Beruflich Dokumente
Kultur Dokumente
Outline
Reactor concepts
Downstream processes
Outline
Reactor concepts
Downstream processes
Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns
Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns
Applications
Synthesis gas production Methanol synthesis Ammonia synthesis Fischer-Tropsch synthesis Gas cleaning (adsorption)
Chemical Reactors and their Applications
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Advantages/Disadvantages
Easy to construct Inexpensive Applicable when the reactions are not very exo-/endothermic
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Advantages/Disadvantages
Applicable for exo-/endothermic reactions
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Advantages/Disadvantages
Expensive High surface area for heat exchange Very good very temperature control Applicable for very exo/endothermic reactions
Chemical Reactors and their Applications
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30 m 40-10000 6-12 m
Tube diameter:
70-160 mm
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Intra-particle diffusion/conduction may be rate determining for large particles ( egg-shell particles).
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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns
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Applications
Catalytic cracking processes Fischer-Tropsch synthesis Polymerization Waste combustion Drying
Chemical Reactors and their Applications
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Continuous regeneration
Chemical Reactors and their Applications
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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns
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baffle design
(baffles reduces solid body rotation)
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Axial flow impellers are suitable to blend liquids and suspend solids in liquids.
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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns
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Typical application
Polymerization
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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns
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Bubble Columns
Concept Gas dispersed in a continuous liquid phase. Two phases: liquid/gas. Three phases: slurry/gas
Typical applications
Natural gas conversion Waste water treatment Bio-processes
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Bubble Columns
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Bubble Columns
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Bubble Columns
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Bubble Columns
Summary Advantages/Disadvantages
Non-uniform product if bubble size distribution is heterogeneous Uniform temperature Efficient heat-exchange
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Outline
Reactor concepts
Downstream processes
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Natural gas
Vital component of the world's supply of energy (approx. 20%). Fuel Most common feedstock for hydrogen production or synthesis gas production.
Production of base chemicals (methanol, ammonia)
Typical composition
CH4 CO2 N2 H 2S 70-90% 0-8% 0-5% 0-5%
C2H6-C4H10 0-20%
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Steam reforming
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Steam reforming
Primary reformer
CH4 + H2O CO + 3H2 Hr=206 kJ/mol
CO + H2O CO2 + H2 Hr= -41 kJ/mol
(Water gas shift)
1100-1200K
15-30 bar >3
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Steam reforming
Burner configurations
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Steam reforming
Catalyst deactivates
Retaining productivity by increasing temperature
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Steam reforming
Carbon formation 2CO C + CO2 Hr= -173 kJ/mol (The Boudouard reaction) CH4 C + 2H2 Hr= 75 kJ/mol (Decomposition of methane) CO + H2 C + H2O Hr= -132 kJ/mol (Heterogeneous water gas reaction)
Carbon deposits deactivates the catalyst.
Addition of CO2 reduces carbon formation Pre-reformer if higher hydrocarbons are present Common S/C-ratio is 2.54.5
Chemical Reactors and their Applications
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Steam reforming
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Steam reforming
Adiabatic Pre-reformer
CnHm + nH2O nCO + (n+m/2)H2
CO + 3H2 CH4 + H2O
Hr>0
Hr= -206 kJ/mol
Overall heat of reaction is exothermic or thermoneutral. Reactions are catalyzed over Ni-catalyst.
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Steam reforming
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Steam reforming
Hydro-desulfurizer (HDS)
Sulfur compounds are present in practically all gas feedstocks. Ni-catalysts are poisoned by sulfur compounds desulfurization
Cyclic organic sulfur compounds are hydrogenated to H2S over CoMo or Ni-Mo catalysts. H2S and other sulfur species are adsorbed over a bed of zinc-oxide.
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Steam reforming
Advantages/Disadvantages
No need for expensive oxygen plant.
Material limitations on temperature limited conversion. High H2/CO ratio, suitable for hydrogen production with CO2 capture, not for methanol- or FT-synthesis. Carbon formation
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Partial oxidation
CH4 + O2 CO + 2H2 CH4 + 2O2 CO2 + 2H2O CO + O2 CO2 H2 + O2 H2O
Hr= -36 kJ/mol Hr= -803 kJ/mol Hr= -284 kJ/mol Hr= -242 kJ/mol
Temperature 1600-1900K
150 bar <2 Pressure H2/CO
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Partial oxidation
Advantages/Disadvantages
Less expensive than SR-plants.
H2/CO ratio suitable for methanol- or FT-synthesis
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Autothermal reforming
Catalytic/non-catalytic partial oxidation provides heat for steam reforming More energy efficient
Temperature Pressure H2/CO 1200-1400K 20-100 bar 2-3
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Autothermal reforming
Advantages/Disadvantages
Less expensive than SR-plants.
Higher conversion than SR (higher operating temperature).
No soot problems
Needs expensive oxygen plant.
(dependent on downstream process) Often used as a secondary reformer downstream an SR.
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Multifunctional reactors
Membrane reactors
Combine air separation and partial oxidation in one unit by introduce oxygen permeable membranes.
Remove H2 in the reactor by using membranes and thereby avoid equilibrium limitations
Lower reaction temperatures can be used.
Chemical looping reforming Continuous circulation of metal particles which serve as oxygenand heat carrier (metal oxide) for partial oxidation of methane. Two reactors are required: Air reactor and fuel reactor.
Simple separation of oxygen. No explosive mixtures.
Chemical Reactors and their Applications
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Multifunctional reactors
Sorption enhanced reaction process (SERP) Remove CO2 in the SR-process by using adsorbents mixed with the catalyst particles and thereby avoid equilibrium limitations. The adsorbent is regenerated by either increasing the temperature or reducing the pressure (temperature- or pressure swing).
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Outline
Reactor concepts
Downstream processes
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Downstream processes
Ammonia synthesis Methanol synthesis Fischer-Tropsch synthesis
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Ammonia synthesis
Ammonia Base chemical for:
Nitrogen fertilizers (CaNO3,KNO3) Explosive industry
Production history 1905; Birkeland/Eyde succeeded in producing CaNO3 from air. 1913; The Haber/Bosch-process was developed.
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Ammonia synthesis
N2 + 3H2 2NH3 Hr = -91.4 kJ/mol Ideal H2/N2-ratio is 3. Steam reforming is suitable reforming process due to high H2/COratio. It is combined with an air-blown ATR that introduces N2. Equilibrium limited High pressure (100-250 bar) and low temperature (675-770K). Low single-pass conversion Recycling necessary. CO and CO2 has to be removed prior to the ammonia synthesis several extra process units.
Chemical Reactors and their Applications
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Ammonia synthesis
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Ammonia synthesis
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Ammonia synthesis
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Ammonia synthesis
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Methanol synthesis
Methanol Base chemical for:
Formaldehyde Acetic acid
Production history 1923; BASF was the first to synthesize methanol from syngas. 1960s; New catalysts were developed for low-pressure production.
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Methanol synthesis
CO + 2H2 CH3OH CO2 + 3H2 CH3OH + H2O CO + H2O CO2 + H2 Hr = -90.8 kJ/mol Hr = -49.6 kJ/mol Hr = -41 kJ/mol
Ideal H2/CO-ratio is 2. Low single-pass conversion Recycling necessary. Equilibrium limited High pressure (50-100 bar) and low temperature (500-550K). T < 570K due to catalyst sintering. The catalyst has to be very selective since methanol is thermodynamically less stabile than i.e. CH4. Cu/ZnO/Al2O3
Chemical Reactors and their Applications
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Methanol synthesis
Reactor (ICI)
40% of the feed enters the reactor 60% of the feed is used as quench.
Separator
Gas and liquid are separated after several cooling steps.
Distillation
Column 1: Gases and light impurities are removed. Column 2: Methanol is separated from heavy alcohols and water.
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Methanol synthesis
Lurgi reactor
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Methanol synthesis
Slurry reactor (fluidized bed) Inert hydrocarbon liquid (absorbs heat, uniform temp.) Solid catalyst. Higher single-pass conversion less compression costs.
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Methanol synthesis
Direct conversion of methane CH4+ O2 CH3OH Hr = -126 kJ/mol Significant efficiency increase. No CO2 production. Low yields.
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Fischer-Tropsch synthesis
Applicability Fuels Waxes History 1923; Fischer/Tropsch converted synthesis gas into a wide range of hydrocarbons and/or alcohols. WW II; Germany applied FT-synthesis to make fuels. 1950s; South Africa started to make fuels and base chemicals in FT-plants to reduce the dependence on imported oil.
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Fischer-Tropsch synthesis
CO + 2H2 -CH2- + H2O Chain growth. High exothermicity.
Effective heat removal is a major consideration in reactor design.
Hr = -165 kJ/mol
Converted over Fe- or Co-based catalysts. Selective productivity is not possible product ranges.
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Fischer-Tropsch synthesis