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Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur.

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Presentation on theme: "Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur."— Presentation transcript:

1 Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

2 The clean methane is then reacted with steam over a catalyst of nickel oxide. This is called steam reforming:steamnickel oxide steam reforming CH 4 + H 2 O → CO + 3H 2

3 Secondary reforming addition of air to convert the methane that did not react during steam reforming. 2CH 4 + O 2 → 2CO + 4H 2 CH 4 + 2O 2 → CO 2 + 2H 2 O

4 Wikipedia Haber Process The synthesis of ammonia using an iron oxide catalyst:

5 N 2 + 3H 2 ⇌ 2NH 3 ΔH o = −92.4 kJmol -1mol

6 At 15–25 MPa (150–250 bar)MPabar between 300 and 550 °C, passing the gases over four beds of catalyst, with cooling between each pass to maintain a reasonable equilibrium constant. equilibrium constant

7 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed)

8 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed) 2.N 2 (adsorbed) → 2N (adsorbed)

9 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed) 2.N 2 (adsorbed) → 2N (adsorbed) 3.H 2 (g) → H 2 (adsorbed)

10 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed) 2.N 2 (adsorbed) → 2N (adsorbed) 3.H 2 (g) → H 2 (adsorbed) 4.H 2 (adsorbed) → 2H (adsorbed)

11 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed) 2.N 2 (adsorbed) → 2N (adsorbed) 3.H 2 (g) → H 2 (adsorbed) 4.H 2 (adsorbed) → 2H (adsorbed) 5.N (adsorbed) + 3H (adsorbed) → NH 3 (adsorbed)

12 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed) 2.N 2 (adsorbed) → 2N (adsorbed) 3.H 2 (g) → H 2 (adsorbed) 4.H 2 (adsorbed) → 2H (adsorbed) 5.N (adsorbed) + 3H (adsorbed) → NH 3 (adsorbed) 6.NH 3 (adsorbed) → NH 3 (g)

13 he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:reaction mechanism 1.N 2 (g) → N 2 (adsorbed) 2.N 2 (adsorbed) → 2N (adsorbed) 3.H 2 (g) → H 2 (adsorbed) 4.H 2 (adsorbed) → 2H (adsorbed) 5.N (adsorbed) + 3H (adsorbed) → NH 3 (adsorbed) 6.NH 3 (adsorbed) → NH 3 (g)

14 1.On each pass only about 15% conversion 2.unreacted gases are recycled 3.eventually overall conversion of 98%

15 The production of ammonium nitrate in industry although simple chemistry is technologically challenging:

16 The acid-base reaction of ammonia with nitric acid gives a solution of ammonium nitrate:[2]acid-base reactionammonia nitric acid[2]

17 The production of ammonium nitrate in industry although simple chemistry is technologically challenging: The acid-base reaction of ammonia with nitric acid gives a solution of ammonium nitrate:[2]acid-base reactionammonia nitric acid[2] HNO 3 (aq) + NH 3 (g) → NH 4 NO 3 (aq).

18 The production of ammonium nitrate in industry although simple chemistry is technologically challenging: The acid-base reaction of ammonia with nitric acid gives a solution of ammonium nitrate:[2]acid-base reactionammonia nitric acid[2] HNO 3 (aq) + NH 3 (g) → NH 4 NO 3 (aq). anhydrous ammonia gas and concentrated nitric acid. This reaction is violent and very exothermic.

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21 1.100 million tons of nitrogen fertilizer per yearfertilizer

22 1.100 million tons of nitrogen fertilizer per yearfertilizer 2.3-5% of world natural gas production

23 1.100 million tons of nitrogen fertilizer per yearfertilizer 2.3-5% of world natural gas production 3.~1-2% of the world's annual energysupply

24 1.100 million tons of nitrogen fertilizer per yearfertilizer 2.3-5% of world natural gas production 3.~1-2% of the world's annual energysupply 4.sustains one-third of the Earth's population

25 1.100 million tons of nitrogen fertilizer per yearfertilizer 2.3-5% of world natural gas production 3.~1-2% of the world's annual energysupply 4.sustains one-third of the Earth's population 5.environmental consequences.

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27 age at: www.idsia.ch/~juergen/haberbosch.htmlwww.idsia.ch/~juergen/haberbosch.html

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30 The Haber process now produces 100 million tons of nitrogen fertilizer per year, mostly in the form of anhydrous ammonia, ammonium nitrate, and urea. 3-5% of world natural gas production is consumed in the Haber process (~1-2% of the world's annual energy supply)[1][13][14][15]. That fertilizer is responsible for sustaining one- third of the Earth's population, as well as various deleterious environmental consequences.[2][5] Generation of hydrogen using electrolysis of water, using renewable energy, is not currently competitive cost-wise with hydrogen from fossil fuels, such as natural gas, and is responsible for 4% of current hydrogen production. Notably, the rise of this industrial process led to the "Nitrate Crisis" in Chile, when the industrials who owned the nitrate mines (most of them British) left the country — since the natural nitrate mines were no longer profitable — closing the mines and leaving a large unemployed Chilean population behind.fertilizerammoniaammonium nitrateurea[1][13][14][15][2][5]Chile [edit] See alsoedit

31 The steam reforming, carbon dioxide removal and methanation operate at pressures of about 2.5–3.5 MPa (25–35 bar),

32 Synthesis gas preparation First, the methane is cleaned, mainly to remove sulphur impurities that would poison the catalysts.sulphur The clean methane is then reacted with steam over a catalyst of nickel oxide. This is called steam reforming:steamnickel oxide 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. 2CH4 + O2 → 2CO + 4H2 CH4 + 2O2 → CO2 + 2H2O

33 Synthesis gas preparation First, the methane is cleaned, mainly to remove sulphur impurities that would poison the catalysts.sulphur The clean methane is then reacted with steam over a catalyst of nickel oxide. This is called steam reforming:steamnickel oxide 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. 2CH4 + O2 → 2CO + 4H2 CH4 + 2O2 → CO2 + 2H2O

34 There are many engineering and construction companies that offer proprietary designs for ammonia synthesis plants. Haldor Topsoe of Denmark, Lurgi AG of Germany, Uhde of Germany, Saipem/Snamprogetti of Italy and Kellogg, Brown and Root of the United States are among the most experienced companies in that field.[7]Haldor Topsoe DenmarkLurgi AGGermanyUhdeGermany Saipem/SnamprogettiItalyKellogg, Brown and Root[7] Nowadays, the bulk of the hydrogen required is produced from methane (natural gas) using heterogeneous catalysis, because this requires far less external energy input compared to the electrolysis of water. However, the source of the hydrogen makes no difference to the Haber-Bosch process, which is only concerned with synthesizing ammonia from nitrogen and hydrogen.hydrogenmethanenatural gas heterogeneous catalysis

35 Nowadays, the bulk of the hydrogen required is produced from methane (natural gas) using heterogeneous catalysis, because this requires far less external energy input compared to the electrolysis of water. However, the source of the hydrogen makes no difference to the Haber-Bosch process, which is only concerned with synthesizing ammonia from nitrogen and hydrogen.hydrogenmethanenatural gas heterogeneous catalysis

36 png - en.citizendium.org/images/6/6a/Steam-Methane

37 age at: www.initrogen.org/fileadmin/timeline/1913.htmlwww.initrogen.org/fileadmin/timeline/1913.html

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39 Then the water gas shift reaction yields more hydrogen from CO and steam.water gas shift reaction CO + H2O → CO2 + H2 The gas mixture is now passed into a methanator, which converts most of the remaining CO into methane for recycling: CO + 3H2 → CH4 + H2O This last step is necessary as carbon monoxide poisons the catalyst. The overall reaction so far turns methane and steam into carbon dioxide, steam, and hydrogen.

40 Reaction 5 occurs in three steps, forming NH, NH2, and then NH3. Experimental evidence points to reaction 2 as being the slow, rate-determining step.rate-determining step A major contributor to the elucidation of this mechanism is Gerhard Ertl.[9][10][11][12]Gerhard Ertl[9][10][11][12]

41 he chemical compound ammonium nitrate, the nitrate of ammonia with the chemical formula NH4NO3, is a white powder at room temperature and standard pressure. It is commonly used in agriculture as a high-nitrogen fertilizer, and it has also been used as an oxidizing agent in explosives, including improvised explosive devices.chemical compoundnitrateammoniaNHNOagriculturefertilizeroxidizing agent explosivesimprovised explosive devices Ammonium nitrate, when mixed with water, will create a cold substance that can be used as a cold pack.

42 The processes involved in the production of ammonium nitrate in industry, although simple in chemistry, challenge technology: The acid-base reaction of ammonia with nitric acid gives a solution of ammonium nitrate:[2]acid-base reactionammonia nitric acid[2] HNO3(aq) + NH3(g) → NH4NO3(aq). For industrial production, this is done using anhydrous ammonia gas and concentrated nitric acid. This reaction is violent and very exothermic.

43 After the solution is formed, typically at about 83% concentration, the excess water is evaporated to an ammonium nitrate (AN) content of 95% to 99.9% concentration (AN melt), depending on grade. The AN melt is then made into "prills" or small beads in a spray tower, or into granules by spraying and tumbling in a rotating drum. The prills or granules may be further dried, cooled, and then coated to prevent caking. These prills or granules are the typical AN products in commerce.

44 The Haber process combines nitrogen and hydrogen to produce ammonia, part of which can be oxidised to nitric acid and combined with the remaining ammonia to produce the nitrate. Another production method is used in the so-called Odda process.Haber processnitric acidOdda process


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