Identification of reaction zones in a commercial Sasol-Lurgi fixed bed dry bottom gasifier operating on North Dakota lignite

The Sasol-Lurgi fixed bed dry bottom gasification technology has the biggest market share in the world with 101 gasifiers in operation. To be able to further improve the technology and also to optimise the operating plants, it is important that the fundamentals of the process are understood. The main objective of this study was to determine the reaction zones occurring in the Sasol-Lurgi fixed bed dry bottom (S-L FBDB) gasifier operating on North Dakota lignite. A Turn-Out sampling method and subsequent chemical analyses of the gasifier fuel bed samples was used to determine the reaction zones occurring in the commercial MK IV, S-L FBDB gasifier operating on North Dakota lignite. The reaction zones were further compared with the same reactor operating on bituminous coal.Based on the results obtained from this study it was found that about two thirds of the gasifier volume was used for drying and de-volatilising the lignite thus leaving only about a third of the reactor volume for gasification and combustion. Nonetheless, due to the high reactivity of the lignite, the char was consumed within a third of the remaining gasifier volume. Clear overlaps between the reaction zones were observed in the gasifiers thus confirming the gradual transition from one reaction zone to another as reported in literature. Due to the high moisture content in the lignite, the pyrolysis zone in the gasifiers operating on North Dakota lignite occurred lower/deeper in the gasifier fuel bed as compared to the same gasifier operating on South African bituminous coal from the Highveld coalfield. All the other reaction zones in the gasifier operating on bituminous coal were also higher in the bed compared to the lignite operation. This can therefore explain the higher gas outlet temperatures for the S-L FBDB gasifiers operating on higher rank coals when compared to the gasifiers operating on lignite. The fact that the entire reactor volume was utilized for drying, de-volatilisation, gasification and combustion with carbon conversion of >98% makes the S-L FBDB gasifier very suitable for lignite gasification.     

Carbon particle type characterization of the carbon behaviour impacting on a commercial-scale Sasol-Lurgi FBDB gasifier

Char-form analysis, whilst not yet an ISO standard, is a relatively common characterization method applied to pulverized coal samples used by power utilities globally. Fixed-bed gasification coal feeds differ from pulverized fuel combustion feeds by nature of the initial particle size (+6 mm, −75 mm). Hence it is unlikely that combustion char morphological characterization schemes can be directly applied to fixed-bed gasifier chars. In this study, a unique carbon particle type analysis was developed to characterize the physical (and inferred chemical) changes occurring in the particles during gasification based on coal petrography and combustion char morphology. A range of samples sequentially sampled from a quenched commercial-scale Sasol-Lurgi fixed-bed dry-bottom (FBDB) Gasifier were thus analysed.It was determined that maceral type (specifically vitrinite and inertinite) plays a pivotal role in the changes experienced by carbon particles when exposed to increasing temperature within the gasifier. Whole vitrinite particles and vitrinite bands within particles devolatilized first, followed at higher temperatures by reactive inertinite types. By the end of the pyrolysis zone, all the coal particles were converted to char, becoming consumed in the oxidation/combustion zone as the charge further descended within the gasifier.The carbon particle type results showed that both the porous and carbominerite char types follow similar burn-out profiles. These char types formed in the slower pyrolysis region within the pyrolysis zone, increasing to around 10% by volume within the reduction zone, where 53% carbon conversion occurred. Both of these char forms were consumed by the time the charge reached the ash-grate at the base of the reactor, and therefore did not contribute to the carbon loss in the ash discharge. It would appear as if the dense char and intermediate char types are responsible for the few percent carbon loss that is consistently obtained at the gasification operations.The carbon particle type analysis developed for coarse coal to the gasification process was shown to provide a significant insight into the behaviour of the carbon particles during gasification, both as a stand alone analysis and in conjunction with the other chemical and physical analyses performed on the fixed-bed gasifier samples.     

Trace element behaviour in the Sasol-Lurgi MK IV FBDB gasifier. Part 1 - The volatile elements: Hg, As, Se, Cd and Pb

Coal-fired power and heat production are the largest single source of Hg in the atmosphere, and in March 2005, the US-EPA ruled regarding Hg reduction from coal utilization in the USA. Appropriate Hg pollution control of technology, as well as reductions in the uses of Hg and coal-containing Hg can readily reduce the releases of Hg from coal utilities. Integrated multi-pollutant (SOx, NOx, particulate matter and Hg) control technologies may be a cost-effective approach. Prior to considering mitigation technologies, it is necessary to understand the quantity of mercury in the feed coal, its mode of occurrence (i.e. mineral or organic associations), its partitioning behaviour during the process, and the volume and species in which it is being emitted via stacks. These factors have all been investigated up to the point of release for the Sasol gasification and steam-raising plants, including other trace elements.The focus of this paper is to discuss the more recent environmental research developments by Sasol, where trace element simulation and validation of model predictions have been undertaken for the Sasol-Lurgi gasification process operating on lump coal. Fact-Sage thermodynamic equilibrium modeling was used to simulate the trace elements: Hg, As, Se, Cd and Pb gas phase and ash phase partitioning and speciation behaviour occurring in a fixed-bed pressurised gasifier. A Sasol-Lurgi Mark IV (MK IV) fixed-bed dry bottom (FBDB) gasifier was mined via turn-out sampling in order to determine the trace element changes through the gasifier, findings being used to validate the modeled results. This paper will focus on the behaviour of the volatile Class I trace elements: Hg, As, Se, Cd and Pb within the Sasol-Lurgi MK IV FBDB gasifier as function of coal quality. This study excludes the downstream gas cleaning partitioning and speciation behaviour of these elements, which will form the basis of a future paper.Good agreement between model-predictions and measurements have been attained in this study, with the exception of As. Hg, Cd, Pb, As and Se were all found to be highly volatile, partitioning into the gas phase. Hg was found to be the most volatile element during fixed-bed gasification and is present in the gas phase in the form of elemental Hg (g). As, Se, Cd and Pb have lower volatilities when compared to Hg, and they vary in an order: Hg > Se > Cd > Pb > As. Speciation predictions showed that: Hg, AsH₃, H₂Se, PbSe, Cd, CdS, and PbS/Pb/PbCl, species could potentially exist in the raw gas phase.     

Efficient synthesis of zwitterionic sulfobetaine group functional polyurethanes via “click” reaction

A novel polyurethane material containing zwitterionic sulfobetaine groups has been synthesized using the copper‐catalyzed 1,3‐dipolar cycloaddition (azide‐alkyne click chemistry). A standard two‐step polyaddition method was used to produce the well‐defined polyurethane based on polycarbonatediol (PCDL) with alkyne groups. These polyurethanes containing alkyne units were then efficiently clicked using 3‐((2‐azidoethyl)dimethylammonio)propane‐1‐sulfonate (DMPS‐N₃). The novel PU material was characterized by ¹H NMR, Fourier transform infrared (FTIR) spectrometer, gel permeation chromatography (GPC), elemental analysis, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical analysis (DMA). This facile “click” reaction provides a useful tool for the development of novel functional polyurethanes for biomedical applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of the new cellulose derivative films based on the hydroxyethyl cellulose prepared from esparto “stipa tenacissima” cellulose of Eastern Morocco. II. Esterification with acyl chlorides in a homogeneous medium

Esparto “Stipa tenacissima” cellulose esters derivatives: HECA‐COO? C₄H₈? COOC₂H₅, HECA‐COO? C₈H₁₆? COOC₂H₅, and HECA‐COO? C₆H₄? COOC₂H₅ were successfully prepared in Tetrahydrofuran (THF)/triethylamine system with a degree of substitution (DS), respectively, DS_AD‐Et=0.32, DS_SB‐Et=0.22, and DS_TRP‐Et=0.50 using hydroxyethyl cellulose acetate (HECA; DS_AC=0.50) as intermediate product, and we avoided the drawbacks of cellulose solubility. The structural modifications were investigated using Fourier transform infrared spectroscopy (FTIR), Proton nuclear magnetic resonance (¹H‐NMR), Carbon‐13 nuclear magnetic resonance (¹³C‐NMR), and Distortionless Enhancement by Polarization Transfer 135° (DEPT‐135). The results from these analyses revealed the presence of the characteristic groups indicating that the grafting reaction was successful. The crystallinity and the structure order changes during the esterification reactions were recorded by X‐ray diffraction (XRD), it is found that the crystallinity degree decrease from 63.1% for Esparto “Stipa tenacissima” cellulose to 27.74% for HECA. The thermal stability of the esterified and unmodified cellulose samples was studied by thermogravimetric analysis (TGA)‐differential thermal analysis (DTA); the modified HECA exhibits a decrease in thermal stability relatively to the unmodified HECA, and this may be related to the groups grafted. The resulted cellulose esters HECA‐P_x (x = 1, 2, or 3) were soluble in THF and present an amorphous structure justified by XRD spectra. It was noted by TGA‐DTA analysis that the cellulose esters with low melting range were proved as thermoplastic polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Fabrication of pH‐ or temperature‐responsive single wall carbon nanotubes via a graft from photopolymerization

An ultraviolet light initiated “graft from” polymerization method to fabricate polymer‐functionalized single wall carbon nanotubes (SWNTs) with pendant pH‐ and temperature‐responsive polymer chains is utilized. The attached polymer chains, formed from methacrylic acid and poly(ethylene glycol) methyl ether methacrylate monomers, are well established for its pH‐responsive swelling/deswelling behavior. This special property was utilized here to control the aqueous dispersibility of the carbon nanotubes. Furthermore, poly(N‐isopropylacrylamide), a temperature‐responsive polymer, was utilized in the fabrication of SWNTs whose dispersibility was dependent on solution temperature. The morphology of the polymer‐functionalized carbon nanotubes was characterized by scanning electron microscopy (SEM) before and after functionalization. Environmental SEM was used to further characterize the morphology of the functionalized SWNTs. In addition, covalent bonding of the polymer to the carbon nanotube surface was established using Raman and Fourier transform infrared spectroscopic techniques. The physical and chemical properties of the functionalized nanotubes were further characterized by energy‐dispersive X‐ray spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2980–2986, 2012     

“Click” Polymer‐Supported Palladium Nanoparticles as Highly Efficient Catalysts for Olefin Hydrogenation and Suzuki Coupling Reactions under Ambient Conditions

Complexation of palladium(II) acetate [Pd(OAc)₂] or dipotassium tetrachloropalladate [K₂PdCl₄] to “click” polymers functionalized with phenyl, ferrocenyl and sodium sulfonate groups gave polymeric palladium(II)‐triazolyl complexes that were reduced to “click” polymer‐stabilized palladium nanoparticles (PdNPs). Transmission electron microscopy (TEM) showed that reduction using sodium borohydride (NaBH₄) produced PdNPs in the 1–3 nm range of diameters depending on the nature of the functional group, whereas slow reduction using methanol yielded PdNPs in the 22–25 nm range. The most active of these PdNPs (0.01% mol Pd), stabilized by poly(ferrocenyltriazolylmethyl)styrene, catalyzed the hydrogenation of styrene at 25 °C and 1 atm hydrogen, with turnover numbers (TONs) of 200,000. When stabilized by the water‐soluble poly(sodium sulfonate‐triazolylmethyl)styrene, the PdNPs (0.01% mol Pd) catalyze the Suzuki–Miyaura coupling between iodobenzene (PhI) and phenylboronic acid [PhB(OH)₂] in water/ethanol (H₂O/EtOH) at 25 °C with TONs of 8,200. This high catalytic activity is comparable to that obtained with “click” dendrimer‐stabilized PdNPs under ambient conditions.     

Peculiar sandwich-like π–π interaction regulating the nonplanarity of the model heme crystals

X-ray crystallographic analysis of bis(pyridine N-oxide) complexes of iron(III) porphyrinates has revealed that the two pyridine rings of the axial ligands correctly sandwich the porphyrin ring to induce the deformation of commonly observed S₄ saddled porphyrin ring.     

Tailor‐Made Functional Polymethacrylates with Dual Characteristics of Self‐Healing and Shape‐Memory Based on Dynamic Covalent Chemistry

New shape memory polymers with self‐healing behavior are obtained by thermoreversible Diels–Alder (DA) cross‐linking of a furfuryl group‐containing star‐block copolymer with 1,1′‐(methylenedi‐4,1‐phenylene)bismaleimide. The star‐block copolymer consisting of a 3‐arm polycaprolactone (PCL) core and a polyfurfuryl methacrylate shell is synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. For this, a 3‐arm macro‐RAFT agent based on PCL is converted with an appropriate amount of furfuryl methacrylate in the presence of a radical initiator. Films of the DA network are partly insoluble at ambient temperatures. After annealing at 120 °C the films become completely soluble because of the progressing retro‐DA reaction. Evaporation of the solvent and subsequent annealing at 60 °C restores the original insoluble state of the material. By means of a scratch test and tensile tests on cut and subsequently mended samples it is shown that the retro‐DA reaction facilitates self‐healing. Additionally, the films show pronounced shape memory effects with reasonable shape recovery and fixity ratios, which are attributed to the melting and crystallization of the PCL phase.     

On the Role of Extensional Flow in Morphology and Property Modifications of MWCNT/Polyamide‐Based Fibers

Unfilled and MWCNT‐filled PA fibers are prepared and the effect of the extensional flow on their mechanical performance and morphological variations is investigated. Morphological analyses using SEM, TEM, and SAXS suggest a stronger orientation of the MWCNTs along the fiber direction with increasing extensional flow. A particular MWCNT bundle formation in the PA drawn nanocomposite fibers is observed for the first time, and a pull‐out of the central nanotube in some bundles is noted. The maintenance of the “shish‐kebab” structure upon extensional flow is responsible for the mechanical improvements and dimensional stability in MWCNT‐filled PA fibers.

     

Effective MgO surface doping of Cu/Zn/Al oxides as water–gas shift catalysts

Trace amounts of MgO were doped on Cu/ZnO/Al₂O₃ catalysts with the Cu/Zn/Al molar ratio of 45/45/10 and tested for the water–gas shift (WGS) reaction. A mixture of Zn(Cu)–Al hydrotalcite (HT) and Cu/Zn aurichalcite was prepared by co-precipitation (cp) of the metal nitrates and calcined at 300 °C to form the catalyst precursor. When the precursor was dispersed in an aqueous solution of Mg(II) nitrate, HT was reconstituted by the “memory effect.” During this procedure, the catalyst particle surface was modified by MgO-doping, leading to a high sustainability. Contrarily, cp-Mg/Cu/Zn/Al prepared by Mg²⁺, Cu²⁺, Zn²⁺ and Al³⁺ co-precipitation as a control exhibited high activity but low sustainability. Mg²⁺ ions were enriched in the surface layer of m-Mg–Cu/Zn/Al, whereas Mg²⁺ ions were homogeneously distributed throughout the particles of cp-Mg/Cu/Zn/Al. CuO particles were significantly sintered on the m-catalyst during the dispersion, whereas CuO particles were highly dispersed on the cp-catalyst. However, the m-catalyst was more sustainable against sintering than the cp-catalyst. Judging from TOF, the surface doping of MgO more efficiently enhanced an intrinsic activity of the m-catalyst than the cp-catalyst. Trace amounts of MgO on the catalyst surface were enough to enhance both activity and sustainability of the m-catalyst by accelerating the reduction–oxidation between Cu⁰ and Cu⁺ and by suppressing Cu⁰ (or Cu⁺) oxidation to Cu²⁺.     

Supramolecular π–π assembly of a neutral [Cu(salen)] complex via the templating effect of an ionic inorganic complex Na2[Cu(mnt)2] forming a framework type material having well-defined channels

A classical ionic inorganic complex Na₂[Cu(mnt)₂] (mnt²⁻ = maleonitriledithiolate = 1,2-dicyanoethylenedithiolate), that acts as a template in assembling neutral [Cu(salen)] (salen = bis(salicylidene)ethylenediamine) complexes forming a framework type arrangement, is accommodated in the channel formed in the crystal structure of a new type of host–guest compound [Cu(salen)]₄ · Na₂[Cu(mnt)₂] (1). The non-covalent supramolecular interactions among [Cu(salen)] complexes and between [Cu(salen)] and [Cu(mnt)₂]²⁻ complexes in the crystal lattice of 1 result in weak antiferromagnetic coupling.     

Polymerization of methyl methacrylate with a thermal iniferter: Diethyl 2,3‐dicyano‐2,3‐di(p‐tolyl)succinate

A hexa‐substituted ethane type compound, diethyl‐2,3‐dicyano‐2,3‐di(p‐tolyl)succinate (DCDTS), was successfully synthesized and used for initiation of methyl methacrylate (MMA) polymerization. The reaction demonstrated the characteristics of a “living” polymerization; i.e., both the yield and the molecular weight of the resulting polymers increased linearly with increasing reaction time, the molecular‐weight distribution of PMMA obtained was ～1.60 and almost unaffected by the conversion, and the resultant polymer can be chain extended by adding fresh MMA. End group analysis of the resultant PMMA confirmed that DCDTS behaves as a thermal iniferter for MMA polymerization. A block copolymer was prepared from the resultant PMMA, which contains a hexa‐substituted C? C bond functional end group. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2566–2572, 2001     

Realization and control of multiple temperature zones in liquid‐containing gas–solid fluidized bed reactor

Fluidized bed reactors (FBRs) have been developed to establish multiple temperature zones for various industrial processes. To overcome the common weakness, this work proposed to spray liquid into bottom and upper zones, respectively, to realize multiple temperature zones FBR (MTZFBR). Temperature, pressure, and acoustic emission techniques were applied to fully characterize liquid interaction and hydrodynamics. Compared with the bottom liquid‐spraying approach, the upper liquid‐spraying approach showed higher temperature difference (ΔT) and better fluidization stability, thus was selected for further control studies. Effects of liquid flow rate, static bed height, and inlet gas temperature on MTZFBR were studied systematically. The results showed that increasing liquid evaporation behavior or decreasing liquid bridge behavior enhance ΔT and fluidization stability and vice versa. G–L–S fluidization pattern depended mostly on the liquid behaviors and fluidization stability, and thus the stabilized MTZFBR could be regarded as a coexisted mode of two distinctive G–L–S fluidization patterns. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1454–1466, 2016     

Update: An Efficient Synthesis of Poly(ethylene glycol)‐Supported Iron(II) Porphyrin Using a Click Reaction and its Application for the Catalytic Olefination of Aldehydes

The facile synthesis of polyethylene glycol (PEG)‐immobilized iron(II) porphyrin using a copper‐catalyzed azide‐alkyne [3+2] cycloaddition “click” reaction is reported. The prepared complex 5 (PEG‐C₅₁H₃₉FeN₇O) was found to be an efficient catalyst for the selective olefination of aldehydes with ethyl diazoacetate in the presence of triphenylphosphine, and afforded excellent olefin yields with high (E) selectivities. The PEG‐supported catalyst 5 was readily recovered by precipitation and filtration, and was recycled through ten runs without significant activity loss.     

Target Hopping as a Useful Tool for the Identification of Novel EphA2 Protein–Protein Antagonists

Lithocholic acid (LCA), a physiological ligand for the nuclear receptor FXR and the G‐protein‐coupled receptor TGR5, has been recently described as an antagonist of the EphA2 receptor, a key member of the ephrin signalling system involved in tumour growth. Given the ability of LCA to recognize FXR, TGR5, and EphA2 receptors, we hypothesized that the structural requirements for a small molecule to bind each of these receptors might be similar. We therefore selected a set of commercially available FXR or TGR5 ligands and tested them for their ability to inhibit EphA2 by targeting the EphA2‐ephrin‐A1 interface. Among the selected compounds, the stilbene carboxylic acid GW4064 was identified as an effective antagonist of EphA2, being able to block EphA2 activation in prostate carcinoma cells, in the micromolar range. This finding proposes the “target hopping” approach as a new effective strategy to discover new protein–protein interaction inhibitors.     

Controlled radical polymerization catalyzed by CuCl/BDE complex in water medium. I. Polymerization of styrene and synthesis of poly(St‐b‐MMA)

The controlled radical polymerization of styrene in water medium, in the presence of polyoxyethylene nonyl phenyl ether, catalyzed and initiated by CuCl/BDE [bis(N,N′‐dimethylaminoethyl)ether]/R—X was studied. The results show that the molecular weight increased with conversion of the monomer. Using this controlled system, the block copolymer, poly(St‐b‐MMA), was successful synthesized in water medium. In reference to the system of CuCl/BDE/PhCH₂Cl, the polymerization may also occur in the micelle to produce a superhigh molecular mass (M_n = 1,500,000) polymer with monodispersion (MWD, M_w/M_n = 1.03). The Cu(I) and Cu(II) partition ratio in two phases, which may affect the reversible deactivation and debase the catalyst efficiency, was detected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 802–807, 2000     

Treatment of the refinery wastewater in a gas–liquid–solid three‐phase flow airlift loop bioreactor

Aerobic treatment of refinery wastewater was carried out in a 200 dm³ gas–liquid–solid three‐phase flow airlift loop bioreactor, in which a biological membrane replaced the activated sludge. The influences of temperature, pH, gas–liquid ratio and hydraulic residence time on the reductions in chemical oxygen demand (COD) and NH₄‐N were investigated and discussed. The optimum operation conditions were obtained as temperature of 25–35 °C, pH value of 7.0–8.0, gas–liquid ratio of 50 and hydraulic residence time of 4 h. The radial and axial positions had little influence on the local profiles of COD and NH₄‐N. Under the optimum operating conditions, the effluent COD and NH₄‐N were less than 100 mg dm^?3 and 15 mg dm^?3 respectively for more than 40 days, satisfying the national primary discharge standard of China (GB 8978‐1996). Copyright © 2005 Society of Chemical Industry