Bubble Column Apparatus for Separating Wax from Catalyst Slurry

Novel methods and devices for production of liquid hydrocarbon products from gaseous reactants are disclosed. In one aspect, a method for separating a liquid hydrocarbon, typically a wax, from a catalyst containing slurry is provided, comprising passing the slurry through at least one downcomer extending from an overhead separation chamber and discharging into the bottom of a slurry bubble column reactor. The downcomer includes a cross-flow filtration element for separating a substantially particle-free liquid hydrocarbon for downstream processing. In another aspect, a method for promoting plug-flow movement in a recirculating slurry bubble column reactor is provided, comprising discharging the recirculating slurry into the reactor through at least one downcomer which terminates near the bottom of the reactor. Devices for accomplishing the above methods are also provided

Influence of Reduction Promoters on Stability of Cobalt/γ-Alumina Fischer-Tropsch Synthesis Catalysts

This focused review article underscores how metal reduction promoters can impact deactivation phenomena associated with cobalt Fischer-Tropsch synthesis catalysts. Promoters can exacerbate sintering if the additional cobalt metal clusters, formed as a result of the promoting effect, are in close proximity at the nanoscale to other cobalt particles on the surface. Recent efforts have shown that when promoters are used to facilitate the reduction of small crystallites with the aim of increasing surface Co0 site densities (e.g., in research catalysts), ultra-small crystallites (e.g., \u3c 2–4.4 nm) formed are more susceptible to oxidation at high conversion relative to larger ones. The choice of promoter is important, as certain metals (e.g., Au) that promote cobalt oxide reduction can separate from cobalt during oxidation-reduction (regeneration) cycles. Finally, some elements have been identified to promote reduction but either poison the surface of Co0 (e.g., Cu), or produce excessive light gas selectivity (e.g., Cu and Pd, or Au at high loading). Computational studies indicate that certain promoters may inhibit polymeric C formation by hindering C-C coupling

Methanol Steam Reforming: Na Doping of Pt/YSZ Provides Fine Tuning of Selectivity

In this work, we found that sodium doping can be used to improve CO2 selectivity for supported Pt catalyst during methanol steam reforming. These materials are usually very active in the low temperature range; however, they are characterized by high selectivity of CO, which is a poison in downstream polymer electrolyte membrane fuel cells (PEM-FC) application. With Na doping, we found that CO2 selectivity was higher than 90% when 2.5 wt.% of sodium was added to Pt/YSZ. We have speculated that the different product distribution is due to a different reaction pathway being opened for CH3OH decomposition. Methanol decarbonylation was favored when Na was absent or low, while a formate decarboxylation pathway was favored when Na content reached 2.5 wt.%. The proposal is rooted in the observed weakening of the C-H bond of formate, as demonstrated in in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and kinetic isotope effect (KIE) experiments for the water-gas shift reaction conducted at low temperature. When adsorbed methoxy, produced when methanol is dissociatively adsorbed, was converted in the presence of H2O in DRIFTS spectroscopy, formate species were prevalent for a 2% Pt–2.5% Na/YSZ catalyst, while only a minor contribution was observed for 2% Pt/YSZ. Moreover, the formate produced on Na-doped Pt/YSZ exhibited ν(CH) stretching bands at low wavenumber, consistent with C–H bond weakening, thus favoring dehydrogenation (and decarboxylation). It is proposed that when Na is present, formate is likely an intermediate, and because its dehydrogenation is favored, selectivity can be fine-tuned between decarbonylation and decarboxylation based on Na dopant level

Identification of tetragonal and cubic structures of zirconia using synchrotron x-radiation source

X-ray diffraction from a synchrotron source was employed in an attempt to identify the crystal structures in zirconia ceramics produced by the sol-gel method. The particles of chemically precipitated zirconia, after calcination below 600 °C, are very fine, and have a diffracting particle size in the range of 7-15 nm. As the tetragonal and cubic structures of zirconia have similar lattice parameters, it is difficult to distinguish between the two. The tetragonal structure can be identified only by the characteristic splittings of the Bragg profiles from the c index planes. However, these split Bragg peaks from the tetragonal phase in zirconia overlap with one another due to particle size broadening. In order to distinguish between the tetragonal and cubic structures of zirconia, three samples were studied using synchrotron radiation source. The results indicated that a sample containing 13 mol % yttria-stabilized zirconia possessed the cubic structure with ao — 0.51420 ± 0.00012 nm. A sample containing 6.5 mol % yttria stabilized zirconia was found to consist of a cubic phase with ao — 0.51430 ± 0.00008 nm. Finally, a sample which was precipitated from a pH 13.5 solution was observed to have the tetragonal structure with ao = 0.51441 ± 0.00085 nm and co = 0.51902 ± 0.00086

Hydrocracking of Octacosane and Cobalt Fischer–Tropsch Wax over Nonsulfided NiMo and Pt-Based Catalysts

The effect of activation environment (N2, H2 and H2S/H2) on the hydrocracking performance of a NiMo/Al catalyst was studied at 380 °C and 3.5 MPa using octacosane (C28). The catalyst physical structure and acidity were characterized by BET, XRD, SEM-EDX and FTIR techniques. The N2 activation generated more active nonsulfided NiMo/Al catalyst relative to the H2 or H2S activation (XC28, 70–80% versus 6–10%). For a comparison, a NiMo/Si-Al catalyst was also tested after normal H2 activation and showed higher activity at the same process conditions (XC28, 81–99%). The high activity of the NiMo/Al (N2 activation) and NiMo/Si-Al catalysts was mainly ascribed to a higher number of Brønsted acid sites (BAS) on the catalysts. The hydrocracking of cobalt wax using Pt/Si-Al and Pt/Al catalysts confirmed the superior activity of the Si-Al support. A double-peak product distribution occurred at C4–C6 and C10–C16 on all catalysts, which illustrates secondary hydrocracking and faster hydrocracking at the middle of the chain. The nonsulfided NiMo/Al and Pt/Al catalysts, and NiMo/Si-Al catalyst produced predominantly diesel (sel. 50–70%) and gasoline range (sel. \u3e 50%) hydrocarbons, respectively, accompanied by some CH4 and light hydrocarbons C2–C4. On the other hand, the hydrocarbon distribution of the Pt/Si-Al varied with conditions (i.e., diesel sel. 87–90% below 290 °C or gasoline sel. 60–70% above 290 °C accompanied by little CH4) The dependence of the isomer/paraffin ratio on chain length was studied as well. The peak iso/paraffin value was observed at C10–C13 for the SiAl catalyst

Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of iron catalyst particles and the formation of ultra-fine particles

Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

In this reporting period, a study of ultra-fine iron catalyst filtration was initiated to study the behavior of ultra-fine particles during the separation of Fischer-Tropsch Synthesis (FTS) liquids filtration. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. The change of particle size during the slurry-phase FTS has monitored by withdrawing catalyst sample at different TOS. The measurement of dimension of the HRTEM images of samples showed a tremendous growth of the particles. Carbon rims of thickness 3-6 nm around the particles were observed. This growth in particle size was not due to carbon deposition on the catalyst. A conceptual design and operating philosophy was developed for an integrated wax filtration system for a 4 liter slurry bubble column reactor to be used in Phase II of this research program. The system will utilize a primary inertial hydroclone followed by a Pall Accusep cross-flow membrane. Provisions for cleaned permeate back-pulsing will be included to as a flux maintenance measure

Separation of Fischer-Tropsch Wax Products from Ultrafine Iron Catalyst Particles

The morphological and chemical nature of ultrafine iron catalyst particles (3-5 nm diameters) during activation/FTS was studied by HRTEM, EELS, and Moessbauer spectroscopy. With the progress of FTS, the carbide re-oxidized to magnetite and catalyst activity gradually decreased. The growth of oxide phase continued and average particle size also increased simultaneously. The phase transformation occurred in a ''growing oxide core'' manner with different nano-zones. The nano-range carbide particles did not show fragmentation or attrition as generally observed in micrometer range particles. Nevertheless, when the dimension of particles reached the micrometer range, the crystalline carbide phase appeared to be sprouted on the surface of magnetite single crystal. In the previous reporting period, a design and operating philosophy was developed for an integrated wax filtration system for a 4 liter slurry bubble column reactor to be used in Phase II of this research program. During the current reporting period, we have started construction of the new filtration system and began modifications to the 4 liter slurry bubble column reactor (SBCR) reactor. The system will utilize a primary wax separation device followed by a Pall Accusep or Membralox ceramic cross-flow membrane. As of this writing, the unit is nearly complete except for the modification of a moyno-type pump; the pump was shipped to the manufacturer to install a special leak-free, high pressure seal

Fischer–Tropsch Synthesis: Effect of Ammonia on Product Selectivities for a Pt Promoted Co/Alumina Catalyst

The effects of co-fed ammonia in synthesis gas on the activity and product selectivities of a typical cobalt catalyst (0.5% Pt–25% Co/Al2O3) were investigated during the Fischer–Tropsch synthesis using a continuously stirred tank reactor (CSTR). The product selectivities were compared at a similar CO conversion level for various concentrations (10–1000 ppmv) of ammonia, as well as clean (un-poisoned) conditions. The addition of 10–1000 ppmv ammonia (concentration of ammonia with respect to the syngas feed) significantly decreased activity; the percentage of deactivation was similar (∼40%) for the various concentrations of ammonia used. At similar CO conversions, the addition of ammonia caused an increase in olefin selectivity and the corresponding paraffin and alcohol selectivities were decreased compared to the ammonia free synthesis conditions. Olefin selectivity increased with increasing concentration of ammonia, and the paraffin and alcohol selectivities were decreased with increasing ammonia concentration. At similar CO conversions, ammonia addition exhibited a positive effect on hydrocarbon selectivity (i.e., lower light gas products and higher C5+) and also light gas product selectivities (C1–C4) were decreased and C5+ selectivity increased with increasing concentration of ammonia compared to ammonia free conditions

Fischer–Tropsch: Product Selectivity–The Fingerprint of Synthetic Fuels

The bulk of the products that were synthesized from Fischer–Tropsch synthesis (FTS) is a wide range (C1–C70+) of hydrocarbons, primarily straight-chained paraffins. Additional hydrocarbon products, which can also be a majority, are linear olefins, specifically: 1-olefin, trans-2-olefin, and cis-2-olefin. Minor hydrocarbon products can include isomerized hydrocarbons, predominantly methyl-branched paraffin, cyclic hydrocarbons mainly derived from high-temperature FTS and internal olefins. Combined, these products provide 80–95% of the total products (excluding CO2) generated from syngas. A vast number of different oxygenated species, such as aldehydes, ketones, acids, and alcohols, are also embedded in this product range. These materials can be used to probe the FTS mechanism or to produce alternative chemicals. The purpose of this article is to compare the product selectivity over several FTS catalysts. Discussions center on typical product selectivity of commonly used catalysts, as well as some uncommon formulations that display selectivity anomalies. Reaction tests were conducted while using an isothermal continuously stirred tank reactor. Carbon mole percentages of CO that are converted to specific materials for Co, Fe, and Ru catalysts vary, but they depend on support type (especially with cobalt and ruthenium) and promoters (especially with iron). All three active metals produced linear alcohols as the major oxygenated product. In addition, only iron produced significant selectivities to acids, aldehydes, and ketones. Iron catalysts consistently produced the most isomerized products of the catalysts that were tested. Not only does product selectivity provide a fingerprint of the catalyst formulation, but it also points to a viable proposed mechanistic route