ACS Publications. Most Trusted. Most Cited. Most Read
Ammonia Concentrator for Repeatable Adsorption/Desorption Using Nickel Hexacyanoferrate as Adsorbent and Production of Solid Ammonium Bicarbonate
More

OR SEARCH CITATIONS

My Activity
Publications

Figure 1Loading Img
Download Hi-Res ImageDownload to MS-PowerPointCite This:ACS Sustainable Chem. Eng. 2024, 12, 6, 2183-2190
  • Open Access
Research Article

Ammonia Concentrator for Repeatable Adsorption/Desorption Using Nickel Hexacyanoferrate as Adsorbent and Production of Solid Ammonium Bicarbonate
Click to copy article linkArticle link copied!

  • Hatsuho Usuda*
    Hatsuho Usuda
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    *Email: [email protected]. Phone: +81-29-861-3650.
    More by Hatsuho Usuda
    Orcidhttps://orcid.org/0000-0002-6551-5676
  • Tomoji Watanabe
    Tomoji Watanabe
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    More by Tomoji Watanabe
  • Takamitsu Ishikawa
    Takamitsu Ishikawa
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    More by Takamitsu Ishikawa
  • Naoki Nakashima
    Naoki Nakashima
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    More by Naoki Nakashima
  • Keiko Noda
    Keiko Noda
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    More by Keiko Noda
  • Akira Takahashi
    Akira Takahashi
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    More by Akira Takahashi
    Orcidhttps://orcid.org/0000-0002-8375-7177
  • Tohru Kawamoto*
    Tohru Kawamoto
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    *Email: [email protected]. Phone: +81-29-861-5141.
    More by Tohru Kawamoto
    Orcidhttps://orcid.org/0000-0002-3984-2980
  • Kimitaka Minami*
    Kimitaka Minami
    National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    *Email: [email protected]. Phone: +81-29-861-3108.
    More by Kimitaka Minami
    Orcidhttps://orcid.org/0000-0003-1195-9498
Open PDFSupporting Information (1)

ACS Sustainable Chemistry & Engineering

Cite this: ACS Sustainable Chem. Eng. 2024, 12, 6, 2183–2190
Click to copy citationCitation copied!
https://doi.org/10.1021/acssuschemeng.3c05679
Published January 30, 2024

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

CC-BY-NC-ND 4.0 .

Abstract

Click to copy section linkSection link copied!
High Resolution Image
Download MS PowerPoint Slide

Ammonia serves as both a valuable substance and an environmental pollutant. Its recovery and reuse offer a promising approach to mitigate environmental impacts while reducing costs for treatment, production, and CO2 emissions. In this article, we present a flow system to develop efficient methods for the recovery and reuse of ammonia. In this system, adsorption and desorption were subsequently conducted without relocating the adsorbent column. In the experiment, the adsorbent was composed of nickel hexacyanoferrate (NiHCF) granules, the inlet gas contained approximately 19,000 ppm of NH3 in the air, and the washing liquid for the desorption was NH4HCO3 solution. The outlet NH3 concentration decreased to 3 vol % of the inlet at first and then gradually increased. During desorption, ammonium concentration in the washing liquid increased, and the pH was kept around 8 due to CO2 introduction. After the adsorption and desorption cycles, the washing liquid was cooled to 5 °C, and a NH4HCO3 solid was precipitated. Moreover, NH4HCO3 solid was obtained inasmuch as the adsorbed amount after repeating the adsorption and desorption several times. This study demonstrates the continuous operation of adsorption and desorption cycles and that NiHCF granules can adsorb and desorb NH3 repeatedly.

This publication is licensed under

CC-BY-NC-ND 4.0 .
  • cc licence
  • by licence
  • nc licence
  • nd licence
Copyright © 2024 The Authors. Published by American Chemical Society

Subjects

what are subjects

Keywords

what are keywords

Synopsis

Ammonia concentrator enabled repeatable adsorption from the air, desorption into a liquid, and production of solid ammonium bicarbonate.e

Introduction

Click to copy section linkSection link copied!
Nitrogen compounds are crucial substances in industries and agriculture. One of the nitrogen compounds, ammonia (NH3), is generated at an approximate annual production rate of 180 million metric tons. (1) The majority of NH3 is synthesized from atmospheric nitrogen (N2) using the Haber-Bosch process, which results in the emission of approximately 451 million tons of CO2, accounting for approximately 1% of global annual CO2 emissions as of 2010. (2) The produced ammonia serves as a fundamental component in the synthesis of various industrial products and fertilizers, significantly contributing to the augmentation of crop yields. Following the utilization of NH3, however, nitrogen compounds are released into the environment through wastewater, exhaust gases, and in agricultural practices, namely, urine and feces, in diverse forms including NH3, ammonium ions (NH4+), organic nitrogen, nitrate ions (NO3–), and NOx, consequently exerting detrimental effects on the environment. (3−6) To mitigate this pollution, denitrification and denitration methods have been created, albeit requiring a certain amount of energy for the conversion of nitrogen compounds back into atmospheric N2. (7,8) In the current artificial nitrogen cycle, substantial energy and a considerable amount of CO2 emissions are required to convert atmospheric nitrogen (N2) into utilizable nitrogen compounds and subsequently revert them through a detoxification process. While the artificial nitrogen cycle has spurred significant advancements in industry and agriculture, its sustainability from a global environmental perspective is questionable.
The development of a sustainable nitrogen cycle is required for significant decreases in energy consumption and CO2 emissions. A key solution toward achieving this sustainability lies in the recovery and reuse of NH3. There are various ways to remove NH3 from waste gas such as water scrubbing, (9) ultraviolet light, (10) catalytic reactions, (11−13) and biofilters, (14−17) but they are not intended for the reuse of NH3. For example, water scrubbing, a commonly employed method for ammonia removal, falls short in terms of selectivity for the efficient reuse of NH3.
Our research group has conducted studies on NH3 recovery and reuse methods using Prussian blue (PB) and Prussian blue analogs (PBAs) as highly selective adsorbents with superior adsorption capacities compared to other ammonia adsorbents. (18−20) PBAs are microporous materials denoted as AyM[M′(CN)6]x (A = Na+, K+, NH4+, etc., M and M′ = Fe, Cu, Co, Ni, Co, etc.) and exhibit characteristic adsorption and desorption characteristics depending on the variations in M, M′, and composition x and y. (21−25) There are two types of adsorption sites in PBAs as shown in Figure 1a. (19) One is the interstitial site, which is a confined space where a positive ion such as potassium and ammonium is preferentially adsorbed, and the other is a vacancy site, which is surrounded by six open metal sites where NH3 and water (H2O) are known to be adsorbed. The use of PBA adsorbents holds promise for NH3 reuse because the adsorbed NH3 can be desorbed through heating or washing with water or specific solutions. (19,25−29) Moreover, the PBA adsorbents have already been applied to discarded ammonia gas and showed a significant decrease in ammonia concentration in the gas. (27,28)

Figure 1

Figure 1. (a) Crystal structure of NiHCF, which has interstitial sites and vacancy sites. (b) Photograph of NiHCF granules.

High Resolution Image
Download MS PowerPoint Slide
We attempted washing desorption and subsequent solid recovery for NH3 recovery because ammonium salt offers several advantages as a NH3 species, on the points of energy efficiency and the production of safer products with enhanced portability compared to NH3 gas, liquid NH3, or NH3 solutions. In a previous study, we demonstrated the desorption of adsorbed NH3 on copper hexacyanoferrate (CuHCF), which is a type of PBA, by washing it with a saturated ammonium bicarbonate (NH4HCO3) solution, and the precipitation of NH4HCO3 solid by introducing CO2 gas into the solution. (26) The NH3 desorption characteristics using an NH4HCO3 solution were evaluated for various PBAs, revealing that nickel hexacyanoferrate exhibited a high desorption ratio and structural stability throughout the NH3 adsorption and desorption process. (29) The desorption method utilizing the NH4HCO3 solution has so far been demonstrated only in batch experiments, employing separate equipment for the adsorption and desorption processes. However, the batch operation will not be applicable to the treatment of waste gas that is emitted continuously because it can only treat the gas off-and-on, requiring a lot of labor for its operation. Therefore, it is crucial to develop a system that enables continuous operation for practical applications.
In this study, we perform adsorption and desorption within a continuous flow system, utilizing a gas flow line and a liquid flow line without the need to relocate the adsorbent column. This system will have economic advantages in that it does not require heat for desorption and it does not emit washing liquid as wastewater because the washing liquid can be repeatedly used. In the experiment, the inlet gas contained approximately 19,000 ppmv of NH3 in the air, and the washing liquid for the desorption was NH4HCO3 solution. The NH3 concentration in the inlet gas was determined to be comparable to that in the batch experiment in the previous report, (29) but the applicable concentration will be lowered in a future study. After the adsorption and desorption cycles, the washing liquid was cooled to 5 °C for the precipitation of the NH4HCO3 solid. Nickel hexacyanoferrate (NiHCF) was adopted as an adsorbent because its desorption efficiency and structural stability were proved to be high enough during NH3 adsorption and desorption using NH4HCO3 solution as a washing liquid. (29)

Materials and Methods

Click to copy section linkSection link copied!

Materials

We developed granular NiHCF containing 5 wt % of poly(vinyl alcohol) (PVA) as a binder. NiHCF was synthesized aiming for Ni[Fe(CN)6]0.66 (Figure 1a) where the NH3 desorption occurs in saturated NH4HCO3 solution in the case of NiHCF. (29) The shape of the NiHCF granules was cylindrical with a diameter and length of approximately 5 and 10 mm, respectively (Figure 1b). NH4HCO3 was commercially available from Fujifilm Wako Pure Chemical (Osaka, Japan) and was used without further purification.

Adsorption and Desorption

The experimental setup of NH3 adsorption and desorption is shown in Figure 2. Pressure meters (GC31, NAGANO KEIKI Co., LTD, Tokyo, Japan) and flow meters (FD-XS8, KEYENCE Corp., Osaka, Japan) are denoted as Pn and Fn (n = 1, 2, and 3), respectively. The diaphragm pumps 1 and 2 are FF20KPDC-M, and 3 is NF1.60KTDC. The pumps were commercially available from KNF (Freiburg, Germany). MFC 1, 2, and 3 are mass flow controllers CUBEMFC1005-4S2-50-NH3-CR-003-SWL, CUBEMFC1005-4S2-2L-AIR-003-SWL, and CUBEMFC1005-4S2-50-CO2-003-SWL commercially available from FCON CO., Ltd. (Kochi, Japan). The adsorbent column contained 177 g of NiHCF granules washed with NH4HCO3 solution in advance such that the conditions of NiHCF in the first cycle are similar to those of the second and third cycles.

Figure 2

Figure 2. Experimental setup of the NH3 adsorption and desorption. MFC stands for the mass flow controller. The adsorption and desorption lines are shown as red solid lines with closed arrows, and blue thin lines with open arrows, respectively. The thicker lines and the thinner lines represent gas and liquid lines, respectively. Pn and Fn represent the pressure and flow meter, respectively.

High Resolution Image
Download MS PowerPoint Slide
During adsorption, the flow rates of dry air and NH3 were 1970 and 40 mL/min, respectively. Therefore, the NH3 concentration of inlet gas was approximately 19,000 ppmv. H2O concentration was calculated as 31,000 ppmv from vapor pressure and the gas flow rates. NH3, CO2, and H2O concentrations in the outlet gas were measured using Fourier transform infrared red spectroscopy (FTIR) with an OMEGA5 commercially available from Bruker (MA, USA). Its detection limits for NH3, CO2, and H2O were 0.4, 2, and 300 ppmv, respectively. The adsorption was continued until the outlet NH3 concentration reached 95 vol % of the inlet NH3 concentration to obtain breakthrough curves for adsorption behavior; then, the experiment moved to the desorption step.
In the desorption experiment, 700 mL of NH4HCO3 solution was used as the washing liquid, whose initial NH4HCO3 concentration was 1.6 mol/L, which is the saturated concentration at 5 °C. The washing liquid was stored in an NH4HCO3 solution tank and sent to the adsorbent container by pump 1 at flow rates of 25–40 mL/min to wash the NiHCF granules after adsorption. Pump 2 downstream of the adsorbent sends the washing liquid back to the NH4HCO3 solution tank at the same rate as pump 1. A part of the washing liquid was sent into the CO2 tank from the NH4HCO3 solution tank by pump 3 at a flow rate of 120 mL/min in the CO2 tank to make contact with the CO2 gas. The stop valves 1 and 2 were closed to prevent leaks of gases evaporated from the adsorbent and washing liquid during desorption. The stop valve 3 was basically closed throughout the experiment but opened once every 60 min during desorption to collect 1 mL of washing liquid. The collected washing liquid was subjected to pH and K+ concentration measurements using a compact pH meter LAQUAtwin and a compact K+ meter LAQUAtwin (HORIBA, Ltd., Kyoto, Japan), respectively; subsequently, the liquid was diluted twice with a 50 g/L boric solution to prevent NH3 evaporation. The liquid was further diluted 10,000 times with water and filtered using a PTFE membrane filter with a pore size of 0.45 μm (Omnpore, Metrohm) for measurements using ion chromatography (IC), ECO IC (Metrohm AG, Herisau, Switzerland). In the IC, ammonia nitrogen concentration in the samples was measured as ammonium ion because the eluent was 1.7 mmol/L nitric acid/0.7 mmol/L dipicolinic acid and its pH was low, which changes an ammonia molecule to an ammonium ion in solution.
The adsorption and desorption cycle was repeated three times without exchanging the NiHCF granules and washing liquid. After three cycles of adsorption and desorption, the washing liquid was kept at 5 °C to yield precipitate. For the analysis of nickel elution into the washing liquid from the adsorbent granules, an aliquot of the washing liquid was diluted 500 times with 2 wt % nitric acid and filtered using a PTFE membrane filter with a pore size of 0.45 μm. The nickel concentration was measured by using a microwave plasma atomic emission spectrometer (MP-AES, Agilent 4100; Agilent Technologies Japan Ltd.).
The amounts of NH3 species in the NiHCF granules before and after the three cycles of adsorption and desorption were evaluated by washing the granules four times with 0.2 mol/L NaHSO4 solution at a liquid/solid ratio >60 and shaken at 600 rpm for more than 24 h. The granules and solution were then separated through centrifugation at 3000 rpm for 10 min using a 5702 centrifuge 5702 (Eppendorf Co.). The ammonium nitrogen concentration in the supernatant was measured after the filtration using a PTFE membrane filter with a pore size of 0.45 μm and the NH3 species that remained in the NiHCF granules were calculated.

Characterization

To obtain the NH3 adsorption capacity for NiHCF powder in pure NH3, the measurement of the NH3 adsorption isotherm was conducted as follows. First, the hydration water in the NiHCF sample in a sample tube was removed by heat treatment at 150 °C at 10 Pa for 24 h using a pretreatment apparatus (BELPREP VAC MicrotracBEL Inc.). Subsequently, the sample tubes were purged with N2 gas. NH3 isotherms for the NiHCF samples were obtained using a gas-adsorption system (BELSORP-max, MicrotracBEL Inc.) at 25 °C. The criterion of equilibrium in this measurement was a pressure change below 0.3% in 10 min.

Results and Discussion

Click to copy section linkSection link copied!

Adsorbent Information

The crystal structure of synthesized NiHCF (Figure S2a) agreed with the reported NiHCF structures. (30,31) The composition of nickel, hexacyanoferrate, and potassium in the NiHCF granules was Ni:Fe:K = 1:0.69:0.1 (Table S1). The smaller Fe proportion compared to Ni suggests that a [Fe(CN)6]3– vacancy existed. The NH3 isotherm of the NiHCF powder is shown in Figure 3. The adsorbed NH3 amount exceeded 8 mmol/g at the NH3 pressure corresponding to the NH3 partial pressure in the inlet gas in the flow experiment. The NiHCF granules were washed with NH4HCO3 solution, and their XRD profile (Figure S1a), FTIR spectra (Figure S1b), and composition were analyzed. The XRD and FTIR results were comparable with those after NH3 desorption with NH4HCO3 solution. (29) The composition became Ni:Fe:K = 1:0.75:0.0 (Table S1) suggesting that K in NiHCF exchanged with the ammonium ions in the NH4HCO3 solution.

Figure 3

Figure 3. NH3 adsorption isotherms of NiHCF powder at 25 °C. The blue broken line indicates the partial pressure of NH3 in the inlet gas.

High Resolution Image
Download MS PowerPoint Slide

Adsorption and Desorption Experiments

The results of the adsorption experiments are plotted in Figure 4a as the NH3 concentrations of the inlet and outlet gas. The inlet NH3 concentration was maintained at approximately 19,000 ppmv throughout the adsorption experiment. The outlet NH3 concentration in the first cycle was at first 490 ppmv meaning that 97 vol % of NH3 was trapped in the adsorbent, and gradually increased, drawing a breakthrough curve until 14.6 h where the outlet NH3 concentration reached more than 95 vol % of inlet NH3 concentration and the experiment moved to a desorption step.

Figure 4

Figure 4. Results of NH3 adsorption and desorption. (a) NH3 concentration of the gas flow getting in/out of the NiHCF adsorbent in the three cycles of adsorption, which have a desorption step after the adsorption. (b) Ammonium nitrogen concentration (blue square) and pH (orange cross) in the washing liquid during desorption.

High Resolution Image
Download MS PowerPoint Slide
Discontinuous falls in the breakthrough curve were observed at total flowing gas times of 3.5 and 7.6 h in the first cycle when the experiment was temporarily stopped for more than 12 h because the experiments were conducted only during the day. The falls are considered to be caused by diffusion of NH3 in the granules, resulting in a decrease in the NH3 density around the surface of the NiHCF granules and adsorbed more NH3 when the experiment was repeated than before the experiment was temporarily stopped. The same trends were observed for the second and third cycles.
The outlet NH3 concentrations in the first and second adsorption were approximately 19,000 ppmv right before desorption, and they decreased to 3000 and 4600 ppmv after desorption, respectively, indicating that a part of the trapped NH3 was successfully desorbed into the washing liquid. The initial outlet NH3 concentration in each cycle increased as the cycle increased. The amount of the total trapped NH3 during adsorption was 1420 mmol (1st cycle: 620 mmol, second cycle: 390 mmol, third cycle: 300 mmol), which were calculated from the summation of the gap between the NH3 amounts in the inlet and outlet gases (SI).
CO2 concentrations in the outlet gas were 38,000, 79,000, and 110,000 ppmv at the beginning of each of the first, second, and third adsorption terms, respectively, and immediately decreased to a few thousand ppmv (Figure S3). The amounts of emitted CO2 were 70, 160, and 190 mmol in the first, second, and third adsorption terms, respectively, and the total amount was 420 mmol. The high CO2 concentrations at the beginning are considered to be caused by CO2 evaporated from the washing liquid and stored in the dead volume of the equipment. Another possible CO2 source is the washing liquid on the granule surface, whose amount was too little to afford all of the CO2 emission in the outlet gas. The CO2 evaporation will be reduced by designing the system with little dead volume or improving the CO2-introducing method.
The crystal structure and chemical conditions of the NiHCF granules did not significantly change during the adsorption and desorption experiment (Figure S1). This result is consistent with that of a previous study. (29) The structural stability of NiHCF shows durability in practical use. Moreover, there was no significant difference observed among the granules on the upstream, midstream, and downstream sides in the adsorbent column, which indicates that the gas flowed through the entire column. The composition of nickel and iron became Ni:Fe = 1:0.79 (Table S1). The relative decrease of Ni against Fe is considered to be caused by elution into the washing liquid because Ni was detected at 3000 ppm in the washing liquid, whereas Fe was not.
The desorption results are exhibited in Figure 4b as plots of the ammonium nitrogen concentration and pH in the washing liquid. The initial ammonium nitrogen concentration was 1.6 mol/L, which is approximately the saturated concentration of NH4HCO3 at 5 °C. The final concentration of the first, second, and third cycles were 2.0, 2.5, and 2.7 mol/L, respectively. The increase in the ammonium nitrogen concentration at each cycle indicates that the adsorbed NH3 in the NiHCF granules was successfully desorbed into the washing liquid. In the first cycle, the washing liquid flow was temporarily stopped at the total washing time of 3.5 h, but the ammonium nitrogen concentration was kept constant until the next start. The unchanging concentration shows that the NH3 species did not rapidly escape from the washing liquid. The total amount of NH3 desorbed from the NiHCF granules was 680 mmol (1st cycle: 280 mmol, second cycle: 270 mmol, and third cycle: 130 mmol), indicating that the desorption amount was lower than half of the adsorption amount. The remaining NH3 species in the NiHCF granules was 6.0 mmol/g-adsorbent after the third desorption according to the results of desorption using acid for the NiHCF granules.
The pH increased to 8.1 when desorption started and gradually decreased to 7.9, as shown in Figure 4b. This trend is considered a result of the balance between the CO2 dissolution rate and the NH3 desorption rate. At first, NH3 dissolved in the washing liquid more than CO2 resulting in an increase in the pH; subsequently, as CO2 dissolved, the pH became lower. In this pH region, more than 90% of the NH3 species exist as NH4+ ions, and more than 90% of the CO2 species exist as bicarbonate ions (HCO3–) according to the calculation using the dissociation constants of NH3 (pKa = 0.21 (32)), H2CO3 (pKa = 6.35), and HCO3– (pKa = 10.33). (33)
The molar ratio of NH3 and CO2 was calculated from equilibrium constants and pH. Before desorption, the ratio was NH3:CO2 = 16:17; then, it became NH3:CO2 = 27:26 at the end of the third cycle. The NH4 concentration increased through desorption but the change in the molar ratio of NH3 and CO2 was small since CO2 was introduced into the washing liquid simultaneously.
The nickel concentration in the washing liquid was 3200 ppm at the end of cycle 3, which means that 4.8 mol % of nickel was eluted from NiHCF granules into the washing liquid. However, the ammonia concentrator presented in this study does not emit wastewater, and the elution is considered to stop at the equilibrium. Therefore, the elution will not significantly affect the cycle durability of the NiHCF granules.

Precipitation

Precipitation was observed in the washing liquid-cooled to 5 °C after three cycles of the NH3 adsorption and desorption experiment. After washing with ethanol, the color derived from the nickel ions became invisible in the precipitate, as shown in Figure 5a.

Figure 5

Figure 5. (a) Washed precipitate obtained after desorption. (b) FTIR spectra of the obtained precipitate and commercial NH4HCO3.

High Resolution Image
Download MS PowerPoint Slide
The FTIR spectra of the obtained precipitate and commercial NH4HCO3 are exhibited in Figure 5b. Both spectra showed comparable features, indicating that the precipitate was NH4HCO3. Possible ammonium salts are ammonium bicarbonate, ammonium carbamate, and ammonium carbonate. The FTIR spectra of the precipitation were comparable to a reported one of ammonium bicarbonate and different from a reported one of ammonium carbamate and ammonium carbonate. (34) The amount of precipitated NH4HCO3 was 300 mmol, which is 36% of the expected amount calculated from the IC result in the saturated concentration at 5 °C. One of water-based adsorption, coupling thermal stripping, and acid absorption can also be a technique to obtain solid ammonium salt as ammonium sulfate. (35) However, it will require five times more energy compared to the cooling precipitation. The alkali-halide salt adsorption is not applicable to real discarded gas that contains water vapor since the alkali-halide salts are usually deliquescent.

Material Balance

The NH3 species in NiHCF granules was 1.9 mmol/g-granule before the first adsorption and most of them are considered to be NH4+ according to the FTIR result in Figure S1b denoted as “washed with NH4HCO3 solution”. This result suggests that NH4+ did not desorb into the NH4HCO3 solution. The NiHCF granules in the column were 177 g, which should have 340 mmol of NH3 species before adsorption. In total, in the first set of the adsorption and desorption experiment, 4050 mmol of NH3 entered into the adsorbent column, and 1310 mmol was trapped in the column; 680 mmol was then desorbed in the washing liquid. The desorbed amount was less than the trapped amount, and the remaining 630 mmol of NH3 species were supposed to be NH4+ mainly (Figure S1b). This tendency agrees well with our previous results. (29) Considering the material balance and the amount of NH3 species in the granules before the first adsorption, 970 (340 + 1310 – 680) mmol of NH3 species should remain in the NiHCF granules. Particularly, the NH3 species in the granules was demonstrated as 1000 mmol, which is comparable to the value calculated from the adsorbed and desorbed amounts. After adsorption in cycle 3, the NH3 species in the adsorbent was calculated as 1130 (1000 + 130) mmol since the desorption amount was 130 mmol. This means that the adsorbed amount per NiHCF granule weight after adsorption in cycle 3 was 6.4 (1130/177) mmol/g-granule, which is 78% of the adsorbed amount in 19,000 ppmv of NH3 gas according to the isotherm in Figure 3. Possible reasons for the gap between the adsorbed amounts in the column experiment and isotherm are as follows: the NH3 has not diffused into the center of the granules yet; the adsorption capacity per weight was decreased owing to the PVA contained in the granules at approximately 5 wt % of their weight.
The bars in Figure 6 show the adsorbed and desorbed amount in the first set (Figure 4) and the second set where the second set of 3 cycles of the adsorption and desorption experiment was conducted in the same protocol as the first set after changing the washing liquid to a new one. Both the adsorption and desorption amounts in the first set decreased as the cycle number increased, suggesting that the adsorption and desorption were hindered as the NH4+ concentration increased in the washing liquid. It was also because the system was turned to desorption from adsorption before the adsorption amount reached saturation. The decrease in the adsorption amount does not mean a lack of sustainability. The adsorption amount should be the same as the desorption amount if all of the NH3 can be desorbed. However, the results indicate that there are two kinds of adsorption sites; one can easily release NH3, and the other cannot as reported in previous research. Moreover, the desorption efficiency was different depending on the NH4+ concentration in the washing liquid. In the first set, the adsorbed NH3 amount in cycle 2 was more than the desorbed amount in cycle 1, indicating that the adsorption capacity was more than the amount adsorbed in cycle 1, and the same trend was observed in cycles 2 and 3 of the first set. The gap between the adsorbed and desorbed amount in Figure 6 was 340, 127, and 164 mmol in cycles 1, 2, and 3, respectively, of the first set. In the second set, the adsorbed amount decreased while the desorbed amount was constant, and finally, in cycle 3, the adsorbed and desorbed NH3 amounts became comparable demonstrating a possibility of NH3 desorption as much as adsorption.

Figure 6

Figure 6. Adsorbed and desorbed NH3 amounts in each cycle. Red bars: adsorbed amount of NH3. blue bars: desorbed amount of NH3. The 2nd set of 3 cycles of the adsorption and desorption experiment was conducted in the same way as the 1st set (Figure 4) after changing the washing liquid used in the 1st set to a new one. The right axis exhibits the NH3 amount normalized by the adsorbent weight. The broken and dotted lines are the adsorbed and desorbed amounts in the reported batch experiment in the case of NiHCF, respectively. (29)

High Resolution Image
Download MS PowerPoint Slide
Comparisons with the batch experiment for NiHCF (29) are shown in Figure 6. The adsorption amount was less than that in the batch experiment, as shown in Figure 6. This is because adsorption had not reached saturation when the experiment turned to desorption on the contrary to the batch experiment.
The material balance of the NH3 species in cycle 3 of the second set is shown in Figure 7 to discuss the possibility of constant adsorption and desorption. NH3 was provided to the adsorbent column at 1150 and 920 mmol was not trapped by the NiHCF granules, showing that 230 mmol was once trapped, and the same amount was desorbed into the washing liquid. Afterward, the same amount of NH3 in the washing liquid became solid NH4HCO3. This material balance suggests that after several sets of adsorption, desorption, and precipitation processes, the same amount of NH4HCO3 could be recovered as that of trapped NH3 in the adsorbent. A certain amount of NH3 was lost as outlet gas because adsorption was continued until NH3 concentration in the outlet gas became 95 vol % of that in the inlet gas in this experiment to obtain breakthrough curves. In an application, the double or triple tower system will be adopted, and an adsorbent column can be switched from adsorption to desorption when the NH3 concentration in outlet gas reaches 0.1 vol % or less. This greatly reduces the loss of NH3. The loss also occurs in a batch experiment due to the large dead volume. (26) The loss due to the dead volume will decrease as the size scale of the system becomes larger. However, there is a thermodynamic limit of NH3 loss the dead volume among the NiHCF granules in a column will not be zero even if the size scale of the NH3 concentrator becomes larger. The gas phase in the adsorbent column was 26 vol % which was calculated from the bulk density of NiHCF granules and the density of NiHCF itself. The thermodynamic limit of NH3 loss was less than 0.01 mol % of NH3 trapped in the column when being calculated from the equilibrium of NH3 concentration in the gas phase and the adsorbed NH3 in NiHCF granules.

Figure 7

Figure 7. Material balance of NH3 species during the process of adsorption, desorption, and precipitation in cycle 3 of the 2nd set. The units of the numbers is mmol.

High Resolution Image
Download MS PowerPoint Slide

Conclusions

Click to copy section linkSection link copied!
Significant sequential adsorption and desorption of NH3 were proved to be possible using NiHCF granules as an adsorbent and NH4HCO3 solution as the washing liquid. This method enabled a continuous operation of adsorption and desorption compared to a batch process, which requires different sets of equipment for adsorption and desorption. Successful implementation of NH3 adsorption and desorption within this system would demonstrate the feasibility of a two- or multitower-type operation.
The system presented in this study is very economic at the points of no heat desorption and no wastewater. The verification test of this ammonia concentrator will be conducted, and a more detailed economic analysis will be done in the near future.

Supporting Information

Click to copy section linkSection link copied!

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.3c05679.

  • Experimental setup of NH3 adsorption and desorption; additional results of characterization of the NiHCF adsorbent; and CO2 concentration in the outlet gas during adsorption (PDF)

Terms & Conditions

Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.

Author Information

Click to copy section linkSection link copied!
  • Corresponding Authors
  • Authors
    • Tomoji Watanabe - National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    • Takamitsu Ishikawa - National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    • Naoki Nakashima - National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    • Keiko Noda - National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan
    • Akira Takahashi - National Institute of Advanced Industrial Science and Technology (AIST), Nanomaterials Research Institute, 1-1-1 Higashi, Tsukuba 305-8565, Japan;  Orcidhttps://orcid.org/0000-0002-8375-7177
  • Author Contributions

    The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

  • Funding

    This research was funded by the New Energy and Industrial Technology Development Organization (NEDO; grant number JPNP18016).

  • Notes
    The authors declare no competing financial interest.

Abbreviations

Click to copy section linkSection link copied!
PB

prussian blue

PBA

prussian blue analogs

CuHCF

copper hexacyanoferrate

NiHCF

nickel hexacyanoferrate

PVA

poly(vinyl alcohol)

MFC

mass flow controller

References

Click to copy section linkSection link copied!

This article references 35 other publications.

  1. 1
    U.S. Geological Survey. Nitrogen (Fixed)─Ammonia Miner. Commod. Summ. 2022.
    Google Scholar
    There is no corresponding record for this reference.
  2. 2
    Boerner, L. K. Industrial Ammonia Production Emits More CO2 than Any Other Chemical-Making Reaction. Chemists Want to Change That Chem. Eng. News 2019, 97(24), https://cen.acs.org/environment/green-chemistry/Industrial-ammonia-production-emits-CO2/97/i24
    Google Scholar
    There is no corresponding record for this reference.
  3. 3
    Krupa, S. Effects of Atmospheric Ammonia (NH3) on Terrestrial Vegetation: A Review. Environ. Pollut. 2003, 124 (2), 179– 221,  DOI: 10.1016/S0269-7491(02)00434-7
    Google Scholar
    3
    Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review
    Krupa, S. V.
    Environmental Pollution (Oxford, United Kingdom) (2003), 124 (2), 179-221CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Science Ltd.)
    A review of atm. ammonia (NH3) and ammonium (NH4+) deposition and their effects on plants. At the global scale, among all N (nitrogen) species in the atm. and their deposition on to terrestrial vegetation and other receptors, NH3 (ammonia) is considered to be the foremost. The major sources for atm. NH3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH3 can result in visible foliar injury on vegetation. NH3 is deposited rapidly within the first 4-5 km from its source. However, NH3 is also converted in the atm. to fine particle NH4+ (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH3 are native vegetation > forests > agricultural crops. There are also a no. of studies on N deposition and lichens, mosses, and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO2 (sulfur dioxide) concns. In addn. to direct foliar injury, adverse effects of NH3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal assocns. and inter species competition or biodiversity. In all these cases, the joint effects of NH3 with other air pollutants such as all-pervasive O3 or increasing CO2 concns. are poorly understood. While NH3 uptake in higher plants occurs through the shoots, NH4+ uptake occurs through the shoots, roots and through both pathways. However, NH4+ is immobile in the soil and is converted to NO3- (nitrate). In agricultural systems, addns. of NO3- to the soil (initially as NH3 or NH4+) and the consequent increases in the emissions of N2O (nitrous oxide, a greenhouse gas) and leaching of NO3- into the ground and surface waters are of major environmental concern. At the ecosystem level NH3 deposition cannot be viewed alone, but in the context of total N deposition. There are a no. of forest ecosystems in North America that were subjected to N satn. and the consequent neg. effects. There are also heathlands and other plant communities in Europe that were subjected to N-induced alterations. Regulatory mitigative approaches to these problems include the use of N satn. data or the concept of crit. loads. Current information suggests that a crit. load of 5-10 kg ha-1 year-1 of total N deposition (both dry and wet deposition combined of all atm. N species) would protect the most vulnerable terrestrial ecosystems (heaths, bogs, cryptogams) and values of 10-20 kg ha-1 year-1 would protect forests, depending on soil conditions. However, to derive the best anal., the crit. load concept should be coupled to the results and consequences of N satn.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjtFWls7o%253D&md5=556aa826aa45367db1327c701b03e205
  4. 4
    Pitcairn, C. E. R.; Leith, I. D.; Sheppard, L. J.; Sutton, M. A.; Fowler, D.; Munro, R. C.; Tang, S.; Wilson, D. The Relationship between Nitrogen Deposition, Species Composition and Foliar Nitrogen Concentrations in Woodland Flora in the Vicinity of Livestock Farms. Environ. Pollut. 1998, 102 (1), 41– 48,  DOI: 10.1016/S0269-7491(98)80013-4
    Google Scholar
    4
    The relationship between nitrogen deposition, species composition and foliar nitrogen concentrations in woodland flora in the vicinity of livestock farms
    Pitcairn, C. E. R.; Leith, I. D.; Sheppard, L. J.; Sutton, M. A.; Fowler, D.; Munro, R. C.; Tang, S.; Wilson, D.
    Environmental Pollution (1998), 102 (Suppl. 1), 41-48CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Science Ltd.)
    Measurements of atm. ammonia concn. along a gradient of decreasing concn., species compn. and tissue nitrogen content of a range of plant species were made in woodland in the vicinity of four intensive animal units in Scotland. Ammonia concns. were large at woodland edges close to the livestock buildings (annual means 20-60 μg m-3) and exceed crit. levels for NH3 (8 μg m-3 annual mean). Surveys of species compn. of ground flora along an 0.5 km transect from livestock buildings show marked changes within 300 m downwind of the buildings. Species such as Deschampsia flexuosa, Holcus lanatus, Rubus idaeus and Urtica dioica were abundant close to livestock units and their percentage cover decreased rapidly with distance from source, while the more N-sensitive species such as Oxalis acetosella, Galium odoratum, mosses and ferns which are found upwind and outside the influence of the NH3 source, were scarce at all sites receiving >25 kg ha-1 N year-1. Visible injury to pine and spruce needles was obsd. immediately downwind of the buildings. Foliar nitrogen concn. of a no. of species was large close to the buildings and declined with distance. Total nitrogen deposition at the woodland boundaries is estd. to range from 40 to 80 kg N ha-1 year-1 at the 4 sites and exceeds crit. loads for acidic coniferous forest, i.e. 15-20 kg N ha-1 year-1 to protect ground flora, and is also often in excess of that (11-50 kg N ha-1 year-1) proposed to protect tree health. Foliar nitrogen content of mosses, (LN, % dry wt.) is related to nitrogen deposition (FN, kg N ha-1 year-1) according to LN = 3.81(1-e-0.04FN).
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXjvVaqsg%253D%253D&md5=d133fe6dd8afdf4d47ad73b2bd1a34c3
  5. 5
    Sheppard, L. J.; Leith, I. D.; Crossley, A.; Van Dijk, N.; Fowler, D.; Sutton, M. A.; Woods, C. Stress Responses of Calluna Vulgaris to Reduced and Oxidised N Applied under “Real World Conditions.. Environ. Pollut. 2008, 154 (3), 404– 413,  DOI: 10.1016/j.envpol.2007.10.040
    Google Scholar
    5
    Stress responses of Calluna vulgaris to reduced and oxidised N applied under real world conditions'
    Sheppard, Lucy J.; Leith, Ian D.; Crossley, A.; Van Dijk, N.; Fowler, D.; Sutton, M. A.; Woods, C.
    Environmental Pollution (Amsterdam, Netherlands) (2008), 154 (3), 404-413CODEN: ENPOEK; ISSN:0269-7491. (Elsevier B.V.)
    Effects and implications of reduced and oxidized N, applied under real world' conditions, since May 2002, are reported for Calluna growing on an ombrotrophic bog. Ammonia has been released from a 10 m line source generating monthly concns. of 180-6 μg m-3, while ammonium chloride and sodium nitrate are applied in rainwater at nitrate and ammonium concns. below 4 mM and providing up to 56 kg N ha-1 year-1 above a background deposition of 10 kg N ha-1 year-1. Ammonia concns., >8 μg m-3 have significantly enhanced foliar N concns., increased sensitivity to drought, frost and winter desiccation, spring frost damage and increased the incidence of pathogen outbreaks. The mature Calluna bushes nearest the NH3 source have turned bleached and moribund. By comparison the Calluna receiving reduced and oxidized N in rain has shown no significant visible or stress related effects with no significant increase in N status. Exposure to NH3 reduces stress resistance and increases visible damage in mature Calluna.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXosVOlur4%253D&md5=04353a218d084a5fcadb1ce2ec8d6320
  6. 6
    van den Berg, L. J. L.; Peters, C. J. H.; Ashmore, M. R.; Roelofs, J. G. M. Reduced Nitrogen Has a Greater Effect than Oxidised Nitrogen on Dry Heathland Vegetation. Environ. Pollut. 2008, 154 (3), 359– 369,  DOI: 10.1016/j.envpol.2007.11.027
    Google Scholar
    6
    Reduced nitrogen has a greater effect than oxidized nitrogen on dry heathland vegetation
    van den Berg, L. J. L.; Peters, C. J. H.; Ashmore, M. R.; Roelofs, J. G. M.
    Environmental Pollution (Amsterdam, Netherlands) (2008), 154 (3), 359-369CODEN: ENPOEK; ISSN:0269-7491. (Elsevier B.V.)
    We investigated the effects of different ratios of reduced (NH4+) vs. oxidized (NO3-) nitrogen in deposition on heathland and species-rich grassland vegetation at high nitrogen deposition levels in large mesocosms filled with nutrient-poor soils to which different NH4+/NO3- ratios were applied. The response of the forbs, Antennaria dioica, Arnica montana, Gentiana pneumonanthe, Thymus serpyllum, the grasses Danthonia decumbens, Deschampsia flexuosa, Nardus stricta and the shrub Calluna vulgaris was recorded. The forb A. dioica and the grass D.decumbens preferred low NH4+/NO3- ratios and were characterized by a neg. correlation between NH4+/NO3- ratios and biomass and survival, whereas the grasses N. stricta and D. flexuosa showed no correlation with NH4+/NO3- ratios. Lime addn. eliminated the neg. effects of high NH4+ concns. in deposition for A. dioica and the grass D. decumbens. The implications of these findings for heathland vegetations are discussed. Reduced nitrogen and high NH4+/NO3- ratios in deposition are responsible for a decline of forbs in Western European heathlands.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXosVOltbg%253D&md5=b229c3b84c46721d4a897fc916837d8b
  7. 7
    Nutrient Reduction Technology Cost Estimations for Point Sources in the Chesapeake Bay Watershed Prepared by The Nutrient Reduction Technology Cost Task Force A Stakeholder Group of the Chesapeake Bay Program November 2002 , 2002. https://www.chesapeakebay.net/content/publications/cbp_13140.pdf.
    Google Scholar
    There is no corresponding record for this reference.
  8. 8
    Mladenović, M.; Paprika, M.; Marinković, A. Denitrification Techniques for Biomass Combustion. Renew. Sustain. Energy Rev. 2018, 82, 3350– 3364,  DOI: 10.1016/j.rser.2017.10.054
    Google Scholar
    There is no corresponding record for this reference.
  9. 9
    Melse, R. W.; Ogink, N. W. M. Air Scrubbing Techniques for Ammonia and Odor Reduction at Livestock Operations: Review of on-Farm Research in the Netherlands. Trans. Am. Soc. Agric. Eng. 2005, 48 (6), 2303– 2313,  DOI: 10.13031/2013.20094
    Google Scholar
    9
    Air scrubbing techniques for ammonia and odor reduction at livestock operations: review of on-farm research in the netherlands
    Melse, R. W.; Ogink, N. W. M.
    Transactions of the ASAE (2005), 48 (6), 2303-2313CODEN: TAAEAJ; ISSN:0001-2351. (American Society of Agricultural Engineers)
    A review. Acid scrubbers and biotrickling filters have been developed for ammonia (NH3) removal at pig and poultry houses in The Netherlands over the last 20 years to prevent acidification and eutrophication of soils. Because of growing suburbanization, odor removal is increasingly considered important as well. In this review, we report the results of the on-farm research on full-scale operated scrubbers for treatment of exhaust air from animal houses with regard to NH3 and odor removal in The Netherlands. The NH3 removal of acid scrubbers ranged from 40% to 100% with an overall av. of 96%. The NH3 removal of biotrickling filters ranged from -8% to +100% with an overall av. of 70%. Min. empty bed air residence times (EBRTs) were 0.4 to 1.1 s. For acid scrubbers, process control with pH measurement and automatic water discharge is sufficient to guarantee sufficient NH3 removal. For biotrickling filters, however, improvement of process control is necessary to guarantee sufficient NH3 removal. The odor removal of acid scrubbers ranged from 3% to 51% with an overall av. of 27%. The odor removal of biotrickling filters ranged from -29% to +87% with an overall av. of 51%. Min. EBRTs were 0.5 to 2.3 s. Further research is necessary to explain this variation and to improve the odor removal efficiency of both acid scrubbers and biotrickling filters.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhsFejs74%253D&md5=a796b248b4cd95f67a5c643237c21312
  10. 10
    Maurer, D. L.; Koziel, J. A. On-Farm Pilot-Scale Testing of Black Ultraviolet Light and Photocatalytic Coating for Mitigation of Odor, Odorous VOCs, and Greenhouse Gases. Chemosphere 2019, 221, 778– 784,  DOI: 10.1016/j.chemosphere.2019.01.086
    Google Scholar
    10
    On-farm pilot-scale testing of black ultraviolet light and photocatalytic coating for mitigation of odor, odorous VOCs, and greenhouse gases
    Maurer, Devin L.; Koziel, Jacek A.
    Chemosphere (2019), 221 (), 778-784CODEN: CMSHAF; ISSN:0045-6535. (Elsevier Ltd.)
    Technologies for controlling gaseous emissions of livestock is of interest to producers, the public, and regulatory agencies. In our previous lab-scale study, the use of a photocatalytic coating on surfaces subjected to black UV light reduced emissions of key odorant compds. relevant to the livestock industry. Thus, an on-farm pilot-scale expt. was conducted at a com. swine barn to evaluate a photocatalytic coating on surfaces subjected to UV light under field conditions. A flow-through reactor was constructed with a TiO2-based photocatalytic coating on the interior surfaces and black UV light fixtures. The reactor was deployed in a room downstream of the entire swine barn exhaust. Gas samples were collected from three sampling ports in the reactor, one at the inlet (control), the midpoint (half treatment) and the outlet (treatment). Compared to the control, significant redns. in emissions were obsd. for p-cresol (22%), odor (16%) and nitrous oxide (9%). A significant increase in carbon dioxide (3%) was also measured. Results show that the TiO2-based photocatalytic coating and black UV light are effective in mitigating odor, a key VOC responsible for downwind swine odor, and one important greenhouse effect gas when subjected to swine barn exhaust.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFSktr8%253D&md5=d5c7fa41bbff4af63c2d25965c660fd8
  11. 11
    Li, G.; Kanezashi, M.; Yoshioka, T.; Tsuru, T. Ammonia Decomposition in Catalytic Membrane Reactors: Simulation and Experimental Studies. AIChE J. 2013, 59 (1), 168– 179,  DOI: 10.1002/aic.13794
    Google Scholar
    11
    Ammonia decomposition in catalytic membrane reactors: Simulation and experimental studies
    Li, Gang; Kanezashi, Masakoto; Yoshioka, Tomohisa; Tsuru, Toshinori
    AIChE Journal (2013), 59 (1), 168-179CODEN: AICEAC; ISSN:0001-1541. (John Wiley & Sons, Inc.)
    Catalytic decompn. of NH3 with H2-selective microporous silica membranes for COx-free hydrogen prodn. was studied theor. and exptl. The simulation study shows that NH3 conversion, H2 yield and H2 purity increase with the Damkoehler no. (Da), and their improvement is affected by the effect of H2 extn. as well as NH3 and N2 permeation through the membranes. The exptl. study of NH3 decompn. was carried out in a bimodal catalytic membrane reactor (BCMR), consisting of a bimodal catalytic support and a H2-selective silica layer. Catalytic membranes showed H2 permeances of 6.2-9.8 × 10-7 mol m-2 s-1 Pa-1, with H2/NH3 and H2/N2 permeance ratios of 110-200 and 200-700, resp., at 773 K. The effect of operating conditions on membrane reactor performance with respect to NH3 conversion, H2 yield and H2 purity was investigated, and the results were in agreement with those calcd. by the proposed simulation model.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xls1Wmu78%253D&md5=f2a5067722fbe935865181ffe570765b
  12. 12
    Lamb, K. E.; Dolan, M. D.; Kennedy, D. F. Ammonia for Hydrogen Storage; A Review of Catalytic Ammonia Decomposition and Hydrogen Separation and Purification. Int. J. Hydrogen Energy 2019, 44 (7), 3580– 3593,  DOI: 10.1016/j.ijhydene.2018.12.024
    Google Scholar
    12
    Ammonia for hydrogen storage; A review of catalytic ammonia decomposition and hydrogen separation and purification
    Lamb, Krystina E.; Dolan, Michael D.; Kennedy, Danielle F.
    International Journal of Hydrogen Energy (2019), 44 (7), 3580-3593CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
    Ammonia is of interest as a hydrogen storage and transport medium because it enables liq.-phase hydrogen storage under mild conditions. Although ammonia can be used directly for energy applications, its use in conventional fuel cell elec. vehicles necessitates decompn. into nitrogen and hydrogen, and the purifn. of the hydrogen to the compn. required for com. proton exchange membrane fuel cells. This article provides a review of the material and process considerations for catalytic ammonia decompn. and shows that Ru-based catalysts on conductive support materials are active at < 500 °C, but further understanding around lifetimes and deactivation conditions is required. This review then explores materials and technologies for hydrogen purifn. from decompd. ammonia gas streams, and our expts. show that defect-free dense-metal membranes are uninhibited by ammonia and can achieve the required product purity.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFyntb7L&md5=5888d11e0fb5d9bd1eb390527171f99e
  13. 13
    Yin, S. F.; Xu, B. Q.; Zhou, X. P.; Au, C. T. A Mini-Review on Ammonia Decomposition Catalysts for on-Site Generation of Hydrogen for Fuel Cell Applications. Appl. Catal. A Gen. 2004, 277 (1–2), 1– 9,  DOI: 10.1016/j.apcata.2004.09.020
    Google Scholar
    13
    A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications
    Yin, S. F.; Xu, B. Q.; Zhou, X. P.; Au, C. T.
    Applied Catalysis, A: General (2004), 277 (1-2), 1-9CODEN: ACAGE4; ISSN:0926-860X. (Elsevier B.V.)
    A review. Due to the drive for better environmental protection and energy conversion efficiency, on-site generation of COx-free hydrogen from ammonia decompn. for fuel cell applications has attracted much attention. The development of high performance solid catalysts is essential for the supply of such hydrogen from ammonia. In this mini-review, we provide a summary of the reaction kinetics of catalytic ammonia decompn. Comparisons are then made among the catalysts that have different active components, supports, and promoters. According to the works reported in the literature and our recent research results, Ru is the most active catalyst, carbon nanotubes (CNTs) are the most effective support, and KOH is the best promoter. An increase in Ru dispersion results in better catalytic performance. Both support basicity and cond. are important criteria for a NH3 decompn. catalyst of high efficiency; and it seems possible to generate novel advanced support, such as oxide-CNTs nanocomposite materials, that bears such characteristics. Also, proper removal of the electron-withdrawing entities that originate from the precursors of active component, support or promoter can be effective in enhancing the catalytic activity of a Ru catalyst.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXpsV2qtrg%253D&md5=070267f67fc9283bf683f38bcb462e6d
  14. 14
    Bist, R. B.; Subedi, S.; Chai, L.; Yang, X. Ammonia Emissions, Impacts, and Mitigation Strategies for Poultry Production: A Critical Review. J. Environ. Manage. 2023, 328, 116919  DOI: 10.1016/j.jenvman.2022.116919
    Google Scholar
    14
    Ammonia emissions, impacts, and mitigation strategies for poultry production: A critical review
    Bist, Ramesh Bahadur; Subedi, Sachin; Chai, Lilong; Yang, Xiao
    Journal of Environmental Management (2023), 328 (), 116919CODEN: JEVMAW; ISSN:0301-4797. (Elsevier Ltd.)
    A review. Confined animal feeding operations (CAFOs) are the main sources of air pollutants such as ammonia (NH3) and greenhouse gases. Among air pollutants, NH3 is one of the most concerned gasses in terms of air quality, environmental impacts, and manure nutrient losses. It is recommended that NH3 concns. in the poultry house should be controlled below 25 ppm. Otherwise, the poor air quality will impair the health and welfare of animals and their caretakers. After releasing from poultry houses, NH3 contributes to the form of fine particulate matters in the air and acidify soil and water bodies after deposition. Therefore, understanding the emission influential factors and impacts is crit. for developing mitigation strategies to protect animals' welfare and health, environment, and ecosystems. This review paper summarized the primary NH3 emission influential factors, such as how poultry housing systems, seasonal changes, feed management, bedding materials, animal densities, and animals' activities can impact indoor air quality and emissions. A higher level of NH3 (e.g., >25 ppm) results in lower prodn. efficiency and poor welfare and health, e.g., respiratory disorder, less feed intake, lower growth rates or egg prodn., poor feed use efficiency, increased susceptibility to infectious diseases, and mortality. In addn., the egg quality (e.g., albumen height, pH, and condensation) was reduced after laying hens chronically exposed to high NH3 levels. High NH3 levels have detrimental effects on farm workers' health as it is a corrosive substance to eyes, skin, and respiratory tract, and thus may cause blindness, irritation (throat, nose, eyes), and lung illness. For controlling poultry house NH3 levels and emissions, we analyzed various mitigation strategies such as litter additives, biofiltration, acid scrubber, dietary manipulation, and bedding materials. Litter additives were tested with 50% efficiency in broiler houses and 80-90% mitigation efficiency for cage-free hen litter at a higher application rate (0.9 kg m-2). Filtration systems such as multi-stage acid scrubbers have up to 95% efficiency on NH3 mitigation. However, cautions should be paid as mitigation strategies could be cost prohibitive for farmers, which needs assistances or subsidies from governments.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFeisrbF&md5=00eaccec7e9da27fcfe2dd3e949f2ceb
  15. 15
    Chen, L.; Hoff, S. J.; Koziel, J. A.; Cai, L.; Zelle, B.; Sun, G. Performance Evaluation of a Wood-Chip Based Biofilter Using Solid-Phase Microextraction and Gas Chromatography-Mass Spectroscopy-Olfactometry. Bioresour. Technol. 2008, 99 (16), 7767– 7780,  DOI: 10.1016/j.biortech.2008.01.085
    Google Scholar
    15
    Performance evaluation of a wood-chip based biofilter using solid-phase microextraction and gas chromatography-mass spectroscopy-olfactometry
    Chen, Lide; Hoff, Steven J.; Koziel, Jacek A.; Cai, Lingshuang; Zelle, Brian; Sun, Gang
    Bioresource Technology (2008), 99 (16), 7767-7780CODEN: BIRTEB; ISSN:0960-8524. (Elsevier Ltd.)
    A pilot-scale mobile biofilter was developed where two types of wood chips (western cedar and 2 in. hardwood) were examd. to treat odor emissions from a deep-pit swine finishing facility in central Iowa. The biofilters were operated continuously for 13 wk at different air flow rates resulting in a variable empty bed residence time (EBRT) from 1.6 to 7.3 s. During this test period, solid-phase microextn. (SPME) PDMS/DVB 65 μm fibers were used to ext. volatile org. compds. (VOCs) from both the control plenum and biofilter treatments. Analyses of VOCs were carried out using a multidimentional gas chromatog.-mass spectrometry-olfactometry (MDGC-MS-O) system. Results indicated that both types of chips achieved significant redns. in p-cresol, phenol, indole and skatole which represent some of the most odorous and odor-defining compds. known for swine facilities. The results also showed that maintaining proper moisture content is crit. to the success of wood-chip based biofilters and that this factor is more important than media depth and residence time.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXns1aktbw%253D&md5=ed7cc2c02c92fff816d2c90f4b4f6774
  16. 16
    Chen, L.; Hoff, S.; Cai, L.; Koziel, J.; Zelle, B. Evaluation of Wood Chip-Based Biofilters to Reduce Odor, Hydrogen Sulfide, and Ammonia from Swine Barn Ventilation Air. J. Air Waste Manag. Assoc. 2009, 59 (5), 520– 530,  DOI: 10.3155/1047-3289.59.5.520
    Google Scholar
    16
    Evaluation of wood chip-based biofilters to reduce odor, hydrogen sulfide, and ammonia from swine barn ventilation air
    Chen, Lide; Hoff, Steven; Cai, Lingshuang; Koziel, Jacek; Zelle, Brian
    Journal of the Air & Waste Management Association (2009), 59 (5), 520-530CODEN: JAWAFC; ISSN:1096-2247. (Air & Waste Management Association)
    A pilot-scale biofilter was developed in which two types of wood chips (western cedar [WC] and 2-in. hardwood [HW]) were examd. to treat odor emissions from a deep-pit swine finishing facility in central Iowa. The biofilters were operated continuously for 13 wk at different airflow rates resulting in variable empty bed residence times (EBRTs) from 1.6 to 7.3 s. The effects of three media moisture levels were also evaluated. A dynamic forced-choice olfactometer was used to evaluate odor concns. from both the control (inlet) plenum and biofilter treatments (outlet). Hydrogen sulfide (H2S) and ammonia (NH3) concns. were also measured from these olfactometry samples. Solid-phase microextn. (SPME) polydimethylsiloxane (PDMS)/divinylbenzene (DVB) 65-μm fibers were used to ext. volatile org. compds. from both the control plenum and biofilter treatments. Analyses of sepd. odors were carried out using a gas chromatog.-mass spectrometry-olfactometry (GC-MS-O) system. Static sample results indicated that both types of chips achieved significant redns. in odor (av. 70.1 and 82.3% for HW and WC, resp.), H2S (av. 81.8 and 88.6% for HW and WC, resp.) and NH3 (av. 43.4 and 74% for HW and WC, resp.) concns. GC-MS-O aromagram results showed both treatments reached high odor redn. efficiency (av. 99.4 and 99.8% for HW and WC, resp.). The results also showed that maintaining proper moisture content and a min. EBRT are crit. to the success of wood chip-based biofilters.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXmt1Sgu7c%253D&md5=c5c06f52ec55cce1e2a8ec80052e4435
  17. 17
    Peng, F.; Gao, Y.; Zhu, X.; Pang, Q.; Wang, L.; Xu, W.; Yu, J.; Gao, P.; Huang, J.; Cui, Y. Removal of High-Strength Ammonia Nitrogen in Biofilters: Nitrifying Bacterial Community Compositions and Their Effects on Nitrogen Transformation. Water 2020, 12 (3), 712,  DOI: 10.3390/w12030712
    Google Scholar
    17
    Removal of high-strength ammonia nitrogen in biofilters: nitrifying bacterial community compositions and their effects on nitrogen transformation
    Peng, Fuquan; Gao, Yuexiang; Zhu, Xiang; Pang, Qingqing; Wang, Longmian; Xu, Wenwen; Yu, Jianghua; Gao, Pengcheng; Huang, Jingxian; Cui, Yibin
    Water (Basel, Switzerland) (2020), 12 (3), 712CODEN: WATEGH; ISSN:2073-4441. (MDPI AG)
    Increasing attention has been given to the treatment of livestock and poultry wastewater because of its high ammonium nitrogen (NH4 +-N) content and low carbon/nitrogen ratio (C/N). Ceramic filter medium (CFM) and dewatered aluminum sludge (DAS), which are products from cast-off materials, are used as small-scale combined biol. filters (CFM-DAS) for wastewater treatment. The high and stale removal efficiency of COD (COD), NH4+-N, and total nitrogen (TN) in the DAS filter indicate that DAS plays a major role in pollutant removal. Although significant differences are found between the compn. of nitrifying bacteria in CFM and DAS, the structures of nitrifying communities are evenly distributed in each layer of CFM or DAS irresp. of the running time. Microbial compns. are attributed to the comprehensive effect of various environmental factors such as pH and TN at effluents. In the DAS, Nitrosospira shows significant neg. correlation with the concns. of NH4+-N in effluents, whereas it has pos. correlation with NO3--N, and Nitrososphaera has a significant neg. correlation with NO3--N in effluents. Pearson correlation test reveals that certain genera may be used in estg. or predicting NH4 +-N consumption and NO3--N accumulation in CFM-DAS for treating sewage with a high NH4+-N content.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFKrsLbL&md5=eb6bf74eec688456a98d7387898337c1
  18. 18
    Rieth, A. J.; Dincă, M. Controlled Gas Uptake in Metal–Organic Frameworks with Record Ammonia Sorption. J. Am. Chem. Soc. 2018, 140 (9), 3461– 3466,  DOI: 10.1021/jacs.8b00313
    Google Scholar
    18
    Controlled gas uptake in metal-organic frameworks with record ammonia sorption
    Rieth, Adam J.; Dinca, Mircea
    Journal of the American Chemical Society (2018), 140 (9), 3461-3466CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Ammonia is a vital commodity in our food supply chain, but its toxicity and corrosiveness require advanced protection and mitigation. These needs are not met efficiently by current materials, which suffer from either low capacity or low affinity for NH3. Here, we report that a series of microporous triazolate metal-org. frameworks contg. open metal sites exhibit record static and dynamic ammonia capacities. Under equil. conditions at 1 bar, the materials adsorb up to 19.79 mmol NH3 g-1, more than twice the capacity of activated carbon, the industry std. Under conditions relevant to personal protection equipment, capacities reach 8.56 mmol g-1, 27% greater than the previous best material. Structure-function relationships and kinetic analyses of NH3 uptake in isostructural micro- and mesoporous materials made from Co, Ni, and Cu reveal stability trends that are in line with the water substitution rates in simple metal-aquo complexes. Altogether, these results provide clear, intuitive descriptors that govern the static and dynamic uptake, kinetics, and stability of MOF sorbents for strongly interacting gases.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVGktr4%253D&md5=aa831bb4b13c974c56849071da7a1d73
  19. 19
    Takahashi, A.; Tanaka, H.; Parajuli, D.; Nakamura, T.; Minami, K.; Sugiyama, Y.; Hakuta, Y.; Ohkoshi, S.; Kawamoto, T. Historical Pigment Exhibiting Ammonia Gas Capture beyond Standard Adsorbents with Adsorption Sites of Two Kinds. J. Am. Chem. Soc. 2016, 138 (20), 6376– 6379,  DOI: 10.1021/jacs.6b02721
    Google Scholar
    19
    Historical Pigment Exhibiting Ammonia Gas Capture beyond Standard Adsorbents with Adsorption Sites of Two Kinds
    Takahashi, Akira; Tanaka, Hisashi; Parajuli, Durga; Nakamura, Tohru; Minami, Kimitaka; Sugiyama, Yutaka; Hakuta, Yukiya; Ohkoshi, Shin-ichi; Kawamoto, Tohru
    Journal of the American Chemical Society (2016), 138 (20), 6376-6379CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    Prussian blue is a historical pigment synthesized for the first time at the beginning of 18th century. Here we demonstrate that the historical pigment exhibits surprising adsorption properties of gaseous ammonia. Prussian blue shows 12.5 mmol/g of ammonia capacity at 0.1 MPa, whereas std. ammonia adsorbents show only 5.08-11.3 mmol/g. Dense adsorption was also obsd. for trace contamination in atm. Results also show higher adsorption by Prussian blue analogs with the optimization of chem. compn. The resp. capacities of cobalt hexacyanocobaltate (CoHCC) and copper hexacyanoferrate (CuHCF) were raised to 21.9 and 20.2 mmol/g, the highest value among the recyclable adsorbents. Also, CoHCC showed repeated adsorption in vacuum. CuHCF showed regeneration by acid washing. The chem. state of the adsorbed ammonia depends on the presence of the water in atm.: NH3, which was stored as in the dehydrated case, was converted into NH4+ in the hydrated case.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XntlCnsb4%253D&md5=e11c279799ad669c68d7b58a46452b9e
  20. 20
    Van Humbeck, J. F.; McDonald, T. M.; Jing, X.; Wiers, B. M.; Zhu, G.; Long, J. R. Ammonia Capture in Porous Organic Polymers Densely Functionalized with Bro̷nsted Acid Groups. J. Am. Chem. Soc. 2014, 136 (6), 2432– 2440,  DOI: 10.1021/ja4105478
    Google Scholar
    20
    Ammonia Capture in Porous Organic Polymers Densely Functionalized with Bronsted Acid Groups
    Van Humbeck, Jeffrey F.; McDonald, Thomas M.; Jing, Xiaofei; Wiers, Brian M.; Zhu, Guangshan; Long, Jeffrey R.
    Journal of the American Chemical Society (2014), 136 (6), 2432-2440CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
    The elimination of specific environmental and industrial contaminants, which are hazardous at only part per million to part per billion concns., poses a significant technol. challenge. Adsorptive materials designed for such processes must be engendered with an exceptionally high enthalpy of adsorption for the analyte of interest. Rather than relying on a single strong interaction, the use of multiple chem. interactions is an emerging strategy for achieving this requisite phys. parameter. Herein, we describe an efficient, catalytic synthesis of diamondoid porous org. polymers densely functionalized with carboxylic acids. Phys. parameters such as pore size distribution, application of these materials to low-pressure ammonia adsorption, and comparison with analogous materials featuring functional groups of varying acidity are presented. In particular, BPP-5, which features a multiply interpenetrated structure dominated by <6 Å pores, is shown to exhibit an uptake of 17.7 mmol/g at 1 bar, the highest capacity yet demonstrated for a readily recyclable material. A complementary framework, BPP-7, features slightly larger pore sizes, and the resulting improvement in uptake kinetics allows for efficient adsorption at low pressure (3.15 mmol/g at 480 ppm). Overall, the data strongly suggest that the spatial arrangement of acidic sites allows for cooperative behavior, which leads to enhanced NH3 adsorption.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1eitbs%253D&md5=37866eb89fa69650ce234a3f986b012d
  21. 21
    Welsh, F. S. Particle Characteristics of Prussian Blue in an Historical Oil Paint. J. Am. Inst. Conserv. 1988, 27 (2), 55– 63,  DOI: 10.1179/019713688806046292
    Google Scholar
    There is no corresponding record for this reference.
  22. 22
    Loos-Neskovic, C.; Dierkes, M. H. H.; Jackwerth, E.; Fedoroff, M.; Garnier, E. Fixation of Palladium on Insoluble Simple or Complex Cyano Compounds. Hydrometallurgy 1993, 32 (3), 345– 363,  DOI: 10.1016/0304-386X(93)90046-G
    Google Scholar
    22
    Fixation of palladium on insoluble simple or complex cyano compounds
    Loos-Neskovic, C.; Dierkes, M. H.; Jackwerth, E.; Fedoroff, M.; Garnier, E.
    Hydrometallurgy (1993), 32 (3), 345-63CODEN: HYDRDA; ISSN:0304-386X.
    In order to propose a method for Pd recovery from industrial waste solns. a systematic study of the kinetics and retention capacity on several insol. cyano compds. (simple cyanides, hexacyanoferrates II and III, and hexacyanomanganates) was performed. Sorbents were prepd. either by pptn., or by a method of local growth producing large particles, or by deposition on a carrier material. Among the products studies, nickel hexacyanoferrates II and copper hexacyanoferrates II and III seem to be the most promising. The highest retention capacity was achieved with a copper hexacyanoferrate III prepd. by local growth. The mechanisms of fixation seem to be ion exchange with an oxidn.-redn. process in certain cases.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXitlyisrw%253D&md5=9359b9e40aa1aa56d9a3b3e40f3b06c6
  23. 23
    Manakasettharn, S.; Takahashi, A.; Kawamoto, T.; Noda, K.; Sugiyama, Y.; Nakamura, T. Differences in NH3 Gas Adsorption Behaviors of Metal-Hexacyanoferrate Nanoparticles (M [FeII(CN)6] ·zH2O: M = In3+, Fe3+, and Mn2+). J. Solid State Chem. 2019, 270, 112– 117,  DOI: 10.1016/j.jssc.2018.10.026
    Google Scholar
    23
    Differences in NH3 gas adsorption behaviors of metal-hexacyanoferrate nanoparticles (Mx[FeII(CN)6]y·zH2O:M = In3+, Fe3+, and Mn2+)
    Manakasettharn, Supone; Takahashi, Akira; Kawamoto, Tohru; Noda, Keiko; Sugiyama, Yutaka; Nakamura, Tohru
    Journal of Solid State Chemistry (2019), 270 (), 112-117CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
    Three different metal hexacyanoferrate nanoparticles (M-HCF-NPs, M = In3+, Fe3+, and Mn2+) were characterized by XRD, SEM, elemental analyses, IR and isotherm measurements. The obtained M-HCF-NPs prepd. by a simple mixing procedure have a Prussian blue-type cubic crystal structure and sizes of ∼20 nm. The chem. compns. measured by the elemental analyses are In-HCF = K0.039In[Fe(CN)6]0.75·Cl0.032·3.8H2O, Fe-HCF (PB) = K0.18Fe[Fe(CN)6]0.80·3.8H2O, and Mn-HCF = K1.3Mn[Fe(CN)6]0.84·1.3H2O. Ammonia gas isotherms under vacuum revealed that the ammonia adsorption capacity of the M-HCF-NPs is in order of Mn < In << Fe; however, the ammonia gas adsorption of In-HCF-NPs is faster than those of the Fe-HCF and Mn-HCF-NPs. This difference is considered to be caused by individual M-HCF structures, such as the vacancies in the HCF crystals, and by the interaction of individual M-HCF toward water mols., which promote the conversion of NH3 species into stable NH+4 cations in M-HCF.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1eit77L&md5=ab2cf6d9875061a83a7bb953c4063211
  24. 24
    Parajuli, D.; Kitajima, A.; Takahashi, A.; Tanaka, H.; Ogawa, H.; Hakuta, Y.; Yoshino, K.; Funahashi, T.; Yamaguchi, M.; Osada, M.; Kawamoto, T. Application of Prussian Blue Nanoparticles for the Radioactive Cs Decontamination in Fukushima Region. J. Environ. Radioact. 2016, 151, 233– 237,  DOI: 10.1016/j.jenvrad.2015.10.014
    Google Scholar
    24
    Application of Prussian blue nanoparticles for the radioactive Cs decontamination in Fukushima region
    Parajuli, Durga; Kitajima, Akiko; Takahashi, Akira; Tanaka, Hisashi; Ogawa, Hiroshi; Hakuta, Yukiya; Yoshino, Kazunori; Funahashi, Takayuki; Yamaguchi, Masaki; Osada, Mitsuo; Kawamoto, Tohru
    Journal of Environmental Radioactivity (2016), 151 (Part_1), 233-237CODEN: JERAEE; ISSN:0265-931X. (Elsevier Ltd.)
    Cs decontamination efficiencies of the composites of iron hexacyanoferrate nanoparticles were investigated in comparison with com. Prussian blue and natural zeolite. In pure water soln., the adsorption rate varied with sizes. In ash ext., where Cs adsorbing ability of zeolite was sharply dropped due to its poor selectivity, the impact of coexisting ions was negligible for FeHCF. FeHCF-n11, having the finest primary and secondary particle size, resulted the highest distribution coeff., which was comparable to the high efficiency analogs, CoHCF or NiHCF. This observation suggested the possibility of prepg. the high performance FeHCF by particle size and compn. adjustment. FeHCF nanoparticle in bead form was tested for the removal of radioactive Cs in pilot scale. Due to larger secondary particle size, pronounced effect of soln. temp. on the Cs adsorption kinetics on FeHCF bead was obsd. Adjusting the mass of the adsorbent for the given soln. temp. is recommended for achieving high decontamination rate.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslCqu7%252FK&md5=e23a6b52fbcf1bab3341470d288a4400
  25. 25
    Takahashi, A.; Minami, K.; Noda, K.; Sakurai, K.; Kawamoto, T. Trace Ammonia Removal from Air by Selective Adsorbents Reusable with Water. ACS Appl. Mater. Interfaces 2020, 12 (13), 15115– 15119,  DOI: 10.1021/acsami.9b22384
    Google Scholar
    25
    Trace Ammonia Removal from Air by Selective Adsorbents Reusable with Water
    Takahashi, Akira; Minami, Kimitaka; Noda, Keiko; Sakurai, Koji; Kawamoto, Tohru
    ACS Applied Materials & Interfaces (2020), 12 (13), 15115-15119CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
    NH3 adsorbents, effective even at trace concns., are key counter-measures for particulate air pollution due to NH3 emissions from the agriculture sector. Prussian blue (PB) and its analogs (PBA), porous coordination polymers, have higher NH3 adsorption capacity for 10 ppmv NH3 (ppm in vol., 10 ppmv = 0.0001 vol. percent), ≥8 times that of conventional adsorbents. These compds. can be recycled only via water flushing. The PBA adsorption capacity was restricted to 10 adsorption/desorption cycles; the exptl. air sample was collected from a swine farm composting app. Despite the presence of satd. water vapor in the waste gas, the adsorbents displayed excellent selectivity for NH3 removal from the sample.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXktlOiur4%253D&md5=f29d786f38396e256e738367d56e9a3f
  26. 26
    Usuda, H.; Sakurai, K.; Takahashi, A.; Kawamoto, T.; Minami, K. Ammonium Salt Production in NH3-CO2-H2O System Using a Highly Selective Adsorbent, Copper Hexacyanoferrate. Environ. Pollut. 2021, 288 (June), 117763  DOI: 10.1016/j.envpol.2021.117763
    Google Scholar
    26
    Ammonium salt production in NH3-CO2-H2O system using a highly selective adsorbent, copper hexacyanoferrate
    Usuda, Hatsuho; Sakurai, Koji; Takahashi, Akira; Kawamoto, Tohru; Minami, Kimitaka
    Environmental Pollution (Oxford, United Kingdom) (2021), 288 (), 117763CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Ltd.)
    Ammonia is a beneficial material that is widely used in agriculture, but its emission into the atm. causes air pollution. Recently, Prussian blue (PB) and its analogs (PBA) were found to be ammonia adsorbents with high selectivity and capacity. In this study, we utilized a highly potent PBA adsorbent, copper hexacyanoferrate (CuHCF), to desorb ammonia and turn it into a reusable form. Because the reported NH3-CO2-H2O system phase diagram suggests the possibility of the recovery of solid NH4HCO3, we examd. whether adsorbed ammonia desorbs into the satd. ammonium hydrogencarbonate soln. (sat. NH4HCO3aq). We demonstrated that 40% of adsorbed ammonia desorbed into sat. NH4HCO3aq. After the desorption, CO2 was blown into the washing liq., and NH4HCO3 pptd., which was confirmed by Fourier transform IR spectroscopy. The molar amt. of solid NH4HCO3 was almost equal to that of desorbed ammonia. Our findings pave the way for recovery of ammonia as a valuable product from waste gas.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsFOrsrnN&md5=9d388e4da43f71bcda7c2c94a15e8667
  27. 27
    Takahashi, A.; Minami, K.; Noda, K.; Sakurai, K.; Kawamoto, T. Harvesting a Solid Fertilizer Directly from Fetid Air. ACS Sustainable Chem. Eng. 2021, 9 (50), 16865– 16869,  DOI: 10.1021/acssuschemeng.1c06161
    Google Scholar
    27
    Harvesting a Solid Fertilizer Directly from Fetid Air
    Takahashi, Akira; Minami, Kimitaka; Noda, Keiko; Sakurai, Koji; Kawamoto, Tohru
    ACS Sustainable Chemistry & Engineering (2021), 9 (50), 16865-16869CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
    The application of air as a resource for food prodn. and in other industries is a promising route for achieving a sustainable human society. Herein, we demonstrated the harvesting of solid-state ammonium bicarbonate from fetid air in an actual piggery. The process was achieved by condensation and sublimation, using new selective adsorbents of a copper Prussian blue analog for trace ammonia, which enabled the utilization of use air as a resource and the redn. of harmful chems. in the air.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisFymsLrO&md5=944e9a15d9073ff0a51887343c83f8ca
  28. 28
    Minami, K.; Takahashi, A.; Sakurai, K.; Mikasa, H.; Takasaki, M.; Doshu, N.; Aoyama, K.; Nakamura, T.; Iwai, R.; Kawamoto, T. Apparatus for Ammonia Removal in Livestock Farms Based on Copper Hexacyanoferrate Granules. Biosyst. Eng. 2022, 216, 98– 107,  DOI: 10.1016/j.biosystemseng.2022.02.002
    Google Scholar
    28
    Apparatus for ammonia removal in livestock farms based on copper hexacyanoferrate granules
    Minami, Kimitaka; Takahashi, Akira; Sakurai, Koji; Mikasa, Hiroaki; Takasaki, Mikihiro; Doshu, Naoaki; Aoyama, Katsuya; Nakamura, Tohru; Iwai, Ryota; Kawamoto, Tohru
    Biosystems Engineering (2022), 216 (), 98-107CODEN: BEINBJ; ISSN:1537-5110. (Elsevier Ltd.)
    Ammonia generated by livestock is a source of strong odor and pollution. In livestock management, ammonia neg. impacts not only animal health, but also productivity. A large-capacity and high-selectivity ammonia adsorbent that can be regenerated with water or dil. acids has been previously developed. In this study, ammonia adsorption and adsorbent regeneration apparatuses using this adsorbent are constructed and tested for ammonia removal in a pig house. The ammonia adsorption app. adsorbed approx. 0.36 mol of ammonia per h, and the adsorbent regeneration app. desorbed approx. 75% of ammonia adsorbed to the satd. adsorbent over four days. These systems allowed ammonia concn. and temp. to be controlled in closed pigpens, and their effectiveness was verified by rearing 20 pigs in a 21.6 m2 pigpen. In winter, the ammonia concn. in the exptl. area was suppressed to 10 ppmv or less, even with low ventilation, and was 4-7°C warmer than the open control area. As a result, the av. daily wt. gain of the pigs increased by approx. 9% and 7% compared to those of pigs in the closed and open control areas, resp. In summer, the ammonia concn. was 45-70% lower than that of the closed control area. The feed conversion ratio of pigs in the research area was approx. 6% and 9% lower than those of pigs in the closed and open control areas, resp.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvFCkt7jM&md5=ea2c047a3112b68a9e2d66bc1f225c69
  29. 29
    Usuda, H.; Mishima, Y.; Kawamoto, T.; Minami, K. Desorption of Ammonia Adsorbed on Prussian Blue Analogs by Washing with Saturated Ammonium Hydrogen Carbonate Solution. Mol. 2022, 27 (24), 8840,  DOI: 10.3390/molecules27248840
    Google Scholar
    29
    Desorption of Ammonia Adsorbed on Prussian Blue Analogs by Washing with Saturated Ammonium Hydrogen Carbonate Solution
    Usuda, Hatsuho; Mishima, Yoshie; Kawamoto, Tohru; Minami, Kimitaka
    Molecules (2022), 27 (24), 8840CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
    Prussian blue analogs (PBAs) have been reported as promising ammonia (NH3) adsorbents with a high capacity compared to activated carbon, zeolite, and ion exchange resins. The adsorbed NH3 was desorbed by heating and washing with water or acid. Recently, we demonstrated that desorption was also possible by washing with a satd. ammonium hydrogen carbonate soln. (sat. NH4HCO3aq) and recovered NH3 as an NH4HCO3 solid by introducing CO2 into the washing liq. after desorption. However, this has only been proven for copper ferrocyanide and the relationship between the adsorption/desorption behavior and metal ions in PBAs has not been identified. In this study, we investigated the adsorption/desorption behavior of PBAs that are complexes of first row transition metals with hexacyanometalate anions. Six types of PBAs were tested in this study and copper ferricyanide exhibited the highest desorption/adsorption ratio. X-ray diffraction results revealed high structural stability for cobalt hexacyanocobaltate (CoHCC) and nickel ferricyanide (NiHCF). The Fourier transform IR spectroscopy results showed that the NH3 adsorbed on the vacancy sites tended to desorb compared to the NH3 adsorbed on the interstitial sites as ammonium ions. Interestingly, the desorption/adsorption ratio exhibited the Irving-Williams order.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXktlantQ%253D%253D&md5=acd96a50a9defd64d7daca978358fb73
  30. 30
    Wessells, C. D.; Peddada, S. V.; Huggins, R. A.; Cui, Y. Nickel Hexacyanoferrate Nanoparticle Electrodes For Aqueous Sodium and Potassium Ion Batteries. Nano Lett. 2011, 11 (12), 5421– 5425,  DOI: 10.1021/nl203193q
    Google Scholar
    30
    Nickel Hexacyanoferrate Nanoparticle Electrodes For Aqueous Sodium and Potassium Ion Batteries
    Wessells, Colin D.; Peddada, Sandeep V.; Huggins, Robert A.; Cui, Yi
    Nano Letters (2011), 11 (12), 5421-5425CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
    The elec. power grid faces a growing need for large-scale energy storage over a wide range of time scales due to costly short-term transients, frequency regulation, and load balancing. The durability, high power, energy efficiency, and low cost needed for grid-scale storage pose substantial challenges for conventional battery technol. Here, we demonstrate insertion/extn. of sodium and potassium ions in a low-strain nickel hexacyanoferrate electrode material for at least five thousand deep cycles at high current densities in inexpensive aq. electrolytes. Its open-framework structure allows retention of 66% of the initial capacity even at a high (41.7C) rate. At low current densities, its round trip energy efficiency reaches 99%. This low-cost material is readily synthesized in bulk quantities. The long cycle life, high power, good energy efficiency, safety, and inexpensive prodn. method make nickel hexacyanoferrate an attractive candidate for use in large-scale batteries to support the elec. grid.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtl2ktL7J&md5=d1ee3adb1a2dd638a729df1cfdf03be8
  31. 31
    Shrivastava, A.; Liu, S.; Smith, K. C. Linking Capacity Loss and Retention of Nickel Hexacyanoferrate to a Two-Site Intercalation Mechanism for Aqueous Mg 2+ and Ca 2+ Ions †. Phys. Chem. Chem. Phys. 2019, 21, 20177– 20188,  DOI: 10.1039/C9CP04115J
    Google Scholar
    31
    Linking capacity loss and retention of nickel hexacyanoferrate to a two-site intercalation mechanism for aqueous Mg2+ and Ca2+ ions
    Shrivastava, Aniruddh; Liu, Sizhe; Smith, Kyle C.
    Physical Chemistry Chemical Physics (2019), 21 (36), 20177-20188CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
    Prussian blue analogs (PBAs) are promising cation intercalation materials for electrochem. desalination and energy storage applications. Here, we investigate the mechanism of capacity fade and degrdn. of nickel hexacyanoferrate (NiHCFe) during galvanostatic cycling in aq. electrolytes that are rich in either Mg2+ or Ca2+. We combine exptl. characterization, first principles electronic structure calcns., statistical mechanics and lattice-percolation modeling of electron transfer to elucidate the mechanisms responsible for the degrdn. of NiHCFe and its partial retention of capacity. Electrochem. characterization of porous NiHCFe electrodes suggests a two-site intercalation mechanism, while spectroscopy reveals the presence of Ni2+ and Fe(CN)63- ions in the electrolyte post cycling in Mg2+(aq). Using simple copptn. reactions, we show that Mg2+ and Ni2+ can coexist in the lattice framework, forming stable PBAs. Galvanostatic cycling of these PBAs shows that the presence of Mg2+ in the lattice framework results in the dissoln. of Mg1.5FeIII(CN)6 in water during oxidn. We propose that Mg2+ can partially substitute Ni2+ ions in the lattice framework during galvanostatic cycling, displacing the substituted Ni2+ ions into interstitial sites. Based on differential capacitance anal. we show that Mg2+ intercalates into interstitial sites at ∼0.45 V vs. Ag/AgCl and it displaces Ni2+ in the lattice framework at ∼0.05 V vs. Ag/AgCl. Substitution of Ni2+ leads to Fe(CN)63- and Ni2+ ions being removed into the electrolyte during oxidn. Using first principles d. functional theory (DFT) calcns. combined with a statistical mechanics model, we verify the thermodn. feasibility of the proposed reaction mechanism and predict the fraction of Ni2+ ions being substituted by Mg2+ during intercalation. Further, anal. of the electron d. distribution and local d. of states indicates that Mg2+ ions can act as insulating defects in the lattice framework that render certain Fe ions elec. inactive and likely contribute to capacity fade along with dissoln. of Fe(CN)63-.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1Gkt7vI&md5=190bbe68fe7cd1f3ad55d3e25b2c746c
  32. 32
    Hall, H. K. Correlation of the Base Strengths of Amines. J. Am. Chem. Soc. 1957, 79 (20), 5441– 5444,  DOI: 10.1021/ja01577a030
    Google Scholar
    32
    Correlation of the base strengths of amines
    Hall, H. K., Jr.
    Journal of the American Chemical Society (1957), 79 (), 5441-4CODEN: JACSAT; ISSN:0002-7863.
    The base strengths of 25 primary, 21 secondary, and 31 tertiary nonaromatic amines were plotted against the Taft σ*-values (cf. C.A. 51, 17719i). Each class of amines lay on a different line; this indicates that solvation of the ammonium ion through the N+H bonds plays an important role in detg. base strength. All tertiary amines gave an excellent correlation with the sum of the σ* values, regardless of their degree of steric hindrance. This suggests that B-strain is not a factor detg. the pKa value. For secondary and primary amines, only those amines with a low degree of steric hindrance gave a linear plot against σ* values. This is also incompatible with the B-strain theory (for the primary amines), but in good agreement with the solvation theory if solvation of the ammonium ion is regarded as subject to hindrance. These correlations permit the prediction of the pKa values of new amines.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG1cXpslCg&md5=b3b33f0cfad8fcae79e11c9fbbf88b87
  33. 33
    National Astronomical Observatory of Japan. Handbook of Scientific Tables; Maruzen Publishing Co., Ltd., 2012.
    Google Scholar
    There is no corresponding record for this reference.
  34. 34
    Khanna, R. K.; Moore, M. H. Carbamic Acid: Molecular Structure and IR Spectra. Spectrochim. Acta A Mol. Biomol. Spectrosc. 1999, 55 (5), 961– 967,  DOI: 10.1016/S1386-1425(98)00228-5
    Google Scholar
    34
    Carbamic acid: molecular structure and IR spectra
    Khanna, R. K.; Moore, M. H.
    Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (1999), 55A (5), 961-967CODEN: SAMCAS; ISSN:1386-1425. (Elsevier Science B.V.)
    IR absorption spectra of mixed H2O, NH3 and 12CO2/13CO2 ices subjected to 1 MeV proton irradn. were studied. The results of analyses of the spectra suggest formation of carbamic acid at low temps. The stability of this compd. in the solid phase is attributed to intermol. H bonding of the zwitterion (NH3+COO-) structure.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXivVyrsbY%253D&md5=ee72e95efcce50341c937e7667294353
  35. 35
    Tao, W.; Ukwuani, A. T. Coupling Thermal Stripping and Acid Absorption for Ammonia Recovery from Dairy Manure: Ammonia Volatilization Kinetics and Effects of Temperature, PH and Dissolved Solids Content. Chem. Eng. J. 2015, 280, 188– 196,  DOI: 10.1016/j.cej.2015.05.119
    Google Scholar
    35
    Coupling thermal stripping and acid absorption for ammonia recovery from dairy manure: Ammonia volatilization kinetics and effects of temperature, pH and dissolved solids content
    Tao, Wendong; Ukwuani, Anayo T.
    Chemical Engineering Journal (Amsterdam, Netherlands) (2015), 280 (), 188-196CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
    Both liq. dairy manure and manure digestate have high concns. of ammonia. This study coupled thermal stripping with acid absorption to recover ammonia from dairy manure as ammonium sulfate. Ammonia volatilization kinetics and effects of temp., pH, and dissolved solids content on thermal stripping were studied in batch expts. Statistically insignificant differences were found in ammonium sulfate formation and liq. mass transfer of ammonia between the expts. with initial a feed pH of 11 and 9 and between the expts. with filtrate of undigested and digested manure, which have different dissolved solids contents. Temp. had significant effects on thermal stripping of ammonia. When temp. was set at the b.ps. (101-102°) of manure filtrate, ammonia was completely stripped in 3-4 h. It took 5 h to strip 50% of ammonia at 97°. Little ammonia was stripped at 86 and 76°. The satn. concns. of ammonia in manure filtrate was zero at 76-102°. Ammonia mass transfer coeff. upon boiling was 30.3-31.4 mm/h in manure filtrate. Ammonia mass transfer coeff. increased exponentially with temp., indicating a temp. coeff. of 1.164. High-purity ammonium sulfate crystals (≥98%) were produced when sulfuric acid solns. were pre-satd. with ammonium sulfate. When ammonia was completely stripped, ammonium sulfate was formed at 3.70-3.87 g/L filtrate. A preliminary economic anal. shows that this novel technol. is economically promising for practical application, esp. when it is applied to a side-stream of anaerobic digesters.
    >> More from SciFinder ®
    https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVais7rN&md5=d255bece226267a8e4f86ba39b7c86a4

Cited By

Click to copy section linkSection link copied!

This article is cited by 1 publications.

  1. Hanna Fałtynowicz, Jan Kaczmarczyk, Rafał Łużny, Karolina Jaroszewska, Katarzyna Pstrowska, Sylwia Hull, Marek Kułażyński, Karol Postawa. Activated Carbons for Removing Ammonia from Piggery Vent Air: A Promising Tool for Mitigating the Environmental Impact of Large-Scale Pig Breeding. Sustainability 2024, 16 (14) , 6122. https://doi.org/10.3390/su16146122
Download PDF
Go to ACS Sustainable Chemistry & Engineering
Get e-Alerts
Get e-Alerts

ACS Sustainable Chemistry & Engineering

Cite this: ACS Sustainable Chem. Eng. 2024, 12, 6, 2183–2190
Click to copy citationCitation copied!
https://doi.org/10.1021/acssuschemeng.3c05679
Published January 30, 2024

Copyright © 2024 The Authors. Published by American Chemical Society. This publication is licensed under

CC-BY-NC-ND 4.0 .

Article Views

1241

Altmetric

-

Citations

1
Learn about these metrics

Article Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.

Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.

The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated.

  • Abstract

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 1

    Figure 1. (a) Crystal structure of NiHCF, which has interstitial sites and vacancy sites. (b) Photograph of NiHCF granules.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 2

    Figure 2. Experimental setup of the NH3 adsorption and desorption. MFC stands for the mass flow controller. The adsorption and desorption lines are shown as red solid lines with closed arrows, and blue thin lines with open arrows, respectively. The thicker lines and the thinner lines represent gas and liquid lines, respectively. Pn and Fn represent the pressure and flow meter, respectively.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 3

    Figure 3. NH3 adsorption isotherms of NiHCF powder at 25 °C. The blue broken line indicates the partial pressure of NH3 in the inlet gas.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 4

    Figure 4. Results of NH3 adsorption and desorption. (a) NH3 concentration of the gas flow getting in/out of the NiHCF adsorbent in the three cycles of adsorption, which have a desorption step after the adsorption. (b) Ammonium nitrogen concentration (blue square) and pH (orange cross) in the washing liquid during desorption.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 5

    Figure 5. (a) Washed precipitate obtained after desorption. (b) FTIR spectra of the obtained precipitate and commercial NH4HCO3.

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 6

    Figure 6. Adsorbed and desorbed NH3 amounts in each cycle. Red bars: adsorbed amount of NH3. blue bars: desorbed amount of NH3. The 2nd set of 3 cycles of the adsorption and desorption experiment was conducted in the same way as the 1st set (Figure 4) after changing the washing liquid used in the 1st set to a new one. The right axis exhibits the NH3 amount normalized by the adsorbent weight. The broken and dotted lines are the adsorbed and desorbed amounts in the reported batch experiment in the case of NiHCF, respectively. (29)

    High Resolution Image
    Download MS PowerPoint Slide

    Figure 7

    Figure 7. Material balance of NH3 species during the process of adsorption, desorption, and precipitation in cycle 3 of the 2nd set. The units of the numbers is mmol.

    High Resolution Image
    Download MS PowerPoint Slide

  • References

    This article references 35 other publications.

    1. 1
      U.S. Geological Survey. Nitrogen (Fixed)─Ammonia Miner. Commod. Summ. 2022.
      There is no corresponding record for this reference.
    2. 2
      Boerner, L. K. Industrial Ammonia Production Emits More CO2 than Any Other Chemical-Making Reaction. Chemists Want to Change That Chem. Eng. News 2019, 97(24), https://cen.acs.org/environment/green-chemistry/Industrial-ammonia-production-emits-CO2/97/i24
      There is no corresponding record for this reference.
    3. 3
      Krupa, S. Effects of Atmospheric Ammonia (NH3) on Terrestrial Vegetation: A Review. Environ. Pollut. 2003, 124 (2), 179– 221,  DOI: 10.1016/S0269-7491(02)00434-7
      3
      Effects of atmospheric ammonia (NH3) on terrestrial vegetation: a review
      Krupa, S. V.
      Environmental Pollution (Oxford, United Kingdom) (2003), 124 (2), 179-221CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Science Ltd.)
      A review of atm. ammonia (NH3) and ammonium (NH4+) deposition and their effects on plants. At the global scale, among all N (nitrogen) species in the atm. and their deposition on to terrestrial vegetation and other receptors, NH3 (ammonia) is considered to be the foremost. The major sources for atm. NH3 are agricultural activities and animal feedlot operations, followed by biomass burning (including forest fires) and to a lesser extent fossil fuel combustion. Close to its sources, acute exposures to NH3 can result in visible foliar injury on vegetation. NH3 is deposited rapidly within the first 4-5 km from its source. However, NH3 is also converted in the atm. to fine particle NH4+ (ammonium) aerosols that are a regional scale problem. Much of our current knowledge of the effects of NH3 on higher plants is predominantly derived from studies conducted in Europe. Adverse effects on vegetation occur when the rate of foliar uptake of NH3 is greater than the rate and capacity for in vivo detoxification by the plants. Most to least sensitive plant species to NH3 are native vegetation > forests > agricultural crops. There are also a no. of studies on N deposition and lichens, mosses, and green algae. Direct cause and effect relationships in most of those cases (exceptions being those locations very close to point sources) are confounded by other environmental factors, particularly changes in the ambient SO2 (sulfur dioxide) concns. In addn. to direct foliar injury, adverse effects of NH3 on higher plants include alterations in: growth and productivity, tissue content of nutrients and toxic elements, drought and frost tolerance, responses to insect pests and disease causing microorganisms (pathogens), development of beneficial root symbiotic or mycorrhizal assocns. and inter species competition or biodiversity. In all these cases, the joint effects of NH3 with other air pollutants such as all-pervasive O3 or increasing CO2 concns. are poorly understood. While NH3 uptake in higher plants occurs through the shoots, NH4+ uptake occurs through the shoots, roots and through both pathways. However, NH4+ is immobile in the soil and is converted to NO3- (nitrate). In agricultural systems, addns. of NO3- to the soil (initially as NH3 or NH4+) and the consequent increases in the emissions of N2O (nitrous oxide, a greenhouse gas) and leaching of NO3- into the ground and surface waters are of major environmental concern. At the ecosystem level NH3 deposition cannot be viewed alone, but in the context of total N deposition. There are a no. of forest ecosystems in North America that were subjected to N satn. and the consequent neg. effects. There are also heathlands and other plant communities in Europe that were subjected to N-induced alterations. Regulatory mitigative approaches to these problems include the use of N satn. data or the concept of crit. loads. Current information suggests that a crit. load of 5-10 kg ha-1 year-1 of total N deposition (both dry and wet deposition combined of all atm. N species) would protect the most vulnerable terrestrial ecosystems (heaths, bogs, cryptogams) and values of 10-20 kg ha-1 year-1 would protect forests, depending on soil conditions. However, to derive the best anal., the crit. load concept should be coupled to the results and consequences of N satn.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3sXjtFWls7o%253D&md5=556aa826aa45367db1327c701b03e205
    4. 4
      Pitcairn, C. E. R.; Leith, I. D.; Sheppard, L. J.; Sutton, M. A.; Fowler, D.; Munro, R. C.; Tang, S.; Wilson, D. The Relationship between Nitrogen Deposition, Species Composition and Foliar Nitrogen Concentrations in Woodland Flora in the Vicinity of Livestock Farms. Environ. Pollut. 1998, 102 (1), 41– 48,  DOI: 10.1016/S0269-7491(98)80013-4
      4
      The relationship between nitrogen deposition, species composition and foliar nitrogen concentrations in woodland flora in the vicinity of livestock farms
      Pitcairn, C. E. R.; Leith, I. D.; Sheppard, L. J.; Sutton, M. A.; Fowler, D.; Munro, R. C.; Tang, S.; Wilson, D.
      Environmental Pollution (1998), 102 (Suppl. 1), 41-48CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Science Ltd.)
      Measurements of atm. ammonia concn. along a gradient of decreasing concn., species compn. and tissue nitrogen content of a range of plant species were made in woodland in the vicinity of four intensive animal units in Scotland. Ammonia concns. were large at woodland edges close to the livestock buildings (annual means 20-60 μg m-3) and exceed crit. levels for NH3 (8 μg m-3 annual mean). Surveys of species compn. of ground flora along an 0.5 km transect from livestock buildings show marked changes within 300 m downwind of the buildings. Species such as Deschampsia flexuosa, Holcus lanatus, Rubus idaeus and Urtica dioica were abundant close to livestock units and their percentage cover decreased rapidly with distance from source, while the more N-sensitive species such as Oxalis acetosella, Galium odoratum, mosses and ferns which are found upwind and outside the influence of the NH3 source, were scarce at all sites receiving >25 kg ha-1 N year-1. Visible injury to pine and spruce needles was obsd. immediately downwind of the buildings. Foliar nitrogen concn. of a no. of species was large close to the buildings and declined with distance. Total nitrogen deposition at the woodland boundaries is estd. to range from 40 to 80 kg N ha-1 year-1 at the 4 sites and exceeds crit. loads for acidic coniferous forest, i.e. 15-20 kg N ha-1 year-1 to protect ground flora, and is also often in excess of that (11-50 kg N ha-1 year-1) proposed to protect tree health. Foliar nitrogen content of mosses, (LN, % dry wt.) is related to nitrogen deposition (FN, kg N ha-1 year-1) according to LN = 3.81(1-e-0.04FN).
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXjvVaqsg%253D%253D&md5=d133fe6dd8afdf4d47ad73b2bd1a34c3
    5. 5
      Sheppard, L. J.; Leith, I. D.; Crossley, A.; Van Dijk, N.; Fowler, D.; Sutton, M. A.; Woods, C. Stress Responses of Calluna Vulgaris to Reduced and Oxidised N Applied under “Real World Conditions.. Environ. Pollut. 2008, 154 (3), 404– 413,  DOI: 10.1016/j.envpol.2007.10.040
      5
      Stress responses of Calluna vulgaris to reduced and oxidised N applied under real world conditions'
      Sheppard, Lucy J.; Leith, Ian D.; Crossley, A.; Van Dijk, N.; Fowler, D.; Sutton, M. A.; Woods, C.
      Environmental Pollution (Amsterdam, Netherlands) (2008), 154 (3), 404-413CODEN: ENPOEK; ISSN:0269-7491. (Elsevier B.V.)
      Effects and implications of reduced and oxidized N, applied under real world' conditions, since May 2002, are reported for Calluna growing on an ombrotrophic bog. Ammonia has been released from a 10 m line source generating monthly concns. of 180-6 μg m-3, while ammonium chloride and sodium nitrate are applied in rainwater at nitrate and ammonium concns. below 4 mM and providing up to 56 kg N ha-1 year-1 above a background deposition of 10 kg N ha-1 year-1. Ammonia concns., >8 μg m-3 have significantly enhanced foliar N concns., increased sensitivity to drought, frost and winter desiccation, spring frost damage and increased the incidence of pathogen outbreaks. The mature Calluna bushes nearest the NH3 source have turned bleached and moribund. By comparison the Calluna receiving reduced and oxidized N in rain has shown no significant visible or stress related effects with no significant increase in N status. Exposure to NH3 reduces stress resistance and increases visible damage in mature Calluna.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXosVOlur4%253D&md5=04353a218d084a5fcadb1ce2ec8d6320
    6. 6
      van den Berg, L. J. L.; Peters, C. J. H.; Ashmore, M. R.; Roelofs, J. G. M. Reduced Nitrogen Has a Greater Effect than Oxidised Nitrogen on Dry Heathland Vegetation. Environ. Pollut. 2008, 154 (3), 359– 369,  DOI: 10.1016/j.envpol.2007.11.027
      6
      Reduced nitrogen has a greater effect than oxidized nitrogen on dry heathland vegetation
      van den Berg, L. J. L.; Peters, C. J. H.; Ashmore, M. R.; Roelofs, J. G. M.
      Environmental Pollution (Amsterdam, Netherlands) (2008), 154 (3), 359-369CODEN: ENPOEK; ISSN:0269-7491. (Elsevier B.V.)
      We investigated the effects of different ratios of reduced (NH4+) vs. oxidized (NO3-) nitrogen in deposition on heathland and species-rich grassland vegetation at high nitrogen deposition levels in large mesocosms filled with nutrient-poor soils to which different NH4+/NO3- ratios were applied. The response of the forbs, Antennaria dioica, Arnica montana, Gentiana pneumonanthe, Thymus serpyllum, the grasses Danthonia decumbens, Deschampsia flexuosa, Nardus stricta and the shrub Calluna vulgaris was recorded. The forb A. dioica and the grass D.decumbens preferred low NH4+/NO3- ratios and were characterized by a neg. correlation between NH4+/NO3- ratios and biomass and survival, whereas the grasses N. stricta and D. flexuosa showed no correlation with NH4+/NO3- ratios. Lime addn. eliminated the neg. effects of high NH4+ concns. in deposition for A. dioica and the grass D. decumbens. The implications of these findings for heathland vegetations are discussed. Reduced nitrogen and high NH4+/NO3- ratios in deposition are responsible for a decline of forbs in Western European heathlands.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXosVOltbg%253D&md5=b229c3b84c46721d4a897fc916837d8b
    7. 7
      Nutrient Reduction Technology Cost Estimations for Point Sources in the Chesapeake Bay Watershed Prepared by The Nutrient Reduction Technology Cost Task Force A Stakeholder Group of the Chesapeake Bay Program November 2002 , 2002. https://www.chesapeakebay.net/content/publications/cbp_13140.pdf.
      There is no corresponding record for this reference.
    8. 8
      Mladenović, M.; Paprika, M.; Marinković, A. Denitrification Techniques for Biomass Combustion. Renew. Sustain. Energy Rev. 2018, 82, 3350– 3364,  DOI: 10.1016/j.rser.2017.10.054
      There is no corresponding record for this reference.
    9. 9
      Melse, R. W.; Ogink, N. W. M. Air Scrubbing Techniques for Ammonia and Odor Reduction at Livestock Operations: Review of on-Farm Research in the Netherlands. Trans. Am. Soc. Agric. Eng. 2005, 48 (6), 2303– 2313,  DOI: 10.13031/2013.20094
      9
      Air scrubbing techniques for ammonia and odor reduction at livestock operations: review of on-farm research in the netherlands
      Melse, R. W.; Ogink, N. W. M.
      Transactions of the ASAE (2005), 48 (6), 2303-2313CODEN: TAAEAJ; ISSN:0001-2351. (American Society of Agricultural Engineers)
      A review. Acid scrubbers and biotrickling filters have been developed for ammonia (NH3) removal at pig and poultry houses in The Netherlands over the last 20 years to prevent acidification and eutrophication of soils. Because of growing suburbanization, odor removal is increasingly considered important as well. In this review, we report the results of the on-farm research on full-scale operated scrubbers for treatment of exhaust air from animal houses with regard to NH3 and odor removal in The Netherlands. The NH3 removal of acid scrubbers ranged from 40% to 100% with an overall av. of 96%. The NH3 removal of biotrickling filters ranged from -8% to +100% with an overall av. of 70%. Min. empty bed air residence times (EBRTs) were 0.4 to 1.1 s. For acid scrubbers, process control with pH measurement and automatic water discharge is sufficient to guarantee sufficient NH3 removal. For biotrickling filters, however, improvement of process control is necessary to guarantee sufficient NH3 removal. The odor removal of acid scrubbers ranged from 3% to 51% with an overall av. of 27%. The odor removal of biotrickling filters ranged from -29% to +87% with an overall av. of 51%. Min. EBRTs were 0.5 to 2.3 s. Further research is necessary to explain this variation and to improve the odor removal efficiency of both acid scrubbers and biotrickling filters.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XhsFejs74%253D&md5=a796b248b4cd95f67a5c643237c21312
    10. 10
      Maurer, D. L.; Koziel, J. A. On-Farm Pilot-Scale Testing of Black Ultraviolet Light and Photocatalytic Coating for Mitigation of Odor, Odorous VOCs, and Greenhouse Gases. Chemosphere 2019, 221, 778– 784,  DOI: 10.1016/j.chemosphere.2019.01.086
      10
      On-farm pilot-scale testing of black ultraviolet light and photocatalytic coating for mitigation of odor, odorous VOCs, and greenhouse gases
      Maurer, Devin L.; Koziel, Jacek A.
      Chemosphere (2019), 221 (), 778-784CODEN: CMSHAF; ISSN:0045-6535. (Elsevier Ltd.)
      Technologies for controlling gaseous emissions of livestock is of interest to producers, the public, and regulatory agencies. In our previous lab-scale study, the use of a photocatalytic coating on surfaces subjected to black UV light reduced emissions of key odorant compds. relevant to the livestock industry. Thus, an on-farm pilot-scale expt. was conducted at a com. swine barn to evaluate a photocatalytic coating on surfaces subjected to UV light under field conditions. A flow-through reactor was constructed with a TiO2-based photocatalytic coating on the interior surfaces and black UV light fixtures. The reactor was deployed in a room downstream of the entire swine barn exhaust. Gas samples were collected from three sampling ports in the reactor, one at the inlet (control), the midpoint (half treatment) and the outlet (treatment). Compared to the control, significant redns. in emissions were obsd. for p-cresol (22%), odor (16%) and nitrous oxide (9%). A significant increase in carbon dioxide (3%) was also measured. Results show that the TiO2-based photocatalytic coating and black UV light are effective in mitigating odor, a key VOC responsible for downwind swine odor, and one important greenhouse effect gas when subjected to swine barn exhaust.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhvFSktr8%253D&md5=d5c7fa41bbff4af63c2d25965c660fd8
    11. 11
      Li, G.; Kanezashi, M.; Yoshioka, T.; Tsuru, T. Ammonia Decomposition in Catalytic Membrane Reactors: Simulation and Experimental Studies. AIChE J. 2013, 59 (1), 168– 179,  DOI: 10.1002/aic.13794
      11
      Ammonia decomposition in catalytic membrane reactors: Simulation and experimental studies
      Li, Gang; Kanezashi, Masakoto; Yoshioka, Tomohisa; Tsuru, Toshinori
      AIChE Journal (2013), 59 (1), 168-179CODEN: AICEAC; ISSN:0001-1541. (John Wiley & Sons, Inc.)
      Catalytic decompn. of NH3 with H2-selective microporous silica membranes for COx-free hydrogen prodn. was studied theor. and exptl. The simulation study shows that NH3 conversion, H2 yield and H2 purity increase with the Damkoehler no. (Da), and their improvement is affected by the effect of H2 extn. as well as NH3 and N2 permeation through the membranes. The exptl. study of NH3 decompn. was carried out in a bimodal catalytic membrane reactor (BCMR), consisting of a bimodal catalytic support and a H2-selective silica layer. Catalytic membranes showed H2 permeances of 6.2-9.8 × 10-7 mol m-2 s-1 Pa-1, with H2/NH3 and H2/N2 permeance ratios of 110-200 and 200-700, resp., at 773 K. The effect of operating conditions on membrane reactor performance with respect to NH3 conversion, H2 yield and H2 purity was investigated, and the results were in agreement with those calcd. by the proposed simulation model.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xls1Wmu78%253D&md5=f2a5067722fbe935865181ffe570765b
    12. 12
      Lamb, K. E.; Dolan, M. D.; Kennedy, D. F. Ammonia for Hydrogen Storage; A Review of Catalytic Ammonia Decomposition and Hydrogen Separation and Purification. Int. J. Hydrogen Energy 2019, 44 (7), 3580– 3593,  DOI: 10.1016/j.ijhydene.2018.12.024
      12
      Ammonia for hydrogen storage; A review of catalytic ammonia decomposition and hydrogen separation and purification
      Lamb, Krystina E.; Dolan, Michael D.; Kennedy, Danielle F.
      International Journal of Hydrogen Energy (2019), 44 (7), 3580-3593CODEN: IJHEDX; ISSN:0360-3199. (Elsevier Ltd.)
      Ammonia is of interest as a hydrogen storage and transport medium because it enables liq.-phase hydrogen storage under mild conditions. Although ammonia can be used directly for energy applications, its use in conventional fuel cell elec. vehicles necessitates decompn. into nitrogen and hydrogen, and the purifn. of the hydrogen to the compn. required for com. proton exchange membrane fuel cells. This article provides a review of the material and process considerations for catalytic ammonia decompn. and shows that Ru-based catalysts on conductive support materials are active at < 500 °C, but further understanding around lifetimes and deactivation conditions is required. This review then explores materials and technologies for hydrogen purifn. from decompd. ammonia gas streams, and our expts. show that defect-free dense-metal membranes are uninhibited by ammonia and can achieve the required product purity.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisFyntb7L&md5=5888d11e0fb5d9bd1eb390527171f99e
    13. 13
      Yin, S. F.; Xu, B. Q.; Zhou, X. P.; Au, C. T. A Mini-Review on Ammonia Decomposition Catalysts for on-Site Generation of Hydrogen for Fuel Cell Applications. Appl. Catal. A Gen. 2004, 277 (1–2), 1– 9,  DOI: 10.1016/j.apcata.2004.09.020
      13
      A mini-review on ammonia decomposition catalysts for on-site generation of hydrogen for fuel cell applications
      Yin, S. F.; Xu, B. Q.; Zhou, X. P.; Au, C. T.
      Applied Catalysis, A: General (2004), 277 (1-2), 1-9CODEN: ACAGE4; ISSN:0926-860X. (Elsevier B.V.)
      A review. Due to the drive for better environmental protection and energy conversion efficiency, on-site generation of COx-free hydrogen from ammonia decompn. for fuel cell applications has attracted much attention. The development of high performance solid catalysts is essential for the supply of such hydrogen from ammonia. In this mini-review, we provide a summary of the reaction kinetics of catalytic ammonia decompn. Comparisons are then made among the catalysts that have different active components, supports, and promoters. According to the works reported in the literature and our recent research results, Ru is the most active catalyst, carbon nanotubes (CNTs) are the most effective support, and KOH is the best promoter. An increase in Ru dispersion results in better catalytic performance. Both support basicity and cond. are important criteria for a NH3 decompn. catalyst of high efficiency; and it seems possible to generate novel advanced support, such as oxide-CNTs nanocomposite materials, that bears such characteristics. Also, proper removal of the electron-withdrawing entities that originate from the precursors of active component, support or promoter can be effective in enhancing the catalytic activity of a Ru catalyst.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXpsV2qtrg%253D&md5=070267f67fc9283bf683f38bcb462e6d
    14. 14
      Bist, R. B.; Subedi, S.; Chai, L.; Yang, X. Ammonia Emissions, Impacts, and Mitigation Strategies for Poultry Production: A Critical Review. J. Environ. Manage. 2023, 328, 116919  DOI: 10.1016/j.jenvman.2022.116919
      14
      Ammonia emissions, impacts, and mitigation strategies for poultry production: A critical review
      Bist, Ramesh Bahadur; Subedi, Sachin; Chai, Lilong; Yang, Xiao
      Journal of Environmental Management (2023), 328 (), 116919CODEN: JEVMAW; ISSN:0301-4797. (Elsevier Ltd.)
      A review. Confined animal feeding operations (CAFOs) are the main sources of air pollutants such as ammonia (NH3) and greenhouse gases. Among air pollutants, NH3 is one of the most concerned gasses in terms of air quality, environmental impacts, and manure nutrient losses. It is recommended that NH3 concns. in the poultry house should be controlled below 25 ppm. Otherwise, the poor air quality will impair the health and welfare of animals and their caretakers. After releasing from poultry houses, NH3 contributes to the form of fine particulate matters in the air and acidify soil and water bodies after deposition. Therefore, understanding the emission influential factors and impacts is crit. for developing mitigation strategies to protect animals' welfare and health, environment, and ecosystems. This review paper summarized the primary NH3 emission influential factors, such as how poultry housing systems, seasonal changes, feed management, bedding materials, animal densities, and animals' activities can impact indoor air quality and emissions. A higher level of NH3 (e.g., >25 ppm) results in lower prodn. efficiency and poor welfare and health, e.g., respiratory disorder, less feed intake, lower growth rates or egg prodn., poor feed use efficiency, increased susceptibility to infectious diseases, and mortality. In addn., the egg quality (e.g., albumen height, pH, and condensation) was reduced after laying hens chronically exposed to high NH3 levels. High NH3 levels have detrimental effects on farm workers' health as it is a corrosive substance to eyes, skin, and respiratory tract, and thus may cause blindness, irritation (throat, nose, eyes), and lung illness. For controlling poultry house NH3 levels and emissions, we analyzed various mitigation strategies such as litter additives, biofiltration, acid scrubber, dietary manipulation, and bedding materials. Litter additives were tested with 50% efficiency in broiler houses and 80-90% mitigation efficiency for cage-free hen litter at a higher application rate (0.9 kg m-2). Filtration systems such as multi-stage acid scrubbers have up to 95% efficiency on NH3 mitigation. However, cautions should be paid as mitigation strategies could be cost prohibitive for farmers, which needs assistances or subsidies from governments.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XjtFeisrbF&md5=00eaccec7e9da27fcfe2dd3e949f2ceb
    15. 15
      Chen, L.; Hoff, S. J.; Koziel, J. A.; Cai, L.; Zelle, B.; Sun, G. Performance Evaluation of a Wood-Chip Based Biofilter Using Solid-Phase Microextraction and Gas Chromatography-Mass Spectroscopy-Olfactometry. Bioresour. Technol. 2008, 99 (16), 7767– 7780,  DOI: 10.1016/j.biortech.2008.01.085
      15
      Performance evaluation of a wood-chip based biofilter using solid-phase microextraction and gas chromatography-mass spectroscopy-olfactometry
      Chen, Lide; Hoff, Steven J.; Koziel, Jacek A.; Cai, Lingshuang; Zelle, Brian; Sun, Gang
      Bioresource Technology (2008), 99 (16), 7767-7780CODEN: BIRTEB; ISSN:0960-8524. (Elsevier Ltd.)
      A pilot-scale mobile biofilter was developed where two types of wood chips (western cedar and 2 in. hardwood) were examd. to treat odor emissions from a deep-pit swine finishing facility in central Iowa. The biofilters were operated continuously for 13 wk at different air flow rates resulting in a variable empty bed residence time (EBRT) from 1.6 to 7.3 s. During this test period, solid-phase microextn. (SPME) PDMS/DVB 65 μm fibers were used to ext. volatile org. compds. (VOCs) from both the control plenum and biofilter treatments. Analyses of VOCs were carried out using a multidimentional gas chromatog.-mass spectrometry-olfactometry (MDGC-MS-O) system. Results indicated that both types of chips achieved significant redns. in p-cresol, phenol, indole and skatole which represent some of the most odorous and odor-defining compds. known for swine facilities. The results also showed that maintaining proper moisture content is crit. to the success of wood-chip based biofilters and that this factor is more important than media depth and residence time.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXns1aktbw%253D&md5=ed7cc2c02c92fff816d2c90f4b4f6774
    16. 16
      Chen, L.; Hoff, S.; Cai, L.; Koziel, J.; Zelle, B. Evaluation of Wood Chip-Based Biofilters to Reduce Odor, Hydrogen Sulfide, and Ammonia from Swine Barn Ventilation Air. J. Air Waste Manag. Assoc. 2009, 59 (5), 520– 530,  DOI: 10.3155/1047-3289.59.5.520
      16
      Evaluation of wood chip-based biofilters to reduce odor, hydrogen sulfide, and ammonia from swine barn ventilation air
      Chen, Lide; Hoff, Steven; Cai, Lingshuang; Koziel, Jacek; Zelle, Brian
      Journal of the Air & Waste Management Association (2009), 59 (5), 520-530CODEN: JAWAFC; ISSN:1096-2247. (Air & Waste Management Association)
      A pilot-scale biofilter was developed in which two types of wood chips (western cedar [WC] and 2-in. hardwood [HW]) were examd. to treat odor emissions from a deep-pit swine finishing facility in central Iowa. The biofilters were operated continuously for 13 wk at different airflow rates resulting in variable empty bed residence times (EBRTs) from 1.6 to 7.3 s. The effects of three media moisture levels were also evaluated. A dynamic forced-choice olfactometer was used to evaluate odor concns. from both the control (inlet) plenum and biofilter treatments (outlet). Hydrogen sulfide (H2S) and ammonia (NH3) concns. were also measured from these olfactometry samples. Solid-phase microextn. (SPME) polydimethylsiloxane (PDMS)/divinylbenzene (DVB) 65-μm fibers were used to ext. volatile org. compds. from both the control plenum and biofilter treatments. Analyses of sepd. odors were carried out using a gas chromatog.-mass spectrometry-olfactometry (GC-MS-O) system. Static sample results indicated that both types of chips achieved significant redns. in odor (av. 70.1 and 82.3% for HW and WC, resp.), H2S (av. 81.8 and 88.6% for HW and WC, resp.) and NH3 (av. 43.4 and 74% for HW and WC, resp.) concns. GC-MS-O aromagram results showed both treatments reached high odor redn. efficiency (av. 99.4 and 99.8% for HW and WC, resp.). The results also showed that maintaining proper moisture content and a min. EBRT are crit. to the success of wood chip-based biofilters.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1MXmt1Sgu7c%253D&md5=c5c06f52ec55cce1e2a8ec80052e4435
    17. 17
      Peng, F.; Gao, Y.; Zhu, X.; Pang, Q.; Wang, L.; Xu, W.; Yu, J.; Gao, P.; Huang, J.; Cui, Y. Removal of High-Strength Ammonia Nitrogen in Biofilters: Nitrifying Bacterial Community Compositions and Their Effects on Nitrogen Transformation. Water 2020, 12 (3), 712,  DOI: 10.3390/w12030712
      17
      Removal of high-strength ammonia nitrogen in biofilters: nitrifying bacterial community compositions and their effects on nitrogen transformation
      Peng, Fuquan; Gao, Yuexiang; Zhu, Xiang; Pang, Qingqing; Wang, Longmian; Xu, Wenwen; Yu, Jianghua; Gao, Pengcheng; Huang, Jingxian; Cui, Yibin
      Water (Basel, Switzerland) (2020), 12 (3), 712CODEN: WATEGH; ISSN:2073-4441. (MDPI AG)
      Increasing attention has been given to the treatment of livestock and poultry wastewater because of its high ammonium nitrogen (NH4 +-N) content and low carbon/nitrogen ratio (C/N). Ceramic filter medium (CFM) and dewatered aluminum sludge (DAS), which are products from cast-off materials, are used as small-scale combined biol. filters (CFM-DAS) for wastewater treatment. The high and stale removal efficiency of COD (COD), NH4+-N, and total nitrogen (TN) in the DAS filter indicate that DAS plays a major role in pollutant removal. Although significant differences are found between the compn. of nitrifying bacteria in CFM and DAS, the structures of nitrifying communities are evenly distributed in each layer of CFM or DAS irresp. of the running time. Microbial compns. are attributed to the comprehensive effect of various environmental factors such as pH and TN at effluents. In the DAS, Nitrosospira shows significant neg. correlation with the concns. of NH4+-N in effluents, whereas it has pos. correlation with NO3--N, and Nitrososphaera has a significant neg. correlation with NO3--N in effluents. Pearson correlation test reveals that certain genera may be used in estg. or predicting NH4 +-N consumption and NO3--N accumulation in CFM-DAS for treating sewage with a high NH4+-N content.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsFKrsLbL&md5=eb6bf74eec688456a98d7387898337c1
    18. 18
      Rieth, A. J.; Dincă, M. Controlled Gas Uptake in Metal–Organic Frameworks with Record Ammonia Sorption. J. Am. Chem. Soc. 2018, 140 (9), 3461– 3466,  DOI: 10.1021/jacs.8b00313
      18
      Controlled gas uptake in metal-organic frameworks with record ammonia sorption
      Rieth, Adam J.; Dinca, Mircea
      Journal of the American Chemical Society (2018), 140 (9), 3461-3466CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Ammonia is a vital commodity in our food supply chain, but its toxicity and corrosiveness require advanced protection and mitigation. These needs are not met efficiently by current materials, which suffer from either low capacity or low affinity for NH3. Here, we report that a series of microporous triazolate metal-org. frameworks contg. open metal sites exhibit record static and dynamic ammonia capacities. Under equil. conditions at 1 bar, the materials adsorb up to 19.79 mmol NH3 g-1, more than twice the capacity of activated carbon, the industry std. Under conditions relevant to personal protection equipment, capacities reach 8.56 mmol g-1, 27% greater than the previous best material. Structure-function relationships and kinetic analyses of NH3 uptake in isostructural micro- and mesoporous materials made from Co, Ni, and Cu reveal stability trends that are in line with the water substitution rates in simple metal-aquo complexes. Altogether, these results provide clear, intuitive descriptors that govern the static and dynamic uptake, kinetics, and stability of MOF sorbents for strongly interacting gases.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXisVGktr4%253D&md5=aa831bb4b13c974c56849071da7a1d73
    19. 19
      Takahashi, A.; Tanaka, H.; Parajuli, D.; Nakamura, T.; Minami, K.; Sugiyama, Y.; Hakuta, Y.; Ohkoshi, S.; Kawamoto, T. Historical Pigment Exhibiting Ammonia Gas Capture beyond Standard Adsorbents with Adsorption Sites of Two Kinds. J. Am. Chem. Soc. 2016, 138 (20), 6376– 6379,  DOI: 10.1021/jacs.6b02721
      19
      Historical Pigment Exhibiting Ammonia Gas Capture beyond Standard Adsorbents with Adsorption Sites of Two Kinds
      Takahashi, Akira; Tanaka, Hisashi; Parajuli, Durga; Nakamura, Tohru; Minami, Kimitaka; Sugiyama, Yutaka; Hakuta, Yukiya; Ohkoshi, Shin-ichi; Kawamoto, Tohru
      Journal of the American Chemical Society (2016), 138 (20), 6376-6379CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      Prussian blue is a historical pigment synthesized for the first time at the beginning of 18th century. Here we demonstrate that the historical pigment exhibits surprising adsorption properties of gaseous ammonia. Prussian blue shows 12.5 mmol/g of ammonia capacity at 0.1 MPa, whereas std. ammonia adsorbents show only 5.08-11.3 mmol/g. Dense adsorption was also obsd. for trace contamination in atm. Results also show higher adsorption by Prussian blue analogs with the optimization of chem. compn. The resp. capacities of cobalt hexacyanocobaltate (CoHCC) and copper hexacyanoferrate (CuHCF) were raised to 21.9 and 20.2 mmol/g, the highest value among the recyclable adsorbents. Also, CoHCC showed repeated adsorption in vacuum. CuHCF showed regeneration by acid washing. The chem. state of the adsorbed ammonia depends on the presence of the water in atm.: NH3, which was stored as in the dehydrated case, was converted into NH4+ in the hydrated case.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XntlCnsb4%253D&md5=e11c279799ad669c68d7b58a46452b9e
    20. 20
      Van Humbeck, J. F.; McDonald, T. M.; Jing, X.; Wiers, B. M.; Zhu, G.; Long, J. R. Ammonia Capture in Porous Organic Polymers Densely Functionalized with Bro̷nsted Acid Groups. J. Am. Chem. Soc. 2014, 136 (6), 2432– 2440,  DOI: 10.1021/ja4105478
      20
      Ammonia Capture in Porous Organic Polymers Densely Functionalized with Bronsted Acid Groups
      Van Humbeck, Jeffrey F.; McDonald, Thomas M.; Jing, Xiaofei; Wiers, Brian M.; Zhu, Guangshan; Long, Jeffrey R.
      Journal of the American Chemical Society (2014), 136 (6), 2432-2440CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)
      The elimination of specific environmental and industrial contaminants, which are hazardous at only part per million to part per billion concns., poses a significant technol. challenge. Adsorptive materials designed for such processes must be engendered with an exceptionally high enthalpy of adsorption for the analyte of interest. Rather than relying on a single strong interaction, the use of multiple chem. interactions is an emerging strategy for achieving this requisite phys. parameter. Herein, we describe an efficient, catalytic synthesis of diamondoid porous org. polymers densely functionalized with carboxylic acids. Phys. parameters such as pore size distribution, application of these materials to low-pressure ammonia adsorption, and comparison with analogous materials featuring functional groups of varying acidity are presented. In particular, BPP-5, which features a multiply interpenetrated structure dominated by <6 Å pores, is shown to exhibit an uptake of 17.7 mmol/g at 1 bar, the highest capacity yet demonstrated for a readily recyclable material. A complementary framework, BPP-7, features slightly larger pore sizes, and the resulting improvement in uptake kinetics allows for efficient adsorption at low pressure (3.15 mmol/g at 480 ppm). Overall, the data strongly suggest that the spatial arrangement of acidic sites allows for cooperative behavior, which leads to enhanced NH3 adsorption.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1eitbs%253D&md5=37866eb89fa69650ce234a3f986b012d
    21. 21
      Welsh, F. S. Particle Characteristics of Prussian Blue in an Historical Oil Paint. J. Am. Inst. Conserv. 1988, 27 (2), 55– 63,  DOI: 10.1179/019713688806046292
      There is no corresponding record for this reference.
    22. 22
      Loos-Neskovic, C.; Dierkes, M. H. H.; Jackwerth, E.; Fedoroff, M.; Garnier, E. Fixation of Palladium on Insoluble Simple or Complex Cyano Compounds. Hydrometallurgy 1993, 32 (3), 345– 363,  DOI: 10.1016/0304-386X(93)90046-G
      22
      Fixation of palladium on insoluble simple or complex cyano compounds
      Loos-Neskovic, C.; Dierkes, M. H.; Jackwerth, E.; Fedoroff, M.; Garnier, E.
      Hydrometallurgy (1993), 32 (3), 345-63CODEN: HYDRDA; ISSN:0304-386X.
      In order to propose a method for Pd recovery from industrial waste solns. a systematic study of the kinetics and retention capacity on several insol. cyano compds. (simple cyanides, hexacyanoferrates II and III, and hexacyanomanganates) was performed. Sorbents were prepd. either by pptn., or by a method of local growth producing large particles, or by deposition on a carrier material. Among the products studies, nickel hexacyanoferrates II and copper hexacyanoferrates II and III seem to be the most promising. The highest retention capacity was achieved with a copper hexacyanoferrate III prepd. by local growth. The mechanisms of fixation seem to be ion exchange with an oxidn.-redn. process in certain cases.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK3sXitlyisrw%253D&md5=9359b9e40aa1aa56d9a3b3e40f3b06c6
    23. 23
      Manakasettharn, S.; Takahashi, A.; Kawamoto, T.; Noda, K.; Sugiyama, Y.; Nakamura, T. Differences in NH3 Gas Adsorption Behaviors of Metal-Hexacyanoferrate Nanoparticles (M [FeII(CN)6] ·zH2O: M = In3+, Fe3+, and Mn2+). J. Solid State Chem. 2019, 270, 112– 117,  DOI: 10.1016/j.jssc.2018.10.026
      23
      Differences in NH3 gas adsorption behaviors of metal-hexacyanoferrate nanoparticles (Mx[FeII(CN)6]y·zH2O:M = In3+, Fe3+, and Mn2+)
      Manakasettharn, Supone; Takahashi, Akira; Kawamoto, Tohru; Noda, Keiko; Sugiyama, Yutaka; Nakamura, Tohru
      Journal of Solid State Chemistry (2019), 270 (), 112-117CODEN: JSSCBI; ISSN:0022-4596. (Elsevier B.V.)
      Three different metal hexacyanoferrate nanoparticles (M-HCF-NPs, M = In3+, Fe3+, and Mn2+) were characterized by XRD, SEM, elemental analyses, IR and isotherm measurements. The obtained M-HCF-NPs prepd. by a simple mixing procedure have a Prussian blue-type cubic crystal structure and sizes of ∼20 nm. The chem. compns. measured by the elemental analyses are In-HCF = K0.039In[Fe(CN)6]0.75·Cl0.032·3.8H2O, Fe-HCF (PB) = K0.18Fe[Fe(CN)6]0.80·3.8H2O, and Mn-HCF = K1.3Mn[Fe(CN)6]0.84·1.3H2O. Ammonia gas isotherms under vacuum revealed that the ammonia adsorption capacity of the M-HCF-NPs is in order of Mn < In << Fe; however, the ammonia gas adsorption of In-HCF-NPs is faster than those of the Fe-HCF and Mn-HCF-NPs. This difference is considered to be caused by individual M-HCF structures, such as the vacancies in the HCF crystals, and by the interaction of individual M-HCF toward water mols., which promote the conversion of NH3 species into stable NH+4 cations in M-HCF.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXit1eit77L&md5=ab2cf6d9875061a83a7bb953c4063211
    24. 24
      Parajuli, D.; Kitajima, A.; Takahashi, A.; Tanaka, H.; Ogawa, H.; Hakuta, Y.; Yoshino, K.; Funahashi, T.; Yamaguchi, M.; Osada, M.; Kawamoto, T. Application of Prussian Blue Nanoparticles for the Radioactive Cs Decontamination in Fukushima Region. J. Environ. Radioact. 2016, 151, 233– 237,  DOI: 10.1016/j.jenvrad.2015.10.014
      24
      Application of Prussian blue nanoparticles for the radioactive Cs decontamination in Fukushima region
      Parajuli, Durga; Kitajima, Akiko; Takahashi, Akira; Tanaka, Hisashi; Ogawa, Hiroshi; Hakuta, Yukiya; Yoshino, Kazunori; Funahashi, Takayuki; Yamaguchi, Masaki; Osada, Mitsuo; Kawamoto, Tohru
      Journal of Environmental Radioactivity (2016), 151 (Part_1), 233-237CODEN: JERAEE; ISSN:0265-931X. (Elsevier Ltd.)
      Cs decontamination efficiencies of the composites of iron hexacyanoferrate nanoparticles were investigated in comparison with com. Prussian blue and natural zeolite. In pure water soln., the adsorption rate varied with sizes. In ash ext., where Cs adsorbing ability of zeolite was sharply dropped due to its poor selectivity, the impact of coexisting ions was negligible for FeHCF. FeHCF-n11, having the finest primary and secondary particle size, resulted the highest distribution coeff., which was comparable to the high efficiency analogs, CoHCF or NiHCF. This observation suggested the possibility of prepg. the high performance FeHCF by particle size and compn. adjustment. FeHCF nanoparticle in bead form was tested for the removal of radioactive Cs in pilot scale. Due to larger secondary particle size, pronounced effect of soln. temp. on the Cs adsorption kinetics on FeHCF bead was obsd. Adjusting the mass of the adsorbent for the given soln. temp. is recommended for achieving high decontamination rate.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslCqu7%252FK&md5=e23a6b52fbcf1bab3341470d288a4400
    25. 25
      Takahashi, A.; Minami, K.; Noda, K.; Sakurai, K.; Kawamoto, T. Trace Ammonia Removal from Air by Selective Adsorbents Reusable with Water. ACS Appl. Mater. Interfaces 2020, 12 (13), 15115– 15119,  DOI: 10.1021/acsami.9b22384
      25
      Trace Ammonia Removal from Air by Selective Adsorbents Reusable with Water
      Takahashi, Akira; Minami, Kimitaka; Noda, Keiko; Sakurai, Koji; Kawamoto, Tohru
      ACS Applied Materials & Interfaces (2020), 12 (13), 15115-15119CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)
      NH3 adsorbents, effective even at trace concns., are key counter-measures for particulate air pollution due to NH3 emissions from the agriculture sector. Prussian blue (PB) and its analogs (PBA), porous coordination polymers, have higher NH3 adsorption capacity for 10 ppmv NH3 (ppm in vol., 10 ppmv = 0.0001 vol. percent), ≥8 times that of conventional adsorbents. These compds. can be recycled only via water flushing. The PBA adsorption capacity was restricted to 10 adsorption/desorption cycles; the exptl. air sample was collected from a swine farm composting app. Despite the presence of satd. water vapor in the waste gas, the adsorbents displayed excellent selectivity for NH3 removal from the sample.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXktlOiur4%253D&md5=f29d786f38396e256e738367d56e9a3f
    26. 26
      Usuda, H.; Sakurai, K.; Takahashi, A.; Kawamoto, T.; Minami, K. Ammonium Salt Production in NH3-CO2-H2O System Using a Highly Selective Adsorbent, Copper Hexacyanoferrate. Environ. Pollut. 2021, 288 (June), 117763  DOI: 10.1016/j.envpol.2021.117763
      26
      Ammonium salt production in NH3-CO2-H2O system using a highly selective adsorbent, copper hexacyanoferrate
      Usuda, Hatsuho; Sakurai, Koji; Takahashi, Akira; Kawamoto, Tohru; Minami, Kimitaka
      Environmental Pollution (Oxford, United Kingdom) (2021), 288 (), 117763CODEN: ENPOEK; ISSN:0269-7491. (Elsevier Ltd.)
      Ammonia is a beneficial material that is widely used in agriculture, but its emission into the atm. causes air pollution. Recently, Prussian blue (PB) and its analogs (PBA) were found to be ammonia adsorbents with high selectivity and capacity. In this study, we utilized a highly potent PBA adsorbent, copper hexacyanoferrate (CuHCF), to desorb ammonia and turn it into a reusable form. Because the reported NH3-CO2-H2O system phase diagram suggests the possibility of the recovery of solid NH4HCO3, we examd. whether adsorbed ammonia desorbs into the satd. ammonium hydrogencarbonate soln. (sat. NH4HCO3aq). We demonstrated that 40% of adsorbed ammonia desorbed into sat. NH4HCO3aq. After the desorption, CO2 was blown into the washing liq., and NH4HCO3 pptd., which was confirmed by Fourier transform IR spectroscopy. The molar amt. of solid NH4HCO3 was almost equal to that of desorbed ammonia. Our findings pave the way for recovery of ammonia as a valuable product from waste gas.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXhsFOrsrnN&md5=9d388e4da43f71bcda7c2c94a15e8667
    27. 27
      Takahashi, A.; Minami, K.; Noda, K.; Sakurai, K.; Kawamoto, T. Harvesting a Solid Fertilizer Directly from Fetid Air. ACS Sustainable Chem. Eng. 2021, 9 (50), 16865– 16869,  DOI: 10.1021/acssuschemeng.1c06161
      27
      Harvesting a Solid Fertilizer Directly from Fetid Air
      Takahashi, Akira; Minami, Kimitaka; Noda, Keiko; Sakurai, Koji; Kawamoto, Tohru
      ACS Sustainable Chemistry & Engineering (2021), 9 (50), 16865-16869CODEN: ASCECG; ISSN:2168-0485. (American Chemical Society)
      The application of air as a resource for food prodn. and in other industries is a promising route for achieving a sustainable human society. Herein, we demonstrated the harvesting of solid-state ammonium bicarbonate from fetid air in an actual piggery. The process was achieved by condensation and sublimation, using new selective adsorbents of a copper Prussian blue analog for trace ammonia, which enabled the utilization of use air as a resource and the redn. of harmful chems. in the air.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3MXisFymsLrO&md5=944e9a15d9073ff0a51887343c83f8ca
    28. 28
      Minami, K.; Takahashi, A.; Sakurai, K.; Mikasa, H.; Takasaki, M.; Doshu, N.; Aoyama, K.; Nakamura, T.; Iwai, R.; Kawamoto, T. Apparatus for Ammonia Removal in Livestock Farms Based on Copper Hexacyanoferrate Granules. Biosyst. Eng. 2022, 216, 98– 107,  DOI: 10.1016/j.biosystemseng.2022.02.002
      28
      Apparatus for ammonia removal in livestock farms based on copper hexacyanoferrate granules
      Minami, Kimitaka; Takahashi, Akira; Sakurai, Koji; Mikasa, Hiroaki; Takasaki, Mikihiro; Doshu, Naoaki; Aoyama, Katsuya; Nakamura, Tohru; Iwai, Ryota; Kawamoto, Tohru
      Biosystems Engineering (2022), 216 (), 98-107CODEN: BEINBJ; ISSN:1537-5110. (Elsevier Ltd.)
      Ammonia generated by livestock is a source of strong odor and pollution. In livestock management, ammonia neg. impacts not only animal health, but also productivity. A large-capacity and high-selectivity ammonia adsorbent that can be regenerated with water or dil. acids has been previously developed. In this study, ammonia adsorption and adsorbent regeneration apparatuses using this adsorbent are constructed and tested for ammonia removal in a pig house. The ammonia adsorption app. adsorbed approx. 0.36 mol of ammonia per h, and the adsorbent regeneration app. desorbed approx. 75% of ammonia adsorbed to the satd. adsorbent over four days. These systems allowed ammonia concn. and temp. to be controlled in closed pigpens, and their effectiveness was verified by rearing 20 pigs in a 21.6 m2 pigpen. In winter, the ammonia concn. in the exptl. area was suppressed to 10 ppmv or less, even with low ventilation, and was 4-7°C warmer than the open control area. As a result, the av. daily wt. gain of the pigs increased by approx. 9% and 7% compared to those of pigs in the closed and open control areas, resp. In summer, the ammonia concn. was 45-70% lower than that of the closed control area. The feed conversion ratio of pigs in the research area was approx. 6% and 9% lower than those of pigs in the closed and open control areas, resp.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB38XhvFCkt7jM&md5=ea2c047a3112b68a9e2d66bc1f225c69
    29. 29
      Usuda, H.; Mishima, Y.; Kawamoto, T.; Minami, K. Desorption of Ammonia Adsorbed on Prussian Blue Analogs by Washing with Saturated Ammonium Hydrogen Carbonate Solution. Mol. 2022, 27 (24), 8840,  DOI: 10.3390/molecules27248840
      29
      Desorption of Ammonia Adsorbed on Prussian Blue Analogs by Washing with Saturated Ammonium Hydrogen Carbonate Solution
      Usuda, Hatsuho; Mishima, Yoshie; Kawamoto, Tohru; Minami, Kimitaka
      Molecules (2022), 27 (24), 8840CODEN: MOLEFW; ISSN:1420-3049. (MDPI AG)
      Prussian blue analogs (PBAs) have been reported as promising ammonia (NH3) adsorbents with a high capacity compared to activated carbon, zeolite, and ion exchange resins. The adsorbed NH3 was desorbed by heating and washing with water or acid. Recently, we demonstrated that desorption was also possible by washing with a satd. ammonium hydrogen carbonate soln. (sat. NH4HCO3aq) and recovered NH3 as an NH4HCO3 solid by introducing CO2 into the washing liq. after desorption. However, this has only been proven for copper ferrocyanide and the relationship between the adsorption/desorption behavior and metal ions in PBAs has not been identified. In this study, we investigated the adsorption/desorption behavior of PBAs that are complexes of first row transition metals with hexacyanometalate anions. Six types of PBAs were tested in this study and copper ferricyanide exhibited the highest desorption/adsorption ratio. X-ray diffraction results revealed high structural stability for cobalt hexacyanocobaltate (CoHCC) and nickel ferricyanide (NiHCF). The Fourier transform IR spectroscopy results showed that the NH3 adsorbed on the vacancy sites tended to desorb compared to the NH3 adsorbed on the interstitial sites as ammonium ions. Interestingly, the desorption/adsorption ratio exhibited the Irving-Williams order.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3sXktlantQ%253D%253D&md5=acd96a50a9defd64d7daca978358fb73
    30. 30
      Wessells, C. D.; Peddada, S. V.; Huggins, R. A.; Cui, Y. Nickel Hexacyanoferrate Nanoparticle Electrodes For Aqueous Sodium and Potassium Ion Batteries. Nano Lett. 2011, 11 (12), 5421– 5425,  DOI: 10.1021/nl203193q
      30
      Nickel Hexacyanoferrate Nanoparticle Electrodes For Aqueous Sodium and Potassium Ion Batteries
      Wessells, Colin D.; Peddada, Sandeep V.; Huggins, Robert A.; Cui, Yi
      Nano Letters (2011), 11 (12), 5421-5425CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)
      The elec. power grid faces a growing need for large-scale energy storage over a wide range of time scales due to costly short-term transients, frequency regulation, and load balancing. The durability, high power, energy efficiency, and low cost needed for grid-scale storage pose substantial challenges for conventional battery technol. Here, we demonstrate insertion/extn. of sodium and potassium ions in a low-strain nickel hexacyanoferrate electrode material for at least five thousand deep cycles at high current densities in inexpensive aq. electrolytes. Its open-framework structure allows retention of 66% of the initial capacity even at a high (41.7C) rate. At low current densities, its round trip energy efficiency reaches 99%. This low-cost material is readily synthesized in bulk quantities. The long cycle life, high power, good energy efficiency, safety, and inexpensive prodn. method make nickel hexacyanoferrate an attractive candidate for use in large-scale batteries to support the elec. grid.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXhtl2ktL7J&md5=d1ee3adb1a2dd638a729df1cfdf03be8
    31. 31
      Shrivastava, A.; Liu, S.; Smith, K. C. Linking Capacity Loss and Retention of Nickel Hexacyanoferrate to a Two-Site Intercalation Mechanism for Aqueous Mg 2+ and Ca 2+ Ions †. Phys. Chem. Chem. Phys. 2019, 21, 20177– 20188,  DOI: 10.1039/C9CP04115J
      31
      Linking capacity loss and retention of nickel hexacyanoferrate to a two-site intercalation mechanism for aqueous Mg2+ and Ca2+ ions
      Shrivastava, Aniruddh; Liu, Sizhe; Smith, Kyle C.
      Physical Chemistry Chemical Physics (2019), 21 (36), 20177-20188CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)
      Prussian blue analogs (PBAs) are promising cation intercalation materials for electrochem. desalination and energy storage applications. Here, we investigate the mechanism of capacity fade and degrdn. of nickel hexacyanoferrate (NiHCFe) during galvanostatic cycling in aq. electrolytes that are rich in either Mg2+ or Ca2+. We combine exptl. characterization, first principles electronic structure calcns., statistical mechanics and lattice-percolation modeling of electron transfer to elucidate the mechanisms responsible for the degrdn. of NiHCFe and its partial retention of capacity. Electrochem. characterization of porous NiHCFe electrodes suggests a two-site intercalation mechanism, while spectroscopy reveals the presence of Ni2+ and Fe(CN)63- ions in the electrolyte post cycling in Mg2+(aq). Using simple copptn. reactions, we show that Mg2+ and Ni2+ can coexist in the lattice framework, forming stable PBAs. Galvanostatic cycling of these PBAs shows that the presence of Mg2+ in the lattice framework results in the dissoln. of Mg1.5FeIII(CN)6 in water during oxidn. We propose that Mg2+ can partially substitute Ni2+ ions in the lattice framework during galvanostatic cycling, displacing the substituted Ni2+ ions into interstitial sites. Based on differential capacitance anal. we show that Mg2+ intercalates into interstitial sites at ∼0.45 V vs. Ag/AgCl and it displaces Ni2+ in the lattice framework at ∼0.05 V vs. Ag/AgCl. Substitution of Ni2+ leads to Fe(CN)63- and Ni2+ ions being removed into the electrolyte during oxidn. Using first principles d. functional theory (DFT) calcns. combined with a statistical mechanics model, we verify the thermodn. feasibility of the proposed reaction mechanism and predict the fraction of Ni2+ ions being substituted by Mg2+ during intercalation. Further, anal. of the electron d. distribution and local d. of states indicates that Mg2+ ions can act as insulating defects in the lattice framework that render certain Fe ions elec. inactive and likely contribute to capacity fade along with dissoln. of Fe(CN)63-.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhs1Gkt7vI&md5=190bbe68fe7cd1f3ad55d3e25b2c746c
    32. 32
      Hall, H. K. Correlation of the Base Strengths of Amines. J. Am. Chem. Soc. 1957, 79 (20), 5441– 5444,  DOI: 10.1021/ja01577a030
      32
      Correlation of the base strengths of amines
      Hall, H. K., Jr.
      Journal of the American Chemical Society (1957), 79 (), 5441-4CODEN: JACSAT; ISSN:0002-7863.
      The base strengths of 25 primary, 21 secondary, and 31 tertiary nonaromatic amines were plotted against the Taft σ*-values (cf. C.A. 51, 17719i). Each class of amines lay on a different line; this indicates that solvation of the ammonium ion through the N+H bonds plays an important role in detg. base strength. All tertiary amines gave an excellent correlation with the sum of the σ* values, regardless of their degree of steric hindrance. This suggests that B-strain is not a factor detg. the pKa value. For secondary and primary amines, only those amines with a low degree of steric hindrance gave a linear plot against σ* values. This is also incompatible with the B-strain theory (for the primary amines), but in good agreement with the solvation theory if solvation of the ammonium ion is regarded as subject to hindrance. These correlations permit the prediction of the pKa values of new amines.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaG1cXpslCg&md5=b3b33f0cfad8fcae79e11c9fbbf88b87
    33. 33
      National Astronomical Observatory of Japan. Handbook of Scientific Tables; Maruzen Publishing Co., Ltd., 2012.
      There is no corresponding record for this reference.
    34. 34
      Khanna, R. K.; Moore, M. H. Carbamic Acid: Molecular Structure and IR Spectra. Spectrochim. Acta A Mol. Biomol. Spectrosc. 1999, 55 (5), 961– 967,  DOI: 10.1016/S1386-1425(98)00228-5
      34
      Carbamic acid: molecular structure and IR spectra
      Khanna, R. K.; Moore, M. H.
      Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (1999), 55A (5), 961-967CODEN: SAMCAS; ISSN:1386-1425. (Elsevier Science B.V.)
      IR absorption spectra of mixed H2O, NH3 and 12CO2/13CO2 ices subjected to 1 MeV proton irradn. were studied. The results of analyses of the spectra suggest formation of carbamic acid at low temps. The stability of this compd. in the solid phase is attributed to intermol. H bonding of the zwitterion (NH3+COO-) structure.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK1MXivVyrsbY%253D&md5=ee72e95efcce50341c937e7667294353
    35. 35
      Tao, W.; Ukwuani, A. T. Coupling Thermal Stripping and Acid Absorption for Ammonia Recovery from Dairy Manure: Ammonia Volatilization Kinetics and Effects of Temperature, PH and Dissolved Solids Content. Chem. Eng. J. 2015, 280, 188– 196,  DOI: 10.1016/j.cej.2015.05.119
      35
      Coupling thermal stripping and acid absorption for ammonia recovery from dairy manure: Ammonia volatilization kinetics and effects of temperature, pH and dissolved solids content
      Tao, Wendong; Ukwuani, Anayo T.
      Chemical Engineering Journal (Amsterdam, Netherlands) (2015), 280 (), 188-196CODEN: CMEJAJ; ISSN:1385-8947. (Elsevier B.V.)
      Both liq. dairy manure and manure digestate have high concns. of ammonia. This study coupled thermal stripping with acid absorption to recover ammonia from dairy manure as ammonium sulfate. Ammonia volatilization kinetics and effects of temp., pH, and dissolved solids content on thermal stripping were studied in batch expts. Statistically insignificant differences were found in ammonium sulfate formation and liq. mass transfer of ammonia between the expts. with initial a feed pH of 11 and 9 and between the expts. with filtrate of undigested and digested manure, which have different dissolved solids contents. Temp. had significant effects on thermal stripping of ammonia. When temp. was set at the b.ps. (101-102°) of manure filtrate, ammonia was completely stripped in 3-4 h. It took 5 h to strip 50% of ammonia at 97°. Little ammonia was stripped at 86 and 76°. The satn. concns. of ammonia in manure filtrate was zero at 76-102°. Ammonia mass transfer coeff. upon boiling was 30.3-31.4 mm/h in manure filtrate. Ammonia mass transfer coeff. increased exponentially with temp., indicating a temp. coeff. of 1.164. High-purity ammonium sulfate crystals (≥98%) were produced when sulfuric acid solns. were pre-satd. with ammonium sulfate. When ammonia was completely stripped, ammonium sulfate was formed at 3.70-3.87 g/L filtrate. A preliminary economic anal. shows that this novel technol. is economically promising for practical application, esp. when it is applied to a side-stream of anaerobic digesters.
      >> More from SciFinder ®
      https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVais7rN&md5=d255bece226267a8e4f86ba39b7c86a4

  • Supporting Information

    Supporting Information

    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acssuschemeng.3c05679.

    • Experimental setup of NH3 adsorption and desorption; additional results of characterization of the NiHCF adsorbent; and CO2 concentration in the outlet gas during adsorption (PDF)


    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.