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?