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Episode 3 : Production of Synthesis Gas by Steam Methane Reforming

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Episode 3 : Production of Synthesis Gas by Steam Methane Reforming
History of Synthesis Gas
In 1780, Felice Fontana discovered that combustible gas develops if water vapor is passed over carbon at temperatures over 500 °C. This CO and H2 containing gas was called water gas and mainly used for lighting purposes in the19th century.

As of the beginning of the 20th century, H2/CO-mixtures were used for syntheses of hydrocarbons and then, as a consequence, also called synthesis gas.

Haber and Bosch discovered the synthesis of ammonia from H2 and N2 in 1910 and the first industrial ammonia synthesis plant was commissioned in 1913.
The production of liquid hydrocarbons and oxygenates from syngas conversion over iron catalysts was discovered in 1923 by Fischer and Tropsch.
Much of the syngas conversion processes were being developed in Germany during the first and second world wars at a time when natural resources were becoming scare and alternative routes for hydrogen production, ammonia synthesis, and transportation fuels were a necessity.
In 1943/44, this was applied for large-scale production of artificial fuels from synthesis gas in Germany.

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Episode 3 : Production of Synthesis Gas by Steam Methane Reforming

  1. 1. SAJJAD KHUDHUR ABBAS Chemical Engineering , Al-Muthanna University, Iraq Oil & Gas Safety and Health Professional – OSHACADEMY Trainer of Trainers (TOT) - Canadian Center of Human Development Episode 3 : Production of Synthesis Gas by Steam Methane Reforming
  2. 2. History of Synthesis Gas • In 1780, Felice Fontana discovered that combustible gas develops if water vapor is passed over carbon at temperatures over 500 °C. This CO and H2 containing gas was called water gas and mainly used for lighting purposes in the19th century. • As of the beginning of the 20th century, H2/CO- mixtures were used for syntheses of hydrocarbons and then, as a consequence, also called synthesis gas.
  3. 3. • Haber and Bosch discovered the synthesis of ammonia from H2 and N2 in 1910 and the first industrial ammonia synthesis plant was commissioned in 1913. • The production of liquid hydrocarbons and oxygenates from syngas conversion over iron catalysts was discovered in 1923 by Fischer and Tropsch. • Much of the syngas conversion processes were being developed in Germany during the first and second world wars at a time when natural resources were becoming scare and alternative routes for hydrogen production, ammonia synthesis, and transportation fuels were a necessity. • In 1943/44, this was applied for large-scale production of artificial fuels from synthesis gas in Germany.
  4. 4. To this day, however, methanol and ammonia are still produced from syngas using essentially the same processes originally developed and, apart from hydrogen production, constitute the major uses of syngas.
  5. 5. What is synthesis gas ? In its simplest form, syngas (also called producer gas, town gas, blue water gas, and synthesis gas) is composed of carbon monoxide (CO) and hydrogen (H2).The name comes from its use. Syngas is combustible and often used as a fuel of internal combustion engines. It has less than half the energy density of natural gas.
  6. 6. syngas can be produced from any hydrocarbon feedstock, including: natural gas, naphtha, residual oil, petroleum coke, and coal. The lowest cost routes for syngas production, however, are based on natural gas, the cheapest option. The choice of technology for syngas production also depends on the scale of the synthesis operation.
  7. 7. Syngas production from solid fuels can require an even greater capital investment with the addition of feedstock handling and more complex syngas purification operations. The syngas composition, most importantly the H2/CO ratio, varies as a function of production technology and feedstock. Steam methane reforming yields H2/CO ratios of 3/1, while coal gasification yields ratios closer to unity or lower.
  8. 8. Physical Properties of Hydrogen (H2): With only one proton and one electron, hydrogen is the lightest of all chemical elements. At ambient temperature, molecular hydrogen, H2, is a colourless and odorless gas. hydrogen condenses to a colorless liquid, it freezes at –259.15 °C. H2 is14 times lighter than air. ValueUnitproperty 2.016g mol–1Molar mass 898J mol–1Heat of vaporization Properties at 273.15 K, 101.3 kPa 0.0899kg m–3Density 0.1645W m–1 K–1Thermal conductivity Cp = 22.0, Cv = 6.51J mol–1 K–1Molar heat
  9. 9. ValueUnitProperty Boiling point (101.3 kPa) 20.37KTemperature 70.00kg m–3 Density (liquid) 1.319kg m–3Density (gas) Liquid at boiling point (101.3 kPa) Cp = 22.0, Cv = 6.51J mol–1 K–1Molar heat –7918J mol–1Enthalpy 0.117W m–1 K–1Thermal conductivity Gas at boiling point (101.3 kPa) Cp = 23.49, Cv = 12.8J mol–1 K–1Specific heatcapacity –7020J mol–1Enthalpy 0.0185W m–1 K–1Thermal conductivity Critical Point 33.00KTemperature 1339kPaPressure 30.09kg m–3Density
  10. 10. Chemical properties of hydrogen In air, H2 combusts to water with a hardly visible, weakly bluish flame. Hydrogen combines with almost any other element. Metal compounds with negatively charged hydrogen are called metal hydrides (e.g. CaH2, NaH, LiH).Hydrogen has a reducing effect on a lot of metal oxides when heated. Thus CuO with H2, for example, reacts to Cu and H2O. Hydrogen has a reducing effect on a lot of metal oxides when heated.
  11. 11. Physical and Chemical Properties of Carbon Monoxide (CO): Carbon monoxide is colourless, odourless and tasteless. It is highly toxic,poorly soluble in water (solubility: 23 mL L–1 at 20 °C and 1 bar). ValueUnitProperty 28.010g mol–1Molar mass 10.9 – 76% Volume fractionExplosion range (in air at 101.3 kPa) Properties at 273.15 K, 101.3 kPa 1.250kg m–3Density Cp = 29.05,Cv = 20.68 J mol–1 K–1Molar heat 0.02324W m–1 K–1Thermal conductivity
  12. 12. ValueUnitProperty Boiling point (101.3 kPa) 81.65KTemperature Melting point (101.3 kPa) 74.15KTemperature Critical point 132.29KTemperature 3496KpaPressure 301kg m–3Density
  13. 13. Chemical properties of CO Together with air, carbon monoxide forms explosive mixtures in the concentration range of a CO-volume fraction of (10.9-76%).In engineering, it is obtained by separation from synthesis gas. The reason for its toxicity is it’s property to displace the oxygen from the hemoglobin-complex of blood, since the affinity of hemoglobin (Hb) to CO is about 300 times higher than to O2. The hemoglobin of a heavy smoker of cigarettes can reach a CO-saturation of up to 15% in the course of a day.
  14. 14. Uses of syngas 1. Syngas can be used to produce a variety of chemicals like ammonia and methanol. 2. Syngas itself can be used as a fuel in internal combustion engine. 3. Syngas is also used as an intermediate in producing synthetic petroleum for use as a fuel or lubricant via the Fischer– Tropsch process and previously the Mobil methanol to gasoline process. 4. syngas can be used to produce organic molecules such as synthetic natural gas (SNG-methane).
  15. 15. At these days, synthesis gas is mainly used for production of the products listed: UsesProduct AmmoniaH2 and N2 Formic acidCO Acetic acidH2 and CO MethanolMixtures of (H2, CO and CO2)
  16. 16. Production of Synthesis Gas from Hydrocarbons: In the production of synthesis gases from hydrocarbons, the components hydrogen and carbon monoxide usually appear as complementary products, carbon dioxide can be obtained as a by-product. There are Several Methods to Production the Synthesis Gas from Hydrocarbons : 1.Steam Reforming 2.Partial Oxidation (PO ). 3.Autothermal Reforming ( ATR).
  17. 17. The Process Selection depends on Two factors: 1.The desired product composition (H2/CO ratio ). 2.The feedstock available like natural gas, residual gases from refineries,LPG(Liquefied Petroleum Gas), naphtha, heavy oils, distillation residues, pitch and coal. The selected process in this project is Production Synthesis Gas by steam reforming of Methane Gas due to ratio (H2/CO)is equal to 3/1 and the feed is methane gas. the economic cost of the steam must be taken into account
  18. 18. The Advantages of (SMR): Steam reforming of natural gas are : Efficient Economical widely used process for hydrogen and monoxide production provides near- and mid-term energy security and environmental benefits The SMR produces a H2/CO ratio equal to three
  19. 19. We choose methane as a feed because of : • Methane is a wide distribution in nature. • cheap • Make a Less problems with the reformer. • Make a longer age for reformer than other feed stockes.
  20. 20. Methane Methane is a chemical compound with the chemical formula CH4 (one atom of carbon and four atoms of hydrogen). It is the simplest alkane and the main component of natural gas. Methane is a colorless, odorless gas with a wide distribution in nature. It is the principal component of natural gas, a mixture containing about 75% CH4, 15% ethane (C2H6), and 5% other hydrocarbons, such as propane (C3H8) and butane (C4H10). ValueUnitProperty CH4Molecular formula 16.04g mol-1Molar Mass 0.656g cm-3Density at 25 °C , 1 atm 0.142mPa.sViscosity at -170 °C 5.34J g-1 k-1Specific heat capacity at -100 °C -182°CMelting point 43.4cm s-1Flame Velocity
  21. 21. Critical Values - 82.5°CTemperature 4.67MPaPressure 0.162g cm-3Density
  22. 22. Sources of Methane Natural sources 1.Wetlands 2.Oceans 3.Geological sources 4.Wild animals 5.Wildfires Non Natural sources (Artificiality) 1.Oil and Gas System 2.Landfills 3.Wastewater 4.Coal Mines 5.Agriculture
  23. 23. Steam Reforming (Tubular Reforming) Steam Reforming Methane (SMR) has been used for several decades since it has been developed in 1926 and over the years substantial improvements have been introduced. SMR process consists of gas feed pre-heating and pre-treatment, reforming. Steam reforming of methane is the main industrial route to produce synthesis gas (a mixture of hydrogen and carbon monoxide). In the steam reforming process, a light hydrocarbon feedstock (such as natural gas, refinery gas, LNG, or naphtha) is reacted with steam at elevated temperatures(typically 700° C to 900° C), and elevated pressures (15 to 30 bar) in nickel-based catalyst filled tubes to produce a synthesis gas. This gas consists primarily of hydrogen and carbon monoxide. , but other gases such as carbon dioxide and nitrogen, as well as water vapor are also present.The typical steam to carbon ratio falls in the range of (2.8 to 3.2 to 1).
  24. 24. steam reforming (SR) is highly endothermic and it is carried out at high temperature (700 - 900 ºC) and at pressures between 15 and 30 bar.
  25. 25. The standard enthalpies of reaction (at 298 K) are given in brackets. The most important reactions in steam reforming (SR) of methane are: 1. CH4(g) + H2O(g) ↔ CO(g) + 3H2(g) (∆H = +206 kJ/mol) 2. CO(g) + H2O(g) ↔ CO2(g) + H2(g) (∆H = -41 kJ/mol) Reactions and thermodynamics
  26. 26. Catalyst All tubular reformers use catalyst inside the tubes in order to reduce the operating temperature. This is important in order to reduce the tube stresses resulting from high pressure and high temperatures The Ni-catalyst is needed since methane is a very thermodynamically stable molecule even at high temperatures. nickel catalyst filled tubes to produce a synthesis gas. Ni-catalyst is often in the form of thick-walled Raschig rings, with 16 mm in diameter and height, and a 6 – 8 mm hole in the middle.
  27. 27. Challenges During the production of Synthesis gas, CO2 is also produced. The SMR process in centralized plants emits more than twice the CO2 than hydrogen produced. To avoid emission of CO2 into the atmosphere, CO2 can be concentrated, captured, and sequestered.
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  29. 29. Thanks for Watching Please follow me / SAJJAD KHUDHUR ABBAS
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Episode 3 : Production of Synthesis Gas by Steam Methane Reforming History of Synthesis Gas In 1780, Felice Fontana discovered that combustible gas develops if water vapor is passed over carbon at temperatures over 500 °C. This CO and H2 containing gas was called water gas and mainly used for lighting purposes in the19th century. As of the beginning of the 20th century, H2/CO-mixtures were used for syntheses of hydrocarbons and then, as a consequence, also called synthesis gas. Haber and Bosch discovered the synthesis of ammonia from H2 and N2 in 1910 and the first industrial ammonia synthesis plant was commissioned in 1913. The production of liquid hydrocarbons and oxygenates from syngas conversion over iron catalysts was discovered in 1923 by Fischer and Tropsch. Much of the syngas conversion processes were being developed in Germany during the first and second world wars at a time when natural resources were becoming scare and alternative routes for hydrogen production, ammonia synthesis, and transportation fuels were a necessity. In 1943/44, this was applied for large-scale production of artificial fuels from synthesis gas in Germany.

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