Industrial Technology

Industrial Technology
Dr.-Ing. George Power Porto
Industrial gases
Industrial gases
Group of gases produced commercially for diverse applications (metallurgy, oil refining, fertilizers, medicine, etc.) Manufactured by separation or synthesis processes, and sold in gaseous (compressed), liquid or solid state. Important groups:
Air and its main components (O2, N2, Ar) Noble gases (He, Kr, Ne, Xe) Other elementary gases (H2, Cl2, F2) Compounds (NH3, CO2, N2O, CH4, C2H2, etc.)
Industrial Technology 2
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Earths atmosphere as a source of industrial gases

Composition of atmospheric air at sea level (dry basis)*:
Component Nitrogen Oxygen Formula N2 O2 % vol. 78,03 20,99
Average molar mass (g/mol):
M 0,7803 28,02 0,2099 32,00 0,0094 39,94 0,0003 44,01 28,97
Argon
Carbon dioxide Neon Helium Krypton
Ar
CO2 Ne He Kr
0,94
0,03 0,00123 0,0004 0,00005
Xenon
Hydrogen Methane Nitrous oxide
Xe
H2 CH4 N2O
0,000006
0,01 0,0002 0,00005
*) Atmospheric air also contains variable amounts of water vapor (humidity), ozone and suspended particles.
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History of cryogenic technology

In the past, the components of air were considered permanent gases because they couldnt be liquefied at high pressure. In 1895 Carl von Linde developed and patented a technical method for liquefaction of atmospheric gases and mixtures of gases like air. The first air separation unit was built and put in operation in 1902. The original Linde process, modified with substantial improvements (regenerative cooling, expansion turbines, cold box, etc.), is the basis of industrialization of air and other cryogenic gases (Tb < 150 C).
02/04/2012 Industrial Technology
Carl von Linde (1842 1934)
Thermodynamic background
A gas can be liquefied only at a temperature below its critical point (O2 154.6 K, N2 126.2 K) Necessary low temperatures for liquefaction of air components (O2 90.2 K, N2 77.4 K, Ar 87.3 K) can be reached with application of the Joule-Thomson effect (cooling due to expansion) With the same principle other industrial gases can be liquefied, hydrogen and helium require precooling with liquid air.
02/04/2012 Industrial Technology
Compressor
Inlet valve
200 bar
Outlet valve
Heat exchanger
Expansion valve 20 bar
Liquid air
Principle of the Linde process 5
Principle of cryogenic liquefaction

Make-up gas
Compressor
Heat exchanger
Expansion valve
s
Scheme of Linde-Hampson process Temperature-Entropy diagram
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Process steps
Filtration of atmospheric air (dust and particle removal) Pre-compression and purification (removal of water vapor, carbon dioxide, hydrocarbons) Main compression Regenerative cooling Expansion y liquefaction Fractioning in double rectifier column Separate purification of argon (optional)
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Generic Air Separation Unit (ASU)

Nitrogen Vaporizer
Product compression Local pipeline users GAR GAN GOX
Main heat exchangers cold box

Warm
Argon
GAN
LIN Truck loading area

Gaseous
Warm Cold
Internal refrigeration or liquefier cold box
Rectifier column cold box
LAR
Argon purifier
Air feed
Filter
PPU (Mole Sieve)
Product storage LOX
Oxygen
Compressor Partially condensed air
Liquid Gaseous H2O H2O, CO2, HC Impurity removal
Key:
(By-) Product
Customers
Liquid
Oxygen
Nitrogen Argon Water
GOX
GAN GAR H2O
LOX
LIN LAR H2 O
Carbon dioxide
Hydrocarbons
CO2
HC
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PFD filtration, pre-compression and purification
Waste nitrogen
Molecular Sieve
6 7 atm Air Filter Compressor Refrigeration unit Purified air to liquefaction Separator Heater Condensed water Waste nitrogen from main heat exchanger
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PFD main compression, cooling, liquefaction and separation

Sub cooler
1.4 bar
Expansion valve
5.5 bar
Enriched liquid air w/ 40% O2
Lower Column
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Example PFD of LIN plant
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Examples
Fractioning column
Cold box
Largest air separation plant in Campeche (Mexico) Capacity: 1.500 MMSCFD (50.000 t/d) of nitrogen for enhanced oil recovery processes
Applications
Oxygen (100 million ton/y)

Metallurgy (production of iron, steel and other metals) Welding and cutting (oxyacetylene torch) Chemical processes Oxidant for missile and rocket fuels Medicine Protecting inert gas (food industry, fuels) Stainless steel manufacturing Diode, transistor and integrated circuit manufacturing Medicine, cryopreservation Cryogenic coolant Inert gas for welding (MIG, TIG) Lightning (incandescent lamps) Protecting gas in food industry Insulator (window panes)
Nitrogen
Argon

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Hydrogen
Simplest, lightest and most abundant element (75% of the universes mass, and 93% of the solar system) Represents only 0.12% of the earths mass and 2.9% of the earths crust and is never found in elementary state Together with carbon, oxygen and nitrogen, hydrogen is an important component of organic molecules essential for life
Large gaseous planets like Saturn are made mainly of hydrogen and helium
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Uses
More than 600 billion m3 (30 million tons) of hydrogen are produced annually for:
Energy source: welding, rocket fuel, reaction and internal combustion engines Reducing agent for metallic oxides Synthesis reactions (ammonia, methanol, hydrogen chloride) Petroleum refining and petrochemical industry Liquid and gasous fuel manufacturing from coal Food industry (hydrogenated fats, gas packaging) Cryogenic technology
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Manufacturing methods
Hydrogen can be easily obtained by electrolysis of water (concentrated KOH soution for higher conductivity), however with high energy costs: H2O (l) H2 (g) + O2 (g) The most common industrial method is steam reforming of natural gas (and other hydrocarbons) : CnHm + n H2O n CO (g) + (n+m)/2 H2 (g)
Step 1: reforming
Methane (and other hydrocarbons) react with steam in a steam reformer at 800 900 C and 1.6 MPa, in ceramic tubes impregnated with nickel catalyst and externally heated with combustion of natural gas (endothermic reaction) : CH4 + H2O CO + 3 H2 H = +191,7 kJ/mol Conversion rate can be increased with a higher water vapor to methane ration (up to 3:1), this also reduces undesired products Although reaction is favored by low pressure, higher operation pressures (up to 20 atm) because of the desired product state (pressurized hydrogen)
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Step 2: Shift reaction

More hydrogen can be obtained in the water gas shift reactor, by use of an iron oxide catalyst: CO + H2O CO2 + H2 H = 40,4 kJ/mol This exothermic reaction is carried out in one or two stages: a high temperature shift (HTS), at 350 C, and a low temperature shift (LTS), at 190 210 C Carbon monoxide is converted in carbon dioxide, which is easily separated during purification
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Step 3: Purification
Chlorine and sulfur must be removed from feed stream to extend catalyst life. Product stream contains, apart from H2, H2O, CO2, CO, CH4 y other impurities Great part of H2O can be removed by condensation (compression and cooling) CO2 can be removed by liquid absorption In a final methanation step, residual traces of carbon oxides are converted Modern plants use Pressure Swing Adsorption (PSA) to produce high purity (99.99%) hydrogen.
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Flow diagram
Steam reforming plant with HTS y PSA in Texas City, Texas Capacity: 110.000 Nm3/h Purity: 99.99% mol
Source: http://www.linde-processengineering.com/process_plants/hydrogen_syngas_plants/gas_generation/ steam_reforming.php
Flow diagram for hydrogen production by steam reforming of natural gas

Source: http://www.alternative4energy.com
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Equipment detail
(Left) Modular reformer

Source: Rttger Carbotech Engineering, 2003
(Right) PSA units (Bottom) Skid with modular reformer block

Source: Mahler IGS, 2003
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Carbon dioxide
Colorless and odorless gas, present in biological processes and in the atmosphere (385 ppm, increment 2 ppm/year) Diverse uses:
Food industry (carbonated drinks, fermentation, decaffeination, nutrient in greenhouses) Refrigerant (liquid, dry ice) Technical uses: Lasers, polymers, fire extinguishers, welding, semiconductor manufacturing
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The global carbon cycle
Units: Flows GtC/a, Reservoirs GtC

Source: GLOBE Carbon Cycle, 2007
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Production methods
Carbonate decomposition CaCO3 CaO + CO2 Fermentation C6H12O6 2 CO2 + 2 C2H5OH Byproduct of hydrogen production CH4 + 2 H2O CO2 + 4 H2 Combustion of carbon and hydrocarbons CH4 + 2 O2 CO2 + 2 H2O
Flow diagram
LIST OF EQUIPMENT 1. Blower 2. CO2 generator 3. Stripping tower 4. Cooler/washer 5. Absorption tower 6. Exchanger 7. Cooler 8. Rich solution pump 9. Lean solution pump 10. Recycler pump 11. Recycle cooler 12. Product cooler Flue gas
Lean MEA solution

Rich MEA solution CO2 vapor Na2CO3 solution
Source: The Wittemann Company, LLC www.wittemann.com
Agua refrigerante
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Flow diagram (cont.)
LIST OF EQUIPMENT (cont.) 14. KMnO4 bubbler tanks 15. Adsorption tower WittFill/activated carbon 16. CO2 compressor 17. Intercooler 18. Aftercooler 19. High pressure precooler 20. Double CO2 drying tower 21. CO2 condenser 22. Liquid CO2 stripper 23. Liquid CO2 reboiler 24. Liquid CO2 pump 25. Liquid CO2 storage tank
KMnO4 WittFill Cooling water Activated carbon
Desiccant (silica gel) Liquid CO2 Cold refrigerant Hot refrigerant
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Acetylene (ethine)
Is the simplest alkyne (C2H2) 80% of acetylene production goes in organic synthesis reactions The remainder 20% is used in oxyacetylene torch (autogenous welding, torch cutting T > 3300 C) Highly inflammable and reactive, it must be stored in acetone in pressurized bottles filled with porous material for stabilization
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Production methods
High-temperature hydrocarbon pyrolysis (2000 C) or in electric-arc furnace: 2 CH4 C2H2 + 3 H2 By-products: hydrogen, soot and other pyrolysis gases Reaction of calcium carbide with water: CaC2 + 2 H2O C2H2 + Ca(OH)2 Obsolete method, high electrical energy consumption in the production of calcium carbide, product contaminated with raw material impurities. Previously used gas lamps.
PFD electric arc pyrolisis

Cyclone CH4 Scrubber Electrostatic precipitator
Electric arc reactor Water
Carbon black (soot)

C2H2 with pyrolysis gases 83 C Oil
Water with soot
Water
H2 with pyrolysis gases
C2H2 to purification Absorber 02/04/2012 Oil Oil filter Condenser Phase separator 29
Acetylene bottles
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Industrial Technology

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Industrial Technology

Dr.-Ing. George Power Porto

Earths atmosphere as a source of industrial gases

Average molar mass (g/mol):

M 0,7803 28,02 0,2099 32,00 0,0094 39,94 0,0003 44,01 28,97

History of cryogenic technology

Carl von Linde (1842 1934)

Expansion valve 20 bar

Principle of the Linde process 5

Principle of cryogenic liquefaction

Generic Air Separation Unit (ASU)

Product compression Local pipeline users GAR GAN GOX

Main heat exchangers cold box

LIN Truck loading area

Internal refrigeration or liquefier cold box

Rectifier column cold box

PPU (Mole Sieve)

Product storage LOX

Liquid Gaseous H2O H2O, CO2, HC Impurity removal

PFD filtration, pre-compression and purification

PFD main compression, cooling, liquefaction and separation

Enriched liquid air w/ 40% O2

Example PFD of LIN plant

Step 2: Shift reaction

Flow diagram for hydrogen production by steam reforming of natural gas

(Left) Modular reformer

(Right) PSA units (Bottom) Skid with modular reformer block

The global carbon cycle

Units: Flows GtC/a, Reservoirs GtC

Lean MEA solution

Flow diagram (cont.)

KMnO4 WittFill Cooling water Activated carbon

Desiccant (silica gel) Liquid CO2 Cold refrigerant Hot refrigerant

PFD electric arc pyrolisis

Electric arc reactor Water

Carbon black (soot)

Water with soot

H2 with pyrolysis gases

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