This work was primarily supported by ARPA-E, a part of the US Department of Energy, by the Minnesota Environment and Natural Resources Trust Fund, as recommended the Legislative-Citizen Commission on Minnesota Resources, and by MNDRIVE, an initiative of the University of Minnesota. Additional support came from the Dreyfus Foundation.

1. Pilot Plant Start-up
<ol>
	<li>Nitrogen production system
	<ol>
		<li>Turn on the air dryer, the air compressor, and the nitrogen generator. Verify that there is at least 800 kPa of air in the air compressor tank. This keeps sending nitrogen to the buffer tank until there is no more than 0.004% (40 ppm) oxygen in the nitrogen.</li>
		<li>Turn on the nitrogen gas booster. The gas booster starts to fill the nitrogen supply tanks, at pressures as high as 17 MPa.</li>
	</ol>
	</li>
	<li>Hydrogen production system
	<ol>
		<li>Turn on the chiller, the water deionization unit, and the electrolyzer. The electrolyzer will not operate without a venting system, because there is a flow sensor that measures the negative pressure venting in order to let the electrolyzer start. The hydrogen is produced with a rate of 0.54 kg/h, and the discharge pressure will be about 1.5 MPa.</li>
		<li>Turn on the hydrogen gas booster. Verify that the chiller is operational and the cooling liquid is flowing through. The hydrogen supply tanks will be filled up to 17 MPa.</li>
	</ol>
	</li>
	<li>Ammonia skid start-up
	<ol>
		<li>Use the computer in the control room to do the following:
		<ol>
			<li>Verify the emergency exits for the building.</li>
			<li>Make sure that the oxygen, hydrogen, and ammonia concentrations in the building are less than 20%, 19 ppm, and 35 ppm, respectively.</li>
			<li>Verify that the hydrogen and nitrogen supply tanks are charged to 17 MPa.</li>
			<li>Make sure that the ammonia sampler and the weight tank valves are bypassed.</li>
			<li>Pressurize the skid with nitrogen by setting the skid&#39;s nitrogen inlet regulator to 2.5 MPa. Set the nitrogen pressure regulator to 300 psi and then open the nitrogen bypass valve to fill the skid with nitrogen to 300 psi. Then close the nitrogen valve when that pressure is reached. Set the hydrogen regular to 1,200 psi and open the hydrogen valve to allow the skid to fill to 1,200 psi. Then close the hydrogen bypass valve.</li>
			<li>Open the hydrogen inlet valve and set the skid&#39;s hydrogen inlet regulator to 10 MPa.</li>
			<li>Set the NH3 pressure regulator to 1 MPa.</li>
			<li>Use the GUI controlling software to close/open multiple bypass valves on the skid, the compressor, and the air valves.</li>
			<li>Use the GUI controlling software to turn a couple of the PID controllers to ensure that the skid is fed with a 1:3 ratio of N2:H2.</li>
			<li>From the control room, and using the master GUI controlling software, start the skid. The compressor starts to recirculate the gas in the skid, and inject the fresh feed.</li>
			<li>In the GUI controlling software, set the reaction and condensation temperature. The reactor and condenser temperatures are set at 440 &#176;C and -25 &#176;C, respectively. 
			NOTE: It takes up to 4 days for the reactor to get to the set point temperature and achieve a steady state condition.</li>
		</ol>
		</li>
	</ol>
	</li>
</ol>
2. Experimental Apparatus Start-up
<ol>
	<li>Reactor preparation and reduction
	<ol>
		<li>Weigh 3 g of the pre-reduced catalyst. Reduce the particle size of the catalyst particles to less than 1 mm using a mortar and pestle.</li>
		<li>Load the catalyst into 0.25 in tubing, and place quartz wool on both sides.</li>
		<li>Use a PID controller, and increase the reactor temperature to the reaction temperature (400 &#176;C) with appropriate ramps, while flowing hydrogen through the reactor with a flow rate of 500 standard cubic centimeters per minute (SCCM). Use the ramps (summarized in Table 1). 
		NOTE: The temperature increase should be very smooth in order to obtain the proper catalyst activity.</li>
		<li>Continue the reduction process for 24 h. Ensure that no air or impurity comes into contact with the catalyst. Always keep the reactor under a nitrogen blanket.</li>
	</ol>
	</li>
	<li>Absorber preparation
	<ol>
		<li>Load 80 g of the CaCl2 absorbent into the absorber column (ID: 2.3 cm, Length: 30 cm). According to different absorbent sizes, different absorber packing supports will be used on both sides of the absorber, in order to immobilize the packed bed.</li>
		<li>To remove any humidity, increase the absorber temperature to 350 &#176;C while flowing nitrogen with the flow rate of 200 SCCM for 24 h.</li>
	</ol>
	</li>
	<li>Starting reaction separation tests
	<ol>
		<li>Increase the reactor and absorber temperature to 400 &#176;C and 180 &#176;C, respectively. 
		NOTE: Use proper temperature ramps to increase the reactor temperature. Use transformers to make the temperature control smoother. Keep the system in idle mode under the nitrogen blanket. Before starting any test, charge the system with nitrogen to 5 MPa a few times, and then release the pressure.</li>
		<li>Use the GUI to control the hydrogen and nitrogen mass flow controllers.</li>
		<li>Charge the apparatus to the target pressures with nitrogen and hydrogen, with the ratio of 1:3.</li>
		<li>Once the target pressure is achieved, close the inlet valves, open the reactor outlet valve, and turn on the recirculating pump. Due to the exothermic reaction and absorption, the reactor and absorber temperatures might require more careful control at the beginning of the process.</li>
		<li>Continue the test for 5 h, until the point when the absorber starts to breakthrough.</li>
	</ol>
	</li>
	<li>Desorption of ammonia
	<ol>
		<li>Open the inlet and outlet valves.</li>
		<li>Reduce the system&#39;s pressure to atmospheric pressure and increase the temperature of the absorber while flowing nitrogen with a flow rate of 100 SCCM for 5 h to desorb ammonia from the absorbent material.</li>
	</ol>
	</li>
</ol>

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	<li>Erisman, J. W., Sutton, M. A., Galloway, J., Klimont, Z., Winiwarter, W. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=How+a+century+of+ammonia+synthesis+changed+the+world.">How a century of ammonia synthesis changed the world.</a> Nat Geosci. 1 (10), 636-639 (2008).</li><li>Vojvodic, A., Medford, A. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Exploring+the+limits:+A+low-pressure,+low-temperature+Haber-Bosch+process.">Exploring the limits: A low-pressure, low-temperature Haber-Bosch process.</a> Chem Phys Lett. 598, 108-112 (2014).</li><li>Jennings, J. R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Catalytic Ammonia Synthesis. , (1991).</li><li>. Nitrogen (Fixed) - Ammonia Available from: <a target="_blank" href="https://minerals.usgs.gov/minerals/pubs/commodity/nitrogen/mcs-2016-nitro.pdf">https://minerals.usgs.gov/minerals/pubs/commodity/nitrogen/mcs-2016-nitro.pdf</a> (2016)</li><li>Wojcik, A., Middleton, H., Damopoulos, I., Van herle, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia+as+a+fuel+in+solid+oxide+fuel+cells.">Ammonia as a fuel in solid oxide fuel cells.</a> J Power Sources. 118 (1-2), 342-348 (2003).</li><li>Zamfirescu, C., Dincer, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Using+ammonia+as+a+sustainable+fuel.">Using ammonia as a sustainable fuel.</a> J Power Sources. 185 (1), 459-465 (2008).</li><li>Christensen, C. H., Johannessen, T., S&#248;rensen, R. Z., N&#248;rskov, J. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Towards+an+ammonia-mediated+hydrogen+economy?.">Towards an ammonia-mediated hydrogen economy?.</a> Catalysis Today. 111 (1-2), 140-144 (2006).</li><li>Hummelsh&#248;j, J. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=reversible+high-density+hydrogen+storage+in+compact+metal+ammine+salts.">reversible high-density hydrogen storage in compact metal ammine salts.</a> J Am Chem Soc. 130 (27), 8660-8668 (2008).</li><li>Ni, M., Leung, M. K. H., Leung, D. Y. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia-fed+solid+oxide+fuel+cells+for+power+generation-A+review.">Ammonia-fed solid oxide fuel cells for power generation-A review.</a> Int J Energy Res. 33 (11), 943-959 (2009).</li><li>Zamfirescu, C., Dincer, I. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia+as+a+green+fuel+and+hydrogen+source+for+vehicular+applications.">Ammonia as a green fuel and hydrogen source for vehicular applications.</a> Fuel Process Technol. 90 (5), 729-737 (2009).</li><li>Ertl, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+Science+and+Catalysis-Studies+on+the+Mechanism+of+Ammonia+Synthesis:+The+P.+H.+Emmett+Award+Address.">Surface Science and Catalysis-Studies on the Mechanism of Ammonia Synthesis: The P. H. Emmett Award Address.</a> Catal Rev. 21 (2), 201-223 (2006).</li><li>Nielsen, A., Kjaer, J., Bennie, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rate+equation+and+mechanism+of+ammonia+synthesis+at+industrial+conditions.">Rate equation and mechanism of ammonia synthesis at industrial conditions.</a> J Catal. 3 (1), 68-79 (1964).</li><li>. DE-FOA-0001569 Sustainable Ammonia Synthesis Available from: <a target="_blank" href="https://science.energy.gov/~/media/grants/pdf/foas/2016/SC_FOA_0001569.pdf">https://science.energy.gov/~/media/grants/pdf/foas/2016/SC_FOA_0001569.pdf</a> (2016)</li><li>Sustainable Ammonia Synthesis - Exploring the scientific challenges associated with discovering alternative, sustainable processes for ammonia production. DOE Roundtable Report Available from: <a target="_blank" href="https://science.energy.gov/~/media/bes/pdf/reports/2016/SustainableAmmoniaReport.pdf">https://science.energy.gov/~/media/bes/pdf/reports/2016/SustainableAmmoniaReport.pdf</a> (2016)</li><li>Reese, M., Marquart, C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Performance+of+a+Small-Scale+Haber+Process.">Performance of a Small-Scale Haber Process.</a> Ind Eng Chem Res. 55 (13), 3742-3750 (2016).</li><li>Schl&#246;gl, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Catalytic+Synthesis+of+Ammonia-A+"Never-Ending+Story".">Catalytic Synthesis of Ammonia-A "Never-Ending Story".</a> Ange Chemie Int Ed. 42 (18), 2004-2008 (2003).</li><li>Dyson, D. C., Simon, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetic+Expression+with+Diffusion+Correction+for+Ammonia+Synthesis+on+Industrial+Catalyst.">Kinetic Expression with Diffusion Correction for Ammonia Synthesis on Industrial Catalyst.</a> Ind Eng Chem Fund. 7 (4), 605-610 (1968).</li><li>Temkin, M., Pyzhev, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Kinetics+of+ammonia+synthesis+on+promoted+catalysts.">Kinetics of ammonia synthesis on promoted catalysts.</a> Acta Physiochim USSR. 12, 327-356 (1940).</li><li>Annable, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Application+of+the+Temkin+kinetic+equation+to+ammonia+synthesis+in+large-scale+reactors.">Application of the Temkin kinetic equation to ammonia synthesis in large-scale reactors.</a> Chem Eng Sci. 1 (4), 145-154 (1952).</li><li>Guacci, U., Traina, F., Ferraris, G. B., Barisone, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=On+the+Application+of+the+Temkin+Equation+in+the+Evaluation+of+Catalysts+for+the+Ammonia+Synthesis.">On the Application of the Temkin Equation in the Evaluation of Catalysts for the Ammonia Synthesis.</a> Ind Eng Chem Prod DD. 16 (2), 166-176 (1977).</li><li>Hummelsh&#248;j, J. S., S&#248;rensen, R. Z., Kustova, M. Y., Johannessen, T., N&#248;rskov, J. K., Christensen, C. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Generation+of+nanopores+during+desorption+of+NH3+from+Mg(NH3)6Cl2.">Generation of nanopores during desorption of NH3 from Mg(NH3)6Cl2.</a> J Am Chem Soc. 128 (1), 16-17 (2006).</li><li>Huberty, M. S., Wagner, A. L., McCormick, A., Cussler, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia+absorption+at+haber+process+conditions.">Ammonia absorption at haber process conditions.</a> AIChE Journal. 58 (11), 3526-3532 (2012).</li><li>Himstedt, H. H., Huberty, M. S., McCormick, A. V., Schmidt, L. D., Cussler, E. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia+synthesis+enhanced+by+magnesium+chloride+absorption.">Ammonia synthesis enhanced by magnesium chloride absorption.</a> AIChE Journal. 61 (4), 1364-1371 (2015).</li><li>Malmali, M., Wei, Y., McCormick, A., Cussler, E. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ammonia+Synthesis+at+Reduced+Pressure+via+Reactive+Separation.">Ammonia Synthesis at Reduced Pressure via Reactive Separation.</a> Ind Eng Chem Res. 55 (33), 8922-8932 (2016).</li><li>Wagner, K., Malmali, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Column+absorption+for+reproducible+cyclic+separation+in+small+scale+ammonia+synthesis.">Column absorption for reproducible cyclic separation in small scale ammonia synthesis.</a> AIChE Journal. , (2017).</li></ol>

The authors have nothing to disclose.

Critical Steps of the Reaction-absorption Experimental Apparatus:
Make sure that there is no impurity in the nitrogen and hydrogen system. The absorbent materials will change after each cycle. In most cases, at high temperature and in the presence of ammonia, the absorbent materials fuse and form a large solid concrete. According to the thermodynamic properties of each metal halide and ammine complex, the appropriate temperatures for absorption and desorption should be employed. Before each test,...

Ammonia is a key industrial chemical. It is produced through the Haber-Bosch process, which is known as one of the most important innovations of the 20th century1,2. Ammonia synthesis is carried out in the presence of a heterogeneous catalyst at elevated temperatures (&#62; 375 &#176;C) and pressures (&#62;100 bar)3. Such high temperature and pressure requirements make ammonia synthesis very energy- and capital-intensive. Approximately, 150 million tons of ammonia are produced each year4, which accounts for 1-3% of the world&#39;s energy consumption, 5% of the natural gas consumption, and up to 3% of the climate-changing gas emissions5,6,7.
Ammonia has two major potential uses. First, ammonia is a synthetic nitrogen fertilizer1. Without this fertilizer, half of the current population would not have access to sufficient food. Second, ammonia can serve as an energy vector, either as a carbon-neutral liquid fuel or as an indirect hydrogen carrier8,9,10,11. Typically, renewable resources (e.g. wind) are available in underpopulated rural areas, where it can be captured; this type of isolated wind and solar energy is called &#34;stranded&#34;. In this scenario, the electrical and thermal energies from the renewable energy source are converted to energy-dense carbon-neutral liquid ammonia. The liquid ammonia produced can then be shipped to urban centers, where it can be directly used in ammonia-based fuel cells12 and internal combustion engines13, or it can be decomposed into hydrogen and then be used in hydrogen fuel cells or hydrogen stations. As a result, we can move the wind of the U.S. prairies to the crowded urban areas of the U.S.
Mostly because of the fertilizer use, ammonia manufacture is a major industry. At room temperature, the ammonia synthesis reaction is exothermic and hence&#8212;at least, in principle&#8212;spontaneous14, however, achieving the reaction under ambient conditions is extremely difficult because of the strong nitrogen-nitrogen bond15. To overcome this, Fritz Haber famously used high temperatures to achieve fast kinetics, but these high temperatures meant that the reverse reaction inhibited the production. To reduce the inhibitions of this reverse reaction, Haber used high pressure to improve conversion. He carried out the large-scale reaction in a gun barrel, which still decorates the BASF plant in Ludwigshafen.
The necessity to use both high temperature and pressure when the reaction could potentially run under much more modest conditions has frustrated chemists for over a century2. Even after the process was commercialized, Karl Bosch and a huge cohort at BASF churned through the entire periodic table looking for better catalysts. While Bosch had little success, the search still continues. Even last year, a new research program aimed at seeking a new catalyst was initiated16,17. The detailed chemistry of ammonia synthesis is now well understood14, and if the search for the new catalyst is successful, it would certainly be worth the effort. However, in our view, the past failures reduce the chance of future success.
In the following text, small-scale ammonia synthesis process is described, and the motivation to investigate an alternative process is explained.
The Small-Scale Process:
Wind-Generated Ammonia 
We are improving the Haber-Bosch process for synthesizing ammonia, seeking a much smaller, simpler process which can be operated locally but produces negligible amounts of carbon dioxide. The feasibility of local ammonia manufacture from wind has already been demonstrated in a pilot plant located in Morris, MN, and shown in Figure 118. Morris sits on the Buffalo Ridge, a formation of sixty miles of rolling hills in the southwest corner of Minnesota. The ridge has unusually steady, strong wind, rolling across the prairie. As a result, it is a mecca for wind-generated electricity.
With this electricity, we already manufacture ammonia from wind, using this plant which is forty thousand times smaller than the existing commercial operations for fossil fuels. Some wind-generated electricity is used to make nitrogen from air by pressure swing adsorption, an established method for air separation used, for example, for patients with emphysema who need oxygen-enriched air. However, more of the electricity is used to make hydrogen by electrolysis of water. These gases are combined over a conventional catalyst in the process shown schematically in Figure 2. After the reaction, the gases are separated by chilling to condense the liquid ammonia. The unreacted gases, as well as the uncondensed ammonia, are recycled.
Details of the Pilot Plant 
In our pilot plant, the University of Minnesota Renewable Hydrogen and Ammonia Pilot Plant, the electric power is provided from a co-located 1.65 MW wind turbine. The pilot plant uses approximately 10% of the power generated, with the remaining power used at the University of Minnesota, Morris campus.
The hydrogen production system uses an electrolyzer, a booster compressor, and a thermal chiller. This system produces 0.54 kg of hydrogen gas per hour, which is stored at 2,400 psi using 24 kWh of electricity. Water from an on-site well is purified using a reverse osmosis and deionization system. The water is then supplied to the electrolyzer at a rate of up to 15 L/h. Nitrogen is generated using a nitrogen generator, a pre-air compressor, an air dryer, and a booster compressor. The nitrogen gas is stored at 2,400 psi using approximately 6 kWh of electricity.
The synthesis of ammonia uses a custom skid. It includes a compressor, a reactor, a refrigeration cooling loop, and a 20 kW electric heater. The skid uses approximately 28 kWh of electricity to produce 2.7 kg of ammonia per hour which is then stored at 150 psi. The ammonia production process is controlled with integrated PLC and HMI systems. The produced hydrogen and nitrogen are stored on site in 18 nitrogen storage tanks and 54 hydrogen storage tanks. The ammonia is also stored onsite within a 3,100-gallon vessel.
Wind Generation is Expensive 
The electricity for this process is made from wind, and so the fuel for making ammonia is free, without using any fossil fuel. However, the capital costs for this pilot plant are dominated by the investments for hydrogen production and for ammonia synthesis. The operations to date suggest that the cost of making small-scale ammonia are about twice that of conventional ammonia based on fossil fuels. While we continue to optimize our process, we believe that small-scale wind generated ammonia will not be competitive at the current natural gas prices. The capital costs per mass ammonia made could be reduced by a larger conventional process, or by an alternative process like that described next in this paper.
The Absorption Process:
Absorption Enhances Production 
The catalyst used for ammonia synthesis has remained almost unchanged during the last century19. As a result, we have carried out a different approach in this research. We apply the current catalyst and operating temperature, but absorb ammonia at modest pressures as soon as it is formed. We recycle any unreacted hydrogen and nitrogen. The process is schematically like that in Figure 3, similar to the conventional process, but with a packed bed absorber replacing the condenser.
Initial Reaction Kinetics Do Not Change 
Experiments with this system at low conversion show an initial reaction rate that is consistent with many of the earlier studies on this system3,14,15,20,21,22,23, as shown in Figure 4. The left panel shows the initial rates, which vary strongly with temperature. While these rates also vary with pressure, the variations are smaller, as shown in the right panel. In our new process, we use the same catalyst and similar operating conditions, but seek ways to improve ammonia production by using absorption at a lower pressure. We thus hope to reduce the capital costs for ammonia synthesis.
Absorption Enhances Conversion 
In our work, we replaced the condenser in the small process with a packed bed, which is a cylindrical vessel filled with small particles of the absorbent. We have emphasized absorbents made primarily of magnesium chloride and calcium chloride11,24. Such ammine absorbents have two effects. First, they reduce the ammonia concentration present in the recycled gases to near zero. Second, they effectively reduce the time for separation to near zero. This strategy is productive25,26,27. For example, in Figure 5, we show that the rate of making ammonia, which is proportional to the drop in the total pressure in the system, is much greater with absorption than without. In particular, the reaction at 90 bar, shown by the red circles, is less complete than the reaction with the absorbent, shown by the blue triangles27. This is true even though the reaction without absorbent takes place at a pressure almost twice that of the reaction with absorption. In earlier experiments (not shown here), we also showed that the eventual conversion of the process is about 20% without absorbent but over 95% with absorbent.
The rate of reaction varies much less with temperature with absorption than without. This is shown in Figure 6, which again reports ammonia synthesis as total pressure versus time27. Changing the reaction temperature by 60 &#176;C has little effect on the reaction rate. This contrasts with the initial rates in Figure 4, which shows a change of reaction rate of almost an order of magnitude. The results in Figure 4 and Figure 6 are different because the effect of the reverse reaction has been reduced, so the chemical kinetics are no longer the only step responsible for the overall rate.

<table><tbody><tr><td>&lt;strong&gt;Experimental Apparatus&lt;/strong&gt;</td><td></td><td></td><td></td></tr><tr><td>Magnesium Chloride</td><td>Sigma Aldrich</td><td>7786-30-3</td><td>St. Louis, MO</td></tr><tr><td>Calcium Chloride</td><td>Sigma Aldrich</td><td>10043-52-4</td><td>St. Louis, MO</td></tr><tr><td>Ultra Pure Hydrogen</td><td>Matheson</td><td>SG PHYF30050</td><td>New Brighton, MN</td></tr><tr><td>Ultra Pure Nitrogen</td><td>Matheson</td><td>SG G1881112</td><td>New Brighton, MN</td></tr><tr><td>Iron Based Catalyst</td><td>Clariant/Sud Chemie</td><td>-</td><td>Charlotte, NC</td></tr><tr><td>Variable Piston Pump</td><td>PumpWorks Inc.</td><td>PW2070N</td><td>Minneapolis, MN</td></tr><tr><td>Omega Ceramic Heater</td><td>Omega</td><td>CRFC-36/115-A</td><td>Stamford, CT</td></tr><tr><td>PID Controller</td><td>Omega</td><td>CN96211TR</td><td>Stamford, CT</td></tr><tr><td>Signal Conditioner</td><td>Omega</td><td>DRG-SC-TC</td><td>Stamford, CT</td></tr><tr><td>Pressure Transducer</td><td>WIKA</td><td>50426877</td><td>Lawrenceville, Georgia</td></tr><tr><td>Mass Flow Controller</td><td>Brooks Instruments</td><td>SLA5850</td><td>Hatefield, PA</td></tr><tr><td>&lt;strong&gt;Name&lt;/strong&gt;</td><td>&lt;strong&gt;Company&lt;/strong&gt;</td><td>&lt;strong&gt;Catalog Number&lt;/strong&gt;</td><td>&lt;strong&gt;Comments&lt;/strong&gt;</td></tr><tr><td>&lt;strong&gt;Pilot Plant&lt;/strong&gt;</td><td></td><td></td><td></td></tr><tr><td>Electrolyzer</td><td>Proton OnSite</td><td>H6 Series</td><td>Wallingford, CT</td></tr><tr><td>Gas Booster</td><td>PDC Machine</td><td>3 2500&amp;nbsp;</td><td>Warminster, PA</td></tr><tr><td>Wind Turbine</td><td>Vestas</td><td>V82</td><td>Portland, OR</td></tr><tr><td>Chiller</td><td>Thermal Care</td><td>SQ Series</td><td>Niles, IL</td></tr><tr><td>Water Purifier</td><td>Elga Pure Lab</td><td>S-15</td><td></td></tr><tr><td>Nitrogen Generator</td><td>Innovative Gas System</td><td>NS-10</td><td>Huoston, TX</td></tr><tr><td>Air Compressor</td><td>Hydrovane</td><td>HV05</td><td></td></tr></tbody></table>

ammonia synthesis at low pressure

Ammonia can be synthesized at low pressure by the use of an ammonia selective absorbent. The process can be driven with wind energy, available locally in areas requiring ammonia for synthetic fertilizer. Such wind energy is often called &#34;stranded,&#34; because it is only available far from population centers where it can be directly used.
In the proposed low pressure process, nitrogen is made from air using pressure swing absorption, and hydrogen is produced by electrolysis of water. While these gases can react at approximately 400 &#176;C in the presence of a promoted conventional catalyst, the conversion is often limited by the reverse reaction, which makes this reaction only feasible at high pressures. This limitation can be removed by absorption on an ammine-like calcium or magnesium chloride. Such alkaline metal halides can effectively remove ammonia, thus suppressing the equilibrium constraints of the reaction. In the proposed absorption-enhanced ammonia synthesis process, the rate of reaction may then be controlled not by the chemical kinetics nor the absorption rates, but by the rate of the recycle of unreacted gases. The results compare favorably with ammonia made from a conventional small scale Haber-Bosch process.

A pilot plant in Morris, MN has demonstrated the feasibility of using wind for local ammonia manufacture18, as shown in Figure 1. The wind generates electricity, which is used to make nitrogen and hydrogen through the pressure swing absorption of air and through the electrolysis of water, respectively. A reactor uses a conventional catalyst to combine the nitrogen and hydrogen gases, making ammonia. The ammonia is then separated using ...

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Ammonia Synthesis at Low Pressure

Ammonia can be synthesized at low pressure by using a conventional catalyst and an ammonia selective absorbent.

Ammonia can be synthesized at low pressure by the use of an ammonia selective absorbent. The process can be driven with wind energy, available locally in ...

Research

JoVE Journal

Bioengineering

26.4K Views.  University of Minnesota – Twin Cities. Ammoniak kan gesynthetiseerd worden bij lage druk met behulp van een conventionele katalysator en een selectieve absorberende van ammoniak.

Video: Ammonia Synthesis at Low Pressure

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials.

Herein the procedures for plasma enhanced chemical vapor deposition of perfluoroalkanes on microporous materials such as metal-organic frameworks to enhance their stability and hydrophobicity are described. Furthermore, breakthrough testing of milligram quantities of samples is described in detail.

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

Chemistry

Calibrated Passive Sampling - Multi-plot Field Measurements of NH3 Emissions with a Combination of Dynamic Tube Method and Passive Samplers

Agricultural ammonia (NH3) emissions (90% of total EU emissions) are responsible for about 45% airborne eutrophication, 31% soil acidification and 12% fine dust formation within the EU15. But NH3 emissions also mean a considerable loss of nutrients. Many studies on NH3 emission from organic and mineral fertilizer application have been performed in recent decades. Nevertheless, research related to NH3 emissions after application fertilizers is still limited in particular with respect to relationships to emissions, fertilizer type, site conditions and crop growth. Due to the variable response of crops to treatments, effects can only be validated in experimental designs including field replication for statistical testing. The dominating ammonia loss methods yielding quantitative emissions require large field areas, expensive equipment or current supply, which restricts their application in replicated field trials. This protocol describes a new methodology for the measurement of NH3 emissions on many plots linking a simple semi-quantitative measuring method used in all plots, with a quantitative method by simultaneous measurements using both methods on selected plots. As a semi-quantitative measurement method passive samplers are used. The second method is a dynamic chamber method (Dynamic Tube Method) to obtain a transfer quotient, which converts the semi-quantitative losses of the passive sampler to quantitative losses (kg nitrogen ha-1). The principle underlying this approach is that passive samplers placed in a homogeneous experimental field have the same NH3 absorption behavior under identical environmental conditions. Therefore, a transfer co-efficient obtained from single passive samplers can be used to scale the values of all passive samplers used in the same field trial. The method proved valid under a wide range of experimental conditions and is recommended to be used under conditions with bare soil or small canopies (&#60;0.3 m). Results obtained from experiments with taller plants should be treated more carefully.

Calibrated Passive Sampling - Multi-plot Field Measurements of NH3 Emissions with a Combination of Dynamic Tube Method and Passive Samplers

Ammonia emissions are a major threat to the environment by eutrophication, soil acidification and fine particle formation and stem mainly from agricultural sources. This method allows ammonia loss measurements in replicated field trials enabling statistical analysis of emissions and of relationships between crop development and emissions.

Agricultural ammonia (NH3) emissions (90% of total EU emissions) are responsible for about 45% airborne eutrophication, 31% soil acidification and 12% ...

Environment

Ammonia Fiber Expansion (AFEX) Pretreatment of Lignocellulosic Biomass

Lignocellulosic materials are plant-derived feedstocks, such as crop residues (e.g., corn stover, rice straw, and sugar cane bagasse) and purpose-grown energy crops (e.g., miscanthus, and switchgrass) that are available in large quantities to produce biofuels, biochemicals, and animal feed. Plant polysaccharides (i.e., cellulose, hemicellulose, and pectin) embedded within cell walls are highly recalcitrant towards conversion into useful products. Ammonia fiber expansion (AFEX) is a thermochemical pretreatment that increases accessibility of polysaccharides to enzymes for hydrolysis into fermentable sugars. These released sugars can be converted into fuels and chemicals in a biorefinery. Here, we describe a laboratory-scale batch AFEX process to produce pretreated biomass on the gram-scale without any ammonia recycling. The laboratory-scale process can be used to identify optimal pretreatment conditions (e.g., ammonia loading, water loading, biomass loading, temperature, pressure, residence time, etc.) and generates sufficient quantities of pretreated samples for detailed physicochemical characterization and enzymatic/microbial analysis. The yield of fermentable sugars from enzymatic hydrolysis of corn stover pretreated using the laboratory-scale AFEX process is comparable to pilot-scale AFEX process under similar pretreatment conditions. This paper is intended to provide a detailed standard operating procedure for the safe and consistent operation of laboratory-scale reactors for performing AFEX pretreatment of lignocellulosic biomass.

Ammonia Fiber Expansion AFEX Pretreatment of Lignocellulosic Biomass

Ammonia fiber expansion (AFEX) is a thermochemical pretreatment technology that can convert lignocellulosic biomass (e.g., corn stover, rice straw, and sugarcane bagasse) into a highly digestible feedstock for both biofuels and animal feed applications. Here, we describe a laboratory-scale method for conducting AFEX pretreatment on lignocellulosic biomass.

Lignocellulosic materials are plant-derived feedstocks, such as crop residues (e.g., corn stover, rice straw, and sugar cane bagasse) and purpose-grown ...

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH3NH3I) and methylammonium bromide (CH3NH3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH3NH3PbX3 with X = I, Br, Cl and their mixture) films with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH3NH3PbI3-xBrx by exposing the substrate to vapors of a mixture of CH3NH3I and CH3NH3Br at reduced pressure and 120 &#176;C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH3NH3PbI3-xBrx with 0&#160;&#8804; x&#160;&#8804; 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV&#160;&#8804; Eg&#160;&#8804; 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH3NH3PbI3-xClx. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.

Here, we present a protocol for the synthesis of CH3NH3I and CH3NH3Br precursors and the subsequent formation of pinhole-free, continuous CH3NH3PbI3-xBrx thin films for the application in high efficiency solar cells and other optoelectronic devices.

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, ...

Measurement of the Potential Rates of Dissimilatory Nitrate Reduction to Ammonium Based on 14NH4+/15NH4+ Analyses via Sequential Conversion to N2O

The importance of understanding the fate of nitrate (NO3&#8722;), which is the dominant N species transferred from terrestrial to aquatic ecosystems, has been increasing because global nitrogen loads have dramatically increased following industrialization. Dissimilatory nitrate reduction to ammonium (DNRA) and denitrification are both microbial processes that use NO3&#8722; for respiration. Compared to denitrification, quantitative determinations of the DNRA activity have been carried out only to a limited extent. This has led to an insufficient understanding of the importance of DNRA in NO3&#8722; transformations and the regulating factors of this process. The objective of this paper is to provide a detailed procedure for the measurement of the potential DNRA rate in environmental samples. In brief, the potential DNRA rate can be calculated from the 15N-labeled ammonium (15NH4+) accumulation rate in 15NO3&#8722; added incubation. The determination of the 14NH4+ and 15NH4+ concentrations described in this paper is comprised of the following steps. First, the NH4+ in the sample is extracted and trapped on an acidified glass filter as ammonium salt. Second, the trapped ammonium is eluted and oxidized to NO3&#8722; via persulfate oxidation. Third, the NO3&#8722; is converted to N2O via an N2O reductase deficient denitrifier. Finally, the converted N2O is analyzed using a previously developed quadrupole gas chromatography&#8211;mass spectrometry system. We applied this method to salt marsh sediments and calculated their potential DNRA rates, demonstrating that the proposed procedures allow a simple and more rapid determination compared to previously described methods.

Measurement of the Potential Rates of Dissimilatory Nitrate Reduction to Ammonium Based on 14NH4+/15NH4+ Analyses via Sequential Conversion to N2O

A series of methods to determine the potential DNRA rate based on 14NH4+/15NH4+ analyses is provided in detail. NH4+ is converted into N2O via several steps and analyzed using quadrupole gas chromatography&#8211;mass spectrometry.

The importance of understanding the fate of nitrate (NO3&#8722;), which is the dominant N species transferred from terrestrial to aquatic ecosystems, has ...

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for specialized equipment to achieve modest pressures, and can even be used to achieve higher pressures in more specialized equipment and sturdier reaction vessels. At the end of the reaction, the vials can be easily depressurized by opening at room temperature. In the present example CO2 serves as both a putative directing group as well as a way to passivate amine substrates, thereby preventing oxidation during the organometallic reaction. In addition to being easily added, the directing group is also removed under vacuum, obviating the need for extensive purification to remove the directing group. This strategy allows the facile &#947;-C(sp3)-H arylation of aliphatic amines and has the potential to be applied to a variety of other amine-based reactions.

Achieving Moderate Pressures in Sealed Vessels Using Dry Ice As a Solid CO2 Source

Here we present a protocol for performing reactions in simple reaction vessels under low-to-moderate pressures of CO2. The reactions can be performed in a variety of vessels simply by administering the carbon dioxide in the form of dry ice, without the need for costly or elaborate equipment or set-ups.

Herein is presented a general strategy to perform reactions under mild to moderate CO2 pressures with dry ice. This technique obviates the need for ...

Fast and Accurate Exhaled Breath Ammonia Measurement

This exhaled breath ammonia method uses a fast and highly sensitive spectroscopic method known as quartz enhanced photoacoustic spectroscopy (QEPAS) that uses a quantum cascade based laser. The monitor is coupled to a sampler that measures mouth pressure and carbon dioxide. The system is temperature controlled and specifically designed to address the reactivity of this compound. The sampler provides immediate feedback to the subject and the technician on the quality of the breath effort. Together with the quick response time of the monitor, this system is capable of accurately measuring exhaled breath ammonia representative of deep lung systemic levels. 
Because the system is easy to use and produces real time results, it has enabled experiments to identify factors that influence measurements. For example, mouth rinse and oral pH reproducibly and significantly affect results and therefore must be controlled. Temperature and mode of breathing are other examples. As our understanding of these factors evolves, error is reduced, and clinical studies become more meaningful. This system is very reliable and individual measurements are inexpensive. 
The sampler is relatively inexpensive and quite portable, but the monitor is neither. This limits options for some clinical studies and provides rational for future innovations.

Ammonia is an important physiologic metabolite relevant to various disease and wellness states. It is also a difficult molecule to measure in breath, which demands particular precautions be taken to obtain accurate results. Not all factors influencing ammonia are known, but progress can be difficult without accounting for these factors.

This exhaled breath ammonia method uses a fast and highly sensitive spectroscopic method known as quartz enhanced photoacoustic spectroscopy (QEPAS) that ...

Medicine

Synthesis of Metal Nanoparticles Supported on Carbon Nanotube with Doped Co and N Atoms and its Catalytic Applications in Hydrogen Production

A method for facile synthesis of nanostructured catalysts supported on carbon nanotubes with atomically dispersed cobalt and nitrogen dopant is presented herein. The novel strategy is based on a facile one-pot pyrolysis treatment of cobalt (II) acetylacetonate and nitrogen-rich organic precursors under Ar atmosphere at 800 &#176;C, resulting in the formation of Co- and N- co-doped carbon nanotube with earthworm-like morphology. The obtained catalyst was found to have a high density of defect sites, as confirmed by Raman spectroscopy. Here, cobalt (II) nanoparticles were stabilized on the atomically dispersed cobalt- and nitrogen-doped carbon nanotubes. The catalyst was confirmed to be effective in the catalytic hydrolysis of ammonia borane, in which the turnover frequency was 5.87 mol H2&#183;molCo-1&#183;min-1, and the specific hydrogen generation rate was determined to be 2447 mL H2&#183;gCo-1&#183;min-1. A synergistic function between the Co nanoparticle and the doped carbon nanotubes was proposed for the first time in the catalytic hydrolysis of ammonia borane reaction under a mild condition. The resulting hydrogen production with its high energy density and minimal refueling time could be suitable for future development as energy sources for mobile and stationary applications such as road trucks and forklifts in transport and logistics.

Here, we present a protocol to synthesize Co nanoparticles supported on carbon nanotubes with Co- and N- dopants for hydrogen productions.

A method for facile synthesis of nanostructured catalysts supported on carbon nanotubes with atomically dispersed cobalt and nitrogen dopant is presented ...

Le Ch&#226;telier's Principle

Source: Laboratory of Dr. Lynne O&#39;Connell &#8212; Boston College
When the conditions of a system at equilibrium are altered, the system responds in such a way as to maintain the equilibrium. In 1888, Henri-Lewis Le Ch&#226;telier described this phenomenon in a principle that states, &#34;When a change in temperature, pressure, or concentration disturbs a system in chemical equilibrium, the change will be counteracted by an alteration in the equilibrium composition.&#34;
This experiment demonstrates Le Ch&#226;telier&#39;s principle at work in a reversible reaction between iron(III) ion and thiocyanate ion, which produces iron(III) thiocyante ion:
Fe3+(aq) + SCN- (aq) <img alt="Reversibly Equals" src="/files/ftp_upload/10138/reversible.jpg" /> FeSCN2+ (aq)
The concentration of one of the ions is altered either by directly adding a quantity of one ion to the solution or by selectively removing an ion from the solution through formation of an insoluble salt. Observations of color changes indicate whether the equilibrium has shifted to favor formation of the products or the reactants. In addition, the effect of a temperature change on the solution at equilibrium can be observed, which leads to the ability to conclude whether the reaction is exothermic or endothermic.

Le Chatelier&#039;s Principle: Effect of Concentration and Temperature on Chemical Equilibrium

Source: Laboratory of Dr. Lynne O&#39;Connell &#8212; Boston College
When the conditions of a system at equilibrium are altered, the system responds in ...

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General Chemistry

Preparation of Amines: Alkylation of Ammonia and Amines

Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines along with a quaternary ammonium salt through successive SN2 reactions. This process of making the quaternary salt through the direct alkylation method is called exhaustive alkylation.
Each alkylation step makes the nitrogen center more nucleophilic, which triggers successive alkylations until a quaternary ammonium salt is formed. Considering this, specific reaction conditions, such as excess ammonia, must be used to exclusively make primary amines.
Since tertiary halides are more hindered, they are not the substrates of choice for alkylation reactions. Although secondary alkyl halides are far less hindered and can be alkylated, they are also not preferred as substrates due to their tendency to undergo elimination reactions.
Since ammonia is cheaply available, alkylations using ammonia as the substrate are the most common.

Alkylation is one of the methods used to prepare amines. Direct alkylation of ammonia or a primary amine with an alkyl halide gives polyalkylated amines ...

Ammonia Synthesis at Low Pressure

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