Comparative study on liquid versus gas phase hydrochloric acid hydrolysis for microcrystalline cellulose isolation from sugarcane bagasse.

Microcrystalline cellulose (MCC) was successfully synthesized from sugarcane bagasse using a rapid, low-temperature hydrochloric acid (HCl) gas treatment. The primary aim was to develop an energy-efficient "green" cellulose extraction process. Response surface methodology optimized the liquid-phase hydrolysis conditions to 3.3 % HCl at 117 °C for 127 min to obtain MCC with 350 degree of polymerization. An alternative gas-phase approach utilizing gaseous HCl diluted in hot 40 °C air was proposed to accelerate MCC production. The cellulose pulp was moistened to 15-18 % moisture content and then exposed to HCl gas, which was absorbed by the moisture in the cellulose fibers to generate a highly concentrated acidic solution that hydrolyzed the cellulose. The cellulose pulp was isolated from depithed bagasse through soda pulping, multistage bleaching and cold alkali purification. Hydrolysis was conducted by saturating the moist cellulose fibers with gaseous HCl mixed with hot air. Extensive analytical characterization using FT-IR, XRD, SEM, TGA, DSC, particle size, and porosity analyses verified comparable physicochemical attributes between MCC samples prepared via liquid and gas phase methods. The gas-produced MCC revealed 85% crystallinity, 71 Å crystallite dimensions, and thermally stable rod-shaped morphology with an average diameter below 200 µm. The similar material properties validate the proposed gas-based technique as an equally effective yet more energy-efficient alternative to conventional aqueous acid hydrolysis for fabricating highly pure MCC powders from lignocellulose. This sustainable approach enables the value-addition of sugarcane bagasse agro-industrial residue into cellulosic nanomaterials for wide-ranging industrial applications. In summary, the key achievements of this work are rapid MCC production under mild temperatures using HCl gas, optimization of liquid phase hydrolysis, successful demonstration of gas phase method, and extensive characterization verifying equivalence between both protocols. The gas methodology offers a greener cellulose extraction process from biomass.

Eco-friendly anti-corrosion performance of chitosan modified with fused heterocyclic compound on mild steel in acidic medium.

This study aims to explore the prevention of chitosan modified with a fused heterocyclic compound as a sustainable corrosion inhibitor for mild steel in 1 M HCl. Electrochemical instruments, including potentiodynamic polarization techniques, and electrochemical impedance spectroscopy (EIS), were employed to evaluate the corrosion protection performance. The outcomes showed that the chitosan modified with a fused heterocyclic compound has outstanding inhibition performance, with an inhibition effectiveness of 98.25 % at 100 ppm. The anti-corrosion features of modified chitosan were ascribed to the presence of hetero atoms in modified chitosan composite which leads to the creation of a protective layer, The modified chitosan composite behaved as mixed-typed inhibitors, as shown by the PDP results. The modified chitosan composite adsorbs on mild steel in the investigated corrosive media via chemisorption interactions, and its adsorption followed the Langmuir adsorption model. Furthermore, increasing the temperature from 303 to 333 K enhanced the corrosion rate, most likely due to the desorption of the inhibitor agent from the steel surface.

Efficient HCl leaching of platinum group metals from waste three-way catalysts: A study on kinetics and mechanisms.

Waste three-way catalysts (TWCs) have attracted much attention due to the presence of platinum group metals (PGMs) and hazardous substances such as heavy metals and organic matter. The extraction of PGMs from waste TWCs using hydrochloric acid (HCl) has been extensively researched. However, the addition of oxidizing agents like H2O2 and aqua regia is necessary to facilitate PGMs dissolution, which poses significant environmental and operational hazards. Hence, developing a green PGMs recovery process without oxidants is imperative. Previously, we investigated the process of Li2CO3 calcination pretreatment to enhance the leaching of PGMs from waste TWCs by HCl, focusing on the process and mechanism of Li2CO3 calcination pretreatment. In this study, we focused on the leaching process of HCl after pretreatment. Our investigation includes a detailed examination of leaching kinetics and mechanisms. The optimal leaching conditions were: leaching temperature of 150 °C, leaching time of 2 h, HCl concentration of 12 M, and liquid-solid ratio of 10 mL/g. The experiments resulted in maximum leaching rates of about 96%, 97%, and 97% for Pt, Pd, and Rh, respectively. However, given the presence of heavy metals, attention needs to be paid to the harmless treatment of waste acids and leaching residues. The Pt and Pd leaching process is controlled by a mixture of interfacial chemical reactions and internal diffusion, and dominated by internal diffusion, while the leaching process of Rh is controlled by interfacial chemical reactions. Li+ in Li2PtO3, Li2PdO2, and Li2RhO3 preferentially leached and underwent ion-exchange reactions with H+, promoting the dissolution of Pt, Pd, and Rh in HCl.

Dopamine modified natural glucomannan as a highly efficient inhibitor for mild steel: Experimental and theoretical methods.

In this work, Glucomannan was modified with dopamine to synthesize a new polysaccharide Schiff base (GAD). After confirmation of GAD by NMR and FT-IR spectroscopic methods, it was introduced as a sustainable corrosion inhibitor with excellent anti-corrosion action for mild steel in 0.5 M hydrochloric acid (HCl) solution. Employing electrochemical test, morphology measurement, and theoretical analysis, the anticorrosion performance of GAD on mild steel in 0.5 M HCl solution is determined. Maximum efficiency of GAD for suppressing the corrosion rate of mild steel at 0.12 g L-1 reaches 99.0 %. After immersion in HCl solution for 24 h, the results from scanning electron microscopy indicate that GAD is firmly attached to the mild steel surface by making a protective layer. According to the X-ray photoelectron spectroscopy (XPS), FeN bonds existed on the steel surface indicate the presence of chemisorption between GAD and Fe to form stable complexes attracted to the active position on the mild steel. The effects of Schiff base groups on the corrosion inhibition efficiencies were also investigated. Moreover, the inhibition mechanism of GAD was further illustrated by the free Gibbs energy, quantum chemical calculation and molecular dynamics simulation.

Corrosion inhibition of mild steel in hydrochloric acid solution by the expired Ampicillin drug.

This study examines the utilization of the expired drug, namely ampicillin, as a mild steel corrosion inhibitor in an acidic environment. The inhibitor was evaluated using weight loss and electrochemical measurement accompanied with surface analytical techniques. The drug showed a potential inhibitory efficiency of > 95% at 55 °C. The inclusion of the inhibitor increased the charge transfer resistance at the steel-solution interface, according to impedance analyses. According to potentiodynamic polarisation measurements, expired ampicillin drug significantly decreased the corrosion current density and worked as a mixed-type corrosion inhibitor. The Langmuir adsorption isotherm was followed by the adsorption of ampicillin drug on the steel substrate, exhibiting an association of physical and chemical adsorption mechanisms. The surface study performed using contact angle and scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS) measurements supported the inhibitor adsorption on the steel substrate.

Chlorine activation and enhanced ozone depletion induced by wildfire aerosol.

Remarkable perturbations in the stratospheric abundances of chlorine species and ozone were observed over Southern Hemisphere mid-latitudes following the 2020 Australian wildfires1,2. These changes in atmospheric chemical composition suggest that wildfire aerosols affect stratospheric chlorine and ozone depletion chemistry. Here we propose that wildfire aerosol containing a mixture of oxidized organics and sulfate3-7 increases hydrochloric acid solubility8-11 and associated heterogeneous reaction rates, activating reactive chlorine species and enhancing ozone loss rates at relatively warm stratospheric temperatures. We test our hypothesis by comparing atmospheric observations to model simulations that include the proposed mechanism. Modelled changes in 2020 hydrochloric acid, chlorine nitrate and hypochlorous acid abundances are in good agreement with observations1,2. Our results indicate that wildfire aerosol chemistry, although not accounting for the record duration of the 2020 Antarctic ozone hole, does yield an increase in its area and a 3-5% depletion of southern mid-latitude total column ozone. These findings increase concern2,12,13 that more frequent and intense wildfires could delay ozone recovery in a warming world.

Surface Plasmon Resonance Sensitivity Enhancement Based on Protonated Polyaniline Films Doped by Aluminum Nitrate.

Complex composite films based on polyaniline (PANI) doped hydrochloric acid (HCl) incorporated with aluminum nitrate (Al(NO3)3) on Au-layer were designed and synthesized as a surface plasmon resonance (SPR) sensing device. The physicochemical properties of (PANI-HCl)/Al(NO3)3 complex composite films were studied for various Al(NO3)3 concentrations (0, 2, 4, 8, 16, and 32 wt.%). The refractive index of the (PANI-HCl)/Al(NO3)3 complex composite films increased continuously as Al(NO3)3 concentrations increased. The electrical conductivity values increased from 5.10 µS/cm to 10.00 µS/cm as Al(NO3)3 concentration increased to 32 wt.%. The sensitivity of the SPR sensing device was investigated using a theoretical approach and experimental measurements. The theoretical system of SPR measurement confirmed that increasing Al(NO3)3 in (PANI-HCl)/Al(NO3)3 complex composite films enhanced the sensitivity from about 114.5 [Deg/RIU] for Au-layer to 159.0 [Deg/RIU] for Au-((PANI-HCl)/Al(NO3)3 (32 wt.%)). In addition, the signal-to-noise ratio for Au-layer was 3.95, which increased after coating by (PANI-HCl)/Al(NO3)3 (32 wt.%) complex composite layer to 8.82. Finally, we conclude that coating Au-layer by (PANI-HCl)/Al(NO3)3 complex composite films enhances the sensitivity of the SPR sensing device.

Corrosion inhibition of a novel antihistamine-based compound for mild steel in hydrochloric acid solution: experimental and computational studies.

Focused on the assessment of the diphenhydramine hydrochloride (DPH) capabilities as an alternative to conventional and harmful industrial corrosion inhibitors, electrochemical techniques were employed. The optimum concentration of 1000 ppm was determined by molecular simulation and validated through electrochemical experiments. The results acquired from the electrochemical impedance spectroscopy (EIS) study showed that DPH at a concentration of 1000 ppm has a corrosion efficiency of 91.43% after 6 h immersion. The DPH molecules' orientation on the surface was assessed based on EIS predicting horizontal adsorption on the surface. Molecular simulations were done to explore the adsorption mechanism of DPH. The DPH molecules' orientation on the surface was also assessed based on computational studies confirming the horizontal adsorption predicted by EIS.

Corrosion Inhibition of Mild Steel in Hydrochloric Acid Environment Using Terephthaldehyde Based on Schiff Base: Gravimetric, Thermodynamic, and Computational Studies.

Using traditional weight-loss tests, as well as different electrochemical techniques (potentiodynamic polarization and electrochemical impedance spectroscopy), we investigated the corrosion-inhibition performance of 2,2'-(1,4-phenylenebis(methanylylidene)) bis(N-(3-methoxyphenyl) hydrazinecarbothioamide) (PMBMH) as an inhibitor for mild steel in a 1 M hydrochloric acid solution. The maximum protection efficacy of 0.0005 M of PMBMH was 95%. Due to the creation of a protective adsorption layer instead of the adsorbed H2O molecules and acidic chloride ions, the existence of the investigated inhibitor reduced the corrosion rate and increased the inhibitory efficacy. The inhibition efficiency increased as the inhibitor concentration increased, but it decreased as the temperature increased. The PMBMH adsorption mode followed the Langmuir adsorption isotherm, with high adsorption-inhibition activity. Furthermore, the value of the ∆Gadso indicated that PMBMH contributed to the physical and chemical adsorption onto the mild-steel surface. Moreover, density functional theory (DFT) helped in the calculation of the quantum chemical parameters for finding the correlation between the inhibition activity and the molecular structure. The experimental and theoretical findings in this investigation are in good agreement.

A new strategy for de-oxidation of diamond-wire sawing silicon waste via the synergistic effect of magnesium thermal reduction and hydrochloric acid leaching.

With the rapid development of photovoltaic industry, the amount of diamond-wire sawing silicon waste (DWSSW) increased dramatically. Recently, how to achieve cost-effective deoxygenation of DWSSW should be the most critical issue in silicon waste recycling. Herein, a new strategy for de-oxidation from DWSSW, employing Mg vapor as de-oxidation agent and hydrochloric acid (HCl) as leaching agent, under low temperature was suggested. The de-oxidation mechanism and the mineralogical evolution of different phases during the magnesium thermal reduction and acid leaching were clarified. Results showed that the impurity oxygen in DWSSW exists as amorphous SiO2 on the surface of Si particles, which can be eliminated by transforming it into crystalline MgO using magnesium thermal reduction and followed by acid leaching. As the reduction condition was controlled at 1333 K for 2 h, the residual oxygen content in DWSSW was 0.9643% and the de-oxidation fraction attained 93%. Additionally, the removal rate of impurities Al and Fe were 99.06% and 92.20%, respectively, and the Si recovery rate achieved 88%. Taking into consideration the recoverability of Mg, the cost of the process will be reduced significantly, making this process more viable in industry.

Antipsychotic drug waste: A potential corrosion inhibitor for mild steel in the oil and gas industry.

In this study, the corrosion inhibition efficiency of thioridazine hydrochloride (TH), an antipsychotic drug, on mild steel (commonly used pipeline material in the oil and gas industry) in 1 M hydrochloric acid (HCl) was evaluated using electrochemical techniques and weight loss method. Electrochemical impedance spectroscopy (EIS) results suggest that TH significantly enhances the polarization resistance (Rp) of mild steel. Similarly, potentiodynamic polarization results showed that the corrosion current density (icorr) of mild steel decreased significantly with addition of TH. To understand the long-term effect of TH, mild steel was tested for 7 days in 100 ppm TH containing electrolyte. EIS results showed that the Rp did not change significantly after 24 h exposure as compared to 2 h exposure; whereas the Rp increased by 28% after 7-day exposure. Weight loss measurements revealed that the inhibition efficiency of TH is remarkably high (98.8%) after 7-day exposure. The adsorption free energy calculation suggests that at the initial stage (1-day) of mild steel exposure, TH was physically adsorbed onto the surface. However, at a later stage (7- day) the binding of TH was chemical, and hence the corrosion protection increased with increase in the exposure period. As compared to the wide range of corrosion inhibitors reported in the literature, TH has shown to be highly effective for mild steel. Thus, it can be suggested that TH drug waste is a potential corrosion inhibitor for mild steel pipelines in the oil and gas industry.

Experimental study on remediation of low permeability Cu-Zn contaminated clay by vacuum enhanced leaching combined with EDTA and hydrochloric acid.

To improve the washing efficiency for low permeable clay, the method of vacuum enhanced washing technology was proposed. In this study, ethylene diamine tetraacetic acid (EDTA) and hydrochloric acid (HCl) as eluents, the experiments of remediation of Cu-Zn contaminated cohesive soil by traditional soil column leaching and vacuum enhanced leaching was carried out. Results show that compared with traditional leaching method, the vacuum enhanced leaching method can significantly shorten the leaching time and prominently improve the removal rate of heavy metals Cu-Zn. When concentration of EDTA is 0.1 mol/L, the removal rate of Cu-Zn can reach 95.7% and 82.9%, respectively by vacuum-enhanced leaching. When concentration of HCl is 0.2 mol/L, the removal rate of Cu-Zn by vacuum enhanced leaching method can reach 96.2% and 90.2%, respectively. Whereas, the higher the concentration of EDTA and HCl, the slower the leaching rate. At the same concentration, the leaching rate of HCl was faster. After HCl leaching, the soil structure was seriously corroded, and the relative content of mineral composition changed considerably. After EDTA leaching, the corrosion of soil structure is light, and the relative content of mineral composition changes little. The conclusions obtained are of crucial theoretical value and technical support for environmental engineering.

Molecular dynamics study of three amino acids as corrosion inhibitor for copper in hydrochloric acid solution.

Molecular dynamics (MD) simulation is used to study the corrosion inhibition mechanism of cysteine (Cys), glutamic (Glu) and glycine (Gly) for copper in hydrochloric acid solution. The adsorption energy and radial distribution function results show that all three amino acids can spontaneously adsorb on Cu (111) surface by chemical adsorption. The absolute value of adsorption energy and intensity is Cys > Glu > Gly. The diffusion coefficient and relative concentration curve show that all the three amino acids can inhibit the diffusion and aggregation ability of corrosion particles, so the three amino acids not only can slow down the aggregation of corrosive particles, but also effectively repel corrosive particles to protect the substrate. The inhibition ability obtained by the MD simulation shows the trend of Cys > Glu > Gly, which is consistent with the experimental results. The inhibition efficiency is determined by both the adsorption strength on the substrate surface and inhibition ability for the diffusion and aggregation ability of corrosion particles.

Production of prebiotic gellan oligosaccharides based on the irradiation treatment and acid hydrolysis of gellan gum.

Biologically active gellan oligosaccharides (GOSs), newly found plant elicitors and biostimulants, are produced from the hydrolysis of gellan gum. Traditional hydrolysis with concentrated acid suffers from the problems of high pollution and low functional oligosaccharide yield because the process is difficult to control. Irradiation (60Co γ-ray) with a dosage ranging from 0 kGy to 175 kGy was used to degrade gellan gum efficiently and cleanly into low molecular weight (Mw) gellan with an average Mw ranging from 449,119 Da to 72,903 Da. The low Mw gellan irradiated at 70 kGy was further hydrolyzed with low concentration acid (0.5 mol/L HCl) to produce GOSs with DPs mainly 4 and 8, indicating that the Rha-ß-(1 â†’ 3)-Glc bonds in gellan gum were easily cut to produce residues with tetrasaccharide repeat subunits. Besides antioxidant activity, GOSs were also proved with prebiotic activity by in vitro fecal fermentation in a self-designed bionic intestinal reactor.

Croton lechleri Extracts as Green Corrosion Inhibitors of Admiralty Brass in Hydrochloric Acid.

Croton lechleri, commonly known as Dragon's blood, is a tree cultivated in the northwest Amazon rainforest of Ecuador and Peru. This tree produces a deep red latex which is composed of different natural products such as phenolic compounds, alkaloids, and others. The chemical structures of these natural products found in C. lechleri latex are promising corrosion inhibitors of admiralty brass (AB), due to the number of heteroatoms and π structures. In this work, three different extracts of C. lechleri latex were obtained, characterized phytochemically, and employed as novel green corrosion inhibitors of AB. The corrosion inhibition efficiency (IE%) was determined in an aqueous 0.5 M HCl solution by potentiodynamic polarization (Tafel plots) and electrochemical impedance spectroscopy, measuring current density and charge transfer resistance, respectively. In addition, surface characterization of AB was performed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy techniques. Chloroform alkaloid-rich extracts resulted in IE% of 57% at 50 ppm, attributed to the formation of a layer of organic compounds on the AB surface that hindered the dezincification process. The formulation of corrosion inhibitors from C. lechleri latex allows for the valorization of non-edible natural sources and the diversification of the offer of green corrosion inhibitors for the chemical treatment of heat exchangers.

Cooperative Hydrogen-Bond-Donor Catalysis with Hydrogen Chloride Enables Highly Enantioselective Prins Cyclization Reactions.

Cooperative asymmetric catalysis with hydrogen chloride (HCl) and chiral dual-hydrogen-bond donors (HBDs) is applied successfully to highly enantioselective Prins cyclization reactions of a wide variety of simple alkenyl aldehydes. The optimal chiral catalysts were designed to withstand the strongly acidic reaction conditions and were found to induce rate accelerations of 2 orders of magnitude over reactions catalyzed by HCl alone. We propose that the combination of strong mineral acids and chiral hydrogen-bond-donor catalysts may represent a general strategy for inducing enantioselectivity in reactions that require highly acidic conditions.

A moisture-tolerant route to unprotected α/ß-amino acid N-carboxyanhydrides and facile synthesis of hyperbranched polypeptides.

A great hurdle in the production of synthetic polypeptides lies in the access of N-carboxyanhydrides (NCA) monomers, which requires dry solvents, Schlenk line/gloveboxe, and protection of side-chain functional groups. Here we report a robust method for preparing unprotected NCA monomers in air and under moisture. The method employs epoxy compounds as ultra-fast scavengers of hydrogen chloride to allow assisted ring-closure and prevent NCA from acid-catalyzed decomposition under moist conditions. The broad scope and functional group tolerance of the method are demonstrated by the facile synthesis of over 30 different α/ß-amino acid NCAs, including many otherwise inaccessible compounds with reactive functional groups, at high yield, high purity, and up to decagram scales. The utility of the method and the unprotected NCAs is demonstrated by the facile synthesis of two water-soluble polypeptides that are promising candidates for drug delivery and protein modification. Overall, our strategy holds great potential for facilitating the synthesis of NCA and expanding the industrial application of synthetic polypeptides.

Experimental and Theoretical Studies on Extract of Date Palm Seed as a Green Anti-Corrosion Agent in Hydrochloric Acid Solution.

Extracts from plant materials have great potential as alternatives to inorganic corrosion inhibitors, which typically have harmful consequences. Experimental and theoretical methodologies studied the effectiveness of agricultural waste, namely, date palm seed extract as a green anti-corrosive agent in 0.5 M hydrochloric acid. Experimental results showed that immersion time and temperature are closely related to the effectivity of date palm seed as a corrosion inhibitor. The inhibition efficiency reduced from 95% to 91% at 1400 ppm when the immersion time was increased from 72 h to 168 h. The experimental results also indicated that the inhibition efficiency decreased as the temperature increased. The presence of a protective layer of organic matter was corroborated by scanning electron microscopy. The adsorption studies indicated that date palm seed obeyed Langmuir adsorption isotherm on the carbon steel surface, and Gibbs free energy values were in the range of -33.45 to -38.41 kJ·mol-1. These results suggested that the date palm seed molecules interacted with the carbon steel surface through mixture adsorption. Theoretical calculations using density functional theory showed that the capability to donate and accept electrons between the alloy surface and the date palm seed inhibitor molecules is critical for adsorption effectiveness. The HOMO and LUMO result indicated that the carboxyl (COOH) group and C=C bond were the most active sites for the electron donation-acceptance type of interaction and most auxiliary to the adsorption process over the Fe surface.

Biocompatible Wax-Based Microcapsules with Hermetic Sealing for Thermally Triggered Release of Actives.

We present a microfluidic approach that utilizes temperature-responsive and biocompatible palm oil as the shell material in microcapsules to simultaneously achieve hermetic sealing as well as on-demand temperature-triggered release of the encapsulated actives. Unlike common paraffin waxes (e.g., eicosane), microcapsule shells comprising palm oil do not form pores or cracks during freezing and provide a hermetic seal, a nearly perfect seal that separates the core containing the actives from the surrounding environment over a prolonged period of time. This allows effective isolation and protection of complex cargoes such as small molecules with high diffusivity, strong acids, and cosmetic actives including niacinamide. Moreover, the palm oil shell melts above the defined melting temperature, allowing the on-demand release of the encapsulated actives. Furthermore, palm oil is biocompatible, is edible, and leaves a minimal footprint when used in personal care and cosmetic products, offering new perspectives in the design of microcapsules for cosmetic applications.

Eco-friendly isolation and characterization of nanochitin from different origins by microwave irradiation: Optimization using response surface methodology.

The extraction of nanochitin from marine waste has attracted great industrial interest due to its unique properties, namely biodegradability, biocompatibility and as a functional reinforcing agent. Conventional acid hydrolysis isolation of nanochitin requires high temperatures and acid concentration, time and energy. Herein, for the first time, microwave irradiation method was used as an eco-friendly approach to isolate nanochitin from different sources. The isolation conditions were optimized through an experimental Box-Behnken design using surface response methodology. The data showed optimal conditions of 1 M HCl, 10.00 min and 124.75 W to obtain lobster nanocrystals; 1 M HCl, 14.34 min and 50.21 W to obtain shrimp nanocrystals; and 1 M HCl, 29.08 min and 54.08 W to obtain squid pen nanofibres, reducing time and HCl concentration. The obtained isolation yields where of 85.30, 79.92 and 80.59 % for lobster, shrimp and squid, respectively. The morphology of the nanochitins was dependent of the chitin origin, and the lengths of the nanochitins were of 314.74, 386.12 and > 900 nm for lobster, shrimp and squid pen, respectively. The thermal stability of the ensuing nanochitins was maintained after treatment. The results showed that nanochitin could be obtained by using an eco-friendly approach like microwave irradiation.