Chemical Reactors

1
Chemical Reactors and their Applications

Norges teknisk-naturvitenskapelige universitet
Chemical Reactors
and their
Applications
2
3
Outline
Reactor concepts

Natural gas reforming concepts

Downstream processes
4
Outline
Reactor concepts


5
Reactor Concepts
Fixed bed reactors

Fluidized bed reactors

Stirred tank reactors

Slurry loop reactors

Bubble columns

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Reactor Concepts
Fixed bed reactors




Bubble columns

7
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)
8
Fixed Bed Reactors
Challenges/Limitations

Temperature control

Pressure drop

Catalyst deactivation

9
Fixed Bed Reactors

Temperature control

Pressure drop


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Fixed Bed Reactors
Temperature control

Endothermic reactions may die out

Exothermic reactions may damage the reactor

Selectivity control

11
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

Applicable for exo-/endothermic
reactions

13
Fixed Bed Reactors
SO
3
reactor
NH
3
reactor
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Fixed Bed Reactors
Multi-Tube Reactor
Several tubes of small
diameter filled with particles.

Expensive
High surface area for heat
exchange Very good very
temperature control
Applicable for very exo-
/endothermic reactions
15
Fixed Bed Reactors
Steam reformer
Reactor height: 30 m
Number of tubes: 40-10000
Tube length: 6-12 m
Tube diameter: 70-160 mm
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Fixed Bed Reactors

Temperature control

Pressure drop


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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 (d
p
>1mm).

19
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).
20
Fixed Bed Reactors

Temperature control

Pressure drop


21
Fixed Bed Reactors
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.
22
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




Bubble columns

24
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
Polymerization
Waste combustion
Drying
25
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A fluidized bed exhibits liquidlike behavior
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Continuous regeneration
28

Conversion may be poor if gas is bypassing.

Erosion of vessel and pipe lines.

Uniform temperature

Efficient heat-exchange

Can handle rapid deactivating processes.
29
Reactor Concepts
Fixed bed 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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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
32
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.
33

Uniform temperature

Exception: slurries with high concentrations of large particles
(difficult mixing).

34
Reactor Concepts
Fixed bed reactors




Bubble columns

35
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

Uniform temperature

Very efficient heat-exchange

Can operate at high polymer concentrations
37
Reactor Concepts
Fixed bed reactors




Bubble columns

38
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

Non-uniform product if bubble size distribution is heterogeneous

Uniform temperature


43
Outline
Reactor concepts


44
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
CH
4
70-90%
C
2
H
6
-C
4
H
10
0-20%
CO
2
0-8%
N
2
0-5%
H
2
S 0-5%
45
Steam reforming (SR)

Partial oxidation (POX)

Autothermal reforming (ATR)

New reforming concepts

46




47
Steam reforming
48
Steam reforming
Primary reformer
CH
4
+ H
2
O CO + 3H
2
H
r
=206 kJ/mol

CO + H
2
O CO
2
+ H
2
H
r
= -41 kJ/mol (Water gas shift)

Overall heat of reaction is endothermic multi-tube reformer

Reactions are catalyzed over Ni-catalyst.

Temperature 1100-1200K
Pressure 15-30 bar
H
2
/CO >3
49
Steam reforming
Burner configurations
50
Steam reforming
Better temperature control with side fired burners
Catalyst deactivates

Retaining productivity by
increasing temperature
51
Steam reforming
Carbon formation
2CO C + CO
2
H
r
= -173 kJ/mol (The Boudouard reaction)
CH
4
C + 2H
2
H
r
= 75 kJ/mol (Decomposition of methane)
CO + H
2
C + H
2
O H
r
= -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 CO
2
reduces carbon formation
Pre-reformer if higher hydrocarbons are present
Common S/C-ratio is 2.54.5
52
Steam reforming
53
Steam reforming
Adiabatic Pre-reformer
C
n
H
m
+ nH
2
O nCO + (n+m/2)H
2
H
r
>0

CO + 3H
2
CH
4
+ H
2
O H
r
= -206 kJ/mol

Overall heat of reaction is exothermic or thermoneutral.

Reactions are catalyzed over Ni-catalyst.
54
Steam reforming
55
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 H
2
S over Co-
Mo or Ni-Mo catalysts.
H
2
S and other sulfur species are adsorbed over a bed of zinc-oxide.

56
Steam reforming
No need for expensive oxygen plant.

Material limitations on temperature limited conversion.

High H
2
/CO ratio, suitable for hydrogen production with CO
2

capture, not for methanol- or FT-synthesis.

Carbon formation

Steam corrosion problems.

Costs in handling excess H
2
O.
57



58
Partial oxidation
CH
4
+ O
2
CO + 2H
2
H
r
= -36 kJ/mol

CH
4
+ 2O
2
CO
2
+ 2H
2
O H
r
= -803 kJ/mol

CO + O
2
CO
2
H
r
= -284 kJ/mol

H
2
+ O
2
H
2
O H
r
= -242 kJ/mol

Overall heat of reaction is slightly exothermic.

No catalyst (burners)
Pressure 150 bar
H
2
/CO <2
59
Catalytic partial oxidation
Reactions are catalyzed to:
improve selectivities

eliminate the need for burners

eliminate soot formation

lower reaction temperatures

Drawbacks
CH
4
/O
2
mixtures can be explosive.

Problems with selectivities at high pressures
(above 20 bars).
60
Partial oxidation
Less expensive than SR-plants.

H
2
/CO ratio suitable for methanol- or FT-synthesis

Soot problems (POX)

Needs expensive oxygen plant.
(dependent on downstream process)

61



62
Autothermal reforming
Pressure 20-100 bar
H
2
/CO 2-3
Catalytic/non-catalytic
partial oxidation provides
heat for steam reforming

More energy efficient
63
Autothermal reforming
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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65
Multifunctional reactors
Membrane reactors
Combine air separation and partial oxidation in one unit by
introduce oxygen permeable membranes.

Remove H
2
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 oxygen-
and 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.
66
Multifunctional reactors
Sorption enhanced reaction process (SERP)
Remove CO
2
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).
67
Outline
Reactor concepts


68
Ammonia synthesis

Methanol synthesis


69
Ammonia synthesis
Ammonia
Base chemical for:
Nitrogen fertilizers (CaNO
3
,KNO
3
)
Explosive industry

Production history
1905; Birkeland/Eyde succeeded in producing CaNO
3
from air.
1913; The Haber/Bosch-process was developed.
70
Ammonia synthesis
N
2
+ 3H
2
2NH
3
H
r
= -91.4 kJ/mol

Ideal H
2
/N
2
-ratio is 3.
Steam reforming is suitable reforming process due to high H
2
/CO-
ratio. It is combined with an air-blown ATR that introduces N
2
.

Equilibrium limited High pressure (100-250 bar) and low
temperature (675-770K).

Low single-pass conversion Recycling necessary.

CO and CO
2
has to be removed prior to the
ammonia synthesis several extra process units.
71
Ammonia synthesis

72
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
75
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.
76
Methanol synthesis
CO + 2H
2
CH
3
OH H
r
= -90.8 kJ/mol

CO
2
+ 3H
2
CH
3
OH + H
2
O H
r
= -49.6 kJ/mol

CO + H
2
O CO
2
+ H
2
H
r
= -41 kJ/mol

Ideal H
2
/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. CH
4
.

Cu/ZnO/Al
2
O
3
77
Methanol synthesis
Distillation
Column 1: Gases and light
impurities are removed.
Column 2: Methanol is separated
from heavy alcohols and water.
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.

78
Methanol synthesis

Lurgi reactor
Haldor Topse reactor concept
79
Methanol synthesis
Slurry reactor (fluidized bed)
Inert hydrocarbon liquid (absorbs heat, uniform temp.)
Solid catalyst.
Higher single-pass conversion less compression costs.

80
Methanol synthesis
Direct conversion of methane
CH
4
+ O
2
CH
3
OH H
r
= -126 kJ/mol

Significant efficiency increase.
No CO
2
production.
Low yields.
81
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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CO + 2H
2
-CH
2
- + H
2
O H
r
= -165 kJ/mol

Chain growth.

High exothermicity.
Effective heat removal is a major consideration in reactor design.

Converted over Fe- or Co-based catalysts.

Selective productivity is not possible product ranges.
83

T<530 K due to carbon deposition T>570 K to avoid heavy wax formation T<570 K due to hydrocracking

Chemical Reactors

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Chemical Reactors and their Applications

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