Haber process


Haber process
From Wikipedia, the free encyclopedia
The Haber process, also called the Haber–Bosch process, is the reaction of nitrogen and hydrogen, over an iron substrate, to produce ammonia.[1][2][3] The Haber process is important because ammonia is difficult to produce on an industrial scale. Even though 78.1% of the air we breathe is nitrogen, the gas is relatively unreactive because nitrogen molecules are held together by strong triple bonds. It was not until the early 20th century that this method was developed to harness the atmospheric abundance of nitrogen to create ammonia, which can then be oxidized to make the nitrates and nitrites essential for the production of nitrate fertilizer and munitions.

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1 History 2 The process o 2.1 Synthesis gas preparation o 2.2 Ammonia synthesis 3 Reaction Rate and Equilibrium 4 Catalysts 5 Economic and environmental aspects 6 See also 7 References 8 External links

The process was first patented by Fritz Haber. In 1910 Carl Bosch, while working for chemical company BASF, successfully commercialized the process and secured further patents. Haber and Bosch were later awarded Nobel prizes, in 1918 and 1931 respectively, for their work in overcoming the chemical and engineering problems posed by the use of large-scale high-pressure technology. Ammonia was first manufactured using the Haber process on an industrial scale in Germany during World War I to meet the high demand for ammonium nitrate (for use in explosives) at a time when supply of Chile saltpetre from Chile could not be guaranteed because this industry was then almost 100% in British hands. It has been suggested that without this process, Germany would almost certainly have run out of explosives by 1916, thereby ending the war.

The process
The bulk of the chemical technology consists in getting the hydrogen from methane or natural gas using heterogeneous catalysis and then reacting it with the atmospheric nitrogen.

K2CO3 + H2O + CO2→ 2KHCO3 The gas mixture is now passed into a methanator which converts any remaining CO2 into methane for recycling: CO2 + 4H2 → CH4 + 2H2O We now have a gas mixture containing nitrogen and hydrogen in the correct ratio of 1:3. forming an Iron compound. The Carbon Monoxide (CO) is also a catalyst poisoning. . thus affecting the reaction. zinc and aluminium Then the carbon dioxide is removed by reaction with potassium carbonate. This is called steam reforming: CH4 + H2O → CO + 3H2 Secondary reforming then takes place with the addition of air to convert the methane that did not react during steam reforming.Haber process 2/6 Synthesis gas preparation First. mainly to remove sulfur impurities that would poison the catalysts. the methane is cleaned. chromium and copper CO + H2O → CO2 + H2 low temperature → the catalyst here is a mixture of copper. The air added during this step also serves as a nitrogen source for ammonia synthesis: CH4 + 1/2O2 → CO + 2H2 CH4 + 2O2 → CO2 + 2H2O Then occur two’’shifts’’ which convert CO to CO2 by reaction with steam. one at high temperature. This is done by turning sulfur into hydrogen sulfide: CH3SH + H2 → CH4 + H2S and then reacting with zinc oxide to form zinc sulfide: H2S + ZnO → ZnS + H2O The clean methane is then reacted with steam over a catalyst of nickel oxide. which would interact with the Iron catalyst. then one at low temperature: CO + H2O → CO2 + H2 high temperature → the catalyst here is a mixture of iron.

This may increase the rate of the reaction but.64 x 10–4 Pressure is the obvious choice to favour the forward reaction because there are 4 moles of reactant for every 2 moles of product.45 x 10–5 5. pressure is an expensive commodity.34 x 10–3 the catalyst itself requires a temperature of at least 400 °C to be efficient. Thus one as a Function of Temperature[4] might suppose that a low temperature is to be used Temperature (°C) Keq and some other means to increase rate. gaseous ammonia is not removed from the . Pipes and reaction vessels need to be strengthened. since the reaction is exothermic. At room temperature.25 x 10–6 Economically.250 atmospheres (atm) and between 300 and 550 °C. given by: As the temperature increases. In addition. valves more rigorous. Reaction Rate and Equilibrium There are two opposing considerations in this synthesis: the position of the equilibrium and the rate of reaction. Thus the compromise used gives a single pass yield of around 15%. 450 500 550 600 4.51 x 10–5 1. as the catalyst: N2(g) + 3H2(g) → 2NH3(g). so that eventually an overall yield of 98% can be achieved. though. However. the reaction is slow and the obvious solution is to raise the temperature. iron oxide. passing the gases over four beds of catalyst. Another way to increase the yield of the reaction would be to remove the product (i. ammonia gas) from the system. and there are safety considerations of working at 200 atm. according to Le Chatelier's Principle. with cooling between each pass to maintain a reasonable equilibrium constant. 300 4. it also has the effect. of favouring the reverse reaction and thus reducing equilibrium constant. In practice. and the pressure used (around 200 atm) alters the equilibrium concentrations to give a profitable yield.38 x 10–6 2. running pumps and compressors takes considerable energy.Haber process 3/6 Ammonia synthesis The final stage is the crucial synthesis of ammonia using promoted magnetite. ΔHo = -92. the equilibrium is Variation in Keq for the Equilibrium shifted and hence. but any unreacted gases will be recycled.e.4 kJ/mol This is done at 150 . the constant drops dramatically N2 (g) + 3H2 (g) ↔ 2NH3 (g) according to the van't Hoff equation. On each pass only about 15% conversion occurs. 400 1.

35% of world natural gas production is used for ammonia production. today a much less expensive iron catalyst is used almost exclusively. since the temperature is too high. Unreacted hydrogen and nitrogen gases are then returned to the reaction vessel to undergo further reaction. rather.Haber process 4/6 reactor itself. and urea. 6. The hot gases are cooled enough. and so the result is a highly porous material whose large surface area aids its effectiveness as a catalyst. while remaining chemically unchanged at the end of the reaction. but it is removed from the equilibrium mixture of gases leaving the reaction vessel. 2. removing oxygen in the process. NH2. is not currently competitive cost-wise with hydrogen from fossil fuels. for the ammonia to condense and be removed as liquid. using renewable energy. 5.75% of the world's annual energy supply is consumed in the Haber process (3. involving the heterogeneous catalyst. is believed to be as follows: 1. which increases the electron density of the catalyst and so improves its reactivity. and then NH3. and potassium.[9][10][1] and natural gas represents 22% of world energy production. Other minor components of the catalyst include calcium and aluminium oxides. The first Haber– Bosch reaction chambers used osmium and uranium catalysts.) That fertilizer is responsible for sustaining one-third of the Earth's population. 4. to the hot hydrogen feedstock. 0. the iron catalyst is prepared by exposing a mass of magnetite. rate-determining step. it provides an alternative pathway with lower activation energy and hence increases the reaction rate. such as natural gas. ammonium nitrate.[5][6][7][8] Economic and environmental aspects The Haber process now produces 100 million tons of nitrogen fertilizer per year. The reaction mechanism. In industrial practice. Catalysts The catalyst has no effect on the position of equilibrium. whilst maintaining a high pressure. forming NH. This reduces some of the magnetite to metallic iron. However. 3. as well as various deleterious environmental consequences. and is responsible for only 4% of . However. N2(g) → N2(adsorbed) N2(adsorbed) → 2N(adsorbed) H2(g) → H2(adsorbed) H2(adsorbed) → 2H(adsorbed) N(adsorbed) + 3H(adsorbed)→ NH3(adsorbed) NH3(adsorbed) → NH3(g) Reaction 5 occurs in three steps. which support the porous iron catalyst and help it maintain its surface area over time. A major contributor to the elucidation of this mechanism is Gerhard Ertl. mostly in the form of anhydrous ammonia. Experimental evidence points to reaction 2 as being the slow.[13] Generation of hydrogen using electrolysis of water. an iron oxide. the catalyst maintains most of its bulk volume during the reduction.[11] See also[12] for rough estimate of 1% of energy production.

11. Volume 114. Pages 515-526 G. ^ Fertilizer Industry: Processes. G. pp. 2003. G. ^ Wolfe.1076659.1016/0039-6028(82)90135-2 7. Volume 49. Issue 1. when the British industrials left the country -. See also • • • Chemical kinetics Reaction rate Rate equation References 1.closing the mines and leaving a large unemployed Chilean population behind.April 1. Issue 2. Lee and M. David W. N. 5587. Moritz doi:10. Behm. and the Transformation of World Food Production by Vaclav Smil (2001) ISBN 0-262-19449-X 2. ^ International Energy Outlook 2007. Tales from the underground a natural history of subterranean life. 12. R.since the natural nitrate mines were no longer profitable -. ^ The structure of atomic nitrogen adsorbed on Fe(100) Surface Science. Ertl.1016/0021-9517(77)90237-8 6. Notably. ^ a b Enriching the Earth: Fritz Haber.1116/1. Cambridge. Bursten. 1247-1253 doi:10. Carl Bosch. Issues 2-3. 10. Grunze and M. ^ Interaction of nitrogen with iron surfaces : I. 13. ^ "Heterogeneous Catalysts: A study Guide" 4. ^ Kinetics of nitrogen adsorption on Fe(111) Surface Science.1126/science. 1 December 1982.1655 DOI: 10. Lemay. Issue 1.J. 6 September 2002: Vol. Pollution Control and Energy Conservation by Marshall Sittig (1979) Noyes Data Corp. ISBN 0-8155-0734-8 3. J. Mass: Perseus Pub. no. pp. Weiss doi:10. M. 1983 -Volume 1. Pages 18-41 F.Haber process 5/6 current hydrogen production. ^ Science. ^ Chemistry the Central Science" Ninth Ed. ISBN: 0-13-038168-3 5.572299 9. ^ Primary steps in catalytic synthesis of ammonia G. ^ Why Are Nitrogen Prices So High?. the rise of this industrial process led to the "Nitrate Crisis" in Chile. (2001). ^ Highlights. S. Ertl Journal of Vacuum Science & Technology A: Vacuum. 1654 . Weiss doi:10. 1 February 1982. 297. . ISBN 0738201286.1016/0039-6028(82)90702-6 8. Ertl and W. by: Brown. .. July 1977. Volume 123. Bozso. OCLC 46984480. Surfaces.. Ertl. B. and Films -. Fe(100) and Fe(111) Journal of Catalysis. Imbihl. Pages 129-140 R.

Biography of Fritz Haber Uses and Production of Ammonia ”CIEC Catalysis”.org/wiki/Haber_process" Categories: BASF | Chemical processes | Industrial processes | Peak oil .agriculture and the production of food Food Crises and the Role of Agriculture: Past and Current Britannica guide to Nobel Prizes: Fritz Haber Nobel e-Museum . [1] Haber Process for Ammonia Synthesis Retrieved from "http://en.wikipedia.Haber process 6/6 External links • • • • • • • • • What is the Haber-Bosch Process? Haber-Bosch process Fertilizer.

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