Syngas Stoichiometric Adjustment for Methanol Production and Co-Capture of Carbon Dioxide by Pressure Swing Adsorption

Methanol is an important raw material in industry and is commonly produced from syngas. The stoichiometric ratio (H₂–CO₂)/(CO + CO₂) of the methanol synthesis reactor feed stream must be adjusted to approximately 2.1. In this study, the replacement of the solvent unit within a coal to methanol process by a pressure swing adsorption (PSA) unit is proposed. The PSA produces a hydrogen enriched stream, to adjust the stoichiometric ratio of the methanol feed stream, and simultaneously captures the carbon dioxide for future sequestration. The feed flow rate is sub divided into eight 4-bed PSA units, operated with a defined phase lag between them in order to flatten the products (composition and flow rate) oscillations. The results show that the stoichiometric adjustment is possible and that oscillations on the products flow rate and composition are reduced to less than 3%. A carbon dioxide stream of 95.15% is obtained with a recovery of 94.2% and a productivity of 82.7 mol CO₂/kg/day. The power consumption of the global process is 119.7 MW, which includes the requirements for the rinse stream (64.4 MW) and the compression of the CO₂ product to 110 bar for sequestration (55.3 MW).     

Fermentation and oxygen transfer characteristics in serine alkaline protease production by recombinant Bacillus subtilis in molasses‐based complex medium

Serine alkaline protease (SAP) production in a complex medium based on physically pretreated molasses by recombinant Bacillus subtilis carrying pHV1431::subC gene is described. The effects of oxygen transfer were investigated in 3.5 dm³ bioreactor systems with controls for agitation rate, dissolved oxygen, pH, temperature, and foam formation under two different agitation rates, ie N = 500 and 750 min^?1, and four different air flow rates, ie Q/V_R = 0.2, 0.5, 0.7, and 1.0 vvm, at a molasses concentration equivalent to initial sucrose concentration (C_So) of 20 kg m^?3. The yield values (Y_X/S, Y_X/O, Y_S/O) and maintenance coefficient of oxygen (m_O), were calculated. m_O decreased with the increase in the air‐inlet rate. Increase in oxygen transfer rate increased the rate of growth and SAP activity, and affected the cultivation time to achieve maximum expression of SAP activity. At Q/V_R = 0.5 vvm and N = 750 min^?1, SAP activity reached 2250 U cm^?3 at t = 36 h. The oxygen transfer coefficient (K_La) and oxygen uptake rate (?r_O) were measured throughout the fermentations and their variation with the oxygen transfer conditions determined. New correlations for the calculation of K_La and ?r_O are proposed. Copyright © 2004 Society of Chemical Industry     

Instant acquisition of high resolution mobility spectra in a differential mobility analyzer with 100 independent ion collectors: Instrument calibration

Abstract

A parallel plate differential mobility analyzer (DMA) having 100 independent current collectors is calibrated to relate the axial distances L_n between the inlet slit and the detector position to the particle mobility Z at given voltage difference V and sheath gas flow rate Q. Calibrating species are tetraheptylammonium bromide clusters (THABr) and polyethylene glycol (PEG35k, 5?nm in diameter), generated by a bipolar electrospray source, and purified in a cylindrical DMA. Gaussian fitting of the raw discrete mobility spectra in the form of ion current I_n versus collector position L_n , I_n (L_n ), yield the mean value L_o of the collector position maximizing the signal for a given ion. The many (Z,V,L_o ) triads obtained at given Q from many different DMA voltages and standard mobilities collapse into a single 1/(Z_iV_j ) vs L_o curve when slight adjustments are made to the Z_i . For different flow rates, Q/(Z_iV_j ) vs. L_o curves collapse also, as long as the peaks are moderately narrow. However, for sufficiently small Q/Z, the THABr cluster peaks become broad, and the curves Q/(Z_iV_j ) vs. L_o cease to collapse precisely. In contrast, the data for PEG show that this behavior is not a low-Q (Reynolds number) effect from the growth of the two lateral boundary layers, but is rather due to the broad and non-Gaussian peak shapes obtained at low Q or high Z. The calibration is accordingly unaffected by the Reynolds number. This simplicity was unexpected, given the three-dimensional flow in this DMA with growing lateral boundary layers.

Copyright © 2020 American Association for Aerosol Research     

Absorption of carbon dioxide in aqueous colloidal silica solution with NaOH

The absorption rate (R _A ) of carbon dioxide was measured into an aqueous nanometer-sized colloidal silica solution of 0–31 wt% and NaOH of 0–2 kmol/m³ in a flat-stirred vessel for various sizes and speeds of 25 °C and 101.3 N/m² to obtain the volumetric liquid-side mass transfer coefficient (k _L a _L ) of CO₂. The film theory accompanied by chemical reaction between CO₂ and NaOH was used to estimate the theoretical value of absorption rate of CO₂. The empirical correlation formula containing the relationship between k _L a _L and rheological property of the aqueous colloidal silica solution was presented. The value of R _A in the aqueous colloidal silica solution was decreased by the reduction of k _L a _L due to elasticity of the solution.     

Effect of WC on electrodeposition and corrosion behaviour of chromium coatings

To study the effect of WC particles on corrosion behaviour of chromium coating steel samples were plated in Cr(VI) baths with various concentrations of WC. XPS, EPM and XRD were used to study the chemical composition, morphology and texture of the coatings. The corrosion behaviour was studied at different exposure times in solution containing 0.01 mol L^–1 H₂SO₄ + 0.5 mol L^–1 Na₂SO₄ using cyclic voltammetry and impedance spectroscopy. Cyclic polarization measurements suggest that WC particles slow down the processes of passive film dissolution and penetration of aggressive ions to the substrate. Electrochemical impedance spectroscopy (EIS) was used to reveal the details of the corrosion process at the solution/electrode interface. The simulation of EIS data with a proposed equivalent circuit model made it possible to obtain quantitative valuation of the Y₀ (Q_c), Y₀ (Q_s) and R_pore parameters, reflecting corrosion behaviour of samples at the solution/electrode interface. Samples plated in a Cr(VI) bath with WC provided better resistance to corrosion than those plated in a bath without WC. Analysis of the data obtained suggests that WC particles enhance corrosion resistance due to the microstructural features of the coatings.     

Removal of Heavy Metals from Aqueous Solutions by Precipitation-Filtration Using Novel Organo-Phosphorus Ligands

Abstract

An organophosphorus mixture of sodium mono- and di-(n-hexa-decyl) phosphinate was synthesized and purified, and then used as a ligand to remove heavy metals by precipitation from aqueous nitrate, chloride, and sulfate solutions. The new ligand offers more advantages over the previously studied sodium dioctyl and dodecyl phosphinates. The sodium form of the mono- and di-(n-hexa-decyl) phosphinate has a much lower solubility in water, which contributed to much lower back contamination and much lower loss of the reagent, even when excess amount of ligand was employed. Moreover, an excess amount of the ligand did not alter the filtration characteristics of the resultant precipitate. The heavy metals: lead, cadmium, mercury, cobalt, and nickel were precipitated with the sodium mono- and di-(n-hexa-decyl) phosphinate, NaL, in the form of Pb L _2(s), Cd L _2(s), Hg L _2(s), Co L _2(s), and Ni L _2(s). In the absence of free acid in the feed, a maximum removal of each metal corresponded to the stoichiometric ratio. The residual concentrations of each of the metals at the optimum conditions were measured for the different media and found to be lower than 10 ppb, lower than the acceptable levels for most regions. Lead, as a model heavy metal, was studied in more detail. Adding an acid to the feed solution reduced the removal of lead as some of the phosphinate ligand was converted to the acid form. The presence of chloride and sulfate in the feed solution; up to mole ratios to lead of 5000, and of calcium in the feed solution; up to mole ratio to lead of 200, had no effect on the removal of lead. The ligand was more selective to lead than the other four metals, and the selectivity was in the order Pb > Cd > Co & Ni > Hg. The ligand was regenerated up to 99.99% and the metals were recovered in 100 times more concentrated aqueous solutions.     

AIR PURIFICATION AND VAPOR RECOVERY BY PRESSURE SWING ADSORPTION: A COMPARISON OF SILICALITE AND ACTIVATED CARBON

Air purification and vapor recovery by pressure swing adsorption (PSA) were experimentally investigated using the silicalite-DMMP-air system. The results from several cyclic steady-state PSA runs were compared at constant throughput with those from a previous study on the BPL activated carbon-DMMP-air system. The performance of BPL activated carbon was superior to that of silicalite because it demonstrated complete cleanup of the product effluent when starting from a saturated column, whereas, at similar process conditions, silicalite was able to cleanup only a portion of the product effluent. Nevertheless, both silicalite and BPL activated carbon respectively demonstrated enrichments (Y_e/Y_f ) of 12 and 15 using only moderate vacuum. However, there were significant differences in the shapes of the cyclic steady-state product and exhaust profiles which were attributed to differences in the 1) mass transfer rates, 2) adsorption capacities, or 3) possibly shapes of the adsorption isotherms.     

Thermosetting mechanism study of silicon-containing polyarylacetylene via in situ FTIR and solid-state NMR spectroscopy

Silicon-containing polyarylacetylene (abbreviated as PSA) resins, which contain Si-(R₁, R₂) (R₁ and R₂ represent methyl or phenyl groups) and —CC—, exhibits high thermal stability upon curing up to 250 °C. The structure and thermosetting mechanism of PSA were characterized using FTIR, in situ FTIR, ¹³C and ²⁹Si CP-MAS spectroscopy, and thermogravimetric analysis. From the experimental results we can conclude that: (1) biphenyl and naphthalene rings are formed via a Diels–Alder reaction between the Ph—CC and CC groups at 210 °C, (2) the terminal alkyne mainly transforms into ethylenic bonds at 170 and 210 °C, and (3) an oxidation reaction occurs to give the oxide structure (Si—O—Si) and carbon dioxide at 250 °C. A new curing procedure has been proposed to maximize the T_d5 up to 635.2 °C on that basis. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47301.     

Theoretical pressure dependency of carbon dioxide solubility under hydrate–liquid water equilibrium

The effect of pressure on carbon dioxide solubility in water is significantly smaller than that of temperature under hydrate–liquid water (H–L_w) equilibrium. As a result, experimental values of carbon dioxide solubility in the water rich liquid phase under H–L_w equilibrium are often inconclusive and in some cases contradictory. This work proposes a theoretical derivation, based on fundamental thermodynamics, of the gas hydrate former solubility dependency on pressure for any binary system under two‐phase equilibrium. The obtained expression is applied to the carbon dioxide–water system under both hydrate–liquid water and vapour–liquid water equilibrium. It is shown that the solubility of carbon dioxide in the water rich liquid phase increases with increasing pressure under H–L_w equilibrium. The predicted trend is then compared to the limited experimental data available in the literature.     

Chiral copolymers of (R)‐N‐(1‐phenylethyl) methacrylamide and 2‐hydroxyethyl methacrylate: copolymerization characteristics and chiroptical properties

The aim of this investigation was the copolymerization of a chiral monomer, (R)‐N‐(1‐phenylethyl) methacrylamide, with an achiral monomer, 2‐hydroxyethyl methacrylate (HEMA). The copolymerization characteristics as well as the chiroptical properties (optical rotation and circular dichroism) and their variation with copolymer composition and temperature are discussed. The copolymers are statistical and enriched in HEMA. The monomer reactivity ratio of the chiral monomer (r₁) is 0.133 whereas that of HEMA (r₂) is 1.042 based on the Kelen–Tudos method. The sequence of consecutive chiral monomer units predominates for a feed composition between 0.5 and 0.9 (mole fraction). On the other hand, the sequence of HEMA is uniform and it predominates for a feed composition of around 0.5 (mole fraction). The chiroptical properties of the copolymers do not vary linearly with the content of chiral units in the copolymers. The optical rotation and circular dichroism attain optimum values above 30–40 mol% of chiral monomer units in the copolymers. However, the circular dichroism of the copolymers varies linearly with the temperature. The chiral monomer being a more bulky structure is less reactive than HEMA. The nonlinear variation of chiroptical properties of the copolymers with the content of chiral units may be due to the secondary interaction in the copolymers associated with the hydrogen bonding involving the amide linkage (CONH) present in the pendant chromophore of the chiral monomer as well as the hydroxyl pendant group of HEMA and also the aromatic π–π interaction. Copyright © 2009 Society of Chemical Industry     

Mass transfer of carbon dioxide in aqueous colloidal silica solution containing <Emphasis Type="Italic">N</Emphasis>-methyldiethanolamine

The absorption rate (R _A ) of carbon dioxide was measured into an aqueous nanometer sized colloidal silica solution of 0–31 wt% and N-methyldiethanolamine of 0–2 kmol/m3 in a flat-stirred vessel for the various sizes and speeds of at 25 °C and 0.101 MPa to obtain the volumetric liquid-side mass transfer coefficient (k _L a) of CO₂. The film theory accompanied by chemical reaction between CO₂ and N-methyldiethanolamine was used to estimate the theoretical value of absorption rate of CO₂. An empirical correlation formula containing the relationship between k _L a and rheological property of the aqueous colloidal silica solution was presented. The value of R _A in the aqueous colloidal silica solution was decreased by the reduction of k _L a due to elasticity of the solution.     

Spouted bed drying of agricultural grains

It is shown that the presence of a “slotted draft tube” results in reduced air requirements for spouting and improved drying performance. Experimental data are presented on batch as well as continuous spouted bed drying of wheat, paddy, maize and peas. The variables studied are feed moisture content (Q_o), inlet air temperature (T_o), bed mass hold-up (M_p), inlet superficial air velocity (u_o) and bed diameter (D_c) in batch drying, and the above variables and solids feed rate (F_s) in continuous drying. The data on average overall drying rate, ?_m, in kg moisture evaporated per unit time per kg bed solids, is found to be correlatable as ?_m, = k (50Q_o + 0.118T_o ? 12.5) 10^?5, and the single parameter k is presented for wheat, paddy, maize and peas for both batch and continuous modes of spouted bed drying. The correlation obtained should be useful in dryer design for the grains studied as well as for other similar materials.     

Preparation and sorption properties of tunable polyester copolymers containing β‐cyclodextrin

Polyester copolymers were prepared with β‐cyclodextrin (β‐CD) and sebacoyl (SCl) or terephthaloyl (TCl) chloride cross linker agents using a simple, one‐pot synthesis. Variation of the mole ratios (i.e., 1 : 1, 1 : 2, 1 : 3, 1 : 6, and 1 : 9) of β‐CD to diacid chloride linker units resulted in copolymers with differing solubility and chemical stability in aqueous solution. The sorption properties of copolymers such as 1 : 6 and 1 : 9 SCl, and 1 : 9 TCl materials were investigated because of their relative insolubility and resistance to hydrolysis at pH 4.6. The monolayer sorption capacity (Q_m) of the copolymers varied according to the nature of the cross linker and the relative mole ratio of monomers. Q_m values obtained from the Sips isotherm model range from 2.7 to 5.2 mmol/g for the sorption of p‐nitrophenol at 295 K and approach the value of Q_m for a commercially available granular activated carbon sorbent. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enzymatic synthesis of position-specific low-calorie structured lipids

An immobilized sn-1,3-specific lipase from Rhizomucor miehei (IM 60) was used to catalyze the interesterification of tristearin (C_18:0) and tricaprin (C_10:0) to produce low-calorie structured lipids (SL). Acceptable product yields were obtained from a 1:1 mole ratio of both triacylglycerols with 10% (w/w of reactants) of IM 60 in 3 mL hexane. The SL molecular species, based on total carbon number, were 44.2% C₄₁ and 40.5% C₄₉, with 3.8 and 11.5% unreacted tristearin C₅₇ and tricaprin C₂₇, respectively, remaining in the product mixture. The best yield of C₄₁ species (44.3%) was obtained with zero added water. Tricaprylin (C_8:0) was also successfully interesterified with tristearin in good yields at 1:1 mole ratio. Products were analyzed by reverse-phase high-performance liquid chromatography with an evaporative light-scattering detector. Reaction parameters, such as substrate mole ratio, enzyme load, time course, added water, reaction media, and enzyme reuse, were also investigated. Hydrolysis by pancreatic lipase revealed the specific fatty acids present at the sn-1,3 positions of SL. Biocatalysis Symposium Paper, presented at the AOCS Annual Meeting & Expo, Seattle, Washington. May 11–14, 1997.     

Predictive Dynamic Model of Air Separation by Pressure Swing Adsorption

A general dynamic model is developed for separation of air over a carbon molecular sieve and a zeolite adsorbent for production of nitrogen and oxygen. The proposed model is validated using experimental data from working laboratory scale N₂–PSA and laboratory scale O₂–PSA systems. Simulations studies are performed to investigate the effect of changing various process variables, such as the duration of PSA steps, bed length and feed inlet velocity.     

Bivalent Argininamide‐Type Neuropeptide Y Y1 Antagonists Do Not Support the Hypothesis of Receptor Dimerisation

Bivalent ligands are potential tools to investigate the dimerisation of G‐protein‐coupled receptors. Based on the (R)‐argininamide BIBP 3226, a potent and selective neuropeptide Y Y₁ receptor (Y₁R) antagonist, we prepared a series of bivalent Y₁R ligands with a wide range of linker lengths (8–36 atoms). Exploiting the high eudismic ratio (>1000) of the parent compound, we synthesised sets of R,R‐, R,S‐ and S,S‐configured bivalent ligands to gain insight into the “bridging” of two Y₁Rs by simultaneous interaction with both binding sites of a putative receptor dimer. Except for the S,S isomers, the bivalent ligands are high‐affinity Y₁R antagonists, as determined by Ca²⁺ assays on HEL cells and radioligand competition assays on human Y₁R‐expressing SK‐N‐MC and MCF‐7 cells. Whereas the R,R enantiomers are most potent, no marked differences were observed relative to the corresponding meso forms. The difference between R,R and R,S diastereomers was most pronounced (about sixfold) in the case of the Y₁R antagonist containing a spacer of 20 atoms in length. Among the R,R enantiomers, linker length and structural diversity had little effect on Y₁R affinity. Although the bivalent ligands preferentially bind to the Y₁R, the selectivity toward human Y₂, Y₄, and Y₅ receptors was markedly lower than that of the monovalent argininamides. The results of this study neither support the presence of Y₁R dimers nor the simultaneous occupation of both binding pockets by the twin compounds. However, as the interaction with Y₁R dimers cannot be unequivocally ruled out, the preparation of a bivalent radioligand is suggested to determine the ligand–receptor stoichiometry. Aiming at such radiolabelled pharmacological tools, prototype twin compounds were synthesised, containing an N‐propionylated amino‐functionalised branched linker (K_i≥18 nM ), a tritiated form of which can be easily prepared.     

Laminar morphology development and oxygen permeability of LDPE/EVOH blends

Morphology and oxygen barrier properties of LDPE/EVOH blends have been studied. Laminar dispersion of ethylene-vinyl alcohol copolymer (EVOH) with high oxygen barrier properties was obtained in the matrix of low density polyethylene (LDPE) when extruded through an annular blown film die. Various laminar morphologies were observed and the main factors determining the morphology of the blends were viscosity ratio of the components, processing conditions, and compatibilizer level. Oxygen permeation tests have shown that thinner and longer EVOH layers in larger numbers were more effective in reducing the oxygen permeability. The oxygen permeability of the compatibilized blend having 6 phr of LLD-g-MAH was reduced by a factor of 740. The correlation between morphology and oxygen permeability was explained as a function of the EVOH layer size (L × R) and the number of EVOH layers (N), which were closely related to the predeformed domain size (L_o × R_o). The high Weber number (resulted from large L_o × R_o and low interfacial tension) and low viscosity ratio yielded large L × R. However, small L_o × R_o produced high N. Experimental results of oxygen permeability were well correlated with (L × R) × N.     

Sensitivity and contrast of some proton-beam resists

Fifteen negative and four positive resists were tested to determine their proton-beam sensitivity and contrast. The ratio of the required 20-keV electron dose (Q_E) to the required 100-keV proton dose (Q_P) ranged from a low value of 7.8 to a high value of 270. In general, the most sensitive resists had the lowest values of Q_E/Q_P. This result is explained as being due to incomplete coverage by reactive species at low proton doses because the incident protons are spaced too far apart. The product of Q_P and the weight-average molecular weight (M _w) was almost constant for a series of narrow dispersivity polystyrenes over the M _w range of 20,000 to 2,600,000. This product was used as a figure of merit for comparing negative resists.     

Physicochemical and nutraceutical properties of barley grass powder microencapsulated by spray drying

ABSTRACT

Barley grass (Triticum aestivum L.) is popular, commonly known as a nutritional supplement in China. To obtain the highest chlorophyll and flavonoid content as well as other physicochemical characteristics, spray drying from barley grass juice was carried out for two different maltodextrin concentrations (10 and 20%, dried basis) and four different inlet air temperatures (140, 150, 160, and 170°C). After drying, color, water activity, odor, taste, density, particle size, glass transition temperature, and chlorophyll and flavonoid contents of the dried product were measured. Highest contents of flavonoid (5.66?mg/kg) and chlorophyll (7.29?mg/kg) were obtained under 150°C inlet air temperature, 10% maltodextrin concentration, at a feed flow rate of 1.8?L/h for the drying. Corresponding particle size was 19.58–13.33?µm. The glass transition temperature (T_g) increased with the increasing of maltodextrin concentration; and two max T_g of powder obtained from 10 and 20% maltodextrin concentration were 74.4 and 77.4°C, respectively. Retention of taste and flavor were highest with 20% maltodextrin. High inlet air temperature was contributed to the large discrepancy of odor and taste substances. The best color (lightness L*?=?64.44 and greenness b*?=??11.53) was obtained at 150°C inlet air temperature and 10% maltodextrin concentration. Both maltodextrin concentrations resulted in poor flowability of the dried product (C_I?≤?32.51).     

Enantioselective Separation of Racemic Amlodipine by Two-Phase Chiral Extraction Containing O,O′-Dibenzoyl-(2S,3S)-Tartaric Acid as Chiral Selector

A two-phase chiral extraction system containing O,O′-dibenzoyl-(2S,3S)-tartaric acid ((+)-DBTA) in 1-decanol organic phase and aqueous phase was developed for the chiral resolution of amlopidine. The effects of extractant concentration, equilibrium time, and pH of the aqueous phase on the separation performance were investigated. The results indicated that the system afforded a strong chiral separation ability; the (+)-DBTA showed a higher recognition ability toward (S)-amlodipine than the (R)-amlodipine. Upon a single extraction, the enantiomeric excess (%) of (S)-amlodipine could be enriched to 24.27%. The product recovery ratio was 0.74. The distribution ratios for (S)-amlodipine (D _S ), (R)-amlodipine (D _R ) and separation factor (α) were 1.28, 0.78, and 1.64, respectively. Therefore, the pH and concentration of the extractant have the great effects on chiral separation ability. Two-phase chiral extraction has great significance for preparative separation of (S)-amlodipine; it can also be used to design and scale up the enantioselective separation process.