Methanol Production Technology: Todays and future ... · PDF fileJohn Bøgild Hansen -...
Transcript of Methanol Production Technology: Todays and future ... · PDF fileJohn Bøgild Hansen -...
John Bøgild Hansen - Haldor Topsøe Methanol Workshop, Lund University – March 17, 2015
Methanol Production Technology: Todays and future Renewable Solutions
We have been committed to catalytic process technology for more than 70 years Founded in 1940 by Dr. Haldor
Topsøe Revenue: 700 million Euros 2800 employees Headquarters in Denmark Catalyst manufacture in
Denmark and the USA
Topsøe’s position in methanol industry
Number of plants: Accumulated capacity, MTPD:
Number of catalyst charges: 1
1,650 1 1 3,300
2 2
4,950 2 3
6,600 3 4
8,250 3 4 9,900
5 5 11,550
6 6 13,200
7 8
14,850 6 9
16,500 7 10
18,150 7 15
19,800 12 16
21,450 12 17
23,100 13 18
24,750 13 19
26,400 14 20
28,050 14 20
29,700 15 21
31,350 15 22
33,000 16 23
34,650 17 24
36,300 17 25
37,950 18 26
39,600 18 27
41,250 19 28
42,900 20 29
44,550 20 30
46,200 21 31
47,850 22 32
49,500 22 33
51,150 23 34
52,800 24 35
54,450 24 36
56,100 25 37
57,750 25 38
59,400 26 39
61,050 26 40
62,700 27 41
64,350 28 42
66,000 28 42
67,650 29 43
69,300 30 44
70,950 30 44
72,600 31 45
74,250 32 46
75,900 33 47
77,550 33 47
79,200 34 48
80,850 34 48
82,500 35 49
84,150 35 50
85,800 36 51
87,450 36 52
89,100 37 53
90,750 37 54
92,400 37
Methanol synthesis
CO + 2H2 = CH3OH + 91 kJ/mol CO2 + 3H2 = CH3OH+H2O + 41 kJ/mol
Topsøe technologies for shale gas based methanol plants
Tubular reforming
Two-step reforming
Reforming technologies
Synthesis technologies
Distillation technologies
Boiling water reactor
Single column
2 columns
3 columns
Natural gas
Autothermal reforming
Adiabatic reactors
Grade AA
Fuel grade
Steam
Steam
Makeup comp.
Methanol reactor
Raw methanol
Condensate
Steam reformer
Sulphur remov.
Sulphur removal
Natural gas
Prereformer
Methanol production by one-step reforming
Steam
Pre- reformer
Secondary reformer
Steam
Steam
Oxygen
Makeup comp.
Light ends to fuel
Methanol reactor
Water
Raw methanol
Raw methanol storage
Condensate
Steam reformer
Sulphur sat. removal
Hydrogenator
Natural gas
Product methanol
Methanol production by two-step reforming
Economy of scale H2O/CH4
Air
H2O/CH4 O2
Syngas
Air
H2O/CH4 O2
Syngas
Log capacity
Log costs Tubular Reforming
O2-plant
Photo: Øyvind Hagen, Statoil
Tubular reformer for methanol plant based on two-step reforming
Topsøe boiling water cooled methanol reactors at Bandar Imam, Iran
Methanol production by ATR Oxygen/steam
Steam Steam
Raw methanol
Natural gas
Water Condensate Purge
gas Hydrogen recovery
Methanol reactor
Autothermal reformer
Hydro- genator
Sulphur removal
Saturator Pre- reformer
Makeup comp.
Rec. comp.
Topsøe ATR reactor Large single line capacity
Economic of scale
Soot-free process
In industrial operation
Low steam to carbon (S/C < 0.6)
Oxygen
Hydrocarbon + steam
CTS burner
Synthesis gas
Combustion zone
Catalyst
Pressure shell
Refractory
Projects using ATR for synthesis gas generation
Oryx, Qatar (GTL) 34,000 BPD
Escravos, Nigeria (GTL) 34,000 BPD
Viva, Nigeria (methanol) 10,000 MTPD
Sasolburg, South Africa (syngas) 2 x 215,000 Nm3/h
Increased loop efficiency – Production gain – Increased carbon efficiency – Lower energy consumption
Longer catalyst lifetime – Less replacements – Increased plant availability
Industrial experience
Days on Stream
Cat
alys
t act
ivity
MK-151 FENCE™
MK-121 MK-101
20%
20%
MK-151 FENCE™
MK-121
MK-101
Statoil, Norway, 2500 MTPD 28.8 GJ/MT => 69 % effeiciency Industrial benefits
Reformers for Methanol Plant utilising CO2
¾CH4 + ½H2O + ¼CO2 = CH3OH
Fuel Cell and Electrolyser
½O2
H2 H2O
½O2
H2O + 2e- → H2 + O2-
O2-
O2- → 2e- +½O2
H2 + O2- → H2O + 2e-
O2-
½O2 + 2e- → O2-
SOFC SOEC H2 H2O
H2 + CO + O2 H2O + CO2 + electric energy (∆G) + heat (T∆S) SOFC SOEC
Cu(111), d=0.21nm
Cu(200), d=0.18nm
ZnO(011), d=0.25nm
ZnO(012), d=0.19nm
Cu(111) Cu(111)
H2 H2/H2O
1.5mbar, 220oC 1.5mbar, H2/H2O=3/1, 220oC
The Active Site of Syngas Catalyst
Cu is metallic when catalyzing: - WGS - MeOH synthesis - MeOH reforming
Catalyst dynamic: - Number of active sites depends on conditions
Conversion of methanol as function of CO2 content in stoichiometric gas
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25 30
Percent CO2 in
Car
bon
conv
ersi
on %
J.B. Hansen Data Condensing methanol
K.Klier Data Lab data 225 C
Ageing of methanol catalyst in Normal and Dry Syngas
120
80
40
0 0 200 400 600 800
Time on stream, hours
Rel
ativ
e ac
tivity
10/1-gas
5/5-gas
Methanol from CO2 and Steam
P 1
SOEC
Purge
Water
E 3
E 6
E 7
E 4E 1
CO2
Methanol
MethanolReactor
K 2K 1
K 3
Recycle
Oxygen
Synergy between SOEC and fuel synthesis
SOEC Synthesis CO2
H2O
Syn Gas
Product
Steam
Reactor volume and byproducts as function of CO2 converted in SOEC
0
300
600
900
1200
0
100
200
300
400
500
600
700
0 20 40 60 80 100
Byp
rodu
cts
Rel
ativ
e %
Rea
ctor
Vol
ume
Rel
ativ
e %
Percent CO2 through SOEC
Byproducts
Reactor Volume
Methanol from sustainable sources
BioDME Black Liqour to Green DME Demo
CO2 Black Liq.
Water
WGS Sulphur
Guard
MeOH Synthesis
AGR DME
Unit
GreenSynFuel Project
Mass Flows in Wood to MeOH
Mass Flows in Wood + SOEC to MeOH
Effciencies: Stand alone wood gasifier and gasifier plus SOEC
LHV Efficiency %
Wood Gasifier
alone
Wood gasifier Plus SOEC
Methanol 59.2 70.8 District Heat 22.6 10.8 Total 81.8 81.6
The CO2 Electrofuel Project
CHEMREC Energy to Succeed
Is CO2 electrofuels a viable and competitive technology for the Nordic countries?