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C2PT Catalyst Process Technology

Steam Reforming
Practical Operation

By Gerard B Hawkins
Managing Director, CEO
Contents

Reaction Chemistry
Typical Reformer Configurations

Catalyst Design Criteria

Carbon Formation and Prevention

Catalyst Deactivation

Steaming Reforming Catalysts

Monitoring Reforming Catalysts

Catalyst Loading

Reduction & Start-Up

Tube Wall Temperature Measurement


Steam Reforming Reactions
The conversion of hydrocarbons to a mixture of CO,
CO and H2

Two reactions: Reforming and Shift

Steam Reforming (very endothermic)

CH4 + H2O CO + 3H2


CnH(2n+2) + nH2O nCO + (2n+1)H2

Water gas shift (slightly exothermic)

CO + H2O CO2 + H2

Overall the reaction is highly endothermic


Equilibrium Considerations
Both reforming and shift reactions are reversible

Rate of shift is fast compared to reforming

Methane conversion favoured by:


low pressure
high temperature
high steam to carbon ratio

CO conversion to CO2 favoured by:


low temperature
high steam to carbon ratio

GBHE kinetics developed using full size reformer


tube with whole pellets under industrial conditions
Reformer is a Heat Exchanger
Primary Reformer

The Primary Reformer is a heat exchanger

Its function is to heat up process gas

Catalyst and reaction in the tubes

Combustion on the shell side

Dominant heat transfer by radiation

Multiple fuel supply points


Reformer Furnace

3 major types of reformer

Each tackles the duty in different ways

No clear best choice

Choice dictated by Contractor history

Terrace wall - Foster Wheeler

Side Fired - Topsoe, Selas, Chiyoda

Top Fired - H & G, Davy, Toyo, Howe Baker, Kellogg,


KTI etc
Reformer Furnace

Many reformers now heat transfer limited

Catalyst not limiting reformer size or operation

Especially the case for hydrogen & methanol


plants

Important for design and uprating

Fluegas exit flow and temperature often limits

Heat exchange must not be ignored

Claims of +30% capacity treated with caution


Top Fired Reformer
Side Fired Reformer
Terrace Walled Reformer
Heat Transfer - Top Fired

Nearly all heat transfer is by radiation

Radiation from the fluegas to the tubes

Little direct radiation from refractory to tube

Refractory acts as a reflector

Radiation from flame to tube at tube top


Heat Transfer - Top Fired

Radiative
heat flows
Heat Transfer - Side Fired / Terraced

Same for side fired and terrace walled

Nearly all heat transfer is by radiation

Radiation from the fluegas to the tubes

Major direct radiation from refractory to tube

Significant heat transferred from flame to wall

Carried out by convection

Radiation from flame to tube all down


Typical Reforming Configuration

Steam + Gas
500C

Steam
Reformer

Steam

1200C
Steam

870C

3% CH4
Reformer Firing Balancing

Must have an even heat input to the furnace

Same reasons as for an even process gas flow

Exit temperature variations give high average


approach

Need to keep exit temps the same

Trim air and fuel flows to individual burners

Monitor tube wall temps and exit temps

Must be done as air ducting, tunnels etc may have


a systematic effect upon heat input
Reformer Firing Balancing

Usual problems for uneven heat input:-

Burner problems

Burner fouling with liquid fuels or offgas

Air leaks around burners or tube tops

Tunnel problems (mods or collapses)

Air ducting problems (internal refractory)


Typical Primary Reformer Catalyst
Loading

Half Load Dip - 7.38m


Full Tube Dip
0.89m

Loaded Length - 12.98 m


Tubes 352

VSG-Z101
Tubes id : 95 mm
Loaded Length : 12.98 m

6.49m
Catalyst Types : 50% VSG-Z101
50% VSG-Z102
Loaded density : VSG-Z101 0.857 kg/l
VSG-Z102 0.828 kg/l
VSG-Z102

Total volume loaded 32.38m3


6.49m

Catalyst
Support Grid
Ammonia Plant
Primary Reformer
Reforming involves heating the process gas

The position of equilibrium is constantly changing

The catalyst tries to react the gas to equilibrium

The catalyst is essentially chasing the heat input

Top of tube: slow reaction rate, high heat flux

Bottom of tube: high reaction rate, low heat flux

High approach to equilibrium at top of tube, low


approach at bottom of tube

Can never achieve a zero approach to equilibrium


Approach to Equilibrium

900 Gas T
800
Temperature (C)

700
600
500 ATE
400 Eqm. T
300
200
100
0
0 0.2 0.4 0.6 0.8 1
Fraction down tube
Primary Reformer Catalyst
Requirements
High and Stable Activity

Low Pressure Drop

Good Heat Transfer

High resistance to Carbon Formation

High Strength

Robust Formulation / Simple Operation


High and Stable Activity

Low methane slip

Lower tube wall temperature

Reduced Fuel usage


Low Pressure Drop

Savings in Compression Power / Fuel

Possible Throughput increase


Improved Heat Transfer

Reduced tube wall temperatures

Increase firing /higher throughput

Smaller catalyst particles improve heat transfer


from wall to bulk gas

Smaller particles increase pressure drop

Catalyst shape should be optimised for high heat


transfer with low PD
Steam Reforming Catalysts

Nickel on a ceramic support

Three key factors in catalyst design:

i) geometric surface area


ii) heat transfer from tube to gas
iii) pressure drop

Also of concern:

i) packing in the tube


ii) breakage characteristics
Diffusion Limitation

The reforming reaction is very fast on the Ni sites

Reaction limited to catalyst surface (<0.1mm)

Reaction rate controlled by film diffusion

High geometric surface area gives high activity


Diffusion into and out of Catalyst

Bulk Gas
Ni
Gas Fil
m Sites
H2O
CO
H2

CH4
Catalyst Support
Key Reaction Steps
1. Fast
Diffusion of the molecules in the bulk gas
phase

2. Slow
Diffusion of the molecules through the gas
film

3. Slow
Diffusion through catalyst pores

4. Fast
Absorption of the molecules onto the Ni
sites

5. Fast
Chemical reaction to produce CO2 and H2
Reaction Rate
Reaction rate controlled by film diffusion

- Most of the reaction takes place on


the catalyst surface (<0.1mm)
- Pore diffusion not limiting as film diffusion
controls the overall rate

Catalysts with higher geometric surface area


(GSA) per unit volume of catalyst will have a
higher activity.

Pore size/distribution is not significant for most


commercial grades of reforming catalyst
Un-sintered Catalyst

0.001 mm (1/25 thou)


Sintered Catalyst

0.001 mm (1/25 thou)


Heat Transfer

Gas film
Fluegas T 1200C

Outside Tube Wall T 830C

Inside Tube Wall T 775C


Bulk Process
Gas T 715C
Tube
Wall
Catalyst Heat Transfer

Reforming involves large heat flows into tubes


Absolute requirement to keep tubes cool
Major limitation is at the tube wall
Need to minimize thickness of stationary gas film
at tube wall

The catalyst acts as a heat transfer enhancer to


improve heat transfer from tube wall to gas
Promotes turbulence at the wall
Promotes gas mixing from walls to tube centre

Smaller catalyst particles improve heat transfer


from wall to bulk gas and hence reduce tube wall
temperatures
Catalyst Heat Transfer

Heat transfer to catalyst normally very good (high


GSA)
Minor limitation is radially in the catalyst
Catalyst also improves radial heat transfer
Smaller pellets improve wall transfer
Larger pellets improve radial transfer
Smaller usually better overall
BUT smaller particles increase pressure drop

Catalyst shape needs to be optimized for high heat


transfer with low PD
Catalyst Shape

The traditional catalyst shape is a ring

Smaller rings give higher activity and heat transfer


but higher pressure drop

Shape optimised catalysts offer high GSA and heat


transfer with low PD

Important that shape also provides good packing


and breakage characteristics
Tube Wall Temperature Profile

Top Fired Reformer

860
Tube Wall Temperature (C)

840
820
800
780
760
Base case
740
Base case with twice GSA
720
Base case with twice heat transfer
700
680
660
0 0.2 0.4 0.6 0.8 1
Fraction Down Tube
Heat Transfer and Pressure Drop

1 2 3 4

1 2 3 4
Voidage 0.49 0.6 0.58 0.59
Relative PD 1 0.9 0.9 0.8
Relative HTC 1 1.3 1.1 1
Catalyst Design Criteria
Conclusions
Design of catalyst shape is a complex optimization of:

- Higher GSA (Needed for activity - diffusion control)

- Higher HTC (Needed for cooler reformer tubes)

- Lower Pressure drop (Plant Efficiency / Capacity)

Need also to consider breakage characteristics


and loading pattern inside the reformer tube
VULCAN
VSG-Z101

VULCAN
VSG-Z102
Catalyst Breakage

Catalyst breaks up in service


Main mechanism due to startup / shutdown
The tube when cooling exerts massive forces
(several tonnes)
Forces exerted by carbon formation immeasurable
Pressure drop rises about 10% per year
Minimum Catalyst strength for handling & charging
approx. 10 kgf
The key is to ensure the catalyst does not fragment
into small bits/dust.
Careful charging essential
Breakage Characteristics

Cold Hot Cold


Initial
catalyst level

Expansion of tube Contraction of tube


- some settling - some readjustment
- some breakage

All catalysts show breakage with time


No support can withstand tube forces
Pressure Drop due to Catalyst Breakage

Shape with poor breakage


characteristics Conventional rings
200
pd limit
Relative pd (%)

100

Shape with good breakage


characteristics

0 5 10 15 20
% Breakage

Breakage Characteristics is an
Important Consideration
Breakage Characteristics
Breakage Characteristics
Packing Characteristics

Uniform loading of catalyst


- Uniform tube pressure drops
- Uniform tube temperatures (no hot spots)

Long cylinders with hole(s) through


the centre give good uniform
packing

Short cylinders (tablets) with hole(s)


through the centre can stack resulting
in poor gas distribution down the
reformer tube
Packing Characteristics

Extended External Surface Area - "Cogs"

Void
Catalyst Support

Three types commercially available

Alpha Alumina

Calcium Aluminate

Magnesium Aluminate Spinel


Catalyst Support - Bulk Chemistry

Alpha Calcium Magnesium


Alumina Aluminate Aluminate
Spinel

Structure Corundum Spinel-like Spinel

Stability to Extremely Relatively Relatively


Sintering Stable Stable Stable

Chemical Inert Stable Free MgO


Stability Hydration
(Hydrolysis) under
Steaming
Conditions
Catalyst Support - Surface Chemistry

Alpha Calcium Magnesium


Alumina Aluminate Aluminate
Spinel

Surface Area Low Higher Higher

Basicity Inert Basic Sites Most Basic


Support

Surface No Chemical Moderately Most


Interaction Interaction Reactive Reactive
with Ni / NiO Surface Surface

Some Strongest
bonding of bonding of
Ni 2+ ions Ni 2+ ions
Catalyst Support - Solid Solutions

Magnesium Aluminate Spinel

NiO / Ni Heat

Fresh catalyst
High surface area
NiO / MgO NiAl2O4
Solid solution formed

In use - Low surface area


Difficult to reduce NiO

Important to consider in-service activity


and ease of catalyst reduction
Catalyst Support - Reduction
Temperatures
800 1000 1200 1400 1600

Temperature (F)

Magnesium Aluminate Spinel


Calcium Aluminate
Alpha Alumina

Magnesium aluminate
spinel material usually
supplied pre-reduced

Temperature (C)

400 500 600 700 900


MAXIMUM TUBE WALL TEMPERATURE (C)

860
880
900
920
940

820
840

0
POWER OUTAGE

200
ICI RINGS

400
CATALYST CHANGE
AT 584 DAYS

0
SHAPE
REDUCED

COMP A
RATE 25%

CATALYST CHANGE

200 0
AT 258 DAYS

SHAPE
COMP B
CATALYST CHANGE

200 0
AT 280 DAYS

PD LIMIT RATE

200
REDUCED

COMP B
SHAPE 2 CATALYST CHANGE

0
AT 421 DAYS

DAYS ON LINE
200
400
600
ICI SHAPE
Tube Wall Temperature Stability

TWT
LIMIT

700
800
900
Carbon Formation and Prevention

Carbon formation is totally unwanted

Causes catalyst breakage and deactivation

Leads to overheating of the tubes

In extreme cases carbon formation causes a


pressure drop increase
Cracking
CH4 C + 2H2
C2H6 2C + 3H2 etc

Boudouard
2CO C + CO2

CO Reduction
CO + H2 C + H2O

If carbon formation rate is faster than removal


rate then carbon will be deposited
Carbon Formation - Heavy Feeds

Intermediates
(Olefins, Paraffins, Steam
Catalyzed
CH4, & H2) Reforming
Partial
Decomposition

H2O
CH4, H2, CO2
Hydrocarbon Polymerization
& CO
Feed

H2O
Thermal
Cracking Carbon
Carbon
Gasification
Effect of Carbon Formation
1. Physical poisoning

-Carbon covers the catalyst surface

2. Pressure drop increase

- Usually only in severe situations


- Carbon fills catalyst bed voids
-Carbon formed in catalyst pores will weaken
or break catalyst

3. Hot tubes
- Carbon laydown on the inside of the tube
wall
- Lower catalyst activity
Carbon Formation and Prevention
Reformer tube appearance - Carbon laydown

Hot Band Giraffe Hot Tube


Necking
Carbon Formation and Prevention

Under normal conditions carbon gasification by


steam and CO2 is favored

i.e. gasification rate > C formation rate)

Problems of carbon formation may occur when:

i) steam to carbon ratio is too low


ii) catalyst is not active enough
iii) higher hydrocarbons are present
iv) tube walls are too hot (high flux)
v) catalyst has poor heat transfer characteristics
Carbon Formation and Prevention

Methods of preventing carbon formation:

Use more active catalyst

Use better heat transfer catalyst

Reduce levels of higher hydrocarbons

Increase the steam ratio

Use a potash doped catalyst (VULCAN-


series) which reduces probability of carbon
formation
Carbon Formation and Prevention
Alkali greatly accelerates carbon removal
Addition of potash to the catalyst support reduces
carbon formation in two ways:

a) increases the basicity of the support


b) promotes carbon gasification (aids
adsorption of water)
-
OH

C + H2O CO + H2

Potash is mobile on the catalyst surface


Level of potash required depends on feed and heat
flux
Potash doped catalyst is only needed in the top half
of the reformer tube
Carbon Formation and Prevention

Increasing the content of alkali (potash) allows:

Higher heat flux for light feeds

Heavier hydrocarbons in feed

Lower steam to carbon ratios

Faster carbon removal during steaming


Carbon Formation and Prevention
Increasing potash
addition
K2O wt%
0
Methane feed/Low heat flux

2-3 Methane feed/High heat flux


Propane, Butane feeds (S/C >4)

4-5 Propane, Butane feed (S/C >2.5)


Light naphtha feed (FBP < 120 C)

6-7 Heavy naphtha feed (FBP < 180 C)


Methane Cracking

100 CH4 2H2 + C

No Carbon
Formation
(pH2) 2 10

pCH4

1.0 Carbon Formation


Zone

0.1
550 600 650 700 750 800
Temperature (C )
Methane Cracking - Kinetic Limitation

100

No Carbon
Formation
(pH2) 2 10

pCH4
Carbon Formation
1.0 Zone

Deposition rate Deposition rate


< removal rate > removal rate
Promoted by alkali Promoted by acid
0.1
550 600 650 700 750 800
Temperature (C )
Methane Cracking - Kinetic Limitation

100
Fraction of
tube length
0.6
from top
0.5
10 No Carbon 0.4
(pH2) 2
Formation
pCH4
Carbon Formation
0.3 Zone
1.0

Deposition rate Deposition rate


< removal rate > removal rate
0.1
550 600 650 700 750 800
O
Temperature C
Methane Cracking - Basic Catalyst
Support

100
No Carbon 0.6
Formation 0.5
(pH2) 2 10 0.4

pCH4 Carbon Formation


0.3 Zone
1.0
More basic
0.25 support
0.1

550 600 650 700 750 800


O
Temperature C
Methane Cracking - Increased Potash
Content

100

No Carbon 0.6
Formation 0.5

(pH2) 2 10 0.4
Increasing
pCH4 Potash
0.3 Content
1.0
Carbon
0.25
Formation Zone
0.1
550 600 650 700 750 800
O
Temperature C
Carbon Formation and Prevention

920C
Alkalised Non-Alkalised
Catalyst Catalyst

Carbon Forming Ring Catalyst


Region

820C Optimised Shape


(4-hole Catalyst)

Inside Tube Wall


Temperature

720C

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Top Fraction Down Tube Bottom
Carbon Formation and Prevention

For light feeds and LPG etc. using lightly


alkalized catalyst (VSG-Z102)
- Potash is chemically locked into catalyst
support
- Potash required only in the top 40-50% of
the reformer tube
VSG-Z101

VSG-Z102

- Catalyst life influenced by


Poisoning
Ni sintering
Process upsets etc.
Carbon Formation and Prevention

For heavy feeds, potash needs to be mobile


Utilize VSG-Z101 series catalyst

VSG-Z101

VSG-Z102

Removes carbon on the catalyst surface and


inside of the tube wall

Potash slowly released by a complex reaction


Carbon Formation and Prevention

Potash release mechanism (VSG-Z102 series)


Catalyst Support Material

K2O-Al2O3-SiO2 CaO-Al2O3-SiO2
CO2 + H2
CaO-Al2O3 CaO-MgO-SiO2

MgO-Al2O3 K2CO3

H2O
Note:- MgO is chemically
locked into catalyst support
material 2KOH + CO2
Carbon Formation and Prevention

VSG-Z102 Series catalysts

Catalyst life determined by residual potash


remaining in the catalyst

Minimum amount typically 2-3 %wt at bottom of


potash promoted catalyst bed - but minimum
level depends on feedstock type and
operational severity
Carbon Formation and Prevention

Carbon formation by polymerization

Suppressed by having NiO / MgO solid


solutions as the active catalyst component

Need to increase total NiO content to


overcome loss of steam reforming activity

Zirconia addition also further enhances


catalyst activity
Summary

Potash promotion

Lowers hydrocarbon carbon cracking rate

Increases carbon removal rate

VSG-Z102 series can remove carbon from tube


wall ("mobile" potash)

VSG-Z102 series contain some NiO/MgO solid


solutions to lower polymerisation activity

Greatly facilitates carbon removal during


steaming operation (after severe carbon
formation)
Natural Gas Associated Gas Dual Feedstock Naphtha
Reforming Reforming Reforming Reforming
Catalysts Catalysts Catalysts Catalysts

Un-alkalised Lightly Alkalised Moderately Heavily


Alkalised Alkalised
VSG-Z101 VSG-Z102 VSG-Z102 VSG-Z102

Naphtha 3.0 3.5

Light Naphtha 6.0 8.0 3.0 4.0 2.5 3.0

Butane 4.0 5.0 2.5 3.5 2.0 3.0

Propane / LPG 3.0 4.0 2.5 3.0 2.0 2.5

Refinery Gas 6.0 10.0 3.0 4.0 2.0 3.0 2.0 2.5

Associated Gas 5.0 7.0 2.0 3.0 2.0 2.5

Natural Gas 2.5 4.0 1.5 2.0 1.0 2.0

Pre-reformed 2.0 3.0 1.0 2.0 1.0 2.0


Gas
Catalyst Activity Die Off

2 major factors:

Poisoning by sulfur

Affects upper tube and tube temperatures

Thermal sintering

Affects lower tube and approach


Some effect on upper tubes and tube
temperatures
Poisons

Many poisons affect reforming catalysts

Halides, phosphates, sulfur

Heavy metals, alkali metals etc

Major poisons are:

Sulfur ex feedstock
Phosphate ex BFW
Metals ex BFW or liquid feed
Sulfur Poisoning

Nickel is a very good sulfur adsorbent

Sulfur sticks to the nickel surface

Do not need a lot of sulfur to give problems

Can totally deactivate a reforming catalyst


Sulfur Poisoning

CH4
S S
S S
S Pellet
S Nickel
S
S
H 2O S S
Sulfur Poisoning

Depends upon the catalyst temperature

Occurs in the cooler regions

Upper section of tubes vulnerable

Also depends upon sulfur exit the HDS


Effect of sulfur coverage on activity

0.8
Activity

0.6

0.4

0.2

0
0 0.2 0.4 0.6 0.8 1

Coverage
Sulfur Poisoning

Sulfur poisoning is reversible

Steam the catalyst for 24 hours

Steam slowly strips off the sulfur

Re-oxidizes the catalyst in addition

May lose some activity permanently


Steaming Reforming Catalysts

Steaming of the catalyst is required when there is:

Severe carbon formation


Loss of steam
Incorrect steam to carbon ratio operation
sulfur poisoning

sulfur poisoning
Poor performance of the desulfurization
system
Steaming Reforming Catalysts

Isolate hydrocarbon feed

Maintain steam flow at highest possible level

Adjust reformer firing to achieve 750C reformer


exit temperature or higher if possible

Monitor carbon oxides or H2S in the exit gases

Addition of a small amount of nitrogen into the


steam facilitates reliable sample analysis
Steaming Reforming Catalysts
Potash promoted catalyst

Accelerates carbon gasification during


steaming
Required since carbon laydown often occurs in

the top section of the reformer tubes where high


temperatures needed for steaming are not
easily achieve
Design of catalyst needs to ensure potash

release is controlled during steaming


Release rate for VSG-Z102 series is

approximately double the normal rate during


steaming (24 hours of steaming ages the
catalyst by 48 hours)
Effect of Steaming - Alkalized Catalyst

Potash Retention - Steaming Test

3
Residual wt % of potash

2.5
VSG-Z102
2

1.5
Comp. A
1

0.5
Comp. B
0
500 550 600 650 700 750
Steaming Temperature C (equivalent to 1 year operation)
Steaming Reforming Catalysts

Carbon Removal By Steaming

200 1.6
1.4

Residual Carbon (%)


150 1.2
1
100 0.8
0.6
50 0.4
0.2
0 0
0 5 10 15 20
Time (hours)
Steaming Reforming Catalysts

4.5
Methane slip (mol % dry)

4 HDS
Problem
3.5 Design

3
Catalyst
Steamed
2.5
0 5 10 15 20 25 30 35
Time on line (months)
Steaming Reforming Catalysts

Sulfur removal

Catalyst performance can be restored

High reformer inlet temperature during


steaming is important for successful sulfur
removal

Need to monitor the H2S slip during steaming


Sulfur Levels in Discharged Catalyst

300
sulfur (ppm wt)

Before Steaming
200 After Steaming

100

0
0 10 20
Distance Down Reformer Tube (m)
Steaming Reformer Catalyst
MgO in catalyst support must not be "free"
otherwise during steaming, the MgO will
hydrolyse

MgO + H2O Mg(OH)2

Hydration of the MgO causes rapid loss of


catalyst strength and severe catalyst break-up
and high reformer pressure drop

VSG-Z102 series catalyst contain MgO that is


chemically locked into the the catalyst support -
No hydration
Reformer Catalyst Monitoring
Reformer Catalyst Monitoring

Monitor frequently (daily)

Exit Methane
Tube Wall Temperature (TWT)
Tube Appearance

Monitor Less Frequently

Pressure Drop
Approach to Methane Steam Equilibrium
Reformer Catalyst Monitoring

Methane Slip

Dependant on throughput, heat load & catalyst


activity
If these conditions vary then exit CH4 will vary

Approach to Equilibrium

ATE defined as Difference between Actual


Temperature & Equilibrium Temperature
Better guide to catalyst activity
ATE increases as catalyst activity decreases
Reformer Catalyst Monitoring

Tube Wall Temperature

Dependant on catalyst loading, catalyst


activity & physical catalyst condition
As maximum TWT is approached, rate must be
reduced. In worst case catalyst will need to be
changed.
Appearance

A good indication of how reformer is operating


Tubes should look cool. Poor catalyst
performance will mean tubes looking hot.
Pressure Drop

PD will increase with time due to physical


blockage/breakage of catalyst
Too high PD will result in throughput
limitation
Should back-calculate PD at design
conditions (independent of throughput)

Since PD (velocity) 2

100 2
Normalised PD = Measured PD
( % design
(
Approach to Equilibrium (ATE)

The approach to equilibrium (ATE) at any point


along the catalyst bed is the difference between
the actual gas temperature and the equilibrium
temperature corresponding to the gas
composition.

The ATE can be used as a good measure of the


performance of the catalyst when the operating
temperature of the reactor is held constant, and
when the reaction is equilibrium limited, such as
with primary reforming.
Calculation of ATE
Steam Reforming Reactions

CH4 + H2O CO + 3H2 Methane Steam (MS)

CO + H2O CO2 + H2 Water Gas Shift (WGS)

Since the WGS reaction is so fast it can be


assumed to be at equilibrium under reformer exit
conditions

This means then the equilibrium temperature for


this reaction (TWGS) can be used as a reliable
estimate of the actual reformer exit temperature
(Measurements are unreliable)
For the WGS reaction the equilibrium constant
(KWGS) can be calculated

Then equilibrium tables can be used to determine


the equilibrium temperature for this reaction (TWGS)

For the MS reaction the equilibrium constant (KMS)


can also be calculated and equilibrium tables then
used to determine the equilibrium temperature for
this reaction (TMS)
The ATE can then be calculated as the difference
between TWGS (equal to the actual reformer exit
temperature) and TMS

GBHE uses a computer program to calculate ATE


Example Calculation of ATE

Reformer Exit Composition Reformer Exit


% v/v Pressure = 31.6 ata

H2 68.0
N2 1.6 Reformer Exit
Temperature
CH4 9.6 (TWGS) = 796C
CO 10.2
CO2 10.6
Total 100.0 Dry
H2O 76.6
Total 176.6 Wet
pCH4 = 9.6 x 31.6 = 1.7178 ata
176.6

pH2 = 68.0 x 31.6 = 12.1676 ata


176.6

pH2O = 76.6 x 31.6 = 13.7065 ata


176.6

pCO = 10.2 x 31.6 = 1.8251 ata


176.6
Example Calculation of ATE

KMS = pCH4 . pH2O

pCO . (pH2)3

= 1.7178 x 13.7065

1.8251 x (12.1676) 3

= 7.161 x 10-3

From Tables TMS = 792C

ATE = 796 - 792 = 4C


Catalyst Handling

Catalysts are expensive & should be treated with


care at all stages of:

Handling on arrival
Storage
Charging
Storage in vessel before start-up

Careful & detailed supervision at all stages is


essential

Safety: proper equipment is essential both for the


safety of workers & to prevent damage to catalyst
Handling & Storage
On Arrival

Use suitable fork lift truck or crane to transfer to


storage
Don't drop drums off tail board of lorry
Don't roll drums
Inspect drums for damage & repair broken lids

Storage

Store under cover (long term storage)


Avoid damp / wet conditions
Store drums in upright position
Stack no higher than 4 drums
Catalyst not affected by extremes of
temperature
(-50C to +50C) provided kept dry.
Catalyst Loading

If loading is poor, variety of flows in tubes

Each tube has different exit temperature

Each tube has a close approach

Methane slip not linear with temperature

Mixture of all tubes far from equilibrium

Made worse by the flow imbalance


Base Case
Reformer Exit: 20 ata 870C design
10 C approach to equilibrium

Maldistribution
10 C approach to equilibrium
Tube 1: 105% flow 850C Exit T
Tube 2: 95% flow 890C Exit T
Base Case Maldistribution Case

Tube 1 Tube 2

Exit Temperature (C) 870 850 890

Relative Flow (%) 100 105 95

Approach to Equilibrium (C) 10 10 10

Methane Slip (% dry) 3.583 4.698 2.687

Average Methane Slip (% dry) 3.583 3.743

Average Approach to Equilibrium (C) 10 13.1


Catalyst Charging - Tubes

Inspect empty tubes


Check pressure drop on tubes both empty and

full
'Sock' or 'Unidense' method recommended

Avoid excessive hammering and vibration

Final PDs should be within 5% of mean

Better to discharge tubes with high PDs rather

than over-vibrate tubes with low PDs


Weighing is a useful check on charged bulk

density, but not essential


Catalyst supplied in pre-weighed socks
Sock slightly narrower than tube bore
End of sock folded over
Lowered down tube on rope
Tugged to release fold
Free fall <0.5m allowable
Vibrated with hammer after each sock
PD measured empty / full / full
Adjusted to 3 - 5%
Outage Adjusted
Catalyst Charging - Unidense Method

Norsk Hydro technology


- available through Hydro Agri Europe

Simple & fast loading technique

No pre-socking and no tube vibration required

Applicable to a range of catalyst types & reformer


designs

Offers high uniform catalyst density


Catalyst Charging Unidense Method

Charging Technique

Weighed amount of catalyst is poured into the


tube & the loading rope is gradually pulled out of
the tube as the catalyst layer builds up.

The brushes with flexible springs reduce the


speed of the catalyst particles so that breakage
is avoided.

This results in a loading without bridges & voids,


hence there is no need for tube vibration /
hammering.
Catalyst Charging - Unidense Method

Loading rope with


flexible springs
Charging
chute

Support grid
Catalyst Charging - Unidense Method

Benefits

Reduced loading time


Reduced possibility of bridging / less hot spots

Contributes to lower tube wall temperatures and

prolonged tube life


Narrow pressure drop variation in tubes

Slightly higher PD than sock method

Minimal further settling / PD increase


Precommisioning / Periods of Shutdown

Completely close reactor after charging


Box up under N2 if necessary
After commissioning leave temperature points
connected and check regularly during shutdown
periods
Check drains regularly
After shutdown keep under positive N2 pressure
(natural gas OK for sulfur removal catalysts)
On decommissioning Nickel containing catalysts
must be purged free from carbon oxides before
temperature falls below 250C
Normally

Process feed on flow control


Process steam on ratio control from feed
rate
Purge fuel / flash gas to fuel header
Fuel header on pressure control
Fuel to reformer on flow control
Adjusted to maintain reformer exit temperature
Reduction & Start-Up
Contents

Introduction

Start-up Procedures
Warm-up

Catalyst Reduction

Feed Introduction

Shut-down

Case Studies
Introduction
Steam reformer is complex

heat exchanger
chemical reaction over catalyst
combustion, leading to steam generation

Common symptoms of poor performance

high exit methane slip


high approach to equilibrium
high tube wall temperature
high pressure drop

Need properly active catalyst


Introduction - Catalyst Reduction

As supplied - NiO on support

Active species - Ni Crystallites

Reduction process needed:-

NiO + H2 Ni + H2O
Introduction - Catalyst Reduction

Partial Pressure of H2O / Partial Pressure H2


700
Equilibrium Constant

500

Oxidising Conditions
300

200

Reducing Conditions

100
400 500 600 700 800
(752) (932) (1112) (1292) (1472)

Temperature C (F)
Introduction - Catalyst Reduction

Faster at high temperature

Slower in presence of steam

Thermodynamically, very little hydrogen needed

Support also affects ease of reduction


Introduction - Catalyst Reduction

Requires high temperature


- fire steam reformer

Requires reducing conditions


- supply H2 or reducing gas
- re-circulation or once-through

Since little or no steam reforming is taking place,


less heat is required to warm up gas

50% steam rate, with 5:1 steam:H2 ratio requires


1/7 fuel of normal operation

Extreme danger of local overheating!


Start-Up Procedure

Introduction

Start-up Procedure
Warm-up

Catalyst Reduction

Feed Introduction

Shut-down

Case studies
Start-Up Procedure - Warm Up
Purge plant of air with N2
(Care: must be free of hydrocarbons and carbon
oxides)
Heat reformer above condensation temperature

Add steam when exit header temperature 50C

above condensation temperature


(low pressure favours good distribution and
lowers this temperature)
Increase steam rate to 40 - 50 % of design rate

(min 30%)
Stop N circulation
2

Air warm-up possible, but not for previously


reduced catalyst (possible carbon)
Start-Up Procedure - Warm Up
Rapid warm-up minimises energy usage / time

Limited by mechanical considerations of steam


reformer

Assess effect on plant equipment

thermal expansion of inlet/exit pipes


reformer tube tensioners

reformer tubes

refractory linings

Traditionally: 50C per hour


Modern material: 100C per hour
Catalyst: 150 - 170C per hour
Start-Up Procedure - Warm Up

If upstream pipe-work cold, good practice to warm


up by steam flow to vent to prevent carry-over of
water.

Steam Steam
Reformer
Cold Pipe-work
Start-Up Procedure - Warm Up

Temperatures referred to are true catalyst


temperatures at exit of tube

Measured temperatures during normal operation are


10 -100C cooler due to heat losses

Most catastrophic failures of tubes in top-fired


furnaces occur during start-up

Cannot rely on plant instrumentation during start-up


lower flows than normal
higher heat losses than normal
fewer burners can give severe local effects

Frequent visual inspection of reformer tubes and


refractory essential during start-up
Start-Up Procedure - Tube Life
Effect of Pressure and Temperature
10,000,000

1,000,000

100,000
Tube Life ( hours )

10,000
30 bar 5 bar
1,000

100

10

1
800 900 1000 1100 1200
(1500) (1650) (1830) (2010) (2200)

Tube Wall Temperature C (F)


Start-Up Procedure - Catalyst Reduction

Introduction

Start-up Procedure
Warm-up

Catalyst Reduction

Feed Introduction

Shut-down

Case studies
Start-Up Procedure - Catalyst Reduction

Reduction with Hydrogen

Reduction with Natural Gas

Reduction with other sources of hydrogen

Higher hydrocarbons
Ammonia
Methanol
Catalyst Reduction with Hydrogen

H2 or H2-rich gas can be added at any time to the


steam when plant is free of O2

Steam : hydrogen ratio normally 6:1 - 8:1

Get tube inlet temperature as high as possible

Increase exit temperature to design value


>700C

Hold for 2-3 hours


Catalyst Reduction with Hydrogen

Hydrogen must be free of poisons (S, CI)

Special consideration must be given to the

presence in impure hydrogen sources of:


carbon oxides
hydrocarbons

Also applies to nitrogen (or inert) source used for


purge/warm-up
Catalyst Reduction with Hydrogen

Recirculation loop may include HDS unit (at


temperature)

Carbon oxides above 250C (480F) methanate over


unsulphided CoMo catalyst:

temperature rise 74C per 1% CO converted


temperature rise 60C per 1% CO2 converted

If H2 contains > 3 % CO or > 13 % CO2 or a mixture


corresponding to this then by-pass the HDS system
Catalyst Reduction with Natural Gas

Natural Gas

Will be converted to carbon oxides + hydrogen in


reformer

May crack thermally to give carbon


Catalyst Reduction with Natural Gas

Warm-up as before (N2 then steam)


Introduce natural gas at 5% of design rate

Slowly increase gas rate to give 7:1 steam:carbon

over 2-3 hours


Simultaneously increase reformer exit temperature

to design level i.e. >700C


Increase inlet temperature as much as possible (to

crack natural gas to give H2)


Monitor exit methane hourly

Reduction complete when methane reaches low,

steady value (4 to 8 hours)


Catalyst Reduction with Higher
Hydrocarbons
E.g. propane

Increased possibility of carbon formation


Much greater care needed

Longer time periods needed

More precision in all measurements needed

Hydrogen addition recommended if possible

Purification issues

- Desulfurization
- Methanation of carbon oxides

Not normally recommended


Catalyst Reduction with Ammonia

Crack ammonia in ammonia cracker

Crack ammonia in steam reformer

inject liquid ammonia upstream of steam


reformer
bypass HDS

Procedure as for hydrogen reduction

Exit temperature 800C (1470F) to maximise


ammonia cracking
Catalyst Reduction with Methanol

Uncommon Procedure

Methanol decomposes to give H2 and CO

Regulate flow of liquid methanol to give

6:1 - 8:1 steam:hydrogen ratio exit steam reformer

Do not recycle exit gas (potential methanation of


carbon oxides)
Start-Up Procedure - Feed Introduction

Introduction

Start-up Procedure
Warm-up

Catalyst Reduction

Feed Introduction

Shut-down

Case studies
Start-Up Procedure - Feed Introduction

Introduce feedstock at high steam:carbon ratio (5:1


for natural gas; 10:1 for higher hydrocarbons)

Steam reforming will give small increase in inlet


pressure, cooling of tubes, and lower exit
temperature

Need to increase firing to maintain exit temperature

Then increase feedstock flow

Increase pressure to operating pressure

Adjust steam:carbon ratio to design


Start-Up Procedure - Feed Introduction

Increase flow of natural gas to design


steam:carbon ratio (2 hours)
Maintain exit temperature

Check that exit methane stays low

(reducing steam:carbon ratio will increase


methane slip and heat load)
if not, hold at 7:1 steam : carbon for 2 hours
Increase throughput to design level

Increase pressure to design level

Always increase steam rate before feed rate


Start-Up Procedure - Restart

Shorter re-reduction recommended

Typically 4-6 hours for heavy feeds

Not essential to carry-out reduction with natural


gas or light off-gas feedstock

Start up at 50% design rate, high steam:carbon


ratio
Case Studies

Introduction

Start-up Procedure
Warm-up

Catalyst Reduction

Feed Introduction

Shut-down

Case Studies
Shut-down
Reduce tube exit temperature to 750C

Decrease feed and steam flows in stages to 40%


design

- always decrease hydrocarbon flow first


- adjust firing to keep exit temperature steady

Keep steam flow constant, shut off hydrocarbon


feed

- adjust firing to maintain exit temperature


- purge system of hydrocarbons

Decrease exit temperature to 550C at 100C per


hour
Shut-down

Add flow of N2 and continue cooling

Shut off steam 50C above condensation


temperature

Continue cooling with N2 flow

When catalyst below 50C tubes may be emptied


Case Studies

Introduction

Start-up Procedure
Warm-up

Catalyst Reduction

Feed Introduction

Shut-down

Case Studies
Case Studies - No 1

Large modern top-fired steam reformer

Significant tube failures during start-up

Caused by overfiring at start-up due to a number


of coincident factors
Case Studies - No. 1

Site steam shortages requiring conservation of steam

Pressure to avoid a shut-down (due to low product


stocks)

Burner fuel usually from two sources, mixed:


one low calorific value
one high calorific value

At time of incident, all high calorific value


(unexpectedly) fuel received

Operators had seen many shutdown/start-ups during


past two years
Case Studies - No. 1

Plant trip (loss of feedstock to reformer) due to


valve failure

Feedstock to reformer not isolated adequately by


valve

Setpoint on reformed gas pressure not reduced

Steam introduced for plant restart at reduced rate

All burners lit (deviation from procedure)

Reformer tubes remained at normal operating


pressure of 16 barg
Case Studies - No. 1

Steam reformer tubes "looked normal"


Nearly 3x as much fuel going to burners

than there should have been


High calorific value fuel added an extra

15% heat release


30 minutes

First tubes rupture

High furnace pressure (trip bypassed)

Oxygen in flue gas dropped to zero

Flames seen from peep holes

Normal furnace pressure

Visual inspection revealed "white hot

furnace and tubes peeling open"

Emergency Shutdown Activated!


Case Studies - No. 1
Reformer exit gas temperature on panel never
exceeded 700C

Cannot use this instrumentation as a guide to tube


temperature

Reformer start-up at normal operating pressure


Tube failure temperature 250C lower than
normal for start-up

All burners lit


Far too much heat input resulted in excessive
temperatures

Tubes Fail Rapidly!


Case Studies - No. 2

Ammonia Plant

LTS reduction loop included steam reformer

CO2 released from LTS reduction


Carbon formed in steam reformer
Case Studies - No. 2
LTS reduction with closed loop circulation

Normally condenser, compressor and pre-heat coil

This time included steam reformer, pre-heater and


waste heat boiler

Steam reformer fired to TWT of 900C

LTS reduction liberates CO2

By 2am, LTS reduction almost complete

- 50 % CO2 in recirculation gas


- also some H2 present
Case Studies - No. 2

Steam reformer pushed to give apparent LTS


temperature of 200C
Due to instrument error, in fact 380C

Between 5am - 7 am, steam reformer PD

increased
Tubes looked hot

Reformer steamed for 18 hours

No reduction in PD

Plant shutdown

Reformer catalyst black and badly broken up - due


to severe carbon formation
Case Studies - No. 2
CO2 can shift in LTS to CO
CO2 + H2 CO + H2O
CO in presence of H gives carbon
2
CO + H2 C + H2O
CO can methanate in steam reformer (if some

catalyst reduction due to presence of H2 is seen)


forming CH4
CO + 3H2 CH4 + H2O
This cracks to form carbon

CH4 C + 2H2

Check to ensure that recirculation loops do not


contain high levels of carbon oxides
Importance of Tube Wall Temperature
Measurement

Need accurate information

Tube life
Artificial limitation on plant rate
Effect of Tube Wall Temperature on
Tube Life

20
Tube Life (Years)

Design
10
+ 20C
5
2
1
0.5
0.2

850 900 950 1000


(1560) (1650) (1740) (1830)
Temperature C (F)
Tube Wall Temperature Measurement

Contact

- Surface Thermocouple

"Pseudo-contact

- Gold Cup Pyrometer

Non-contact

Disappearing Filament
Infra Red Optical Pyrometer
Laser Pyrometer
Surface Thermocouples

Continuous measurement, by conduction

"slotting" can weaken tube wall

Spray-welding leads to high readings

Short, unpredictable lives (6 -12 months)

Not commonly used for steam reformer tubes


Disappearing Filament

Hand held instrument

Tungsten filament superimposed on image of


target

Current through filament altered until it


"disappears

Current calibrated to temperature


Range 800-3000C

Very operator sensitive


Largely displaced by IR
Infra-red Pyrometer

Easy to use

Need to correct for emissivity and reflected


radiation

Inexpensive
Laser Pyrometer

Laser pulse fired at target and return signal


detected

Can determine target emissivity

Must correct for background radiation

High spacial selectivity

Very accurate for flat surfaces


Gold Cup Pyrometer

Excludes all reflected radiation

Approximates to black body conditions

High accuracy / reproducibility

BUT

- Limited access
- Awkward to use
Gold Cup Pyrometer

Tube Furnace Wall

Gold Cup
Lance

Water To
Cooling Recorder
Accurate Temperature Measurement

Combination of IR pyrometer and Gold cup pyrometer

Gold cup pyrometer allows calculation of emissivity

Full accurate survey of reformer possible with IR


pyrometer
Temperature Measurement Corrections

epyrometer (Tm)4 = etube (Tt )4 + rtube (Tw)4

Measured True Averaged


target target background
temperature temperature temperature

e = emissivity
r = reflectance
= (1-e)
Accurate Temperature Measurement

(Tm)4 = etube (Tt )4 + (1 - etube) (Tw)4

- Set IR Pyrometer emissivity at 1

- Measure Tm and Tw with Pyrometer

- Measure Tt with Gold Cup

- Calculate etube
Background Temperature Measurement
NORTH

a
1
A

a
2
Comparison of Infra-red Pyrometer and
Calculated Tube Wall Temperature
Measurements
950 1742

Uncorrected Pyrometer
900 1652
Temperature (C)

Temperature (F)
Corrected Pyrometer
850 Calculated 1562

800 1472

= Gold Cup Measurements


750 1382

0 0.2 0.4 0.6 0.8 1


Fraction Down Tube
Tube Wall Temperature Measurement -
Conclusions

IR Pyrometer typically reads high

Top-fired reformer 32C


Side-fired reformer 50C

IR Pyrometer with Gold Cup "calibration

Top-fired reformer 2C
Side-fired reformer 16C
Classroom Exercise 2 - PROBLEM

Reformer exit gas composition (dry %)


H2 73.19
N2 + Ar 1.11
CH4 3.04
CO 15.55
CO2 7.11
Total (dry) 100.00
H2O 41.34
Total (wet) 141.34
Reformer exit pressure 18.11 barg
Reformer exit temperature 875C

Calculate the approach to equilibrium


Classroom Exercise 2 - ANSWER

Exit Pressure (ata) = (18.11 / 1.013) + 1 = 18.88 ata

pCH4 = 3.04 x 18.88 = 0.4061 ata


141.34
pH2 = 73.19 x 18.88 = 9.7766 ata
141.34
pH2O = 41.34 x 18.88 = 5.5221 ata
141.34
pCO = 15.55 x 18.88 = 2.0771 ata
141.34
pCO2 = 7.11 x 18.88 = 0.9497 ata
141.34
KWGS = pH2 . pCO2

pH2O . pCO

= 9.7766 x 0.9497

5.5221 x 2.0771

= 8.09 x 10-1

From Tables TWGS = 875C

Reformer exit temperature = 875C


KMS = pCH4 . pH2O

pCO . (pH2)3

= 0.4061 x 5.5221

2.0771 x (9.7766) 3

= 1.15 x 10-3

From Tables TMS = 874C

ATE = 875 - 874 = 1C