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Production Synthesis Gas

Important base chemical for variety of applications

Mixtures Main uses

H2 Refinery hydrotreating and hydrocracking


3 H2 : 1 N2 Ammonia plant feed
2 H2 : 1 CO Alkenes (Fischer-Tropsch reaction)
2 H2 : 1 CO Methanol plant feed
1 H2 : 1 CO Aldehydes and alcohols (Oxo reactions)
CO Acids (formic and acetic)

Feedstock?? Hydrocarbons
Future
natural gas, oil,coal
Solar??
biomass

Process?? Steam reforming


TUDelft Partial oxidation
Reactions starting from CH4
Steam reforming: CH4 + H2O CO + 3 H2 Hr = 206 kJ/mol

Water gas shift: CO + H2O CO2 + H2 Hr = - 41 kJ/mol

CO2 reforming: CH4 + CO2 2 CO + 2 H2 Hr = 247 kJ/mol

Thermal cracking: CH4 C + 2 H2 Hr = 75 kJ/mol

Boudouard reaction: 2 CO C + CO2 Hr = -173 kJ/mol

Partial oxidation: CH4 + O2 C + 2 2 Hr = -36 kJ/mol

Complete combustion: CH4 + 2 O2 C 2 + 2 2 Hr = -803 kJ/mol

TUDelft What reaction(s) are most attractive??


Conversion Routes to Synthesis Gas
Natural gas Heavy oil fraction Coal
H2O
O2/air
Desulfurization Partial Pulverization
oxidation
H2O Air/O2/(H2O) H2O
O2/air
Steam Autothermic Carbon Gasification
reforming reforming removal

Sulfur Sulfur
removal removal

Purification Purification Purification


Adjustment Adjustment Adjustment

Carbon monoxide, methanol, ammonia, hydrogen, etc.

TUDelft
Steam Reforming Thermodynamics
H2O/CH4 = 1

Heat required

H2/CO = 3

?
Temperature

TUDelft
Equilibrium Compositions
steam reforming versus partial oxidation
Steam reforming Partial oxidation
H2O/CH4 = 1 O2/CH4 = 0.5

H2/CO = 3 H2/CO = 2

TUDelft
Thermodynamics steam reforming
Effect of Temperature and Pressure
H2O/CH4 = 1

With increasing pressure


lower conversion
TUDelft
more CH4
Typical Allothermal Steam Reforming Process
Steam BFW
Cooling Raw syngas
water

Fuel
Tubes filled with Condensate
catalyst Air
Flue gas to stack
L = 7 - 12 m
Superheated
dt = 70 - 130 mm HP Steam BFW
500 - 600 tubes
Convection
Material tubes section
Ni-Cr alloy up to 1150 oC Radiation section

(Tm = 1370 oC)


Process steam
More expensive materials
CO2
at higher T
Natural gas

Reformer Desulfurizer Knock-out drum

Optimal tube diameter?? Heat transfer with dt


TUDelft Pressure drop with dt
Steam Reformer

Radiant
section Convection
section
Air preheater

ISO VIEW
FRONT ELEVATION

TUDelft
Typical Reformer Conditions
Industrial Processes

Process H2O/C Texit (K) pexit (bar) Composition (vol%)2)


(mol/mol) H2 CO CO2 CH4
Hydrogen 2.5 1123 27 48.6 9.2 5.2 5.9
Hydrogen1) 4.5 1073 27 34.6 5.3 8.0 2.4
Ammonia 3.7 1073 33 39.1 5.0 6.0 5.5
Methanol 3.0 1123 17 50.3 9.5 5.4 2.6
Aldehydes/ alcohols 1.8 1138 17 28.0 25.9 19.7 1.1
Reducing gas 1.15 1223 5 70.9 22.4 0.9 1.5
1)
From naphtha
2)
Rest is H2O

Critical points??? Excess H2O


TUDelft CH4 slip
Methane slip
60 80

Methane slip (% unconverted)


H2O/CH4 = 3 p = 30 bar
Methane slip (% unconverted)

70
50 30 bar
H2O/CH4 = 1
60
40 20 bar
50 H2O/CH4 = 2

30 40
10 bar H2O/CH4 = 3
30
20
20 H2O/CH4 = 5
10
10
1 bar
0 0
1000 1050 1100 1150 1200 1000 1050 1100 1150 1200
Temperature (K) Temperature (K)

Practical conditions H2O/CH4 = 2.5 - 4.5


T: 1090 - 1150 K
TUDelft
P: 7 - 30 bar
New Processes
Coke problem, in particular for heavy feed stocks
prereformer at low temperature
Investment very large
autothermic reforming
Exergy loss enormous
membrane reactor

equilibrium is shifted
O2 plant avoided
Other chemical routes
methane
ethane
methanol

TUDelft
Steam Reformer with Prereformer
Fuel

Air
Flue gas to stack
Superheated
HP Steam BFW

770 K
Hot raw syngas Desulfurizer

Process steam
Natural gas

Reformer Pre-reformer
CnHm + H2O CH4 + CO2/CO
TUDelft
Autothermal Reforming
Oxygen

Why O2, not air?


Natural gas
Steam
Burner
Molar feed ratio:
Combustion zone H2O/CH4: 1 - 2
CH4 + O2 CO + 2 H2
2200 K
O2/CH4: 0.6
CH4 + 2 O2 CO2 + 2 H2O
Reforming zone Catalyst
1200 - 1400 K bed
CH4 + H2O CO + 3 H2
CH4 + CO2 2 CO + 2 H2
20 - 100 bar

Syngas
TUDelft
Heat-integrated Reformers
Hot gas from the autothermal reformer used for steam reforming

Natural gas Oxygen


Steam
Syngas

Syngas
Dense phase
with catalyst
Catalyst Catalyst

Oxygen

Natural gas
Steam

Gas-heated Autothermic Combined autothermic


reformer reformer reformer

ICI Combined Reforming Exxon CAR


TUDelft
Exergy
Quality of energy in > quality of energy out
(quantity remains the same: first law)
Exergy losses in process:
External losses: emissions to environment (e.g. in off-gas), similar to
energy losses (spills)
Internal losses: physical (heat exchange, compression) & chemical
(depend on process and reaction conditions)
Exergy analysis methanol production (ICI)
rest rest
9% distillation 7%
reformer 8%
29%
methanol
synthesis
7%
distillation
38%

methanol
synthesis reformer
24% 78%

TUDelft Energy spill Exergy loss


Small-scale hydrogen production - HEV
Fuel
Air
Fuel cell power unit

Power
Reformer Compressor Motor
Fuel tank

Gas cleaning
Air Electric
power
Steam
Electric
H2 power
CO, CO2 Fuel cell
PCU
N2
Exhaust
Battery
Electric power

TUDelft
Coal Gasification
Conversion of solid material coal into gas

Why coal gasification?


Central conversion
Gas handling easier than solids handling
Environmental advantages
Power generation
Higher efficiency
Minimum pollution

TUDelft
Pyrolysis of Coal
C 60 - 95 extended exposure
H 2O

wt% H2 CH
CH4

to high temperatures CO
CH
CO

H 2 - 6 CH4

OH
S C 2H 4

N 0.1- 2 HO
CH4
H2

O 2 - 30 volatile
O

products secondary
S 0.3- 13 CH gas-phase
ash: 20-30 formation OH
CH 3
CH
CH 3 CH 3 reactions
of CH3CH2 H 2O
S
C 2H 5

radicals O
CH2 CH2 OH
H 2S
HO
CO

CH 3
CH2 O H2 O

CH 3
S
H 2O
CH2CH2
CH3
O
H 2S stabilization of radicals
CO

CH2 O H2 O
CH 2 O
CH 2
CH 2 CH2 CH3 polymerization and
CH 2 thermal
HO S condensation
O
O
decomposition
O
OH
HS
O O reactions
O CH HO S H2
O H 3C 2 O S
H 3C N H2
CH 2 CH
S CH 2 O O
2 CO
H2
O
O O
N N

COAL PARTICLE CO S N
H2

CHAR
PARTICLE
TUDelft
Gasification Reactions

Reaction H0800 (kJ/mol)


Heterogeneous reactions
C + H2O CO + H2 136
C + CO2 2 CO 173
2 C + O2 2 CO 222
C + O2 CO2 394
C + 2 H2 CH4 87
Homogeneous reactions
2 CO + O2 2 CO2 572
CO + H2O CO2 + H2 37

In practice: autothermic

Heat needed for heating to reaction T and endothermic


TUDelft steam reforming produced by exothermic combustion
Thermodynamics of Steam Gasification
H2O/C = 1
H2, CH4 CO, CO2, H2O

TUDelft
Thermodynamics of Autothermic Gasification
H2, CH4 CO, CO2, H2O

TUDelft H2O/O2/C depends on T


Heat Effects in Coal Gasification

(b)

O2/H2O ratio???
TUDelft
Gasifier Reactors - Moving Bed (Lurgi)
Lumps of coal

Coal hopper

Distributor
Product gas
Drying /Devolatilization
Gasification
Revolving Temperature? Low
Combustion grate Residence time? Long
Oxygen Particle size? Large
Steam Ash hopper

Ash
TUDelft
Gasifier Types - Entrained Flow (Koppers-Totzek)

Coal dust Product gas Coal dust

Steam Steam

Feed screw Burner


Oxygen Oxygen

Liquid
slag Temperature? High
Residence time? Low
Particle size? Small
TUDelft
Gasifier Reactors - Fluidized Bed (Winkler)
Product gas

Cyclone
Crushed coal
Temperature? Intermediate
Residence time? Intermediate
Particle size? Intermediate

Feed screw
Grid

Oxygen
Steam
Ash
TUDelft
Characteristics of Coal Gasifiers
Coal properties
Caking coals become sticky upon heating
dparticle smaller for high-temperature processes
depending on Gasifier temperature
mineral matter is released as liquid (slagging gasifier) or solid
liquid ash ( vitrified material): no leaching upon disposal

Caking coals applicable in all reactor types?

Reactor Treactor Texit throughput O2-cons. dp coal type


type K K t/d kg/kg coal mm
moving bed 1250-1350 700 1500 0.5 20 non-caking
fluidized bed 1250-1400 1150 3000 0.7 2 reactive
entrained flow 1600-2200 1300 5000 0.9 < 0.1 all

TUDelft
Operating
Operating Ranges
Ranges of
of Industrial
Industrial gasifiers
gasifiers

Moving Entrained
bed flow
Autothermic
Fluidized
bed
p = 30 bar

TUDelft
Gasification Processes in the Development Stage

Dry coal feed most common


Texaco and Dow: coal/water slurry
high reliability but less efficient: evaporation of water required
Fluidized beds: limited carbon conversion ( < 95%)
Additional step: burning of carbon in ash particles

O2-cons. C-conv type Treactor Texit cold gas p


kg/kg coal (%) K K eff. (%) bar
Slagging Lurgi 0.52 99.9 moving >2200 700 88 25
High-temp. Winkler 0.54 96 fluidized <1300 1200 85 10
Texaco 0.9 97 entrained 1600-1800 <1100 74 41
DOW 0.86 99 entrained 1600-1700 <1300 77 22
Shell 0.89 99 entrained 2200 1200 81 30

Cold gas efficiency based on heating value at standard T


TUDelft
Applications of Coal Gasification
Coal Air/ Steam
oxygen

Heat (allothermal)
Gasification

Town gas, SNG Lean gas Reducing gas Hydrogen Synthesis gas

Gas supply Ore Oil Chemical


Combustion Fuel cells
systems reduction refinery industry

Heating Electricity/ Crude iron Electricity Hydrotreated Ammonia


Heating oil fractions Methanol
Diesel

What application most important??


TUDelft
Coal to Methane, Exxon Process
2C + 2H2O CH4 + CO2 H 0

Coal feed
CO2

Recovered
Coal preparation catalyst Sulfur recovery Sulfur

H2/CO recycle

Gasification Gas cleaning Separation SNG


Steam

Ash + catalyst to
recovery

Process technically success, but not built


TUDelft Why??
Combined Cycle Power Generation

Steam
Raw hot
syngas Generator
Syngas
cooler Electricity
Cyclone Turbine

Condenser
BFW

Entrained-flow gasifier
Fly slag Exhaust gas
(1800 K; 30 bar)

Pulv. coal
Steam Waste heat boiler
Compressor Generator
Gas
Electricity
Turbine
Oxygen treatment

Liquid slag Air


Sulfur
Air Combustor
separation

Nitrogen for NOx control


Coal Gasification Electricity generation
TUDelft
Production Raw Syngas for NH3 synthesis
N2 + 3 H2 2 NH3
Note: O-containing molecules poison catalyst (Fe)
purification steps; CO removal, CO2 removal

H2 670 K 660 K 770 K 1020 K 1020 K 1270 K

Steam Autothermic
CH4 Desulfurization
reforming reforming
24 + 27 m3
17 m3 33 m3
Steam Air

640 K 710 K 490 K 510 K 590 K 640 K


Component To compression &
HT CO Shift LT CO Shift CO2 Methanation
(mol%) ammonia synthesis
57 m3 61 m3 removal 25 m3
H2 56.34 60.02 61.15 74.68 74.06 (61 m3)
N2 22.20 20.16 19.77 24.10 24.69
CO 12.76 3.33 0.40 0.49 < 5 ppm
CO2 8.18 15.85 18.24 0.20 < 5 ppm
CH4 0.22 0.21 0.20 0.24 0.95
Ar 0.30 0.25 0.24 0.29 0.30

TUDelft
CO conversion: Water-gas shift
CO + H2O CO2 + H2
Moderately exothermal
p H 2 pCO2 Favorable: low T
Kp =
pCO pH 2O

13 mol%
K CO 640 K 490 K
p

HT shift LT shift

710 K 510 K

Temperature (K) 0.4 mol% COstill too


high for Fe catalyst

TUDelft
CO conversion

Remaining CO removed by methanation


CO + 3 H2 CH4 + H2O
But first CO2 removed by absorption in e.g. alkanolamine

Removal system GJ/mol CO2


MEA 210
MEA with inhibitors 93-140
K2CO3 with additives 62-107
MDEA with additives 40-60

TUDelft