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Chemical Reactors and their Applications


Chemical Reactors and their Applications

Chemical Reactors and their Applications

Outline
Reactor concepts

Natural gas reforming concepts

Downstream processes

Chemical Reactors and their Applications

Outline
Reactor concepts

Natural gas reforming concepts

Downstream processes

Chemical Reactors and their Applications

Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns

Chemical Reactors and their Applications

Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns

Chemical Reactors and their Applications

Fixed Bed Reactors


Concept Collection of fixed solid particles. The particles may serve as a catalyst or an adsorbent. Continuous gas flow (Trickling liquid)

Applications
Synthesis gas production Methanol synthesis Ammonia synthesis Fischer-Tropsch synthesis Gas cleaning (adsorption)
Chemical Reactors and their Applications

Fixed Bed Reactors


Challenges/Limitations
Temperature control Pressure drop Catalyst deactivation

Chemical Reactors and their Applications

Fixed Bed Reactors


Challenges/Limitations
Temperature control Pressure drop Catalyst deactivation

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Fixed Bed Reactors


Temperature control
Endothermic reactions may die out Exothermic reactions may damage the reactor Selectivity control

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Fixed Bed Reactors


Single-Bed Reactor
All the particles are located in a single vessel

Advantages/Disadvantages
Easy to construct Inexpensive Applicable when the reactions are not very exo-/endothermic

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Fixed Bed Reactors


Multi-Bed Reactor
Several serial beds with intermediate cooling/heating stages

Advantages/Disadvantages
Applicable for exo-/endothermic reactions

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Fixed Bed Reactors


NH3 reactor SO3 reactor

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Fixed Bed Reactors


Multi-Tube Reactor
Several tubes of small diameter filled with particles.

Advantages/Disadvantages
Expensive High surface area for heat exchange Very good very temperature control Applicable for very exo/endothermic reactions
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Fixed Bed Reactors


Steam reformer

Reactor height: Number of tubes: Tube length:

30 m 40-10000 6-12 m

Tube diameter:

70-160 mm

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Fixed Bed Reactors


Challenges/Limitations
Temperature control Pressure drop Catalyst deactivation

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Fixed Bed Reactors


Pressure drop
Friction between the gas and particle phase results in a pressure drop.
High pressure drop high compression costs Some systems have low tolerance for pressure drop. The pressure drop is mainly dependent on reactor length, particle diameter, void fraction and gas velocity.

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Fixed Bed Reactors

Large particles has to be used (dp>1mm).

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Fixed Bed Reactors


Porous catalyst particle
The particles are porous to increase the surface area of the catalyst. Reactants are transported inside the pores by means of molecular diffusion and adsorb to the active sites where the reaction occurs. Products desorb and diffuse back to the bulk. Heat is transported by conduction.

Intra-particle diffusion/conduction may be rate determining for large particles ( egg-shell particles).

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Fixed Bed Reactors


Challenges/Limitations
Temperature control Pressure drop Catalyst deactivation

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Fixed Bed Reactors


Catalyst deactivation
The catalyst gets deactivated if the active sites get contaminated.
Sulfur compounds deactivate Ni-catalysts Desulfurization is often necessary prior to reforming. Formation of carbon deposits deactivate the catalysts. Large carbon deposits may clog the tubes, causing hot-spots that damage the reactor. Catalyst regeneration is necessary.
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Fixed Bed Reactors


Summary Advantages/Disadvantages
High conversion is possible Large temperature gradients may occur Inefficient heat-exchange Suitable for slow- or non-deactivating processes

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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns

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Fluidized Bed Reactors


Concept Collection of solid particles dispersed in a continuous phase. The particles may serve as a catalyst, adsorbent or a heat carrier. Continuous flow of gas or liquid

Applications
Catalytic cracking processes Fischer-Tropsch synthesis Polymerization Waste combustion Drying
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Fluidized Bed Reactors

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Fluidized Bed Reactors

A fluidized bed exhibits liquidlike behavior

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Fluidized Bed Reactors

Continuous regeneration
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Fluidized Bed Reactors


Summary Advantages/Disadvantages
Conversion may be poor if gas is bypassing. Erosion of vessel and pipe lines. Uniform temperature Efficient heat-exchange Can handle rapid deactivating processes.
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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns

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Stirred tank Reactors


Concept Forced mixing by use of impeller. Applied in reactive systems when mixing is the rate determining step. Single phase: liquid mixing. Two phases: liquid/gas, liquid/particle Three phases: liquid/particle/gas Typical applications
Chemical component and phase mixing Fermentation reactor Food and paper industry Natural gas conversion/polymerization
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Stirred tank Reactors


The mixing is influenced by:
stirring rate and pumping capacity liquid height

baffle design
(baffles reduces solid body rotation)

size and geometry of the tank

size and geometry of heat equipment


size and type of impeller
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Stirred tank Reactors


Impellers
Radial flow impellers are suitable for dispersion of gas in liquid.

Axial flow impellers are suitable to blend liquids and suspend solids in liquids.

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Stirred tank Reactors


Summary Advantages/Disadvantages
Uniform temperature Efficient heat-exchange
Exception: slurries with high concentrations of large particles (difficult mixing).

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Reactor Concepts
Fixed bed reactors Fluidized bed reactors Stirred tank reactors Slurry loop reactors Bubble columns

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Slurry loop Reactors


Concept Collection of solid catalyst particles dispersed in a liquid phase (slurry). The slurry is circulating at a high velocity impelled by an axial pump. The mixing pattern is very intensive and well defined.

Typical application
Polymerization

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Slurry loop Reactors


Summary Advantages/Disadvantages
Uniform temperature Very efficient heat-exchange Can operate at high polymer concentrations

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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

Natural gas reforming 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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Natural gas reforming concepts


Steam reforming (SR) Partial oxidation (POX) Autothermal reforming (ATR) New reforming concepts

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Natural gas reforming concepts


Steam reforming (SR) Partial oxidation (POX) Autothermal reforming (ATR) New reforming concepts

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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)

Overall heat of reaction is endothermic multi-tube reformer


Reactions are catalyzed over Ni-catalyst.
Temperature
Pressure H2/CO

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

Better temperature control with side fired burners


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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.

Actions to reduce carbon formation


High steam/carbon (S/C) ratio reduces carbon formation.
Expensive to produce steam.

Addition of CO2 reduces carbon formation Pre-reformer if higher hydrocarbons are present Common S/C-ratio is 2.54.5
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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

Steam corrosion problems.


Costs in handling excess H2O.
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Natural gas reforming concepts


Steam reforming (SR) Partial oxidation (POX) Autothermal reforming (ATR) New reforming concepts

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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

Overall heat of reaction is slightly exothermic. No catalyst (burners)

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Catalytic partial oxidation


Reactions are catalyzed to: improve selectivities eliminate the need for burners eliminate soot formation lower reaction temperatures Drawbacks CH4/O2 mixtures can be explosive. Problems with selectivities at high pressures (above 20 bars).
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Partial oxidation
Advantages/Disadvantages
Less expensive than SR-plants.
H2/CO ratio suitable for methanol- or FT-synthesis

Soot problems (POX)


Needs expensive oxygen plant.
(dependent on downstream process)

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Natural gas reforming concepts


Steam reforming (SR) Partial oxidation (POX) Autothermal reforming (ATR) New reforming concepts

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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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Natural gas reforming concepts


Steam reforming (SR) Partial oxidation (POX) Autothermal reforming (ATR) New reforming concepts

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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.
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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

Natural gas reforming 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.
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Ammonia synthesis

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Ammonia synthesis

ICI quench reactor

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Ammonia synthesis

Haldor Topse radial flow reactor

Kellogg vertical reactor

Kellogg horizontal reactor

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Ammonia synthesis

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Methanol synthesis
Methanol Base chemical for:
Formaldehyde Acetic acid

Automobile fuel and fuel additive (MTBE)

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
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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

Haldor Topse reactor concept

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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

T<530 K due to carbon deposition

T>570 K to avoid heavy wax formation

T<570 K due to hydrocracking

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