and gasification), contains many unwanted by-products to be removed before going to next process (Kumar et al., 2009): l l l l l Particulate, removed according to the size by cyclone separators, wet scrubbers, electrostatic precipitators, and barrier filters Alkali compounds, removed by barrier filters (Turn et al., 2001) Nitrogen compounds, removed at high temperature with dolomites, Ni-based catalysts and Fe-based catalysts (Lepp€alahti and Koljonen, 1995) Sulfur compounds, removed by limestone, dolomite or calcium oxide Tar compounds, removed directly in the gasifier with the use of specific catalysts (Han and Kim, 2008) or alternatively in a separate reactor The fate of the syngas depends on the process in which it is involved and the desired final product (Fig 7.1); this chapter wants to provide a general overview on the primary catalytic systems involved in the most widespread conversion processes of the syngas, focusing on the results of the latest research The main process is the methanol synthesis that produces one of the most flexible chemical commodities and energy sources (Ajay et al., 2014) Methanol is used as feedstock in synthesis of formaldehyde and acetic acid; additives in adhesive, foams, plywood subfloors, and windshield washer; methyl tert-butyl ether (MTBE), a gasoline component; and dimethyl ether (DME), a clean-burning fuel Methanol is also used as additive into gasoline or as vehicle fuel itself The Fischer-Tropsch process (FT) converts the syngas into a mixture of products refined to synthetic fuels, lubricants, and petrochemicals (de Klerk, 2000); depending from the sources, the overall process, from the raw material to the final product, is named GTL (gas to liquid), CTL (coal to liquid), or BTL (biomass to liquid) (van de Loosdrecht and Niemantsverdriet, 2013) The Haber-Bosch process (Haber, 2002) allows to obtain ammonia by reacting nitrogen with pure hydrogen, usually obtained from syngas by removal of carbon monoxide with the water-gas shift reaction (Palma et al., 2016) eventually coupled with methanation (R€ onsch et al., 2016), preferential oxidation or by a hydrogen permselective membrane reactor (Piemonte et al., 2010), and CO2 sequestration Ammonia is an important commodity for the fertilizers industry, is the precursor of urea and ammonium salts (nitrates and phosphates), of the nitric acid and polyamides The carbonylation processes allow to introduce the carbonyl group (CO) into organic or inorganic substrate, by reacting with pure carbon monoxide, obtained from syngas by reverse water-gas shift reaction (De Falco et al., 2013) Interesting examples of carbonylation are the Monsanto process (Paulik and Roth, 1968), that allows to prepare the acetic acid by carbonylation of methanol and, the Mond process for the extraction and purification of Nickel (Mond et al., 1890) 220 7.2 Bioenergy Systems for the Future Fischer-Tropsch synthesis The Fischer-Tropsch synthesis (FTS) is an important catalytic process used for the conversion of syngas (derived from coal, natural gas, biomass, or other carboncontaining species) to hydrocarbons with different chain lengths The product selectivity is strongly dependent on temperature, pressure, and catalyst choice (Ghareghashi et al., 2013) Generally, low-temperature FTS is carried out over Co-based catalyst in the temperature interval of 190–250°C and at 20–40 bar yielding products with high average molecular weight (middle distillates and waxes) Conversely, iron-catalyzed process are driven at 340°C and 20 bar, with the aim of obtaining short-chain hydrocarbons (fuels and petrochemicals) (Delparish and Avci, 2016; Shin et al., 2013) In order to face the reaction exothermicity and avoid hot spots or rapid catalyst deactivation, multitubular fixed bed, with external cooling (for LTFTS), and slurry bubble column reactors (for HTFTS) are commercially selected for the FTS process (Park et al., 2011) In the first case, considerable fraction of the liquid reaction products has to be recycled to the reactor to remove the reaction enthalpy, thus increasing pressure drops and making the reactor trickier to be operated and less flexible to be scaled On the other hand, in slurry reactors, the temperature is uniform and pressure drops are low, being related to the hydrostatic pressure of liquid, and the internal mass transfer limitations are ruled out by loading the catalyst as fine powder However, high aspect ratios (reactor height/diameter) and staging have to be used to limit back-mixing phenomena Also, particular attention has to be paid, especially during the size-scaling processes, both to the prevention of the catalyst attrition and to the design of an efficient tool for the separation of the catalyst from the liquid (Visconti et al., 2011) In addition, during FT synthesis, even though the reactants are in the gas phase, the pores of the catalyst are filled with liquid products, and the diffusion rates in the liquid phase are typically three orders of magnitude slower than in the gas phase; the increasing transport limitations may result in CO depletion and lower C5 + selectivity In a fixed-bed reactor, the selectivity problem can be solved by using catalyst pellets where the catalytic material is deposited in a thin outer layer (eggshell catalysts), while in a slurry reactor, the selectivity issue is faced by using small catalyst particles (Liu et al., 2009) However, in the attempt of overcoming the drawbacks of commercially available technologies for FT synthesis, different technologies including the adoption of structured fixed-bed reactors, based on honeycomb monolith foams, knitted wires, or cross flow structures, and microchannel reactors have been recently proposed (Pangarkar et al., 2009; Twigg and Richardson, 2002; Cao et al., 2009) For example, monolithic catalysts assure low pressure drop, high gas-liquid mass transfer rates in two-phase flow, the possibility of using high liquid and gas throughputs, and a good temperature control (Kapteijn et al., 2005; Hilmen et al., 2001) For intensification of mass transfer between synthesis gas, liquid products and solid catalysts, alternative catalyst geometries like honeycombs, structured packings, and foams have also been developed (Guettel et al., 2008a) All group VII metals have noticeable activity for the hydrogenation of carbon monoxide to hydrocarbons However, only ruthenium, iron, cobalt, and nickel have Catalysts for conversion of synthesis gas 221 catalytic characteristics that allow considering them for commercial production However, nickel catalysts, under practical conditions, produce too much methane; moreover, ruthenium is too expensive, and its worldwide reserves are insufficient (Khodakov et al., 2007) Cobalt and iron were proposed as the first catalyst by Fischer and Tropsch Fe-based catalysts, despite being less expensive than Co ones ( Jin and Datye, 2000; van Berge et al., 2000), strongly suffer for deactivation by coke and promote H2O formation by water-gas shift reaction (WGS) Sulfur content lower than 0.2 and 0.1 ppm are mandatory for normal operation of Fe- and Co-based catalysts, respectively (Khodakov et al., 2007) Co catalysts are generally more resistant to attrition and are widely preferred for use in slurry-type reactors Despite the industrialscale development of FTS process, the activity and stability of the catalyst need to be improved At that hand, the addition of suitable promoters and the selection of proper supports provide a reasonable route for the enhancement of FTS catalyst performances In the following sections, the performances of Co- and Fe-based catalysts were reviewed and discussed 7.2.1 Co-based catalysts Al2O3, despite having lower surface area than SiO2 and TiO2, is commonly used as support material for Co due to the strong metal-oxide interactions, its good mechanical performances, and resistance to attrition (de la Osa et al., 2011; Prieto et al., 2009) On the other hand, when Al2O3 is selected as support, it is mandatory to avoid the formation of hardly reducible cobalt aluminates that are responsible for activity reduction ( Jongsomjit et al., 2001) Iglesia et al (Iglesia, 1997) found that for large cobalt particles supported on Al2O3, SiO2, and TiO2, the FT reaction rate depends on the number of available cobalt surface atoms and that hydrocarbon selectivity is only slightly affected by cobalt dispersion A different phenomenon is observed for small cobalt particles, having a strong impact on product selectivity: Particle size in the range ˚ improves olefinic products yields, while for smaller dimensions, C5 + selec60–80 A tivity also decreased (Khodakov, 2009) The synthesis of Co-based catalysts supported on alumina nanofibers was shown to assure a homogenous metal particle-size distribution After catalyst ultrasonication, more active cobalt particles were generated, which marked improved C5 + selectivity lowering methane production In addition, even at high reaction temperature and under much higher CO conversion (79%), a quite stable activity was observed at 230°C, 20 bar, and H2/CO ¼ over 300 h of reaction (Liu et al., 2016) Flame spray pyrolysis technique was also successfully employed for controlling catalytically active Co particles deposition on Al2O3: a good catalytic activity was recorded at the above operative conditions (Minnermann et al., 2013) Conversely, for Co/γ-Al2O3 catalysts, it was shown that partial pores prefilling by incipient wetness impregnation of Al(NO3)3 resulted in catalyst similar to the eggshell systems ( Jacobs et al., 2016), which are able to decrease C1–C4 light gas selectivity, improving, at the same time, C5 + selectivity Due to the need of limiting pressure drop and the consequent necessity of adopting “big” catalyst pellets, low-temperature Fischer-Tropsch synthesis in industrial fixedbed reactors may suffer of strong intraparticle mass transport limitations, which are 222 Bioenergy Systems for the Future known to result in decreased CO conversion rate and C5 + selectivity Upon decoupling the pellet diameter and the diffusive length, eggshell catalysts represent an engineering solution for the intensification of the Fischer-Tropsch reactors In this regard, Fratalocchi et al (Fratalocchi et al., 2015) showed that 600 μm pellets, with catalytically active layers, 75 μm thick, grant a remarkable combination of high CO conversion rate and high C5 + selectivity at 220–240°C, 25 bar, and H2/CO ratio of 1.73, thus resulting extremely interesting for operations in reactors 3–6 m long Concerning the impact of cobalt aluminate formation on catalyst activity, Moodley et al (Moodley et al., 2011) found an enhancement of aluminate content with water partial pressure during FTS at 230°C, 10 bar, and H2/CO ¼ 1.5 The presence of water is also regarded as one of the main causes of catalyst sintering during Fischer-Tropsch process (Bezemer et al., 2010) Sintering mechanism for Co/Al2O3 catalysts in slurry reactors was accelerated by the formation of intermediate surface cobalt-oxide species, and the deactivation was favored by increasing H2/CO ratios in syngas or by the presence of even small amounts of water (Sadeqzadeh et al., 2013) Beside sintering and aluminates formation, the activity drop commonly observed over FTS catalyst is related to the deposition of carbonaceous species on catalyst surface The research of Pena et al (Pen˜a et al., 2014) was focused on the identification of the molecular structure of carbon species formed over a Co/Al2O3 catalyst in a slurry reactor Carbon adsorbed on spent catalyst was mainly constituted by α-olefins, n-paraffins, branched alkanes/alkanes, aldehydes, and ketones, while carboxylic acids were mostly detected at high water partial pressures In particular, the increase in CO conversion enhanced the isomerization of α-olefins favoring the formation of branched alkanes/alkanes Carbon species are probably nucleated on the cobalt particles and then migrate to alumina support and coke localized on the support showed high reluctance toward hydrogenation The addition of promoters to Co/Al2O3 catalysts was shown on one hand, to prevent Co-aluminate formation due to establishment of an intimate contact with the metal (Nabaho et al., 2016a) and, on the other hand, to limit catalyst deactivation Park et al (Park et al., 2012) investigated the impact of phosphorous addition to Co/Al2O3 catalyst on deactivation induced by lumps formation in the presence of water γ-Al2O3, due to its hydrophilic properties, can undergo phase transformation to pseudoboehmite (with low attrition resistance) in the presence of water vapor produced during FT reaction, forming fragmented fine catalyst powder The deposition of heavy hydrocarbons on these fragments causes the formation of aggregate catalyst lumps Conversely, phosphorous addition is able to suppress alumina hydrophilic properties and reduce heavy hydrocarbon deposition on catalyst, thus preventing its deactivation (Fig 7.2) It was also reported (Tan et al., 2011) that the deposition of small boron quantities on Co/γ-Al2O3 catalyst can hinder the deposition, nucleation, and growth of resilient coke on catalyst surface, without affecting initial activity and selectivity at 240°C and 20 bar The addition of noble metal promoters (Pd, Pt, Re, and Ru) was shown to improve activity and stability of Co/Al2O3 catalysts (Ma et al., 2012) Improved CO conversion was observed at 220°C, 22 bar, and H2/CO ¼ over the promoted catalysts, with Pt and Pd enhancing oxygenate formation and Re and Ru slightly decreasing it At fixed Catalysts for conversion of synthesis gas 223 Phosphorous—unmodified catalyst Large phase transform γ-Al2O3 in boehmite Partial hydration responsible of fine powder Emulsion of water and hydrocarbons Catalyst particles Aggregated catalyst lump (co-presence of water and hydrocarbons) Liquid medium Phosphorous—modified catalyst Small phase transform γ-Al2O3 in boehmite Emulsion of water and hydrocarbons Catalyst particles Liquid medium No formation of aggregated catalysts Fig 7.2 Proposed mechanism for Co/Al2O3 catalyst deactivation in a slurry-phase reactor CO conversion (50%), Re and Ru improved CH4 and C5 + selectivity, whereas the opposite effect was observed for Pt and Pd promoters The latter metals also increased 2-C4 olefins selectivity and WGS activity of the final catalyst On the other hand, Pt addition had a negligible effect on C4 olefin isomerization Concerning Co catalysts supported on Al2O3 or SiO2 prepared via plasma technology (Chu et al., 2015), the promotion by noble metals was shown to improve both cobalt dispersion and reducibility, thus enhancing the FT reaction activity Other porous supports (including SiO2, TiO2, activated carbon, and zeolite) are usually selected for commercial Co-based catalysts (Lu et al., 2015; Shi et al., 2012; Eschemann et al., 2015) However, the combination of two types of oxides was found to improve the pore structure, cobalt dispersion, and reducibility The effect of alumina incorporation (0–3 wt%) into a Co/SiO2 catalysts on product gas distribution was investigated by Savost’yanov et al (2017) Trace of alcohols and olefins were only detected over the undoped catalyst and their content increase with alumina loading (Table 7.1) Over the wt% sample, the molecular weight distribution became narrower, increasing the C8–C25 fraction A further reduction of SiO2/Al2O3 ratio caused the opposite effect Combustion synthesis method was employed for the preparation of Co/SiO2 and Co/SiO2-Al2O3 catalysts, and a strong impact of preparation method on product gas distribution was observed (Ail and Dasappa, 2016): the innovative catalyst increased the yield to C6 + products at 230°C, 30 bar, and H2/CO ¼ 2.3, resulting in the formation of long-chain hydrocarbons waxes (C24+) with respect to the middle distillates (C10–C20), normally generated over impregnated catalysts However, the overall C6 + yield was further increased by Al2O3 addition, due to the marked improvement (48%) in cobalt dispersion promoted by alumina Venezia et al (Venezia et al., 2012) modified SiO2 support by TiO2 grafting and observed an improvement in C5 + selectivity especially at high space velocities 224 Bioenergy Systems for the Future C5+ product distribution in the FTS over Co/SiO2-Al2O3 catalysts at 210°C, 20 bar, and H2/CO ratio of (Savost’yanov et al., 2017) Table 7.1 Product distribution (wt%) Paraffins Olefins Alcohols Al2O3 content (wt%) C5–C18 C19–C35 C35+ C5–C18 C5–C18 49.6 54.9 48.1 47.6 42.1 37.5 2.4 2.3 2.2 0.4 0.7 10.1 0.04 0.07 1.2 (GHSV ¼ 7200 hÀ1 at 210°C, 20 bar, and H2/CO ¼ 2) In addition, CoO oxide interaction with the doped support was enhanced, avoiding the particle mobility that can lead to catalyst deactivation by sintering A bimodal ZrO2-SiO2 support was selected for jet fuel direct synthesis via FTS reaction with different 1-olefins as additives (Li et al., 2016a) Olefins cofeeding effectively shifted the product distribution toward jet fuel range, markedly suppressing CH4, CO2, and light hydrocarbons (C2–C4) formation The large pores of the bimodal support, in fact, provided efficient pathways for reactants conversion and products diffusion, while the newly formed small pores assured high metal dispersion Rare-earth oxides, able to remarkably enhance catalyst reducibility, were shown to be beneficial for improving long-chain hydrocarbons selectivity (Spadaro et al., 2005) CeO2 addition (5 and 10 wt%) to Co/ZrO2 catalysts promoted the formation of larger cobalt particles, inhibiting water reoxidation and Co particles aggregation during the reaction and resulting in a better resistance toward deactivation (Zhang et al., 2016a) Fig 7.3 displays CO conversion with time onstream for doped and undoped catalysts: CeO2-modified samples assured a good stability during 100 h of reaction However, the deactivation rate was affected by the amount of ceria added However, a rapid deactivation was observed in the initial stage of the reaction over the 10 wt% catalysts, caused by the initial smaller pores that were filled by the liquid waxes produced during the FTS synthesis Carbon materials, including activated carbon, carbon nanotubes and nanofibers, carbon spheres, and mesoporous carbon, are also reported as catalytic support for Co, due to their several benefits with respect to the conventional oxides supports: these materials display high purity, high mechanical strength and thermal stability, and large surface area (Fu and Li, 2015) Moreover, having a hardly reducible surface, Co particle reducibility can be improved Carbon porous structure can also be properly controlled in order to promote the cobalt dispersion (Ha et al., 2013) Dı´az et al (2013) carried out FT reaction over Co catalysts supported on carbon nanofibers prepared at three different calcination temperatures (750°C, 600°C, and 450°C, denoted as Samples 1, 2, and 3, respectively) At 250°C, 20 bar, and H2/CO ratio of 2, the Samples and 2, having a medium pore radius, displayed high catalytic activity without Catalysts for conversion of synthesis gas 225 Fig 7.3 CO conversion with time onstream over Co/ZrO2 (dotted line), Co/(5)CeO2-ZrO2 (dash-dotted line), and Co/(10) CeO2-ZrO2 (dashed line); 220°C, 20 bar, and H2/CO ¼ CO conversion (%) 100 80 60 40 20 0 10 20 30 40 50 60 70 Time-on-stream (h) 80 90 100 deactivation; however, the promotion of WGS and methanation reaction led to significant CO2 and CH4 production The Sample 3, which was less active and suffered from deactivation, showed an improvement in C5 + selectivity Metal sintering was observed over all the catalysts and, especially, over the Sample 3, due to its lower structural order with respect to the other two catalysts The performances of Co-based catalysts supported on carbon nanotubes (CNT) and graphene nanosheets (GNS) for FT reaction at 220°C, 18 atm, and H2/CO ¼ were compared in order to evaluate the effect of morphology and structure on catalyst stability (Karimi et al., 2015) The difference, in terms of SSA (Table 7.2), between the bare GNS and CNT can be attributed to the nature and textural properties of graphene nanosheets Higher porosity was also observed over the GNS samples, which can be related to the interlayer spacing of them After 480 h of reaction, a specific area reduction of 20% and 3%, respectively, for the CNT and GNS catalysts, was observed Moreover, the extent of pore blockage for the CNT catalyst is higher than that of the GNS sample, as a consequence of its higher rates of sintering and clusters growth During stability tests, dCo Specific surface areas (SSA), porous volume (Vp), and cobalt average crystallite sizes (dCO) for Co/CNT and Co/GNS catalysts (Karimi et al., 2015) Table 7.2 Sample SSA (m2/g) Vp (cm3/g) dCo (nm) CNT Fresh Co/CNT Used Co/CNT GNS Fresh Co/GNS Used Co/GNS 497 372 298 848 602 586 1.034 0.765 0.428 2.2 1.46 1.23 — 8.6 10.08 — 7.8 8.8 226 Bioenergy Systems for the Future increased for both the catalysts; however, a more significant crystal growth was recorded over the Co/CNT catalyst The latter sample displayed a drop of activity of 15.8% in the first 120 h of reaction, while in the remaining period, it only drops of 4.9% Conversely, due to the lower extent of sintering phenomena and GNS hydrophilic properties that limit water deposition and cobalt reoxidation, only a conversion reduction of about 2.7% in the first period and 1.2% between 120 and 480 h was observed over the Co/CNT catalyst The relationship between C5 + selectivity and metal particle sizes for Co catalysts supported on carbon nanotubes and spheres was also studied (Xiong et al., 2011) In order to limit water effect, measurements were carried out at a low CO conversion (4%) The change in C5 + selectivity with particle sizes (Fig 7.4) can be explained considering that large Co particles promote the formation of bridge-type adsorbed CO, more active and more easily dissociated, which enhanced the chain growth and C5 + selectivity Co supported over spheres, however, displayed slightly higher C5 + selectivity for a similar sized particle In fact, over nonporous carbon spheres, all cobalt particles are dispersed on the outer surface of the support Therefore, the hydrogen concentration around the active cobalt particles is the same as that in the reactor, thus leading to less light hydrocarbon production Chernyak et al (2016) investigated the effect of oxidation time (1–15 h) selected during Co supported over carbon nanotubes preparation on their performances for FT synthesis at 190°C, atmospheric pressure, and H2/CO ¼ The sample oxidized for h displayed the highest CO conversion and yield to C5+ products Selectivity to heavy hydrocarbons is almost the same over the catalyst treated for 3, 9, and 15 h while increased over the sample oxidized for h Syngas mixture, especially when produced from coal or biomass, can be CO2rich, and carbon dioxide can significantly affect FT activity Dı´az et al (2014) studied the effect of CO2 cofeeding on the catalytic performances of a Co catalyst supported over carbon nanofibers at 220–250°C, 20 bar, and H2/CO ¼ Increasing temperatures assure higher catalytic activity and the rate of undesired reactions (WGS and methanation) However, once reaction temperature was fixed at 250°C, 100 99 C5+ selectivity (%) Fig 7.4 Influence on Co particle size on C5 + selectivity over Co/ carbon nanotubes (square) and spheres (triangle); 225°C, bar, and CO/H2 ratio of 0.5 98 97 96 95 94 93 92 10 15 20 25 30 35 40 Cobalt particle size (nm) 45 50 Catalysts for conversion of synthesis gas 263 nonnoble-based catalysts used for WGS application, Cu/ZnO/Al2O3 is still considered the best formulation The two-stage process configuration is extremely profitable, because it allows to reach the 99.5% and over of CO conversion; however, it has major drawbacks that result in excessive operative and plants costs; the realization of a single-stage process would therefore be a notable process intensification In this context, the development of highly active catalysts in a temperature range intermediate with respect the conventional two stages is highly wanted The best candidate for these purposes are the noble metal-based catalysts (Grenoble et al., 1981), that show high conversion in a wide range of temperature, even in low concentration, and are compatible with fuel processor systems Gold catalysts (Yang et al., 2013) are really highly active but suffer of rapid deactivation, due to the sintering phenomena, and the preparative methods are extremely complex Similar consideration makes the use of rhodium (Cornaglia et al., 2012) not adequate for WGS applications; much more stable are the platinum-based catalysts (Palma et al., 2014), supported ceria, or ceria-/zirconiamixed oxide (Palma et al., 2015) Despite the excellent performance of the noble-metal-based catalysts, none of the described formulations is able to support a real single-stage process; recently, the development of highly thermal conductive structured catalysts, coupled with highly active catalytic systems, seems to be the best alternative to realize a single-stage WGS process (van Dijk et al., 2010) The use of highly thermal conductive carriers allows to flatten the thermal profile by back diffusion over the bed (Fig 7.15), increasing the temperature at the inlet and decreasing the temperature at the outlet, with a consequent increase of the CO conversion (Palma et al., 2016) 100% 95% Co conversion 90% 85% 80% 75% ΔT-HTS ΔT-LTS ΔT-single stage Equilibrium 70% T [K] Fig 7.15 Schematic representation of two-stage and single-stage WGS processes 264 Bioenergy Systems for the Future The total CO conversion in WGS process is, to the best, the 99.8%; unfortunately, for the most applications, the maximum CO content permitted in hydrogen is in the order of few parts per million (ppm), for example, in polymer electrolyte membrane fuel cell (PEMFC) applications (Garcia et al., 2008), so the purity obtained with the WGS process is totally unsatisfactory; a further purification step is required 7.5.2 Preferential oxidation (PROX) Preferential oxidation is one of the catalytic processes that allow to remove small amounts of CO to reach parts per million (ppm) levels form hydrogen-rich streams (Liu et al., 2012b), by selective oxidation of carbon monoxide It is normally performed in temperature range intermediate between the LTS and the maximum operative temperature of the PEM-FC (80–180°C): CO + 1=2O2 ! CO2 Δo298K ¼ À283 kJ=mol (7.13) Hydrogen combustion may also occur as side reaction, so a highly selective catalyst is therefore required The first selective PROX catalysts were patented in the 1960s and were based on rhodium or ruthenium supported on alumina (Cohn Johann, 1965), however, all the platinum group metals are active A comparative study between the noble metals (Pt, Pd, Rh, and Ru) and base metals (Co/Cu, Ni/Co/Fe, Ag, Cr, Fe, and Mn) has identified both Ru/Al2O3 and Rh/Al2O3 as the most active catalysts in selective CO oxidation, with hydrogen-rich fuel cell feedstreams, providing almost complete conversion from 100°C up (Oh and Sinkevitch, 1993) Interesting results were obtained with bimetallic systems, the Pt-Ru/mordenite catalysts showed superior performance with respect the corresponding monometallic counterparts at 150°C (Hiroshi et al., 2000); however, at higher temperature and with silica as support, the ruthenium derivate provided the best activity (Chin et al., 2006) A promotion effect was obtained also with iron; the Pt-Fe/mordenite system showed an extremely superior performance with respect to the Pt/mordenite catalyst, at various experimental conditions (Watanabe et al., 2003) 7.5.3 Methanation The alternative to PROX, in reducing to ppm the CO content in hydrogen, is the methanation; this reaction consumes three moles of hydrogen for each mole of carbon monoxide, so it is effectively usable only when the carbon monoxide to be removed is really exiguous: CO + 3H2 >CH4 + H2 O Δo298K ¼ + 206 kJ=mol (7.14) Comparative studies between various metals (Fe, Co, Ni, Pd, Pt, and Ru) and various supports (ZrO2, TiO2, SiO2, Al2O3, and MgO) have showed that the Ni/ZrO2 and Ru/TiO2 are effective catalysts for the complete removal of carbon monoxide in hydrogen-rich gas stream, in the presence of 25 vol% of CO2 (Takenaka et al., 2004), identifying the nickel as the most cost effective choice Catalysts for conversion of synthesis gas 7.5.4 265 Reverse water gas shift (rWGS) The reverse water-gas shift reaction is the inverse reaction of WGS, it produces carbon monoxide and water by reacting carbon dioxide and hydrogen, while the equilibrium conversion increases with temperature (Daza and Kuhn, 2016) The RWGS is used to regulate the H2/CO ratio in the syngas, to produce pure carbon monoxide and is involved in the methanol synthesis To obtain a good conversion, the operative temperatures are high, however, to shift the equilibrium toward the products, it is possible to recycle the CO2 excess, increase the concentration of the reactant, or remove the vapor by desiccant bed or by permselective membrane to water (Centi and Perathoner, 2009) Except for the Fe-Cr-based catalysts that are active above 400°C, the most studied catalytic systems are Cu, Pt, and Rh, supported on various oxides; the Cu/Zn/Al2O3 catalysts showed the best performance in the temperature range 200–350°C (Tanaka et al., 2003b); the Pt/CeO2 catalysts are active for medium temperatures (Goguet et al., 2004) while interesting studies were reported on the competitive selectivity of RWGS and methanation over the Rh/TiO2 catalytic systems (Matsubu et al., 2015) References Abbaslou, R.M.M., Soltan, J., Dalai, A.K., 2010 Effects of nanotubes pore size on the catalytic performances of iron catalysts supported on carbon nanotubes for Fischer–Tropsch synthesis Appl Catal A Gen 379 (1–2), 129–134 Ail, S.S., Dasappa, S., 2016 Investigations into enhanced wax production with combustion synthesized Fischer–Tropsch catalysts Energy Convers Manag 116, 80–90 Ajay, K., Ashokkumar, S., Pushpak, B., 2014 Biomass gasification and syngas utilization Sustainable Bioenergy Production CRC Press, Boca Raton, pp 341–360 Alberto, M.-C.G., Emilio, R.-C.A., Jose, P.-A., 2014 Modelado matema´tico de un reactor de sı´ntesis de metanol interenfriamiento y desactivacio´n de catalizador Ing Investig Tecnol 15 (4), 505–515 Al-Dossary, M., Fierro, J.L.G., 2015 Effect of high-temperature pre-reduction in Fischer– Tropsch synthesis on Fe/ZrO2 catalysts Appl Catal A Gen 499, 109–117 Ali, K.A., Abdullah, A.Z., Mohamed, A.R., 2015 Recent development in catalytic technologies for methanol synthesis from renewable sources: a critical review Renew Sust Energ Rev 44, 508–518 Ang, M.L., et al., 2015 High-temperature water–gas shift reaction over Ni/xK/CeO2 catalysts: suppression of methanation via formation of bridging carbonyls J Catal 329, 130–143 Arab, S., et al., 2014 Methanol synthesis from CO2 and H2 in multi-tubular fixed-bed reactor and multi-tubular reactor filled with monoliths Chem Eng Res Des 92 (11), 2598–2608 Arai, H., Mitsuishi, K., Seiyama, T., 1984 TiO2-supported Fe–Co, Co–Ni, AND Ni–Fe alloy catalysts for Fischer-Tropsch synthesis Chem Lett 13 (8), 1291–1294 Arbela´ez, O., et al., 2015 Mono and bimetallic Cu-Ni structured catalysts for the water gas shift reaction Appl Catal A Gen 497, 1–9 Bae, J.W., et al., 2009 Effect of Cu content on the bifunctional Fischer–Tropsch Fe–Cu–K/ ZSM5 catalyst J Ind Eng Chem 15 (6), 798–802 Baranak, M., et al., 2013 Low acidity ZSM-5 supported iron catalysts for Fischer–Tropsch synthesis Catal Today 207, 57–64 266 Bioenergy Systems for the Future Barrientos, J., et al., 2016 Further insights into the effect of sulfur on the activity and selectivity of cobalt-based Fischer–Tropsch catalysts Catal Today 275, 119–126 Basi nska, A., Domka, F., 1993 Iron-ruthenium catalyst for the water-gas shift reaction Catal Lett 17 (3), 327–332 Behrens, M., et al., 2010 The potential of microstructural optimization in metal/oxide catalysts: higher intrinsic activity of copper by partial embedding of copper nanoparticles ChemCatChem (7), 816–818 Bezemer, G.L., et al., 2010 Direct evidence of water-assisted sintering of cobalt on carbon nanofiber catalysts during simulated Fischer À Tropsch conditions revealed with in situ M€ossbauer spectroscopy J Am Chem Soc 132 (25), 8540–8541 Bosch, C., 1914 Producing hydrogen and apparatus therefor Google Patents Braganc¸a, L.F.F.P.G., et al., 2012 Bimetallic Co-Fe nanocrystals deposited on SBA-15 and HMS mesoporous silicas as catalysts for Fischer–Tropsch synthesis Appl Catal A Gen 423–424, 146–153 Calderone, V.R., et al., 2011 Bimetallic catalysts for the Fischer-Tropsch reaction Green Chem 13 (8), 1950–1959 Cano, L.A., et al., 2017 Effect of the support and promoters in Fischer-Tropsch synthesis using supported Fe catalysts Catal Today 282, 204–213 Cao, C., et al., 2009 Intensified Fischer–Tropsch synthesis process with microchannel catalytic reactors Catal Today 140 (3–4), 149–156 Carter, J.L., Savini, C.G., 1969 Ammonia synthesis catalyst Google Patents Centi, G., Perathoner, S., 2009 Opportunities and prospects in the chemical recycling of carbon dioxide to fuels Catal Today 148 (3–4), 191–205 Chen, L., et al., 2014a Nanowire accumulated Fe2O3/SiO2 spherical catalyst for FischerTropsch synthesis Chin J Catal 35 (10), 1661–1668 Chen, C., et al., 2014b The significant role of oxygen vacancy in Cu/ZrO2 catalyst for enhancing water–gas-shift performance Int J Hydrogen Energy 39 (1), 317–324 Cheng, K., et al., 2015 Sodium-promoted iron catalysts prepared on different supports for high temperature Fischer–Tropsch synthesis Appl Catal A Gen 502, 204–214 Chernyak, S.A., et al., 2015 New hybrid CNT–alumina supports for Co-based Fischer–Tropsch catalysts Fuel Process Technol 140, 267–275 Chernyak, S.A., et al., 2016 Co catalysts supported on oxidized CNTs: evolution of structure during preparation, reduction and catalytic test in Fischer-Tropsch synthesis Appl Catal A Gen 523, 221–229 Chew, L.M., et al., 2016 On the role of the stability of functional groups in multi-walled carbon nanotubes applied as support in iron-based high-temperature Fischer–Tropsch synthesis Catal Today 270, 85–92 Chin, S.Y., Alexeev, O.S., Amiridis, M.D., 2006 Structure and reactivity of Pt–Ru/SiO2 catalysts for the preferential oxidation of CO under excess H2 J Catal 243 (2), 329–339 Chinchen, G.C., et al., 1987 Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts: use of 14C-labelled reactants Appl Catal 30 (2), 333–338 Christian Enger, B., Lødeng, R., Holmen, A., 2008 A review of catalytic partial oxidation of methane to synthesis gas with emphasis on reaction mechanisms over transition metal catalysts Appl Catal A Gen 346 (1–2), 1–27 Chu, W., et al., 2015 Design of efficient fischer tropsch cobalt catalysts via plasma enhancement: reducibility and performance (Review) Catal Today 256 (Part 1), 41–48 Cohn Johann, G.E., 1965 Process for selectively removing carbon monoxide from hydrogencontaining gases Google Patents Catalysts for conversion of synthesis gas 267 Comazzi, A., et al., 2017 Fe-based heterogeneous catalysts for the Fischer-Tropsch reaction: sonochemical synthesis and bench-scale experimental tests Ultrason Sonochem 34, 774–780 Cornaglia, C.A., et al., 2012 Effect of the support on the catalytic stability of Rh formulations for the water–gas shift reaction Appl Catal A Gen 435–436, 99–106 Costa, J.L.R., Marchetti, G.S., Carmo Rangel, M., 2002 A thorium-doped catalyst for the high temperature shift reaction Catal Today 77 (3), 205–213 Couto, N., et al., 2013 Influence of the biomass gasification processes on the final composition of syngas Energy Procedia 36, 596–606 Curry-Hyde, H.E., et al., 1993 Improvements to Raney copper methanol synthesis catalysts through zinc impregnation: IV Pore structure and the influence on activity Appl Catal A Gen 95 (1), 65–74 Czuppon, T., Knez, S., Rovner, J., 1992 Ammonia Kirk-Othmer Encyclopedia of Chemical Technology Wiley, Hoboken Das, T.K., et al., 2003 Fischer–Tropsch synthesis: characterization and catalytic properties of rhenium promoted cobalt alumina catalysts Fuel 82 (7), 805–815 Davies, P., et al., 1965 Water-Gas Conversion and Catalysis Thereof United Kingdom Daza, Y.A., Kuhn, J.N., 2016 CO2 conversion by reverse water gas shift catalysis: comparison of catalysts, mechanisms and their consequences for CO2 conversion to liquid fuels RSC Adv (55), 49675–49691 De Falco, M., et al., 2013 Methanol Production from CO2 Via Reverse-Water–Gas-Shift Reaction CO2: A Valuable Source of Carbon Springer, Berlin, pp 171–186 de Klerk, A., 2000 Fischer–Tropsch process Kirk-Othmer Encyclopedia of Chemical Technology John Wiley & Sons, Inc., Hoboken de la Osa, A.R., et al., 2011 Fischer–Tropsch diesel production over calcium-promoted Co/alumina catalyst: Effect of reaction conditions Fuel 90 (5), 1935–1945 Delparish, A., Avci, A.K., 2016 Intensified catalytic reactors for Fischer-Tropsch synthesis and for reforming of renewable fuels to hydrogen and synthesis gas Fuel Process Technol 151, 72–100 den Otter, J.H., et al., 2016 On the superior activity and selectivity of PtCo/Nb2O5 Fischer Tropsch catalysts J Catal 340, 270–275 Dı´az, J.A., et al., 2013 Synthesis of carbon nanofibers supported cobalt catalysts for Fischer– Tropsch process Fuel 111, 422–429 Dı´az, J.A., et al., 2014 Influence of CO2 co-feeding on Fischer–Tropsch fuels production over carbon nanofibers supported cobalt catalyst Catal Commun 44, 57–61 Ding, M., et al., 2013 Impact of H2/CO ratios on phase and performance of Mn-modified Fe-based Fischer Tropsch synthesis catalyst Appl Energy 112, 1241–1246 Ding, M., et al., 2015 Study on reduction and carburization behaviors of iron phases for ironbased Fischer–Tropsch synthesis catalyst Appl Energy 160, 982–989 Dry, R.J., 1988 Possibilities for the development of large-capacity methanol synthesis reactors for synfuel production Ind Eng Chem Res 27 (4), 616–624 Dry, M.E., du Plessis, J.A.K., Leuteritz, G.M., 1966 The influence of structural promoters on the surface properties of reduced magnetite catalysts J Catal (2), 194–199 Duan, X., et al., 2016 Fabrication of K-promoted iron/carbon nanotubes composite catalysts for the Fischer–Tropsch synthesis of lower olefins J Energy Chem 25 (2), 311–317 Eigenberger, G., Ruppel, W., 2000 Catalytic fixed-bed reactors Ullmann’s Encyclopedia of Industrial Chemistry Wiley-VCH, Weinheim Emmett, P.H., Brunauer, S., 1937 The use of low temperature van der Waals adsorption isotherms in determining the surface area of iron synthetic ammonia catalysts J Am Chem Soc 59 (8), 1553–1564 268 Bioenergy Systems for the Future Eschemann, T.O., et al., 2015 Effect of support surface treatment on the synthesis, structure, and performance of Co/CNT Fischer–Tropsch catalysts J Catal 328, 130–138 Eschemann, T.O., Oenema, J., de Jong, K.P., 2016 Effects of noble metal promotion for Co/TiO2 Fischer-Tropsch catalysts Catal Today 261, 60–66 Fisher, I.A., Woo, H.C., Bell, A.T., 1997 Effects of zirconia promotion on the activity of Cu/SiO2 for methanol synthesis from CO/H2 and CO2/H2 Catal Lett 44 (1), 11–17 Flynn, P.C., Wanke, S.E., 1974 A model of supported metal catalyst sintering: I Development of model J Catal 34 (3), 390–399 Foster, A.I., et al., 1979 Process for the synthesis of ammonia using catalysts supported on graphite containing carbon Google Patents Fratalocchi, L., et al., 2015 A novel preparation method for “small” eggshell Co/γ-Al2O3 catalysts: a promising catalytic system for compact Fischer–Tropsch reactors Catal Today 246, 125–132 Frolich, P.K., et al., 1928 Catalysts for the formation of alcohols from carbon monoxide and hydrogen: II—synthesis of methanol with catalysts composed of copper and zinc1 Ind Eng Chem 20 (12), 1327–1330 Front matter Trans Faraday Soc 55, P001–P002 Fu, T., Li, Z., 2015 Review of recent development in Co-based catalysts supported on carbon materials for Fischer–Tropsch synthesis Chem Eng Sci 135, 3–20 Fuglerud, T., Skaugset, P.T., 1999 Catalyst for the synthesis of ammonia from hydrogen and nitrogen Google Patents Fujita, S., et al., 1995 Methanol synthesis from CO2-H2 and from CO-H2 under atmospheric pressure over Pd and Cu catalysts React Kinet Catal Lett 56 (1), 15–19 Gao, X., et al., 2016 Effects of zinc on Fe-based catalysts during the synthesis of light olefins from the Fischer-Tropsch process Chin J Catal 37 (4), 510–516 Garcia, A.C., Paganin, V.A., Ticianelli, E.A., 2008 CO tolerance of PdPt/C and PdPtRu/C anodes for PEMFC Electrochim Acta 53 (12), 4309–4315 Gens, T.A., 1980 Ammonia synthesis catalysts and process of making and using them Google Patents Ghareghashi, A., et al., 2013 A comparison of co-current and counter-current modes for Fischer–Tropsch synthesis in two consecutive reactors of oxidative coupling of methane and Fischer–Tropsch J Nat Gas Sci Eng 14, 1–16 Ghoneim, S.A., El-Salamony, R.A., El-Temtamy, S.A., 2015 Review on innovative catalytic reforming of natural gas to syngas World J Eng Technol (01), 116 Goguet, A., et al., 2004 Spectrokinetic investigation of reverse water-gas-shift reaction intermediates over a Pt/CeO2 catalyst J Phys Chem B 108 (52), 20240–20246 Gourdier, J., et al., 1972 Ammonia synthesis catalyst Google Patents Graaf, G.H., et al., 1986 Chemical equilibria in methanol synthesis Chem Eng Sci 41 (11), 2883–2890 Grabow, L.C., Mavrikakis, M., 2011 Mechanism of methanol synthesis on Cu through CO2 and CO hydrogenation ACS Catal (4), 365–384 Grenoble, D.C., Estadt, M.M., Ollis, D.F., 1981 The chemistry and catalysis of the water gas shift reaction J Catal 67 (1), 90–102 Guettel, R., Kunz, U., Turek, T., 2008a Reactors for Fischer-Tropsch synthesis Chem Eng Technol 31 (5), 746–754 Guettel, R., et al., 2008b Preparation and catalytic evaluation of cobalt-based monolithic and powder catalysts for Fischer À Tropsch synthesis Ind Eng Chem Res 47 (17), 6589–6597 Ha, K.-S., et al., 2013 Ordered mesoporous carbon nanochannel reactors for high-performance Fischer-Tropsch synthesis Chem Commun 49 (45), 5141–5143 Catalysts for conversion of synthesis gas 269 Haber, F., 2002 The synthesis of ammonia from its elements Nobel Lecture, June 2, 1920 Resonance (9), 86–94 Habermehl, R., Atwood, K., 1964 Low temperature carbon monoxide conversion catalysts Prepr Am Chem Soc Div Energy Fuels (1), 10–20 Han, J., Kim, H., 2008 The reduction and control technology of tar during biomass gasification/ pyrolysis: an overview Renew Sust Energ Rev 12 (2), 397–416 He, R.X., et al., 2012 Effects of La-doping on the structure and performance of coppermanganese oxides for the water-gas shift reaction Renew Sustain Energy II 512–515 (Pts 1–4), 2131–2134 Hilmen, A.M., et al., 2001 Fischer–Tropsch synthesis on monolithic catalysts of different materials Catal Today 69 (1–4), 227–232 Hiroshi, U., et al., 1967 The zinc oxide-copper catalyst for carbon monoxide-shift conversion I The dependency of the catalytic activity on the chemical composition of the catalyst Bull Chem Soc Jpn 40 (8), 1981–1986 Hiroshi, I., Hiroyuki, U., Masahiro, W., 2000 Mordenite-supported noble metal catalysts for selective oxidation of carbon monoxide in a reformed gas Chem Lett 29 (11), 1262–1263 Hirotani, K., Nakamura, H., Shoji, K., 1998 Optimum catalytic reactor design for methanol synthesis with TEC MRF-Z ® reactor Catal Surv Jpn (1), 99–106 Hong, Z.-S., et al., 2002 CO2 hydrogenation to methanol Over Cu/ZnO/Al2O3 catalysts prepared by a novel gel-network-coprecipitation method Catal Lett 82 (1), 37–44 Idakiev, V., et al., 1987 Effect of copper oxide on the catalytic activity of iron-chromia catalyst for water gas shift reaction React Kinet Catal Lett 33 (1), 119–124 Iglesia, E., 1997 Design, synthesis, and use of cobalt-based Fischer-Tropsch synthesis catalysts Appl Catal A Gen 161 (1), 59–78 Iida, H., et al., 2013 Fischer Tropsch synthesis over Co/SiO2 and Co-M (M: Ru, Re)/SiO2 catalysts prepared by a high-temperature super-critical drying method Appl Catal A Gen 466, 256–263 Iqbal, S., et al., 2016 Fischer Tropsch synthesis using promoted cobalt-based catalysts Catal Today 272, 74–79 Jacobs, G., et al., 2009 Group 11 (Cu, Ag, Au) promotion of 15%Co/Al2O3 Fischer–Tropsch synthesis catalysts Appl Catal A Gen 361 (1–2), 137–151 Jacobs, G., et al., 2016 Fischer-Tropsch synthesis: Cobalt catalysts on alumina having partially pre-filled pores exhibit higher C5 + and lower light gas selectivities Appl Catal A Gen 516, 51–57 Jacobsen, C.J., 2000 Novel class of ammonia synthesis catalysts Chem Commun 12, 1057–1058 Jalama, K., et al., 2011 A comparison of Au/Co/Al2O3 and Au/Co/SiO2 catalysts in the Fischer–Tropsch reaction Appl Catal A Gen 395 (1–2), 1–9 Jennings, J.R., 2013 Catalytic Ammonia Synthesis: Fundamentals and Practice Springer Science & Business Media, New York Jennings, J.R., et al., 1992 Intermetallic catalysts for methanol synthesis: ternary alloys containing copper and cerium Appl Catal A Gen 81 (2), 257–272 Jeong, H., Cho, C.H., Kim, T.H., 2012 Effect of Zr and pH in the preparation of Cu/ZnO catalysts for the methanol synthesis by CO2 hydrogenation React Kinet Mech Catal 106 (2), 435–443 Jha, A., et al., 2015 Enhancing the catalytic performance of cobalt oxide by doping on ceria in the high temperature water-gas shift reaction RSC Adv (125), 103023–103029 Jin, Y., Datye, A.K., 2000 Phase transformations in iron Fischer–Tropsch catalysts during temperature-programmed reduction J Catal 196 (1), 8–17 270 Bioenergy Systems for the Future Jongsomjit, B., Panpranot, J., Goodwin, J.G., 2001 Co-support compound formation in alumina-supported cobalt catalysts J Catal 204 (1), 98–109 Jung, K.T., Bell, A.T., 2002 Effects of zirconia phase on the synthesis of methanol over zirconia-supported copper Catal Lett 80 (1), 63–68 Ju´nior, I.L., et al., 2005 The role of vanadium on the properties of iron based catalysts for the water gas shift reaction Appl Catal A Gen 283 (1–2), 91–98 Kang, S.-H., et al., 2010 ZSM-5 supported iron catalysts for Fischer–Tropsch production of light olefin Fuel Process Technol 91 (4), 399–403 Kapteijn, F., et al., 2001 New non-traditional multiphase catalytic reactors based on monolithic structures Catal Today 66 (2–4), 133–144 Kapteijn, F., de Deugd, R.M., Moulijn, J.A., 2005 Fischer–Tropsch synthesis using monolithic catalysts Catal Today 105 (3–4), 350–356 Karimi, S., et al., 2015 Enhancement of cobalt catalyst stability in Fischer–Tropsch synthesis using graphene nanosheets as catalyst support Chem Eng Res Des 104, 713–722 Khodakov, A.Y., 2009 Fischer-Tropsch synthesis: relations between structure of cobalt catalysts and their catalytic performance Catal Today 144 (3–4), 251–257 Khodakov, A.Y., Chu, W., Fongarland, P., 2007 Advances in the development of novel cobalt Fischer-Tropsch catalysts for synthesis of long-chain hydrocarbons and clean fuels Chem Rev 107 (5), 1692–1744 Kim, C.-H., Lee, J.S., Trimm, D.L., 2003 The preparation and characterisation of Pd–ZnO catalysts for methanol synthesis Top Catal 22 (3), 319–324 Kjær, J., 1972 Computer Methods in Gas Phase Thermodynamics Haldor Topsøe, Eksp.: Postboks 49 Klier, K., et al., 1982 Catalytic synthesis of methanol from COH2: IV The effects of carbon dioxide J Catal 74 (2), 343–360 Kristiansen, L.A., 1981 Catalyst and method for producing said catalyst Google Patents Kumar, A., Jones, D.D., Hanna, M.A., 2009 Thermochemical biomass gasification: a review of the current status of the technology Energies (3), 556–581 Labuschagne, J., et al., 2016 Application of water-tolerant Co/β-SiC catalysts in slurry phase Fischer–Tropsch synthesis Catal Today 275, 2–10 Lacroix, M., et al., 2011 Silicon carbide foam composite containing cobalt as a highly selective and re-usable Fischer–Tropsch synthesis catalyst Appl Catal A Gen 397 (1–2), 62–72 Lahne, U., Lohm€uller, R., 1986 Sch€uttschichtreaktoren mit gewickelten K€ uhlrohren, eine konstruktive Neuentwicklung zur Durchf€uhrung exothermer katalytischer Prozesse Chem Ing Tech 58 (3), 212–215 Larson, A.T., Brooks, A.P., 1926 Ammonia catalysts1 Ind Eng Chem 18 (12), 1305–1307 Lee, S., 1990 Methanol Synthesis Technology CRC Press, Boca Reaton, FL Lee, J.S., et al., 1995 Modified Cu/ZnO/Al2O3 catalysts for methanol synthesis from CO2/H2 and CO/H2 Catal Lett 34 (1), 93–99 Lee, D.-K., et al., 2010 Distribution of carbon deposits on reduced Co/Y-zeolite catalysts for Fischer–Tropsch synthesis Catal Today 154 (3–4), 237–243 Lee, J.Y., et al., 2011 The CO removal performances of Cr-free Fe/Ni catalysts for high temperature WGSR under LNG reformate condition without additional steam Int J Hydrogen Energy 36 (14), 8173–8180 Lepp€alahti, J., Koljonen, T., 1995 Nitrogen evolution from coal, peat and wood during gasification: Literature review Fuel Process Technol 43 (1), 1–45 Lewis, W.K., Frolich, P.K., 1928 Synthesis of methanol from carbon monoxide and hydrogen1 Ind Eng Chem 20 (3), 285–290 Catalysts for conversion of synthesis gas 271 Li, J.L., Inui, T., 1996 Characterization of precursors of methanol synthesis catalysts, copper/ zinc/aluminum oxides, precipitated at different pHs and temperatures Appl Catal A Gen 137 (1), 105–117 Li, S., et al., 2002 Promoted iron-based catalysts for the Fischer–Tropsch synthesis: design, synthesis, site densities, and catalytic properties J Catal 206 (2), 202–217 Li, J., et al., 2015 Effects of alkali on iron-based catalysts for Fischer-Tropsch synthesis: CO chemisorptions study J Mol Catal A Chem 396, 174–180 Li, J., et al., 2016a Jet fuel synthesis via Fischer–Tropsch synthesis with varied 1-olefins as additives using Co/ZrO2–SiO2 bimodal catalyst Fuel 171, 159–166 Li, C., et al., 2016b Development of high performance graphite-supported iron catalyst for Fischer–Tropsch synthesis Appl Catal A Gen 509, 123–129 Lin, X., et al., 2013 Promotion effect of Nb5 + for Cu/CeO2 water–gas shift reaction catalyst by generating mobile electronic carriers Int J Hydrogen Energy 38 (27), 11847–11852 Liu, W., Hu, J., Wang, Y., 2009 Fischer–Tropsch synthesis on ceramic monolith-structured catalysts Catal Today 140 (3–4), 142–148 Liu, X., et al., 2012a Preparation of Cu/ZrO2 catalysts for methanol synthesis from CO2/H2 Front Chem Sci Eng (1), 47–52 Liu, K., Wang, A., Zhang, T., 2012b Recent advances in preferential oxidation of CO reaction over platinum group metal catalysts ACS Catal (6), 1165–1178 Liu, Y., et al., 2014 Fischer–Tropsch reaction on a thermally conductive and reusable silicon carbide support ChemSusChem (5), 1218–1239 Liu, C., et al., 2016 Synthesis of γ-Al2O3 nanofibers stabilized Co3O4 nanoparticles as highly active and stable Fischer–Tropsch synthesis catalysts Fuel 180, 777–784 L€ ogdberg, S., et al., 2009 Hydrocarbon production via Fischer–Tropsch synthesis from H2-poor syngas over different Fe-Co/γ-Al2O3 bimetallic catalysts Appl Catal B Environ 89 (1–2), 167–182 Lorito, D., et al., 2016 Reconstruction of ceria-supported Pt-Co particles under H2 and CO at 220°C Appl Catal B Environ 197, 56–61 Lu, X., Hildebrandt, D., Glasser, D., 2015 Distribution between C2 and C3 in low temperature Fischer–Tropsch synthesis over a TiO2-supported cobalt catalyst Appl Catal A Gen 506, 67–76 Ma, W., Kugler, E.L., Dadyburjor, D.B., 2007 Potassium effects on activated-carbon-supported iron catalysts for Fischer À Tropsch synthesis Energy Fuel 21 (4), 1832–1842 Ma, X., et al., 2009 Effects of the ratio of Fe to Co over Fe-Co/SiO2 bimetallic catalysts on their catalytic performance for Fischer-Tropsch synthesis J Nat Gas Chem 18 (2), 232–236 Ma, W., et al., 2012 Fischer–Tropsch synthesis: effect of Pd, Pt, Re, and Ru noble metal promoters on the activity and selectivity of a 25%Co/Al2O3 catalyst Appl Catal A Gen 437–438, 1–9 Ma, W., et al., 2016 Effect of H2S in syngas on the Fischer–Tropsch synthesis performance of a precipitated iron catalyst Appl Catal A Gen 513, 127–137 Mahinpey, N., Gomez, A., 2016 Review of gasification fundamentals and new findings: Reactors, feedstock, and kinetic studies Chem Eng Sci 148, 14–31 Makihara, H., et al., 1987 Characteristics of a new methanol synthesis reactor Energy Prog 7, 51–58 Maluf, S.S., Assaf, E.M., 2009 La2 À xCexCu1 À yZnyO4 perovskites for high temperature water-gas shift reaction J Nat Gas Chem 18 (2), 131–138 Martinelli, M., et al., 2014 CO2 reactivity on Fe–Zn–Cu–K Fischer–Tropsch synthesis catalysts with different K-loadings Catal Today 228, 77–88 272 Bioenergy Systems for the Future Martı´nez, A., et al., 2007 A detailed study of the activity and deactivation of zeolites in hybrid Co/SiO2-zeolite Fischer–Tropsch catalysts J Catal 249 (2), 162–173 Martos, C., Dufour, J., Ruiz, A., 2009 Synthesis of Fe3O4-based catalysts for the hightemperature water gas shift reaction Int J Hydrogen Energy 34 (10), 4475–4481 Maschio, G., Lucchesi, A., Stoppato, G., 1994 Production of syngas from biomass Bioresour Technol 48 (2), 119–126 Matsubu, J.C., Yang, V.N., Christopher, P., 2015 Isolated metal active site concentration and stability control catalytic CO2 reduction selectivity J Am Chem Soc 137 (8), 3076–3084 Matulewicz, E.R.A., et al., 1984 Characterization of CuO-ZnO-Al2O3 methanol synthesis catalysts using temperature programmed reduction and thermal stability Thermochim Acta 72 (1–2), 111–116 Milani, D., et al., 2015 A model-based analysis of CO2 utilization in methanol synthesis plant J CO2 Util 10, 12–22 Minnermann, M., et al., 2013 Double flame spray pyrolysis as a novel technique to synthesize alumina-supported cobalt Fischer–Tropsch catalysts Catal Today 214, 90–99 Mittasch, A., Frankenburg, W., 1950 Early studies of multicomponent catalysts Adv Catal 2, 81–104 Mittasch, A., Pier, M., Winkler, K., 1925 Ausfuehrung organischer Katalysen BASF Ag, Ludwigshafen am Rhein Mond, L., Langer, C., Quincke, F., 1890 L.—Action of carbon monoxide on nickel J Chem Soc Trans 57, 749–753 Montebelli, A., et al., 2014a Optimization of compact multitubular fixed-bed reactors for the methanol synthesis loaded with highly conductive structured catalysts Chem Eng J 255, 257–265 Montebelli, A., et al., 2014b Washcoating and chemical testing of a commercial Cu/ZnO/ Al2O3 catalyst for the methanol synthesis over copper open-cell foams Appl Catal A Gen 481, 96–103 Moodley, D.J., et al., 2011 The impact of cobalt aluminate formation on the deactivation of cobalt-based Fischer–Tropsch synthesis catalysts Catal Today 171 (1), 192–200 Moreira, M.N., et al., 2016 Copper based materials for water-gas shift equilibrium displacement Appl Catal B Environ 189, 199–209 Nabaho, D., et al., 2016a Hydrogen spillover in the Fischer–Tropsch synthesis: an analysis of platinum as a promoter for cobalt–alumina catalysts Catal Today 261, 17–27 Nabaho, D., et al., 2016b Hydrogen spillover in the Fischer–Tropsch synthesis: an analysis of gold as a promoter for cobalt–alumina catalysts Catal Today 275, 27–34 Nakhaei Pour, A., Housaindokht, M.R., 2013 Fischer-Tropsch synthesis on iron catalyst promoted with HZSM-5 zeolite: Regeneration studies of catalyst J Nat Gas Sci Eng 14, 49–54 Natta, G., 1955 CatalysisVol Reinhold, New York, NY Nielsen, A., 1971 Review of ammonia catalysis Catal Rev (1), 1–26 Nielsen, A., 1981 Ammonia synthesis: exploratory and applied research Catal Rev 23 (1–2), 17–51 Niemantsverdriet, J.W., et al., 1984 M€ossbauer investigation of bimetallic FeRu/SiO2 and FeRh/SiO2 Fischer-Tropsch catalysts J Mol Catal 25 (1), 285–293 Ning, W., et al., 2013 Influences of K and Cu on coprecipitated FeZn catalysts for Fischer– Tropsch reaction Catal Commun 39, 74–77 Oemar, U., et al., 2016 Sulfur resistant LaxCe1-xNi0.5Cu0.5O3 catalysts for an ultra-high temperature water gas shift reaction Catal Sci Technol (17), 6569–6580 Catalysts for conversion of synthesis gas 273 Oh, S.H., Sinkevitch, R.M., 1993 Carbon monoxide removal from hydrogen-rich fuel cell feedstreams by selective catalytic oxidation J Catal 142 (1), 254–262 Osakoo, N., et al., 2013 Palladium-promoted cobalt catalysts supported on silica prepared by impregnation and reverse micelle for Fischer–Tropsch synthesis Appl Catal A Gen 464–465, 269–280 Ozaki, A., Kenichi, A., 1979 The synthesis of ammonia by heterogeneous catalysis Chem Inform 10 (39), 45–60 Palma, V., Ricca, A., Ciambelli, P., 2013 Methane auto-thermal reforming on honeycomb and foam structured catalysts: the role of the support on system performances Catal Today 216, 30–37 Palma, V., et al., 2014 Comparative studies of low temperature water gas shift reaction over platinum based catalysts Chem Eng 39, 31–36 Palma, V., et al., 2015 Catalysts for the intensification of the water gas shift process In: Oral, A.Y., Bahsi Oral, Z.B., Ozer, M (Eds.), 2nd International Congress on Energy Efficiency and Energy Related Materials (ENEFM2014): Proceedings, Oludeniz, Fethiye/Mugla, Turkey, October 16–19, 2014 Springer International Publishing, Cham, pp 479–484 Palma, V., et al., 2016 Structured catalysts with high thermoconductive properties for the intensification of water gas shift process Chem Eng J 304, 544–551 Pangarkar, K., et al., 2009 Experimental and numerical comparison of structured packings with a randomly packed bed reactor for Fischer–Tropsch synthesis Catal Today 147 (Suppl.), S2–S9 Park, S.-J., et al., 2011 Deactivation behaviors of Pt or Ru promoted Co/P-Al2O3 catalysts during slurry-phase Fischer–Tropsch synthesis Catal Commun 12 (6), 539–543 Park, S.-J., et al., 2012 Crucial factors for catalyst aggregation and deactivation on Co/Al2O3 in a slurry-phase Fischer–Tropsch synthesis Appl Catal A Gen 413–414, 310–321 Patart, M.G., 1922 Procede de la prodiction d’alcools, d’aldehydes et d’acides partir de melanges gazeux maintenus sous pression et soumis l’action d’agents catalytiques ou de l’electricite France Paulik, F.E., Roth, J.F., 1968 Novel catalysts for the low-pressure carbonylation of methanol to acetic acid Chem Commun (London) 24, 1578a Pen˜a, D., et al., 2014 Molecular structure and localization of carbon species in alumina supported cobalt Fischer–Tropsch catalysts in a slurry reactor Catal Today 228, 65–76 Pendyala, V.R.R., et al., 2014 Fischer–Tropsch synthesis: Effect of catalyst particle (sieve) size range on activity, selectivity, and aging of a Pt promoted Co/Al2O3 catalyst Chem Eng J 249, 279–284 Pendyala, V.R.R., et al., 2016 Fischer–Tropsch synthesis: effect of ammonia on supported cobalt catalysts J Catal 337, 80–90 Pereira, L.C., Nilson, A., et al., 2007 Effect of cobalt on the activity of iron-based catalysts in water gas shift reaction In: Fa´bio Bellot Noronha, M.S., Eduardo Falabella, S.-A (Eds.), Studies in Surface Science and Catalysis Elsevier, Amsterdam, pp 225–230 Perez De Berti, I.O., et al., 2016 Effect of activation atmosphere in the Fischer–Tropsch Synthesis using a “quasi-model” catalyst of γ-Fe2O3 nanoparticles supported on SBA-15 J Catal 335, 36–46 Perkas, N., et al., 2014 The sonochemical approach improves the CuO-ZnO/TiO2 catalyst for WGS reaction Phys Chem Chem Phys 16 (16), 7521–7530 Phan, X.K., et al., 2011 Preparation and performance of Cu-based monoliths for methanol synthesis Appl Catal A Gen 405 (1–2), 1–7 Piemonte, V., et al., 2010 Counter-current membrane reactor for WGS process: membrane design Int J Hydrogen Energy 35 (22), 12609–12617 274 Bioenergy Systems for the Future Pirola, C., et al., 2014 Fischer–Tropsch synthesis: EXAFS study of Ru and Pt bimetallic Co based catalysts Fuel 132, 62–70 Plana-Pallejà, J., et al., 2016 Effect of zeolite acidity and mesoporosity on the activity of Fischer–Tropsch Fe/ZSM-5 bifunctional catalysts Appl Catal A Gen 515, 126–135 Popa, T., et al., 2010 High temperature water gas shift catalysts with alumina Appl Catal A Gen 379 (1–2), 15–23 Poutsma, M.L., et al., 1978 Selective formation of methanol from synthesis gas over palladium catalysts J Catal 52 (1), 157–168 Prieto, G., et al., 2009 Cobalt particle size effects in Fischer–Tropsch synthesis: structural and in situ spectroscopic characterisation on reverse micelle-synthesised Co/ITQ-2 model catalysts J Catal 266 (1), 129–144 Qing, M., et al., 2011 Modification of Fe–SiO2 interaction with zirconia for iron-based Fischer–Tropsch catalysts J Catal 279 (1), 111–122 Quincoces, C., Amadeo, N., Gonzalez, M., 1997 Effects of reduction and regeneration conditions on the activity of CuO-ZnO catalysts Stud Surf Sci Catal 111, 535–541 Rafati, M., Wang, L., Shahbazi, A., 2015 Effect of silica and alumina promoters on co-precipitated Fe–Cu–K based catalysts for the enhancement of CO2 utilization during Fischer–Tropsch synthesis J CO2 Util 12, 34–42 Reddy, G.K., Smirniotis, P.G., 2015 WGS reaction over Co-Mo sulphided catalysts Water Gas Shift Reaction Elsevier, Amsterdam, pp 101–126 (Chapter 4) Reddy, G.K., Boolchand, P., Smirniotis, P.G., 2011 Sulfur tolerant metal doped Fe/Ce catalysts for high temperature WGS reaction at low steam to CO ratios—XPS and M€ ossbauer spectroscopic study J Catal 282 (2), 258–269 Rhodes, C., Hutchings, G.J., Ward, A.M., 1995 Water-gas shift reaction: finding the mechanistic boundary Catal Today 23 (1), 43–58 R€ onsch, S., et al., 2016 Review on methanation—from fundamentals to current projects Fuel 166, 276–296 Roy, S., et al., 2004 Monoliths as multiphase reactors: a review AICHE J 50 (11), 2918–2938 Sadeghi, S., et al., 2014 Modeling of the methanol synthesis catalyst deactivation in a spherical bed reactor: an environmental challenge APCBEE Proc 10, 84–90 Sadeqzadeh, M., et al., 2013 Deactivation of a Co/Al2O3 Fischer–Tropsch catalyst by waterinduced sintering in slurry reactor: modeling and experimental investigations Catal Today 215, 52–59 Savost’yanov, A.P., et al., 2017 The impact of Al2O3 promoter on an efficiency of C5+ hydrocarbons formation over Co/SiO2 catalysts via Fischer-Tropsch synthesis Catal Today 279, 107–114 Saw, E.T., et al., 2014 Bimetallic Ni–Cu catalyst supported on CeO2 for high-temperature water–gas shift reaction: methane suppression via enhanced CO adsorption J Catal 314, 32–46 Saw, E.T., et al., 2015 Highly active and stable bimetallic nickel–copper core–ceria shell catalyst for high-temperature water–gas shift reaction ChemCatChem (20), 3358–3367 Schl€ ogl, R., 2008 Ammonia synthesis Handbook of Heterogeneous Catalysis, Wiley-VCH Verlag GmbH & Co KGaA, Weinheim Schwab, G.M., 1952 Alwin Mittasch: Geschichte der Ammoniaksynthese Weinheim, 1951 Verlag Chemie, GmbH, 196 S., Gr 8°, Abb im Text und 12 Bildtafeln Preis Ganzleinen DM 13,20 Zeitschrift f€ur Elektrochemie, Berichte der Bunsengesellschaft f€ ur physikalische Chemie 56 (2), 161–162 Catalysts for conversion of synthesis gas 275 Shi, L., et al., 2012 Studies on surface impregnation combustion method to prepare supported Co/SiO2 catalysts and its application for Fischer–Tropsch synthesis Appl Catal A Gen 435–436, 217–224 Shimomura, M., Nojima, S., 1988 Preparation of monolith-type catalyst for methanol steam reforming Zeolites (4), 341 Shimura, K., et al., 2015 Fischer–Tropsch synthesis over alumina supported bimetallic Co–Ni catalyst: effect of impregnation sequence and solution J Mol Catal A Chem 407, 15–24 Shin, M.-S., et al., 2013 Computational fluid dynamics model of a modular multichannel reactor for Fischer–Tropsch synthesis: maximum utilization of catalytic bed by microchannel heat exchangers Chem Eng J 234, 23–32 Shishido, T., et al., 2006 Cu/Zn-based catalysts improved by adding magnesium for water–gas shift reaction J Mol Catal A Chem 253 (1–2), 270–278 Silva, C.L.S., et al., 2013 Effect of gadolinium on the catalytic properties of iron oxides for WGSR Catal Today 213, 127–134 Smil, V., 1999 Detonator of the population explosion Nature 400 (6743), 415 So¯czynski, J., 1994 Antisintering criteria in the metal—spacer catalytic system Chem Eng Sci 49 (1), 115–121 Somorjai, G.A., Li, Y., 2010 Introduction to Surface Chemistry and Catalysis John Wiley & Sons, Hoboken Spadaro, L., et al., 2005 Metal–support interactions and reactivity of Co/CeO2 catalysts in the Fischer–Tropsch synthesis reaction J Catal 234 (2), 451–462 Stoltze, P., 1995 Structure and surface chemistry of industrial ammonia synthesis catalysts In: Nielsen, A (Ed.), Ammonia: Catalysis and Manufacture Springer Berlin Heidelberg, Berlin, Heidelberg, pp 17–102 Sudsakorn, K., et al., 2001 Preparation of attrition-resistant spray-dried Fe Fischer À Tropsch catalysts using precipitated SiO2 Ind Eng Chem Res 40 (22), 4778–4784 Sun, Y., et al., 2010 High temperature water–gas shift Cu catalysts supported on Ce–Al containing materials for the production of hydrogen using simulated coal-derived syngas Catal Commun 12 (4), 304–309 Sze, M.C., 1976 Process for the preparation of ammonia synthesis catalyst Google Patents Sze, M.C., Wang, R.H., 1976 Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process Google Patents Takenaka, S., Shimizu, T., Otsuka, K., 2004 Complete removal of carbon monoxide in hydrogen-rich gas stream through methanation over supported metal catalysts Int J Hydrogen Energy 29 (10), 1065–1073 Tan, K.F., et al., 2011 Effect of boron promotion on the stability of cobalt Fischer–Tropsch catalysts J Catal 280 (1), 50–59 Tanaka, Y., et al., 2003a Water gas shift reaction over Cu-based mixed oxides for CO removal from the reformed fuels Appl Catal A Gen 242 (2), 287–295 Tanaka, Y., et al., 2003b CO removal from reformed fuel over Cu/ZnO/Al2O3 catalysts prepared by impregnation and coprecipitation methods Appl Catal A Gen 238 (1), 11–18 Tavasoli, A., et al., 2009 Fischer–Tropsch synthesis on mono- and bimetallic Co and Fe catalysts supported on carbon nanotubes Fuel Process Technol 90 (12), 1486–1494 Tekin, K., Karag€oz, S., Bektaş, S., 2014 A review of hydrothermal biomass processing Renew Sust Energ Rev 40, 673–687 Todic, B., et al., 2016 Fischer–Tropsch synthesis product selectivity over an industrial ironbased catalyst: Effect of process conditions Catal Today 261, 28–39 Torres Galvis, H.M., de Jong, K.P., 2013 Catalysts for production of lower olefins from synthesis gas: a review ACS Catal (9), 2130–2149 276 Bioenergy Systems for the Future Torres Galvis, H.M., et al., 2013 Effects of sodium and sulfur on catalytic performance of supported iron catalysts for the Fischer–Tropsch synthesis of lower olefins J Catal 303, 22–30 Turn, S.Q., et al., 2001 An experimental investigation of alkali removal from biomass producer gas using a fixed bed of solid sorbent Ind Eng Chem Res 40 (8), 1960–1967 Twigg, M.V., Richardson, J.T., 2002 Theory and applications of ceramic foam catalysts Chem Eng Res Des 80 (2), 183–189 Valsamakis, I., Flytzani-Stephanopoulos, M., 2011 Sulfur-tolerant lanthanide oxysulfide catalysts for the high-temperature water–gas shift reaction Appl Catal B Environ 106 (1–2), 255–263 van Berge, P.J., et al., 2000 Oxidation of cobalt based Fischer–Tropsch catalysts as a deactivation mechanism Catal Today 58 (4), 321–334 van de Loosdrecht, J., Niemantsverdriet, J.H., 2013 Synthesis gas to hydrogen, methanol, and synthetic fuels Chemical Energy Storage Schlogl, Berlin, (Chapter 5.4) van Dijk, H.A.J., et al., 2010 Development of a single stage heat integrated water–gas shift reactor for fuel processing Chem Eng J 159 (1–3), 182–189 Venezia, A.M., et al., 2012 Co/SiO2 catalysts for Fischer–Tropsch synthesis; effect of Co loading and support modification by TiO2 Catal Today 197 (1), 18–23 Visconti, C.G., et al., 2011 Monolithic catalysts with high thermal conductivity for the Fischer– Tropsch synthesis in tubular reactors Chem Eng J 171 (3), 1294–1307 Wan, H., et al., 2007 Structural properties, reduction and carburization behaviors of Fe/Cu/K/ Al2O3 catalyst for Fischer-Tropsch synthesis Acta Phys -Chim Sin 23 (8), 1151–1156 Wang, D., et al., 2011 Characterization and performance of Cu/ZnO/Al2O3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H2 and CO2 J Nat Gas Chem 20 (6), 629–634 Watanabe, M., et al., 2003 Hydrogen purification for fuel cells: selective oxidation of carbon monoxide on Pt–Fe/zeolite catalysts Appl Catal B Environ 46 (3), 595–600 Waugh, K.C., 1992 Methanol synthesis Catal Today 15 (1), 51–75 Wei, L., et al., 2016 Fischer–Tropsch synthesis over a 3D foamed MCF silica support: toward a more open porous network of cobalt catalysts J Catal 340, 205–218 Witoon, T., et al., 2016 CO2 hydrogenation to methanol over Cu/ZrO2 catalysts: effects of zirconia phases Chem Eng J 293, 327–336 Wu, J., Saito, M., Mabuse, H., 2000 Activity and stability of Cu/ZnO/Al2O3 catalyst promoted with B2O3 for methanol synthesis Catal Lett 68 (1), 55–58 Wu, L., et al., 2015 A preliminary evaluation of ZSM-5/SBA-15 composite supported Co catalysts for Fischer–Tropsch synthesis Fuel Process Technol 134, 449–455 Wu, H.-C., et al., 2016 The effect of an Fe promoter on Cu/SiO2 catalysts for improving their catalytic activity and stability in the water-gas shift reaction Catal Sci Technol (15), 6087–6096 Xing, C., et al., 2015 Hierarchical zeolite Y supported cobalt bifunctional catalyst for facilely tuning the product distribution of Fischer–Tropsch synthesis Fuel 148, 48–57 Xing, C., et al., 2016 A hierarchically spherical Co-based zeolite catalyst with aggregated nanorods structure for improved Fischer–Tropsch synthesis reaction activity and isoparaffin selectivity Microporous Mesoporous Mater 233, 62–69 Xiong, H., et al., 2008 Fischer–Tropsch synthesis: the role of pore size for Co/SBA-15 catalysts J Mol Catal A Chem 295 (1–2), 68–76 Xiong, H., et al., 2011 Correlating the preparation and performance of cobalt catalysts supported on carbon nanotubes and carbon spheres in the Fischer–Tropsch synthesis J Catal 278 (1), 26–40 Catalysts for conversion of synthesis gas 277 Xiong, H., et al., 2015 Effect of Group I alkali metal promoters on Fe/CNT catalysts in Fischer– Tropsch synthesis Fuel 150, 687–696 Xu, J.-D., et al., 2016 Effect of sulfur on α-Al2O3-supported iron catalyst for Fischer–Tropsch synthesis Appl Catal A Gen 514, 103–113 Yan, Z., Bukur, D.B., Goodman, D.W., 2011 Silica-supported rhodium-cobalt catalysts for Fischer–Tropsch synthesis Catal Today 160 (1), 39–43 Yang, M., Allard, L.F., Flytzani-Stephanopoulos, M., 2013 Atomically dispersed Au–(OH)x species bound on titania catalyze the low-temperature water-gas shift reaction J Am Chem Soc 135 (10), 3768–3771 Yoneyama, Y., et al., 2005 Direct synthesis of isoparaffin by modified Fischer–Tropsch synthesis using hybrid catalyst of iron catalyst and zeolite Catal Today 104 (1), 37–40 Yoshihara, J., et al., 1995 Methanol synthesis and reverse water-gas shift kinetics over clean polycrystalline copper Catal Lett 31 (4), 313–324 Youchang, X., Naasz, B.N., Somorjai, G.A., 1986 Alcohol synthesis from Co and H2 over molybdenum sulfide The effect of pressure and promotion by potassium carbonate Appl Catal 27 (2), 233–241 Zaman, M., Khodadi, A., Mortazavi, Y., 2009 Fischer–Tropsch synthesis over cobalt dispersed on carbon nanotubes-based supports and activated carbon Fuel Process Technol 90 (10), 1214–1219 Zhang, Y., et al., 1997 A high activity Cu/ZnO/Al2O3 catalyst for methanol synthesis: preparation and catalytic properties Appl Catal A Gen 158 (1–2), 105–120 Zhang, X., et al., 2016a Effect of CeO2 promotion on the catalytic performance of Co/ZrO2 catalysts for Fischer–Tropsch synthesis Fuel 184, 162–168 Zhang, Y., et al., 2016b MnO2 coated Fe2O3 spindles designed for production of C5+ hydrocarbons in Fischer–Tropsch synthesis Fuel 177, 197–205 Zhou, W.-G., et al., 2015 An effective Co/MnOx catalyst for forming light olefins via Fischer– Tropsch synthesis Catal Commun 60, 76–81 Zhu, M., Wachs, I.E., 2016 Iron-based catalysts for the high-temperature water–gas shift (HTWGS) reaction: a review ACS Catal (2), 722–732 ... 2 .77 1 .79 2.29 2.12 0. 67 1 .72 12.2 15.5 2.52 4.32 4.69 3. 47 4.98 5.81 9.68 4.90 3. 57 3.61 1.62 1 .77 3. 17 1 .79 2.89 1.95 1 .79 2.14 5.55 7. 81 1.83 2.26 4 .72 2.89 4.66 4.36 7. 43 5.42 38.6 27. 7 75 .8... 4.4 2.5 3.5 58.3 75 .2 76 .9 76 .2 59.8 70 .4 72 .1 72 .5 64.2 64.3 69.9 69.6 54.9 66.3 78 .9 67. 6 Catalysts for conversion of synthesis gas 235 supports such as silica and CMK-3, the optimum sodium... carbonylation of methanol and, the Mond process for the extraction and purification of Nickel (Mond et al., 1890) 220 7. 2 Bioenergy Systems for the Future Fischer-Tropsch synthesis The Fischer-Tropsch synthesis