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Tubular reforming

Research I Technology I Catalysts

MRPL Phase-III Refinery Project, Hydrogen Generation Unit

Agenda
 Introduction –Reforming
 Reforming catalyst
 Catalyst operational challenges
 Monitoring of a reformer

Primary reformer

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Chemical reactions in a steam reformer
Reforming:
CH4 + H2O ↔ CO + 3 H2
CnHm + n H2O → n CO + (n + ½m) H2
ex. (C4H10 + 4 H2O → 4 CO + 9 H2)

Shift:
CO + H2O ↔ CO2 + H2

Overall reaction is strongly endothermic



Heat has to be transferred from outside

Operating conditions for tubular reformers

Typical Your plant


Inlet temperature : 450 - 650 ºC 600 - 650 ºC
Exit temperature : 750 - 950 ºC 915 ºC
Pressure: 20 - 45 kg/cm2 g 29.3 kg/cm2 g
Steam/carbon ratio: 1.6 - 7 mole/mole 2.5 mole/mole

Reforming catalysts
Catalyst R-67-7H

Shape Cylinder with 7


axial holes
Size, mm 20x18

Diameter, mm 19 – 20

Height, mm 15 - 18

NiO, wt % >15

MgAl2O4, wt % Balance

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Reforming catalysts
Critical catalyst parameters
 Large nickel surface
– Activity
– Poison capacity
 Carrier thermal stability
 Carbon resistance
 Catalyst Shape:
– Pressure drop
– Crush strength
– Geometric surface area
– Heat transfer

Nickel content vs. reforming activity


Relative reforming activity

Ni content

Sintering
 Decreased activity
 Decreased C tolerance
 Decreased S tolerance

Fresh Used

Fresh

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Topsøe reforming catalysts
Alkali Pre- Noble
Catalyst Metal content carrier
promoted reduced metal

R67 - - - NiO: >15% MgAl2O4

R67R -  - Red Ni: >10% MgAl2O4

NiO: >14% MgAl2O4


RK-201  - -
K: 0.3-0.6% CaAl2O4
Red Ni: >9% MgAl2O4
RK-211    K: 0.3-0.6% CaAl2O4
NiO: >12% MgAl2O4
RK-202  - -
K: 1.0-1.5% CaAl2O4
Red Ni: >9% MgAl2O4
RK-212    K: 1.0-.15% CaAl2O4

Catalyst operational challenges


 Sulphur poisoning
 Carbon formation

Sulphur poisoning

Nickel
terrace

Nickel
step

Nisurface + H2S ↔ S-Nisurface + H2

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Carbon formation

+H2O
C2H6 2 CO + 5 H2
Reforming

2 C + 3 H2
Carbon !

Carbon formation
Two types of carbon formation:

Catalytic cracking Thermal cracking


(on Ni crystals) (on hot surfaces)

Carbon whiskers, physical Hot bands, NO physical


damage of catalyst damage of catalyst

Catalytic carbon formation


 During start up
– Dry hydrocarbons during nitrogen recycle

 During operation
– Complete loss of steam
– Operation at very low steam to carbon ratio

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Nucleation of whisker carbon

Bengaard et al. J. Catal. 209, 354 (2002)

Thermal cracking
 Too low catalyst activity
 Flame impingement

Carbon formation from higher hydrocarbons


Actual (high activity) Actual (low activity)
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Critical
12
hydrocarbon radio
Steam to higher

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8
Carbon formation
6
4
2
0
0 1 2 3 4 5
m from inlet

low Temperature High

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Formation of hot bands
CnHm CnHm

C
nH
500°C C
nH
m m

C nH m
C nH m

C nH m
C nH m
Cn
C nH m
Hm

C nH m

850°C
High Low
activity activity

Monitoring of primary reformer


 Important for optimal plant operation
 Tube wall temperature tells a lot about how reformer
performs
 Never trust DCS data alone – remember visual
inspection of reformer
– Visual inspection may catch problems long before they can be
measured and seen in the DCS

Tube wall temperature (TWT)


 Design TWT important for the tube life time
 Typically designed for a lifetime of 100,000 hours
 A 15-20°C higher temperature than design →
tube lifetime is lowered by 50%
 A 30-40°C higher temperature reduce lifetime by 75%
 A 100°C higher temperature can cause tube rupture very
fast

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Effect of TWT on tube life

100,000
Life time, hours

50,000

30,000

20,000
HK40 IN519 25/35 Nb HP-BST-M

880 920 960 1000


Tube skin temperature, °C

Tube damage
Two types of tube damage:

Creep Very high temperature

When reaching ~5% increased When exposed to very high temperatures


diameter the tube may rupture. mechanical strength is lost.

Visual inspection
 The most important inspection is visual
 You can see differences down to 5-10°C
 You can see single hot spots even if it is far away from
the peep hole
 You should do visual inspection during the night
 You cannot ”see” the real temperature of the tubes
 Visual inspection must be combined with pyrometer
measurements

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Measurement of tube wall temperatures

Keep records of TWT’s


880

870
Temperature C

860

850

840

830 Vise excel regneark med t wall


820

810

800

790
27

45
11

13

15

17

19

21

29

31

33

35
23

25

37

39

41

43
1

9
3

Tube No.

 Keep TWT records, to follow the trend


 Place the TWT in a spread sheet as above
 After installing a new catalyst, TWT are at a minimum

TWT record
average
920.0 60000
TWT
900.0
55000 max TWT
N a t u r a l G a s f lo w , N m 3 /h

880.0
T e m p e ra t u re ( °C )

860.0 50000
min TWT
840.0
45000
820.0 Design
800.0 40000 TWT
780.0 Toutlet
35000
760.0

740.0 30000 NG flow


20.11.00 8.6.01 25.12.01 13.7.02 29.1.03 17.8.03 4.3.04 20.9.04 8.4.05
Date of Data

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What to watch out for in operation
 Start-up
– Heating stagnant/circulation
– Introduction of steam/hydrogen/feed
 Operation
– Increase in production (steam/feed/air)
– Maximum operating parameters
 Shut-down
– Avoid overheating of tubes (Protection steam)
– Avoid oxidation of catalyst

Thank you for your attention

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