• Advances in Energy Research
• /
• v.4 no.2
• /
• pp.177-187
• /
• 2016

Ammonia borane $NH_3BH_3$ solubilized in organic solvent is a potential liquid-state chemical hydrogen storage material. In this study, metal acetylacetonates like $Fe(O_2C_5H_7)_3$, $Co(O_2C_5H_7)_2$, $Ni(O_2C_5H_7)_2$, $Pd(O_2C_5H_7)_2$, $Pt(O_2C_5H_7)_2$ and $Ru(O_2C_5H_7)_3$ are considered for assisting dehydrocoupling of ammonia borane in diglyme (0.135 M) at $50^{\circ}C$. The molar ratio between ammonia borane and metal acetylacetonate is fixed at 100. A protocol for the separation of the soluble and insoluble fractions present in the slurry is proposed; it consists in using acetonitrile to make the precipitation of metal-based compounds easier and to solubilize boron-based intermediates/products. The nature of the metal does not affect the dehydrocoupling mechanisms, the $^{11}B\{^1H\}$ NMR spectra showing the formation of the same reaction intermediates. The aforementioned metal acetylacetonates do mainly have effect on the kinetics of dehydrocoupling. Dehydrocoupling takes place heterogeneously and dehydrogenation of ammonia borane in these conditions leads to the formation of polyborazylene via intermediates like e.g., B-(cyclodiborazanyl) amine-borane and borazine. Our main results are reported and discussed herein.

• Journal of Hydrogen and New Energy
• /
• v.30 no.1
• /
• pp.1-7
• /
• 2019

The preparation and catalytic activities of various transition metal carbide crystallites (VC, MoC, WC) were examined in this study. In particular, the effect of different kinds of transition metal crystallites were scrutinized on the ammonia decomposition reaction. The experimental results showed that BET surface areas ranged from $8.3m^2/g$ to $36.3m^2/g$ and oxygen uptake values varied from $9.1{\mu}mol/g$ to $25.4{\mu}mol/g$. Amongst prepared transition metal carbide crystallites, tungsten compounds (WC) were observed to be most active for ammonia decomposition reaction. The main reason for these results were considered to be related to the extent of electronegativity between these materials. Most of transition metal carbide crystallites were exceeded by Pt/C crystallite. However, the steady state reactivities for some of transition metal carbide crystallites (WC) were comparable to or even higher than that determined for the Pt/C crystallite.

• Journal of the Korean Applied Science and Technology
• /
• v.30 no.3
• /
• pp.371-379
• /
• 2013

In order to improve the selective oxidation reaction of gaseous ammonia at a low temperature, various types of metal-impregnated activated alumina were prepared, and also physical and chemical properties of the conversion of ammonia were determined. Both types of metal (Cu, Ag) impregnated activated alumina show high conversion rate of ammonia at high temperature (over $300^{\circ}C$). However, at lower temperature ($200^{\circ}C$), Ag-impregnated catalyst shows the highest conversion rate (93%). In addition, the effects of lattice oxygen of the developed catalyst was studied. Ce-impregnated catalyst showed higher conversion rate than commercial alumina, but also showed lower conversion rate than Ag-impregnated sample. Moreover, 5 vol.% of Ag activation under hydrogen shows the highest conversion rate result. Finally, through high conversion at low temperature, it was considered that the production of NO and $NO_2$, toxic by-products, were effectively inhibited.

• Journal of Hydrogen and New Energy
• /
• v.34 no.6
• /
• pp.587-593
• /
• 2023

This research project focused on the production of hydrogen through ammonia decomposition reactions while investigating how the reactivity of this process varies when employing different catalysts. Several metal oxide supports (Al₂O₃, La₂O₃, CeO₂) were utilized as catalysts, with active metals from both the transition metal group (Co, Ni, Fe, Cr, Cu) and the noble metal group (Ru, Rh, Pd, Pt) impregnated onto these supports. Furthermore, the study examined how the reactivity evolves with changes in reaction temperature when employing the prepared catalysts. Additionally, the research delved into the distinctive activation energies associated with each of the catalysts. In this research, In the noble metal catalyst system, the order of high activity for ammonia decomposition reaction to produce hydrogen is Ru > Rh > Pt ≈ Pd. In the transition metal catalyst system, the order of high activity is Co > Ni > Fe > Cr > Cu.

• Korean Chemical Engineering Research
• /
• v.46 no.4
• /
• pp.806-812
• /
• 2008

The ammonia decomposition reaction has been of increasing interest as a means of treating ammonia in flue gas in the presence of precious metal catalyst. Various catalysts, $Pt-Rh/Al_2O_3$, $Pt-Rh/TiO_2$, $Pt-Rh/ZrO_2$, $Pt-Pd/Al_2O_3$, $Pd-Rh/Al_2O_3$, $Pd-Rh/TiO_2$, $Pd-Rh/ZrO_2$, $Pt-Pd-Rh/Al_2O_3$, $Pd/Ga-Al_2O_3$, $Rh/Ga-Al_2O_3$, and Ru/Ga-$Al_2O_3$, were synthesized by using excess wet impregnation method. Using a homemade 1/4" reactor at $10,000{\sim}50,000hr^{-1}$ of space velocity in the presence of precious metal catalyst ammonia decomposition reactions were carried out to investigate the catalyst activity. The inlet ammonia concentration was maintained at 2,000 ppm, with an air balance. Both $T_{50}$ and $T_{90}$, defined as the temperatures where 50% and 90% of ammonia, respectively, are converted, decreased significantly when alumina-supported catalysts were applied. In terms of catalytic performance on the ammonia conversion in the presence of hydrogen sulfide, $Pt-Rh/Al_2O_3$ catalyst showed no effect on the poisoning caused by hydrogen sulfide. These results indicate that platinum-rhodium bimetallic catalyst is a useful catalyst for ammonia decomposition.

• Resources Recycling
• /
• v.32 no.6
• /
• pp.45-53
• /
• 2023

This study discussed the trend and future strategy of adsorption technology R&D to effectively recover ammonia emitted from the livestock fields. A proper ammonia adsorbent should incorporate acidic or hydrogen bonding functional groups on the surface, as well as a high specific surface area and a good surface structure appropriate for ammonia adsorption. Activated carbon and minerals such as zeolite have widely been used as ammonia adsorbents, but their adsorption effects are generally low, so any improvement through surface modification should be necessary. For example, incorporation of metal chloride included in a porous adsorbent can promote ammonia adsorption effectiveness. Recently, new types of adsorbents such as MOFs (Metal-Organic Frameworks) and POPs (Porous Organic Polymers) have been developed and utilized. They have shown very high ammonia adsorption capacity because of adjustable and high specific surface area and porosity. In addition, Prussian Blue exhibited high ammonia adsorption and desorption performance and selectivity. This looks relatively advantageous in relation to the recovery of ammonia from livestock waste discharge. In the future, further research should be made to evaluate ammonia adsorption/desorption efficiency and purity using various adsorbents under conditions suitable for livestock sites. Also, effective pre- and/or post-treatment processes should be integrated to maximize ammonia recovery.

• Bulletin of the Korean Chemical Society
• /
• v.21 no.10
• /
• pp.989-994
• /
• 2000

• Polymer(Korea)
• /
• v.25 no.5
• /
• pp.642-648
• /
• 2001

An attempt was made to synthesize an ammonia adsorbent by the photo-induced grafting of styrene (St) onto polypropylene (PP) nonwoven using benzoin ethyl ether (BEE) as a photosensitizer with urea and trimethylol propane triacrylate in methanol medium. As styrene concentration was increased, the graft yield was increased. It was also found that the graft yield increased with reaction time. The polypropylene grafted with styrene (PP-g-St) was sulfonated by chlorosulfonic acid in dichloroethane and complexed with several metal ion, such as $cO^{+2}$, $nI^{+2}$, $cU^{+2}$, $Zn^{+2}$. The amount of ammonia gas adsorbed by these sample was dependent on the degree of sulfonation, adsorption time, and ammonia gas pressure. The adsorption capacity of ammonia gas by the sulfonated PP-g-St(SPP-g-St) nonwoven with 4. 25 mmol $H^+$/g was 6.61 mmol/g. Metal ion complexed SPP-g-St nonwovens had higher adsorption capacity than SPP-g-St nonwoven and the $Co^{+2}$ complexed SPP-g-St showed 9.90 mmol $NH_3$/g, which was much higher than that of active carbon or silica gel.

• Applied Chemistry for Engineering
• /
• v.32 no.6
• /
• pp.671-678
• /
• 2021

Effects of nitric acid treatment of an activated carbon and impregnation of metal chlorides on the activated carbon were investigated to improve ammonia adsorption performance. It was confirmed that functional groups such as hydroxyl and carboxyl groups were introduced onto a surface of the activated carbon with nitric acid treatment. Then, each metal chloride (NiCl₂, MgCl₂, CuCl₂, MnCl₂ or CoCl₂) was impregnated onto the surface-modified activated carbon using an ultrasonic impregnation method. The physicochemical properties and ammonia adsorption performance of various impregnated activated carbons were observed. Metal chlorides were well dispersed by sonication and evenly distributed on the surface of the activated carbon. Despite the reduced specific surface area and pore volume, the surface-modified activated carbon impregnated with metal chlorides exhibited excellent ammonia adsorption performance. In particular, HNO₃-NiCl₂ AC prepared by impregnating NiCl₂ showed the best ammonia adsorption capacity of 3.736 mmol·g^-1, which was improved by about 57 times compared to that of an untreated activated carbon (0.066 mmol·g^-1).

• Journal of the Korean Applied Science and Technology
• /
• v.27 no.2
• /
• pp.208-215
• /
• 2010

EAF dust which is contained around 30% of zinc, 15% of iron and 3% of lead individually, is chemically treated by ammonium chloride, ammonia water, ammonia gas and carbon dioxide, and also tested and identified the ratios of the recovery of In by applied the variations of particle size, pH and heating temperature as well, in order to getting optimized recovery of the In metal after performing all of those processes. Experimental results showed that the rate of Zn recovery is 97% when the mixture of 1.3 of $NH_4Cl$/EAF is heated to the temperature of $400^{\circ}C$ and leached by water, and 95% recovery of In when ammonia gas and carbon dioxide is added simultaneously and adjust the 9.5 of pH to the same mixture above. For the purpose of remove the impurities in the mixed sample, which is prepared by the two samples, indicated above showing as the ratio of 95% and 97% recovery, in case of applied the cementation process to it, and also by electrolytic process, produced the In plate of 95~97%, and acquired 99-99.5% of In metal ingot finally by applied the heating process at $470{\sim}500^{\circ}C$.