Application of the Box-Wilson experimental design method for the spherical oil agglomeration of coal

In this study, the Box-Wilson statistical experimental design method was employed to evaluate the effects of important variables such as bridging liquid (oil) concentration, salt (CaCl₂·2H₂O) concentration and stirring speed on the agglomeration of bituminous coal. Response function coefficients were determined by the regression analysis of experimental data and the predictions were found to be in good agreement with the experimental results. The optimum kerosene concentration, CaCl₂·2H₂O concentration and stirring speed were determined as 30 wt%, 1 M and 1683 rpm, respectively, when considering combustible recovery and ash content.In addition, contact angle and solution surface tension measurements were carried out to evaluate of agglomeration success with the contact angle values and surface tension values. The surface tension of CaCl₂ 2H₂O solutions and the average contact angle increased with increasing CaCl₂·2H₂O concentration.     

Effect of alkali concentrations and operating conditions on agglomeration/defluidization behavior during fluidized bed air gasification

Biomass gasification plays an important role in finding a solution to the energy crisis, and the fluidized bed (FB) is recognized as an important technique for using biomass. However, this process significantly tends toward bed material agglomeration. Accordingly, the aim of this study is to emphasize the effects of operating conditions and different Na concentrations on agglomeration behavior during FB air gasification. Defluidization time decreases as Na concentration increases from 0.8 to 3%. Defluidization time decreases as temperature and the amount of bed materials increase. In addition, no significant change in the trend for this process occurs as the equivalence ratio increases. Adding CaO and Al₂O₃ can significantly prolong this process, and the inhibition level follows the sequence: Al₂O₃ > CaO. The same observations are noted during both incineration and air gasification in the FB at various operating conditions.     

Formation of bed agglomeration in a fluidized multi-waste incinerator

A case study was carried out to investigate the bed agglomeration observed in a fluidized bed incinerator when burning blends of three wastes (carbon soot, biosludge and fuel oil). Several instrumental approaches were employed (i.e. XRF, SEM, XRD, and ICP-AES) to identify the bed materials (fresh sand and degrader sand) and clinkers formed in the full-scale incinerator tests. Several elements (V, Al, S, Na, Fe, Ni, P, and Cl), which normally are associated with the formation of low melting point compounds, were found in the waste blends at high content levels. The clinker bridges were identified to be associated with Al, Fe, V, K, Na, S, Ni, and Si elements.The effects of temperature and blending ratio were investigated in a muffle furnace. Carbon soot is believed to be more susceptible to the clinker formation than the other two fuels. Thermodynamic multi-phase multi-component equilibrium calculations predict that the main low melting point species could be Al₂(SO₄)₃, Fe₂(SO₄)₃, Na₂SO₄, NaCl, Na₂SiO₃ and V₂O₅. This information is useful to understand the chemistry of clinker formation. Also, it helps to develop methods for the control and possible elimination of the agglomeration problem for the design fuels.     

Influence of ionic speciation on electrocatalytic performance of polyaniline coated platinum electrode: Fe(III)/Fe(II) redox reaction

Porous-polyaniline coated Pt electrode (PANI/Pt) was electro-synthesized potentiodynamically in 0.1 M aniline + 0.5 M H₂SO₄ and morphologically characterized by scanning electron microscopy (SEM). Nature of predominant Fe-species in HCl and H₂SO₄ was checked by UV-vis spectrophotometry. Electrocatalysis of Fe(III)/Fe(II) reaction was studied by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) for three different solution compositions viz. (i) FeCl₃/FeCl₂ in 1 M HCl, (ii) FeCl₃/FeCl₂ in 0.5 M H₂SO₄ and (iii) Fe₂(SO₄)₃/FeSO₄ in 0.5 M H₂SO₄. For different thicknesses of PANI, the peak current increased irrespective of the nature of the Fe-species, but the polarity of the charge on the Fe-species showed great influence on reversibility of electrocatalysis by PANI/Pt. The Donnan interaction of the polyaniline modified electrode for the three compositions was investigated with respect to [Fe(CN)₆]³⁻/H₂[Fe(CN)₆]²⁻ which are believed to be the predominant species present in K₃[Fe(CN)₆]/K₄[Fe(CN)₆] solution in 0.5 M H₂SO₄. The electrocatalytic performance of PANI/Pt for Fe(III)/Fe(II) redox reaction was found superior in HCl compared to that in H₂SO₄.     

A green process for recovery of H2SO4 and Fe2O3 from FeSO4·7H2O by modeling phase equilibrium of the Fe(П)– –H+–Cl– system

Ferrous sulfate heptahydrate FeSO₄·7H₂O is a major waste produced in titanium dioxide industry by the sulfate process and has caused heavy environmental problem. A new green process for the treatment of FeSO₄·7H₂O was proposed to make use of iron source and recycle sulfate source as H₂SO₄. It was found that by adding concentrated HCl to the FeSO₄ solution, FeCl₂·4H₂O was crystallized out, which was subsequently calcined to produce Fe₂O₃ and HCl. Concentrated H₂SO₄ solution (about 65 wt %) was obtained by evaporating the FeCl₂·4H₂O‐saturated filtrate. To facilitate the process development and design, the solubilities of FeCl₂·4H₂O in HCl, H₂SO₄, and HCl + H₂SO₄ solutions were measured and the experimental data were regressed with both the mixed‐solvent electrolyte model and the electrolyte NRTL model. On the basis of the prediction of the optimum conditions for the crystallization of FeCl₂·4H₂O, material balance of the new process was calculated. FeCl₂·4H₂O and Fe₂O₃ were obtained from a laboratory‐scale test with about 70% recovery of ferrous source for a single cycle, indicating the feasibility of the process. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4549–4563, 2017     

Thermal and rheological behavior of acrylonitrile–carboxylic acid copolymers and their metal salt complexes

The influence of acrylic, methacrylic, and itaconic acid comonomers in the nitrile oligomerization of acrylonitrile copolymers has been studied by DSC and DSC‐FTIR in air and nitrogen atmospheres. Addition of metal salts in poly(acrylonitrile–acrylic acid) copolymer, PA on thermal and rheological behavior has also been reported. Incorporation of CuSO₄, FeSO₄, ZnSO₄, and Al₂ (SO₄)₃ (1 to 5 wt %) salt in the polymer solution affects its solubility in DMF. The complexes of PA with zinc sulphate, took a longer time to dissolve in DMF, whereas the complexes with Fe(SO₄) and Al₂(SO₄)₃ are almost insoluble in DMF, perhaps due to intermolecular crosslinking. Addition of these metal salts to the PA solution also affects its Brookfield viscosity. The viscosity of 10 wt % polymer solution increases from 400 centipoise (Cps) to 1090 Cps for complex with 5% FeSO₄ (on the weight of dope solids) and 690 Cps for Al₂ (SO₄)₃ and 906 cps for ZnSO₄ complex. However, for CuSO₄ salt complex this value is 770 Cps. FTIR spectra shows the participation of COOH and CN group in the complex formation, which is responsible for enhanced Brookfield viscosity. Thermal behavior of the polymer–metal salt complex showed that these salts also affect the exothermic reaction. The initiation of cyclization reaction takes place at a lower temperature compared to neat acrylonitrile–acrylic acid copolymer. However, the heat liberated per unit time in N₂ atmosphere in case of neat polymer is 6.3 Jg⁻¹ min⁻¹, which reduces to 5.5 Jg⁻¹ min⁻¹ in the case of the PA/Al complex, confirming the role of Al₂ (SO₄)₃ in retarding the rate of cyclization reaction. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 567–582, 1999     

The investigation of coal-pyrite/lignite concentration and their separation in the artificial mixture by oil agglomeration

In this study, the concentration of coal-pyrite and lignite taken from Yozgat-Ayridam (Turkey) Coal Management was investigated by oil agglomeration.In the previous studies, the agglomeration of coal-pyrite was investigated using different bridging liquids (fuel oil, diesel oil and kerosene) and the combination of reagent (KEX, Acorga M5397)+kerosene. When using only bridging liquids, the agglomeration recovery of pyrite was very low. To increase the hydrophobicity of pyrite, KEX was used. However, the pyrite was not agglomerated with an acceptable recovery. But when using Acorga M5397, which is a chelating reagent, the agglomeration recovery of pyrite was increased. The pyrite was agglomerated with a recovery of 76.70 wt% by single-stage agglomeration.In the optimum conditions which were determined for coal-pyrite, the agglomeration recovery of lignite was investigated. It was found that the lignite could not be agglomerated with an acceptable recovery.To investigate the separation of coal-pyrite and lignite, the artificial mixture of coal-pyrite and lignite was prepared with the weight ratio of 1/4 of coal-pyrite and lignite. It was found that the pyrite could be agglomerated at a recovery of 96.54% with three-stage agglomeration process. The lignite concentrate was produced with a recovery of 73.96 wt% and the pyrite content of 0.86 wt%.These findings showed that the coal-pyrite and lignite could be separated by oil agglomeration using appropriate reagent and bridging liquid.     

Behavior of gas bubbles in aqueous electrolyte solutions

A system was investigated in which a swarm of air bubbles was dispersed in aqueous electrolyte solutions. the salts used were: NaCl, NaBr, NaI, Na₂SO₄, Na₃PO₄ LiCl, MgCl₂, MgSO₄, CaCl₂, AlCl₃ and Al₂(SO₄₃. The effects of the salts on the interfacial area of dispersion and on the oxygen transfer coefficient were investigated at various salt concentrations. The results showed a definite dependence of the surface area of dispersion on the valence of the ionic species and salt concentrations. A very satisfactory correlation was obtained for all the salts with the use of ionic strength as the correlating parameter. The mechanism of the coalescence-preventing action of the salts was discussed and explained on the basis of ion—water interactions. The oxygen mass transfer coefficient was found to be only slightly dependent on the presence of electrolytes in the range of concentrations used in this work. The importance and possible practical application of the results were briefly discussed.     

An experimental study of sulphate transformation during pyrolysis of an Australian lignite

The transformation of sulphate minerals during pyrolysis of an Australian lignite has been studied using pure sulphates (CaSO₄, FeSO₄ and Fe₂(SO₄)₃), a high mineral (HM) lignite sample and a low mineral (LM) lignite sample collected from different locations of the same deposit, and samples of acid-washed LM doped with sulphates (CaSO₄+ LM and FeSO₄+ LM), respectively. Thermogravimetric analysis and fixed-bed reactor techniques were used for the pyrolysis experimentation and the lignite samples and their chars were analysed using FTIR and XRD. The TGA experiments showed that CaSO₄ decomposes between 1400 and 1700 K in nitrogen and a 50/50 N₂/CO₂ mixture, while in air CaSO₄ decomposes between 1500 and 1700 K. Using a TGA-MS it was found that only a small fraction of CaSO₄ in CaSO₄+ LM decomposed at 653 K, releasing SO₂. CaSO₄ was still observed in the char recovered at 1073 K as confirmed by the FTIR and XRD analysis. FeSO₄·7H₂O released the bound water below 543 K and the remaining FeSO₄ decomposed between 813 and 953 K. FeSO₄ in FeSO₄+ LM decomposed at 500 K to release SO₂. The inherent sulphates in HM were dominated by iron sulphates which started to decompose and release SO₂ at around 500 K and all sulphate had been decomposed at 1073 K. It was observed that during the fixed-bed pyrolysis at 1073 K in nitrogen, approximately 36% of the total sulphur in the CaSO₄+ LM decomposed, 88% of the total sulphur in the FeSO₄+ LM decomposed and around 76% of the total sulphur in HM decomposed. It was also confirmed that FeSO₄+ LM produced more volatile sulphur than CaSO₄+ LM during pyrolysis.     

Ethanosolv pretreatment of barley straw with iron(III) chloride for enzymatic saccharification

BACKGROUND: Barley straw is a potential lignocellulosic biomass for the production of bioethanol because of its high cellulose and hemicelluloses content. Ethanosolv pretreatment catalyzed with inorganic acids has some undesirable effects, and thus, inorganic salts, such as FeCl₃, were studied as the catalyst in order to enhance enzymatic digestibility. RESULTS: The addition of 0.1 mol L^?1 FeCl₃ (Iron(III) chloride) had a particularly strong effect on the enzymatic digestibility, reaching a value as high as 89%, with cellulose recovery as high as 90% after the ethanosolv pretreatment. The enzymatic digestibility was 89% and 55% after the addition of 0.1 mol L^?1 FeCl₃ and H₂SO₄ (adjusted to the same pH), respectively. The enzymatic hydrolysis rate was significantly accelerated as the ethanosolv temperature increased, reaching the highest enzymatic digestibility of 89% after 72 h at 170 °C. The concentrations of HMF(5‐hydroxy‐2‐ methyl furfural) and furfural were 0.011 and 0.148 g L^?1 in the hydrolysate during FeCl₃‐ethanosolv treatment, which were lower than the concentrations quantified during H₂SO₄‐ethanosolv treatment. After the pretreatment, 88.5% of FeCl₃ was removed through the filtration process. CONCLUSION: The addition of several inorganic salts significantly accelerated enzymatic digestibility in the ethanosolv. FeCl₃ had a particularly strong effect on enzymatic digestibility and cellulose recovery. The formation of HMF and furfural and the remaining amount of FeCl₃ were investigated, and FeCl₃ had no effect on the subsequent processes after pretreatment. Copyright © 2010 Society of Chemical Industry     

Kinetics of the Decolorization by Fenton's Reagent

Fenton's reagent was employed in the decolorization of aqueous solutions of one of three dyestuffs (Acid Red 27, Reactive Blue 81, Acid Blue 62). The decolorization with Fenton's reagent was found to be simple and fast. In order to determine the reaction kinetics of the decolorization the stopped-flow technique under pseudo-first order conditions was used. Experiments were carried out at pH=2, at the excess of ferrous salts (FeCl₂·4H₂O or FeSO₄·7H₂O). The rate constants of the decolorization determined by us are in the same order of magnitude: 90 to 100 dm³/(mol-s) for FeSO₄·7H₂O/H₂O₂, and 40 to 50 dm³/(mol-s) for FeCl₂·4H₂O/H₂O₂ systems. The difference between the rate constants for both ferrous salts indicates that the Fenton's reaction may proceed via different mechanisms.     

Effect of inorganic salts on viscosity of acrylonitrile‐N‐vinylpyrrolidone copolymer solutions

Effects of inorganic salts on viscosities of dimethyl sulphoxide (DMSO) solutions of acrylonitrile(AN)/N‐vinylpyrrolidone(N‐VP) copolymer are discussed. Viscosity was determined by the rotary viscosimeter. It was shown that the solution viscosity decreases quickly with addition of KCl and NaCl and the effect of NaCl is more prominent than that of KCl. As concentration of KCl and NaCl went beyond 0.025 mol/L, the viscosity showed a trend of increase. The viscosity increased considerably with addition of FeCl₃ and CuCl₂. Changes in solution viscosity became less obvious with addition of ZnCl₂. As temperature increased, the viscosity of the copolymer solution containing NaCl decreased most quickly and the copolymer solution consisting of FeCl₃ showed the slowest decrease. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3492–3495, 2003     

Alkali-modified soy proteins: Effect of salts and disulfide bond cleavage on adhesion and viscosity

Soy protein isolates were treated with NaCl, Na₂SO₄, or Na₂SO₃ (disulfide bond-cleaving agent) at a pH of 10.0 and 50°C, and the effects of these salts on viscosity, adhesive strength on woods, and water resistance of the treated isolates were investigated. Viscosity and adhesive strength decreased with increasing concentrations of these salts. At a concentration of 0.1 M, these three salts reduced the viscosity of soy proteins with no significant adverse effects on adhesive strength and water resistance. Addition of 0.1 M NaCl, Na₂SO₄, or Na₂SO₃ reduced adhesive strength insignificantly from 1230 N to 1120, 1060, or 1013 N, respectively. The viscosity of protein isolate modified at pH 10.0 and 50°C in the absence of salts was >30,000 cP. Treatment with NaCl or Na₂SO₄ resulted in viscosity reductions to 6000 or 1050 cP, respectively. The Na₂SO₃ treatment yielded an isolate with the lowest viscosity of 110 cP and which retained adhesive and water-resistive properties. The water resistance of modified soy proteins with and without 0.1 M Na₂SO₃ treatment was not significantly different with 3.3 and 6.6% cumulative delaminations occurring after four water soaking cycles. Treatment with 0.1 M Na₂SO₃ resulted in an isolate with a 28% decrease in disulfide linkages.     

Experimental study of acoustic agglomeration of coal-fired fly ash particles at low frequencies

This paper presents an experimental study of acoustic agglomeration of coal-fired fly ash particles in travelling sound waves. The ranges of variation of the main physical parameters are as follows: acoustic frequency, f = 700-3000 Hz; sound pressure level (SPL), SPL = 130-147 dB; residence time, t = 3-7 s; aerosol number concentration, N₀ = 1.0 × 10⁵-3.7 × 10⁵ /cm³. A 68.4% decrease in total number concentration is gained under an SPL of 147 dB and a frequency of 1400 Hz. Aggregates larger than 10 µm are observed in scanning electron microscopy photographs. The results show that the effect of sound waves is very sensitive to the frequency change, which means that orthokinetic interaction governs the process. There exists an optimum frequency for a given particle size distribution, which decreases slightly as SPL increases. The influences of SPL, residence time and initial total number concentration are also studied.     

Electrochemical behaviour of high nitrogen bearing stainless steel in acidic chloride solution: Effects of oxygen, acid concentration and surface roughness

The effects of oxygen, H₂SO₄ concentration and surface roughness on the electrochemical behaviour of high nitrogen bearing stainless steel (HNS) in acidified 0.5 M NaCl solution were investigated using potentiodynamic polarization method. The results revealed three corrosion potentials indicating an unstable system. The number of the potentials was influenced by H₂SO₄ concentration. Three potentials existed above 0.011 M H₂SO₄, two between 0.011 and 0.0065 M H₂SO₄ and one below 0.0065 M H₂SO₄. Oxygen increased the number of corrosion potential at 0.005 M H₂SO₄ + 0.5 M NaCl solution while surface roughness had no noticeable influence on the number of potentials but increased the values of the corrosion potentials and passivation current densities with increase in the surface roughness. The corrosion mechanism has been discussed using the ideal polarization curve models.     

Coagulation of natural waters with modified ion exchangers

A study has been carried out in order to establish the possibility for natural water coagulation via its treatment with strong acid cation exchangers modified with FeCl₃ or Al₂(SO₄)₃. Various trademarks of ion exchangers have been used, such as Wofatit KPS, Wofatit KS-10, Lewatit S-100, Varion KSM, Amberlite 200 C and Duolite C-26. It has been found that, while using modified ion exchangers the concentration of suspended solids, permanganate oxygen demand and humic acids in treated water are reduced respectively by approximately 95, 86 and 77% with FeCl₃ used as modifier, and 92, 80 and 73% with Al₂(SO₄)₃ as a modifier. The modified ion exchangers can be used for pretreatment of natural water needed for small water make up installations of a module principle. Different modules of these installations can be regenerated in a central station. A scheme has been proposed for natural water treatment combining the process of coagulation with modified ion exchangers and Na-Cl-ion exchange in a mixed bed filter. This can produce conditioned water suitable for thermal plants or for subsequent membrane desalting process.     

The activity of Rh/Al2O3 and Rh-Na/Al2O3 catalysts for PAHs removal in the waste incineration processes: Effects of particulates, heavy metals, and acid gases

This study investigated the activity of Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts for polycyclic aromatic hydrocarbons (PAHs) removal and the influence of particulates, heavy metals, and acid gases (SO₂ and HCl) on the performance of catalysts. The experiments were carried out in a laboratory-scale waste incineration system. Experimental results show that the destruction removal efficiency (DRE) of PAHs by Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts were 80% and 59%, respectively when the flue gas did not contain any pollutants. The concentrations of PAHs increased by using a Rh/Al₂O₃ catalyst when the flue gas contained Cd, Pb, and SO₂ and also increased by using a Rh-Na/Al₂O₃ catalyst when the flue gas contained particulates, Cd, and HCl. Adding Na to the Rh/Al₂O₃ catalyst can inhibit the increases of 3-4 ring PAHs when the flue gas contained Pb. The influence of acid gases on the performance of the Rh/Al₂O₃ and Rh-Na/Al₂O₃ catalysts followed the sequence SO₂ > HCl > SO₂ + HCl. The activity of the catalysts for PAHs removal was significantly suppressed by increased concentrations in particulates and Cd, yet promoted by a high Pb concentration. The results of ESCA analysis indicated that the presence of Cd and Pb did not change the chemical states of Rh and Na, but the presence of SO₂ and HCl did.     

Electrochemical treatment of olive mill wastewater

Background Olive mill wastewater (OMW) constitutes a very strong agro‐industrial wastewater posing severe environmental threats in olive oil producing countries. The main objective of this study was to treat olive mill wastewater by electrochemical oxidation. The variables studied included the type and concentration of electrolyte solutions, voltage and time applied. Results: The electrolyte type and concentration significantly affected the degradation efficiency of the electrochemical oxidation. Optimal conditions for NaCl concentration were 3% (w/v) and 16 V. At these conditions chemical oxygen demand (COD) removal reached 70.8% after 8 h of electrochemical treatment, while color and turbidity were completely removed after short periods of treatment. However, bio‐assays indicated that the ecotoxicity of the treated wastewater remained unchanged, possibly due to the formation of chlorinated by‐products. Na₂SO₄ did not demonstrate sufficient efficiency. The simultaneous use of FeCl₃ and NaCl contributed to electro‐coagulation of OMW. After settlement, two separate phases were formed: the supernatant phase and the settled solids. Under optimal conditions (2% Na₂SO₄ + 1% FeCl₃; 24 V), the removal efficiency of COD reached 85.5% at the supernatant phase. Conclusion: NaCl was an effective electrolyte for OMW treatment. The electro‐coagulation process was also a successful process, but as in the case of NaCl the remaining acute toxicity of treated OMW was high. Copyright © 2007 Society of Chemical Industry     

Single Chromatographic Step for β-Galactosidase Purification: Influence of Salt and Elution Parameters

β-galactosidase purification was performed by ion exchange chromatography in which the main elution parameters and different elution salts (NaCl, KCl, and (NH₄)₂SO₄) were evaluated through distinct purification strategies. Among the salts under analysis, KCl was the best one for β-galactosidase purification, since it reached a 95.1% recovery and an 8.2-fold purification factor. NaCl, which is the most common elution salt found in the literature, obtained a 75.1% recovery and a 7.5-fold purification factor whereas ammonium sulfate, as salt elution, yielded a 72.1% recovery and a 3-fold purification factor in the same conditions.     

Flotation separation of lignosulfonates from the drain water of refractories factories

Conclusions Effluent from refractories factories can be purified to remove lignosulfonates by flotation. The high efficiency of the process (97–98% separation of lignosulfonates) is achieved by preliminary addition of Fe₂(SO₄)₃, FeCl₃, or Fe(OH)₃ before flotation. Chlorides of primary aliphatic amines or quaternary salts of pyridine bases containing from 11 to 16 carbon atoms in the alkyl part of the molecule may be used as the flotation-collector reagent.The degree of flotation-purification of the stocks is determined mainly by the original concentration of the lignosulfonates and the inorganic additives incorporated, the concentration and nature of the flotation reagent, and also the pH of the effluent liquors. The optimum conditions for flotation separation of the lignosulfonates from their 0.01% solutions are created with concentrations of Fe₂(SO₄)₃ of 150, FeCl₃ 120, Fe(OH)₃ 110, and flotation reagent 20–40 mg/liter.After additional purification on sand filters the effluent liquor satisfies the demands of closed watersupply cycles.Translated from Ogneupory, No. 6, pp. 15–18, June, 1979.