1. Production of Syngas and Ethanol Group II

2. Definition of Syngas Syngas is the abbreviated name for synthesis gas. It is a gas mixture that comprises of hydrogen and carbon monoxide. components of syngas

3. Importance of Synthesis Gas The rising cost of petroleum has motivated the examination of alternative feedstocks for chemical production. One such feedstock is synthesis gas. The major components of syngas, hydrogen and carbon monoxide, are the basic building blocks of a number of other products. In the future, syngas will become increasingly important for the production of cleaner fuels. The huge potential market for syngas is illustrated by the fact that almost 20% of the present world primary energy consumption is for transportation fuels only. If the chemical sector is included, the total syngas potential increases to approximately 30%.

4. Routes to Syngas There are three main routes to the production of synthesis gas: steam reforming of natural gas partial oxidation of natural gas partial oxidation of vacuum residuum

5. Methods of Production Steam Reforming of Natural Gas Raw Materials Natural Gas - methane, CO 2, nitrogen, ethane, C 3 Air - nitrogen, oxygen Water - H 2 O Reactions CH 4 +H 2 O → CO+3H 2 3CH 4 +2H 2 O+CO 2 → 4CO+8H 2 Product Syngas - methane, CO 2, CO, hydrogen, nitrogen, water

6. Methods of Production Steam Reforming of Natural Gas SULFUR REMOVAL STEAM REFORMING HEAT RECOVERY CO 2 SEPARATION HYDROGEN SKIMMING natural gas steam raw syngas syngas product 38°C 315 psia 244°C 310 psia 885°C 295psia 49 ° C 280psia 54°C 253 psia 49°C 283 psia

7. Methods of Production Steam Reforming of Natural Gas

8. Methods of Production Partial Oxidation of Natural Gas Raw Materials Natural Gas - methane, CO 2, nitrogen, ethane, C 3 Oxygen - nitrogen, oxygen Steam - H 2 O Reactions CH 4 +0.5O 2 → CO+2H 2 Product Syngas - methane, CO 2, CO, hydrogen, nitrogen, water

9. Methods of Production Partial Oxidation of Natural Gas OXIDIZER REACTOR HEAT RECOVERY WATER SCRUBBER CO 2 SEPARATION natural gas raw syngas syngas product 49°C 962 psia 149°C 980 psia 1350°C 371°C 1000 psia steam oxygen 49°C 965 psia waste water CO 2

10. Methods of Production Partial Oxidation of Natural Gas

11. Methods of Production Partial Oxidation of Vacuum Residuum Raw Materials Vacuum Residuum - carbon, hydrogen, nitrogen, sulfur, ash Oxygen - oxygen, nitrogen Steam - H 2 O Reaction Products Syngas - methane, CO2, CO, hydrogen, nitrogen, water

12. Methods of Production Partial Oxidation of Vacuum Residuum OXIDIZER REACTOR HEAT RECOVERY WATER SCRUBBER natural gas ACID GAS REMOVAL CO SHIFT REACTOR SULFUR RECOVERY raw syngas CO 2 -rich gas soot + inorganic matter tail gas sulfur by-product syngas product 457°C 1000psia 1320°C 49°C 945 psia 425°C 49°C 915 psia steam oxygen 49°C 945 psia

13. Methods of Production Partial Oxidation of Vacuum Residuum

14. Additional Methods for Syngas Production Auto thermal reforming (ATR) Combined reforming

15. Additional Methods for Syngas Production Auto thermal Reforming ATR This process combines partial oxidation and adiabatic steam reforming. A process consist of desulphurization, pre- heater, reactor, heat recovery and separation unit. A mixture of natural gas, oxygen and steam is fed to the reactor. The partial oxidation occur in a combustion area,then the product pass through catalyst bed where reforming reaction occur. The temperature of the produced syngas is less than one of the partial reactor cause the catalyst does not support high T values.

16. Additional Methods for Syngas Production Auto thermal Reforming ATR

17. Additional Methods for Syngas Production Combined Reforming Combined reforming includes steam reformer and auto-thermic reactor. The combined reforming reactor advantages are: Control the H 2 /CO ratio in the synthesis. Oxygen used less than auto-thermic reforming and partial oxidation in the case of nitrogen free syngas. Pressure can be increased with lower exit temperature of the reformer to reduce the size of the reactor 50% compared with steam reforming. Increase the pressure with saving oxygen. Hydrogen removed which leads less NOx emission compared with steam reforming.

18. Ethanol from Synthesis Gas Currently all commercial synthetic ethanol is made by the hydration of ethylene. The rising price of petroleum-based ethylene has motivated the examination of routes to ethanol from syngas. One such route is the direct synthesis of ethanol from syngas.

19. Production of Ethanol Direct Synthesis of Syngas Raw materials Hydrogen, carbon monoxide, carbon dioxide, nitrogen Reactions 4H 2 + 2CO → CH 3 CH 2 OH + H 2 O 6H 2 + 2CO 2 → CH 3 CH 2 OH + 3H 2 O Products methanol, ethanol (main product), propanols, butanols, pentanols, hexanols, heptanols, methane

20. Production of Ethanol Direct Synthesis of Syngas COMPRESSOR COOLING COMPRESSOR 3 PARALLEL REACTOR LOOPS 3 STEAM GENERATORS DISENGAGEMENT VESSEL METHANOL PRODUCT COLUMN AZEOTROPIC DISTILLATION COLUMN ALCOHOL DRYING COLUMN ETHANOL PRODUCT COLUMN syngas aqueous alcohols dried alcohols 60 ° F 127 ° F 870 psia 608 ° F 140 ° F250 ° F azeotrope mixture recycled syngas ethanol product 140 ° F n-propanol Iso-propamol

21. Production of Ethanol Direct Synthesis of Syngas

22. Uses of Syngas generation of industrial gases, fertilizers, chemicals production of transportation fuels used as an intermediary building block for the final production of various fuels such as: synthetic natural gas methanol synthetic petroleum fuels (dimethyl ether – synthesized gasoline and diesel fuel) hydrogen component of syngas can be used to directly power hydrogen fuel cells for electricity generation

23. Uses of Ethanol used extensively as a solvent in the manufacture of varnishes and perfumes used as a cooking and lighting fuel used in an antiseptic manufacture of acetaldehyde and acetic acid as the fluid in thermometers a primary constituent in alcoholic beverages