Reformer catalyst application and

optimisation

Rishabh Upadhyay

25 Mar 2015

Westin Hotel Gurgaon, India

Agenda

Catalyst combination for heavy natural gas feedstock

Pressure drop reduction and efficiency benefit

Steaming of primary reformer for carbon removal

Manage increased plant rate

Global excellence

Importance of monitoring process gas temperature

Catalysts for demanding top fired reformer exceed performance in side fired reformer

Case Study 1: Customer with heavy NG

feed

A large methanol customer in Asia Pacific

Plant capacity ~ 2500 MTPD

Top fired reformer

Recently commissioned competition catalyst faced with challenging conditions

Plant constrained to increase load

Background

Relatively heavy natural gas feedstock

Feedstock availability erratic, several trips seen during operation

Tubes observed with hot spots and patches

Eventually some of the tubes ruptured

Carbon formation suspected

JM conducted Reformer Imager survey to identify potential issues with the reformer

Thermal Imager reformer survey

TWTs were measured accurately at two levels

Several hot spots were found during survey

Few hot spots were above the design temperature

Hot & cold zones identified

Hot spots in blind areas observed with the use of Thermal Imager which has fish-eye lens

Temperature distribution

Benchmarking the reformer

Benchmarked against similar reformers to identify scope of improvement

Number of plants

Carbon Number

Findings & recommendation

Carbon formation suspected due to relatively heavy feed

Using standard catalysts carbon formation is expected

Recommendation:

JM alkalised catalyst at the top to avoid carbon formation

Smaller size for high activity

Larger catalysts at the bottom for optimised pressure drop

Summary

Optimum combination of sizes and variants to:

Avoid carbon formation

Optimum pressure drop

JM catalyst preferred

KATALCOJM 25-4MQ

Small alkalised catalyst at the top

KATALCOJM 57-4GQ

Large catalyst at the bottom

Case Study 2: Pressure drop & extended

life benefit

Customer in USA

Plant capacity ~ 1700 MTPD

Top fired reformer

6 catalyst charges installed in 25 years operation span.

Plant faced the problem of low catalyst life and high pressure drop for 10 years after commissioning.

Background

The plant was commissioned in 1990

Life of catalyst charges and pressure drop both were not satisfactory

Life of each of competitors first 3 charges < 4 years

Customer replaced the charge with another competitor but life achieved was still 4.3 years.

First JM charge achieved a life of 5.6 years.

Longer catalyst life

2.4 yrs 3.4 yrs 3.6 yrs 4.3 yrs

Competitor A

(3 charges) Competitor B

KATALCOJM 25-4Q/23-4Q

Johnson Matthey Catalyst

Life 5.6 years

+30% life

Savings with increased catalyst life

The commercial benefits gained by customer with an increase of 30% in catalyst life

(Basis: Average life of JMs catalyst 5.5 years and that of competitors catalyst 4 years)

Cost of one overhaul

Production loss during shutdown

Cost of one primary reformer catalyst batch

Leading low PD product

KATALCOJM57-4G KATALCOJM57-4XQ

(4-hole) (QUADRALOBE)

Nominal OD (mm) 19mm 19.7mm

Nominal hole dia. (mm) 5.5mm 5.5mm

Length (mm) 19.6 - 20.4 19.6 - 20.4

Nominal TBD (kg/l) 0.9 0.9

Average mean horizontal

(radial) crush strength (kgf) >56 >100

Relative pressure drop 1.0 0.76

GSA (m2/m3) 343 346

For the next charge, JM redesigned the catalyst bed and further optimized by using the new leading low pressure drop product.

Further savings with pressure drop

reduction

2.4 yrs 3.4 yrs 3.6 yrs 4.3 yrs 5.6 yrs 5.1 yrs and running

Competitor A

(3 charges) Competitor B

KATALCOJM 25-4Q/23-4Q

KATALCOJM 25-4GQ/57-4XQ

Johnson Matthey Catalyst

Lower pressure drop

Second charge of Johnson Matthey reduced the pressure drop by 20% and is still in service from last 5.1 years with

satisfactory performance.

Case Study 3: Steaming for carbon

removal

Customer in western Europe

Plant capacity ~ 1450 MTPD

Top fired reformer

Feedstock for the plant is LPG which is a challenging duty.

Plant faced the problem of carbon formation due to feeding LPG condensate during startup.

Carbon formation incident

During startup, LPG condensate trapped in line was fed into the primary reformer which resulted in carbon formation over the catalyst.

The pressure drop over the

reformer increased by 1 bar and went upto 4.2 bar.

Hotspots were observed over the length of tube.

Customer reported the incident to JM and mentioned that they need to keep the plant in operation.

Improvement with higher S:C ratio

JM recommended to operate at higher S:C to control carbon and to steam the catalyst in next available oppurtunity.

Appearance improved in

short period of time with higher S:C operation.

Pressure drop reduced by 0.3 bar.

TWT of the hot tubes also came down.

0 5 10 15 200

50

100

150

200

0

0. 5

1

1. 5

2

Time (Hours)

CO

+ C

O2

Exit

Ste

am

Refo

rm

er (p

pm

)

(29.0)

(14.5)

Pre

ssu

re d

rop (b

ar/p

si)

CO + CO2 Pressure Drop

Steaming of catalyst

Due to some reason, plant tripped after two months operation and allowed full steaming.

Carbon removal profile

Recovery of catalyst activity

Hot patches not visible due to carbon removal by

steaming.

TWT and pressure drop reduced considerably

The catalyst charged performed satisfactorily for

4 more years after carbon

formation incident.

Summary

The high strength of JM catalyst restricted any breakage even after feeding of LPG condensate. This allowed the

customer to recover the pressure drop.

Life of tubes was not adversely affected due to JMs catalyst capability of regaining the activity.

Customer in western Europe

Plant capacity at commissioning~ 1750 MTPD

Present capacity ~ 2050 MTPD

Top fired reformer

ICI catalyst Katalco 57-3 was installed at commissioning and provided 10 years of life.

Plant interested in increasing the capacity.

Case Study 4: Increase in plant rate

managing P

Enhanced shape and higher activity

catalyst catering higher load

KATALCOJM57-4G 4-hole catalyst replaced previous charge and had

achieved a 10 year life

~10% increase in plant load including pre reformer addition.

The higher surface area of 4 hole catalyst helped customer to cater the

increased load

The picture of discharged catalyst pellets points out the high strength of

JM shaped catalyst.

KATALCOJM 57-4G

after 10 yrs service

Reduction in pressure drop

In early 2000, plant increased the production to 2000 MTPD and were interested in any further pressure drop

saving

Installation of new KATALCOJM 57-4XQ has given even lower pressure drop

Pressure drop reduced by 24%

Detailed performance surveys completed

Confirmed expected catalyst performance

Allowed plant to reach record rates

Pressure Drop

2.3 bar (earlier)

1.8 bar with

KATALCOJM57-4XQ

Summary

All 3 charges of catalyst since 1987 have achieved 10 years of operation.

All the charges used different shapes and the performance of all catalyst charges had been excellent.

The variations in shapes and sizes enables JM to optimize the catalyst bed for every customer according to their specific

requirements.

Case Study 5 Feedstock changeover

Customer in India

Capacity 1350 MTPD

Installed in Aug 1999

Feedstock as naphtha (100%) till Apr 2004

Same charge operated on mixed feed (naphtha + NG) till April 2007

100% feedstock converted during April 2007

Smooth feedstock changeover experienced

No issues on performance of primary reformer

Discharged catalysts didnt show loss of potash or strength

Customer in India

Second charge commissioned in 2007 for NG as feedstock

2 decker catalyst combination

50:50 alkalised and non-alkalised

Unidense loading

Operates around 105% of rated capacity

Lasted for 7 years without any issues

Performance

Consistence methane slip

Steady pressure drop

Good physical integrity

Time on line

(days)

Methane slip

(% mol, dry)

Norm. Pressure

drop (kg/cm2)

1737 12.21 2.96

1912 11.52 2.9

2166 12.75 3.06

2235 12.9 3.11

2483 12.49 3.12

2563 12.82 3.03

Capacity of 2500 MTPD

Side fired reformer

No of tubes : 210

Commissioned in 1997

Case Study 6 : Global excellence

Global excellence

Customer has a R&D facility along with methanol plant.

Philosophy : Operating with the best catalysts and absorbents affects the competitive power in a business

with a high installed capacity

Belief : Most catalyst suppliers will state that their product is the best ! Necessitates

need for independent testing.

Global excellence

Customer carried out independent tests on material of shortlisted vendor at their own R&D facility in

2007 to find the best for them.

Johnson Matthey KATALCOJM57-4Q was selected.

First charge was installed in 2007 and changed in 2013, providing 100% more life than previous

charge of competitor.

Second JM primary reformer catalyst charge was installed in 2013 and is providing satisfactory

operation

Case Study 7: Benefits of monitoring

process gas temperature

Customer is a renowned utility provider

Customers experience as a technology licensor & plant designer:

Tubes are largest single capital investment

No economical fixes (large down time & capital cost)

Nine references since 2003

Issues identified:

The detailed reformer inspections and surveys are done only periodically and mainly during

incidents.

Lack of measurement technique of process gas temperature inside tube

Failed Tube

in Operation

CatTracker: Solution for process gas

temperature measurement

Customer installed CatTracker units in their plants offered by Johnson Matthey.

11 thermocouple measurement locations

Positioned at determined points of interest along length

Rugged and flexible with high accuracy

CatTracker Tube

CatTracker

Modified

flange

Top Fired Reformer CatTrackers

Side Fired Reformer CatTrackers

Reformer CatTrackers

process simulation calibration

Use with TWTs to calibrate simulation

Detailed reformer model (JM - REFORM)

Regress model physical parameters

More accurate prediction of catalyst performance

Reformer CatTrackers

example plant normal operating data

9 CatTrackers

Different measurement locations

Reformer CatTrackers start up

monitoring

Through startup CatTracker hotter than both outlets.

. in-tube TIs are leading Indicators

Reformer CatTrackers

Sulphur slip incident detection

Summary

On-line in-tube accurate and well proven temperature measurement

First time direct process gas measurement in a reformer

Provided early indication of sulphur poisoning and enabled customer to take early action preventing adverse effect on

catalyst tube.

CatTrackers also facilitate the customer to avert tube failures and have safer operation.

Steam Reformer

Types

Competing reformer technologies in Asia Pacific:

Top fired

Side fired

Comparison

Temperature profiles for typical top and side fired reformers

Flue gas temperature significantly different

Process gas temperatures similar

Comparison

Top Fired Side Fired

Peak heat flux kW/m2

116.6 87.2

Average heat flux kW/m2

78.2 78.0

Ratio peak/average

149% 112%

Top fired duty is more onerous for catalyst

Higher peak heat flux for same average heat flux

Higher risk of carbon formation at peak heat flux point

Requires catalyst to have higher activity as compared to a side fired furnace

Catalyst operating well in a top fired reformer is more than good enough to work in a side fired reformer

Reformer catalyst market split

Market split between top and side fired furnaces

Top fired share has increased over time

Side fired share has a reducing trend because of single designer in new plants.

Case Study 8 - Reformer analysis

Ammonia plant at 1100TPD

Topsoe side fired reformer

Using JM catalyst successfully used since 2000

Reformer health-check analysis completed by JM

Addressed concerns regarding high TWTs

Tube Wall Temperature pattern

920 oC

East Cell 1

Tubes 121 - 160

West Cell 1

Tubes 81 - 120

East Cell 2

Tubes 41 - 80

West Cell 2

Tubes 1 - 40

Furnace Balancing Furnace Balancing

Poorly Balanced

800 820 840 860 880 9000

10

20

30

40

50

Temperature (C)

Freq

uen

cy

(%

)

Well Balanced

800 820 840 860 880 9000

10

20

30

40

50

Temperature (C)

Freq

uen

cy

(%

)

Standard Deviation a good measure

Max TWT

Ave TWT

TWT Improvement

Max TWT down 40C, Avg TWT down 20C

PRIMARY REFORMER TUBE TEMPS

840.0

850.0

860.0

870.0

880.0

890.0

900.0

910.0

920.0

930.0

940.0

11/0

8/20

00

25/1

0/20

00

15/1

2/20

00

20/1

2/20

00

26/0

1/20

01

02/0

3/20

01

20/0

4/20

01

25/0

5/20

01

28/0

6/20

01

12/0

7/20

01

20/0

7/20

01

06/0

8/20

01

14/0

9/20

01

15/1

0/20

01

23/1

1/20

01

14/1

2/20

01

31/0

1/20

02

27/0

2/20

02

22/0

3/20

02

12/0

4/20

02

09/0

5/20

02

31/0

5/20

02

28/0

6/20

02

09/0

7/20

02

02/0

9/20

02

De

g C

Case Study 8(b)

Plant Name Ammonia 1

Design Capacity 1,500 T/D

Current Capacity 1,725 T/D

Construction Contractor Snamprogetti

Process/Design Contractor Topsoe

Reformer/Furnace Contractor Topsoe

Reformer Type Side fired

Feedstock Nat. Gas

Startup Date 01/12/77

Catalyst performance

Customer chosen to get back to JM catalyst

LOTIS creep stain data visualisation

JM arranged Laser Optical Tube Inspection for tube creep study

Case Study 7(c) Tube inspection

Bottom of tubes

Spiral pattern

of damage

Side fired furnace spiral damage

Flue gas flow paths

Thank you