synthesis gas preparation first methane is cleaned to remove sulphur impurities that would poison...

44
Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.

Upload: silas-anderson

Post on 21-Jan-2016

218 views

Category:

Documents


0 download

TRANSCRIPT

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

Synthesis gas preparation

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

Page 2: Synthesis gas preparation First methane is cleaned 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:

CH4 + H2O → CO + 3H2

Page 3: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

Secondary reforming

addition of air to convert the methane that did not react during steam reforming.

2CH4 + O2 → 2CO + 4H2

CH4 + 2O2 → CO2 + 2H2O

Page 4: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

Wikipedia

Haber Process

The synthesis of ammonia using an iron oxide catalyst:

Page 5: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

N2 + 3H2 ⇌ 2NH3

ΔHo = −92.4 kJmol-1

Page 6: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

At 15–25 MPa (150–250 bar)

between 300 and 550 °C,

passing the gases over four beds of catalyst, with cooling between each pass to maintain a

reasonable equilibrium constant.

Page 7: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

Page 8: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

Page 9: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

3. H2 (g) → H2 (adsorbed)

Page 10: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

3. H2 (g) → H2 (adsorbed)

4. H2 (adsorbed) → 2H (adsorbed)

Page 11: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

3. H2 (g) → H2 (adsorbed)

4. H2 (adsorbed) → 2H (adsorbed)

5. N (adsorbed) + 3H (adsorbed)→ NH3

(adsorbed)

Page 12: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

3. H2 (g) → H2 (adsorbed)

4. H2 (adsorbed) → 2H (adsorbed)

5. N (adsorbed) + 3H (adsorbed)→ NH3

(adsorbed)

6. NH3 (adsorbed) → NH3 (g)

Page 13: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

he reaction mechanism, involving the heterogeneous catalyst, is believed to be as follows:

1. N2 (g) → N2 (adsorbed)

2. N2 (adsorbed) → 2N (adsorbed)

3. H2 (g) → H2 (adsorbed)

4. H2 (adsorbed) → 2H (adsorbed)

5. N (adsorbed) + 3H (adsorbed)→ NH3

(adsorbed)

6. NH3 (adsorbed) → NH3 (g)

Page 14: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

1.On each pass only about 15% conversion

2.unreacted gases are recycled

3.eventually overall conversion of 98%

Page 15: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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

Page 16: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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]

Page 17: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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]

HNO3 (aq) + NH3 (g) → NH4NO3 (aq).

Page 18: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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]

HNO3 (aq) + NH3 (g) → NH4NO3 (aq).

anhydrous ammonia gas and concentrated nitric acid. This reaction is violent and very exothermic.

Page 19: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur
Page 20: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur
Page 21: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

1. 100 million tons of nitrogen fertilizer per year

Page 22: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

1. 100 million tons of nitrogen fertilizer per year

2. 3-5% of world natural gas production

Page 23: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

1. 100 million tons of nitrogen fertilizer per year

2. 3-5% of world natural gas production

3. ~1-2% of the world's annual energysupply

Page 24: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

1. 100 million tons of nitrogen fertilizer per year

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

Page 25: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

1. 100 million tons of nitrogen fertilizer per year

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.

Page 26: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur
Page 27: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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

Page 28: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur
Page 29: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur
Page 30: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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.[edit] See also

Page 31: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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

Page 32: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

Synthesis gas preparationFirst, the methane is cleaned, mainly to remove sulphur impurities that would poison the catalysts.The clean methane is then reacted with steam over a catalyst of nickel oxide. 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.

2CH4 + O2 → 2CO + 4H2CH4 + 2O2 → CO2 + 2H2O

Page 33: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

Synthesis gas preparationFirst, the methane is cleaned, mainly to remove sulphur impurities that would poison the catalysts.The clean methane is then reacted with steam over a catalyst of nickel oxide. 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.

2CH4 + O2 → 2CO + 4H2CH4 + 2O2 → CO2 + 2H2O

Page 34: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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]

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.

Page 35: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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.

Page 36: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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

Page 37: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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

Page 38: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur
Page 39: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

Then the water gas shift reaction yields more hydrogen from CO and steam.

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.

Page 40: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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.

A major contributor to the elucidation of this mechanism is Gerhard Ertl.[9][10][11][12]

Page 41: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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.Ammonium nitrate, when mixed with water, will create a cold substance that can be used as a cold pack.

Page 42: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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] 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.

Page 43: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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.

Page 44: Synthesis gas preparation First methane is cleaned to remove sulphur impurities that would poison the catalysts.sulphur

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.