Carbon dioxide utilization with carbonation using industrial waste-desulfurization gypsum and waste concrete

In this study, we propose a process making calcium carbonate and calcium sulfate and recovering absorbent using ammonia absorbent, carbon dioxide, and industrial waste. The main objective of this study is to confirm the possibility of carbon capture and utilization based on waste materials. We assumed desulfurization gypsum and construction waste (ready mixed concrete washing water, waste concrete, etc.) are CaSO₄, Ca(OH)₂, respectively. And concentration of simulated carbon dioxide gas was 15 vol% similar to flue gas. Calcium carbonate was produced by combination reaction between ionic CO₂ in absorbent and metal ion in the solid waste. Experiments were conducted at normal temperature and pressure. Furthermore, the generated products were characterized by X-ray diffraction, and scanning electron microscope.     

Optimization of Carbon Dioxide and Valeric Acid Utilization for Polyhydroxyalkanoates Synthesis by Cupriavidus necator

The utilization of captured CO₂ as a part of the CO₂ capture and storage system to produce biopolymers could address current environmental issues such as global warming and depletion of resources. In this study, the effect of feeding strategies of CO₂ and valeric acid on cell growth and synthesis of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(3HB-co-3HV)] in Cupriavidus necator was investigated to determine the optimal conditions for microbial growth and biopolymer accumulation. Among the studied CO₂ concentrations (1–20 %), microbial growth and poly(3-hydroxybutyrate) accumulation were optimal at 1 % CO₂ using a gas mixture at H₂:O₂:N₂ = 7:1:91 % (v/v). When valeric acid was fed together with 1 % CO₂, (R)-3-hydroxyvalerate synthesis increased with increasing valeric acid concentration up to 0.1 %, but (R)-3-hydroxybutyrate synthesis was inhibited at >0.05 % valeric acid. Sequential addition of valeric acid (0.05 % at Day 0 followed by 0.025 % at Day 2) showed an increase in 3HV fraction without inhibitory effects on 3HB synthesis during 4 d accumulation period. The resulting P(3HB-co-3HV) with 17–32 mol  % of 3HV is likely to be biocompatible. The optimal concentrations and feeding strategies of CO₂ and valeric acid determined in this study for microbial P(3HB-co-3HV) synthesis can be used to produce biocompatible P(3HB-co-3HV).     

Recovery of Nd and Dy from rare earth magnetic waste sludge by hydrometallurgical process

This paper describes a hydrometallurgical process for recovering neodymium (Nd) and dysprosium (Dy) from a magnetic waste sludge generated from the Nd–Fe–B(–Dy) manufacturing process. Phase analysis by XRD study revealed Nd(OH)₃ and Fe₂O₃ as main mineral phases, and chemical analysis by ICP showed the contents of 35.1 wt% Nd, 29.5 wt% Fe, 1.1 wt% Dy and 0.5 wt% B. A solution of 1 M HNO₃ + 0.3 M H₂O₂ was used to dissolve up to 98 % Nd and 81 % Dy, while keeping Fe dissolution below 15 % within 10 min. Fe dissolved in solution was completely removed as Fe(OH)₃ at pH 3 followed by precipitation of Nd and Dy with oxalic acid (H₂C₂O₄) and recovered 91.5 % of Nd and 81.8 % of Dy from solution. The precipitate containing Nd and Dy was calcined at 800 °C to obtain Nd₂O₃ as final product with 68 % purity, and final recovery of 69.7 % Nd and 51 % of Dy was reported in this process.     

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)/Organomodified Montmorillonite Nanocomposites for Potential Food Packaging Applications

Poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) (PHBHHx) is a versatile, biobased and biodegradable copolymer from the family of polyhydroxyalkanoates. This study aims to further ameliorate its properties in order to enhance its applicability for food packaging purposes through preparation of organomodified montmorillonite clay (OMMT) nanocomposites. Nanocomposites based on pure PHBHHx as well as commercial PHBHHx granulate, after a previous dry-mixing with OMMT in concentrations of 1, 3, 5 and 10 wt%, were prepared using melt blending and compression molding. Investigation of the samples showed well dispersed nanofiller and highly intercalated nanocomposites, resulting in a continuous decrease in gas permeability, lowering O₂, CO₂ and water vapor permeability with about 5–7 % and approximately 40 % at OMMT concentration of 1 and 10 wt%, respectively. Besides gas permeability, other properties were affected as well. Thermal stability of the samples increased gradually up to 5 wt% nanofiller, but was reduced at 10 wt%. In order to investigate the effects of OMMT and molecular weights on PHBHHx crystallization, nanocomposites were also produced by solvent-casting and compared to those obtained by melt-blending. Crystallization was retarded, because of severe lowering of molecular weight due to processing-induced chain scission, catalyzed by OMMT moisture. However, this reduction was counteracted for a large part by using commercial PHBHHx granulate, which has shown better crystallization properties. The samples were rendered increasingly more brittle, displaying higher Young’s modulus and severely reduced elongation at break. From this study it appeared that, upon viewing all affected properties as a whole, the sample based on commercial PHBHHx and containing 3 wt% OMMT shows most promise for possible applications, however further research must be performed in order to exploit their fullest potential.     

Improvement of Synthesis and Dielectric Properties of Polyurethane/Mt-QASs<Superscript>+</Superscript> (Novel Synthesis)

Polyurethane-based nanocomposites were prepared and their dielectric properties were characterized. Polyurethane (PU) composites were prepared with different organoclay content (1, 3, 5, and 10 wt% for all cases). The composites included quaternary ammonium salts such as 1-methyl-di-octyl-1 phenyl ammonium iodide (QAS-1), 1-methyl-di-nonyl-1 phenyl ammonium iodide (QAS-2), and 1-methyl-di-dodecyl-1 phenyl ammonium iodide (QAS-3) which were newly synthesized for modification of Na⁺-montmorillonite. Addition of aluminum silicate enhanced the dielectric properties at a constant concentration. Dielectric constants of nanocomposites compounded with 3 %- and 5 %-organoclay were close in value. The characterization of PU/organoclay composites was carried out using Fourier transform infrared and X-ray diffraction.     

The Effects of Additives on the Biodegradation of Polycaprolactone Composites

Because environmental pollution caused by plastic waste is a major problem investigations concerning biodegradable packaging are important and required. In this study, the biodegradation of PCL composite films with organic (glycerol monooleate and oleic acid) and inorganic additives (organo nano clay) was investigated to understand which additive and the amount of additive was more effective for biodegradation. The relationship between the degree of crystallinity and the effect of additives on the biodegradability of polycaprolactone (PCL) was examined. PCL composite films were prepared using organo nano clay (0.1–0.4–1–3 wt%) and oleic acid (1–3–5 wt%) or GMO (1–3–5 wt%). The 35 films prepared with PCL (P), clay (C), oleic acid (O), or glycerol monooleate (G) are coded as P_C#wt%_O (or G)#wt%. The composite films, P_C0.4_O5 contains 0.4 wt% clay and 5 wt% oleic acid and the P_C3_G1 contains 3 wt% clay and 1 wt% glycerol monooleate. The biodegradation of PCL films in simulated soil was studied for 36 months. The films were periodically removed from the simulated soil and film thicknesses, weight losses, visual changes, crystal structures, and a functional group analyses were performed. PCL composite films are separated into three groups, depending on degradation time, (1) films that degraded before 8 months (fast degradation), (2) films that degraded around 24 months (similar to neat PCL), and (3) films that take longer to degrade (slow degradation). The films in the first group are PCL films with 1 and 3 wt% clay additive and they begin to biodegrade at the 5th month. However, a composite film of PCL with only 0.4 wt% clay and 5 wt% GMO addition has the shortest degradation time and degraded in 5 months. The films in the last group are; P_G3, P_G5, P_C0.1, P_C0.1_O1, and P_C0.1_O5 and they took around 30 months for biodegradation. It was observed that increasing the organo nanoclay additive increases the biodegradability by disrupting the crystal structure and causing a defective crystal formation. The addition of GMO with organo nano clay also accelerates biodegradation. The addition of organo nano clay in an amount as small as 0.1 wt% acts as the nucleating agent, increases the degree of crystallinity of the PCL composites, and slows the biodegradation period by increasing the time.     

Adsorption of Ammonium by Graphene Oxide-Based Composites Prepared by UV Irradiation and Using as Slow-Release Fertilizer

A novel sodium alginate-grafted poly(acrylic acid)/graphene oxide (NaAlg-g-PAA/GO) composite hydrogel was prepared via ultraviolet irradiation, and characterized by infrared spectroscopy spectrometer. X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. It was employed to adsorb NH₄⁺ from aqueous solution and used as slow-release nitrogen fertilizers (SNFs). Result indicated that the adsorption process for NH₄⁺ reached equilibrium within 50 min, with the adsorption capacity of 6.6 mmol g^?1 even if 30 wt% GO was incorporated. The results of adsorption kinetic and isotherm were well described by the pseudo-second-order and Freundlich model. The thermodynamics analysis showed the adsorption process was spontaneous. The study indicated excellent water-holding ratio of soil with 2 wt% SNFs was 81.2%, and nitrogen release was up to 55.1% within 40 days in soil. Overall, NaAlg-g-PAA/GO could be considered as an efficient adsorbent for the recovery of nitrogen with the agronomic reuse as a fertilizer.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

Tensile and Combustion Properties of PP/IFR/POE/nano-CaCO<Subscript>3</Subscript> Composites

The tensile and combustion properties of polypropylene/polyolyaltha olefin composites filled with intumescent flame retardant (IFR) and nanometer calcium carbonate (nano-CaCO₃) were measured. It was found that the values of the Young’s modulus of the composites increased almost linearly, while the values of the tensile yield strength and tensile fracture strength of the composites decreased with increasing the IFR weight fraction; the values of the elongation at break of the composites decreased quickly when the IFR weight fraction was lower than 10 wt%, and then varied slightly when the IFR weight fraction was higher than 10 wt%. Moreover, the morphology of the specimens after combustion was observed and the frame retardant mechanisms of the composites were discussed.     

Removal of H2S using molten carbonate at high temperature

Gasification is considered to be an effective process for energy conversion from various sources such as coal, biomass, and waste. Cleanup of the hot syngas produced by such a process may improve the thermal efficiency of the overall gasification system. Therefore, the cleanup of hot syngas from biomass gasification using molten carbonate is investigated in bench-scale tests. Molten carbonate acts as an absorbent during desulfurization and dechlorination and as a thermal catalyst for tar cracking. In this study, the performance of molten carbonate for removing H₂S was evaluated. The temperature of the molten carbonate was set within the range from 800 to 1000 °C. It is found that the removal of H₂S is significantly affected by the concentration of CO₂ in the syngas. When only a small percentage of CO₂ is present, desulfurization using molten carbonate is inadequate. However, when carbon elements, such as char and tar, are continuously supplied, H₂S removal can be maintained at a high level.To confirm the performance of the molten carbonate gas-cleaning system, purified biogas was used as a fuel in power generation tests with a molten carbonate fuel cell (MCFC). The fuel cell is a high-performance sensor for detecting gaseous impurities. When purified gas from a gas-cleaning reactor was continuously supplied to the fuel cell, the cell voltage remained stable. Thus, the molten carbonate gas-cleaning reactor was found to afford good gas-cleaning performance.     

Production of hydrogen by steam gasification of dehydrochlorinated poly(vinyl chloride) or activated carbon in the presence of various alkali compounds

Steam gasification of dehydrochlorinated poly(vinyl chloride) (PVC) or activated carbon was carried out in the presence of various alkali compounds at 3.0 MPa and 560°C–660°C in a batch reactor or in a semi-batch reactor with a flow of nitrogen and steam. Hydrogen and sodium carbonate were the main products, and methane and carbon dioxide were the minor products. Yields of hydrogen were high in the presence of sodium hydroxide and potassium hydroxide. The acceleration effect of the alkali compounds on the gasification reaction was as follows: KOH > NaOH > Ca(OH)₂ > Na₂CO₃. The rate of gasification increased with increasing partial steam pressure and NaOH/C molar ratio. However, the rate became saturated at a molar ratio of NaOH/C greater than 2.0.     

Long Term Effects of Acid Irrigation at the Höglwald on Seepage Water Chemistry and Nutrient Cycling

In order to test the hypothesis of aluminium toxicity induced by acid deposition, an experimental acid irrigation was carried out in a mature Norway spruce stand in Southern Germany (Höglwald). The experiment comprised three plots: no irrigation, irrigation (170 mm a^?1), and acid irrigation with diluted sulphuric acid (pH of 2.6–2.8). During the seven years of acid irrigation (1984–1990) water containing 0.43 mol_c m^?2 a^?1 of protons and sulphate was added with a mean pH of 3.2 (throughfall?+?acid irrigation water) compared to 4.9 (throughfall) on both control plots. Most of the additional proton input was consumed in the organic layer and the upper mineral soil. Acid irrigation resulted in a long lasting elevation of sulphate concentrations in the seepage water. Together with sulphate both aluminium and appreciable amounts of base cations were leached from the main rooting zone. The ratio between base cations (Ca?+?Mg?+?K) and aluminium was 0.79 during acid irrigation and 0.92 on the control. Neither tree growth and nutrition nor the pool of exchangeable cations were affected significantly. We conclude that at this site protection mechanisms against aluminium toxicity exist and that additional base cation runoff can still be compensated without further reduction of the supply of exchangeable base cations in the upper mineral soil.     

Dynamic studies on lead volatilization from CaO–SiO2–Al2O3 molten slag under N2–CO–CO2, N2–HCl and N2–H2S gas atmospheres

Dynamic studies on the volatilization of lead from CaO–SiO₂–Al₂O₃ molten slags were conducted in a lab-scale melting furnace from 1623 to 1773 K under different mixed gas atmospheres of CO 0.05–0.3 atm to CO₂ 0–0.3 atm to N₂ (balance), HCl 1.7 × 10^?3–6.7 × 10^?3 atm to N₂ (balance), and H₂S 3.0 × 10^?4 to 1.7 × 10^?3 atm to N₂ (balance). The slag samples consisted of the mixed powders of 20–50 wt% CaO, 30–60 wt% SiO₂, and 10–40 wt% Al₂O₃, containing 2000 ppm PbO.Results showed that the rates of volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slags under the N₂–CO–CO₂, N₂–HCl, and N₂–H₂S gas atmospheres were higher than those under the simulated air (N₂–O₂), which increased with CO, HCl, and H₂S partial pressures. At \(p_{{HCl}}\)  =  \(p_{H_{2}S}\)  = 1.7 × 10^?3 atm, the apparent rate constants for the volatilization of lead under the N₂–H₂S and N₂–HCl gas atmospheres were nearly equal, which increased with a rise in temperature. Results also showed that the rate of volatilization of lead from the molten slag decreased drastically with the increasing viscosity of the molten slag, in the viscosity range lower than 3 Pa s. Consequently, the volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slag was significantly influenced by CO, HCl, and H₂S partial pressures and by the viscosity of the molten slag.     

Catalytic gasification of tars from a dumping site

The work deals with catalytic gasification, pyrolysis and non-catalytic gasification of tar from an industrial dumping site. All experiments were carried out in a vertical stainless steel gasification reactor at 800 °C. Crushed calcined dolomite was used as the gasification catalyst. Parameters such as addition of water and air, and the influence of the catalyst in regard to the composition of the process gas were investigated. The catalytic gasification experiment in the steady state produced process gas with the composition: 56 % of H₂, 9 % of CO, 11 % of CH₄ and 12 % of CO₂ (mol.%). Concentration of the C₂ fraction was lower than 1 mol.%. Volume flow of air was later changed from 120 to 230 ml min^?1 reducing the amount of hydrogen to 51 mol.% and that of methane to 10 mol.%. Process gas created in a non-catalytic gasification process contained 26–30 mol.% of methane, 13–15 mol.% of carbon monoxide and 15–17 mol.% of the C₂ fraction and lower amounts of hydrogen (20 mol.%) and carbon dioxide (2–3 mol.%). The highest apparent conversion of tar was reached in the catalytic gasification processes. A higher rate of catalyst deactivation can be observed when water or air is not added.     

Fabrication and Characterization of PLA/PHBV-Chitin Nanocomposites and Their Foams

This paper examines the effect of biobased chitin nanowhisker fillers on the thermal, rheological, physical, mechanical and morphological properties of biobased polylactic acid (PLA) and PLA/polyhydroxybutyrate-co-valerate (PHBV) blended nanocomposites as well as the physical, mechanical and morphological properties of porous PLA and PLA/PHBV nanocomposite foams. Solid nanocomposites of PLA, PLA/PHBV and chitin nanowhiskers were manufactured through melt blending while porous nanocomposites foams were fabricated through a batch foaming process with the aid of CO₂ as blowing agent. It was found that by incorporating small quantities of chitin nanowhiskers (<2 wt%) the mechanical properties of solid specimens are improved while strength and expandability of the foam can be significantly improved, yielding a homogenously distributed cell morphology with average cell size of 1.5 μm.     

Characterization of residue from leached cathode ray tube funnel glass: reutilization as white carbon black

Cathode ray tube (CRT) funnel glass remains an urgent environmental problem and is composed mainly of lead oxide and silicon oxide. In this research, the residue could be obtained from 2 h to 500 rpm activated CRT funnel glass after extracting lead via acid leaching under the conditions of HNO₃ concentration 1.0 mol/L, leaching temperature 95 °C and leaching time 1 h. In order to reutilize the residue, its physico-chemical properties were characterized by scanning electron microscopy, Brunauer–Emmett–Teller, thermogravimetric analysis, X-ray diffraction and Fourier transform infrared spectroscopy. The results indicated that the residue was an amorphous superfine powder with approximately 93 wt% silica oxide and specific surface area of more than 170 m²/g. It can be reutilized as white carbon black.     

Nucleophilic substitution of poly(vinyl chloride) with iminoacetic acid and n-dodecanethiol

The modification of poly(vinyl chloride) was carried out with iminodiacetic acid (IDA, C₄H₇NO₄) and iminodiacetic acid dimethylester (IDADM, C₆H₁₁NO₄), as well as with n-dodecanethiol (DT, C₁₂H₂₆S) in the presence of K₂CO₃. The reaction was carried out at different temperatures below 100 °C with dimethyl formamide (DMF) and cyclohexanone as solvents. IDA did not show any reactivity, probably due to the dipolar character of the molecule. IDADM caused the elimination of HCl, while only substitution ratios of about 3 % were observed. However, the modification of PVC with DT resulted in a substitution rate of 18 % without elimination. DT-PVC showed excellent thermal properties, comparable with those of the unmodified polymer.     

Fabrication of Biodegradable Superabsorbent Using RSM Design for Controlled Release of KNO<Subscript>3</Subscript>

Present study envisaged the sequential experimental design approach for the development of biodegradable Gelatin-Tapoica/polyacrylamide superabsorbent. Percentage water uptake efficacy of candidate sample was optimized using Response Surface Methodology (RSM) design under microwave irradiation. Different process variables such as potassium persulphate and ammonium persulphate (KPS:APS) ratio, pH, reaction time concentration of acrylamide and N,N-methylene-bis-acrylamide (MBA) were investigated as a function of percentage swelling using sequential experimental design. Maximum liquid efficacy of 1550% was obtained at KPS:APS?=?1.0:0.5; acrylamide?=?7.67?×?10^?1 mol L^?1; MBA?=?1.76?×?10^?2 mol L^?1; pH 10 and time?=?110 s. The 3D crosslinked network formed was characterized using Fourier Transformation Infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning Electron Microscopic (SEM) techniques and thermal stability was ensured by Thermal gravimetric Analysis/Differential Thermal Analysis/Differential Thermal Gravimetric (TGA/DTA/DTG) studies. Superabsorbent synthesized could increase the moisture content in different type of soils and was found to enhance the water-holding capability of the soil upto 60 days in clayey, 40 days in sandy and 51 days in mixture of two soils under controlled conditions. Further, candidate polymer was investigated for the in-vitro controlled release of the KNO₃ with diffusion exponent ‘n’ was found to be 0.4326 indicating Fickian type diffusion. Also, initial diffusion coefficient (D_I?=?3.49?×?10^?5 m² h^?1) was found to be greater than the lateral diffusion coefficient (D_L?=?3.76?×?10^?6 m² h^?1) indicated rapid release of KNO₃ during initial hours with slow release afterwards. The ecofriendly nature of the synthesized polymer was also tested by conducting biodegradation studies and it was found to degrade upto 94% and 88.1% within 70 days with degradation rate of 1.34 and 1.26% per day using composting method and vermicomposting method respectively. So, the synthesized candidate polymer was found to be boon for agriculture-horticulture sector with wide applicability.     

Preparation and Characterization of PVC Matrix Composites with Biochemical Sludge

Biochemical sludge (BS), generated in the waste water treatment of paper mills, was pretreated by enzyme hydrolysis. The effect and action mechanism of the enzymatic treatment on the properties of polyvinyl chloride (PVC) matrix composites with BS were discussed. Results showed that when the filler content was 30 wt%, the tensile strength of the PVC composites filled with BS and its modified products which were pretreated by laccase, cellulase and hemicellulase can be increased by 38.64, 67.4, 63.5 and 66.3% than the PVC composite filled with calcium carbonate. When the dosage of filler was 40 wt%, the elastic modulus of PVC composites filled with BS and its above three modified products decreased by 53.3, 52.3, 50.0 and 46.3%, respectively. Meanwhile, the thermal stability of PVC composites can also be improved at the temperature of over 340 °C. It can be concluded that the enzyme pretreatment can improve the application performance of BS usage in PVC matrix composites.