Experience in optimizing ATR performance

with high stability KATALCOJM catalysts

Kevin Mowbray

Johnson Matthey

Introduction

Introduction to autothermal reforming

Catalyst bed fouling and pressure drop build up

Alumina vaporization and transport

High stability reforming catalysts and target tiles

Case study large combined reforming plant

Conclusions

Autothermal reforming

Increasingly common in methanol plants

Beneficial in larger plants

Alternative feeds such as coke oven gas

Brings several benefits

Low methane slip due to high temperature

Stoichiometric synthesis gas

Improve loop efficiency

Can be employed in several flow schemes

Johnson Matthey have experience designing for all cases

Johnson Matthey have experience with alternative feeds

Series & combined reforming

Steam

Steam

Steam

Steam

reformer

Oxygen

Natural gas

Autothermal

reformer

Bypass gas

EMethanex example

3,600mtpd methanol plant

Damietta, Egypt

Combined reforming flow scheme

DPT / Johnson Matthey technology

Johnson Matthey largest autothermal reformer to date

Commissioned Q1 2011

ATR running well

Autothermal reformer

Alumina lumps or target tiles

Catalyst bed

Refractory

support arch

Alumina lumps

Reformed gas outlet

9501020C

Refractory lining

Oxygen inlet

20250C

Process gas inlet

650750C Burner

~1250C

Standard catalyst charge

Alumina hold-down lumps or tiles

Guard layer of low activity large pellets

Alumina condenses on large pellets

Minimizes pressure drop build-up

Main bed of standard catalyst

The hold-down material vaporizes

More important than refractory vaporization

Standard catalyst charge

Alumina lumps or target tiles

Standard catalyst

Alumina lumps

Low activity catalyst

Severely fouled

catalyst forms

in this location

Target tiles

Vaporized tiles and large catalyst

Fouling on main catalyst

Severe fouling of main bed

Rubies

Alumina vaporization

Effect of condensation

Fouls and blocks the flow paths

Increased pressure drop Reduced rate as reformed gas pressure reduces

Mini shutdowns to skim catalyst bed

Short catalyst lifetime

Loss in activity by physical blinding

Difficulty in discharging catalyst

Fouling of waste heat boiler

Often find rubies Al2O3 contaminated with traces of Cr

High stability catalyst charge

Hold down tiles or lumps (KATALCOJM 94-1)

high density stabilized ceramic

reduces vaporization from tiles by >90%

guard bed of high activity (KATALCOJM 89-6Q)

refractory metal on a stabilized ceramic

cools gas rapidly below vaporization temperature

main bed of KATALCOJM 28-4Q

reduces vaporization and pressure drop

KATALCOJM 94-1 and 89-6EQ

Case study

Large combined reforming based methanol plant

1997 2007 ran with alumina based catalysts in ATR

Experienced pressure drop build-up

Bed needed skimming at each maintenance turn around

Installed JM high stability catalysts in 2007

Very low rate of pressure drop rise

Catalysts removed and reloaded due to refractory repair in 2010

Operated through till a planned changed out on 2014

KATALCOJM 89-6 charge in July 2007

KATALCOJM 94-1 tiles

KATALCOJM 28-4Q catalyst

KATALCOJM 94-1 lumps

KATALCOJM 89-6GQ catalyst

KATALCOJM 89-6 charge in July 2007

Pressure drop 0 3 years

Overhaul July 2010

Internal inspection in September 2009 identified problems with the refractory lining

Major repairs planned for July 2010

3 years after KATALCOJM 94-1 and 89-6 was installed

Pressure drop had built up by only a small amount

Tiles and catalyst in as new condition during inspection

Decision made to remove the catalyst and recharge

Some spare catalyst ordered to make up for breakage

KATALCOJM 94-1 tiles

KATALCOJM 94-1 lumps

KATALCOJM 89-6GQ catalyst

KATALCOJM 28-4Q catalyst - top

Findings after 3 years service

KATALCOJM 94-1 tiles and lumps in excellent condition

Small number of tiles with some cracks but reusable

Carefully removed and reused

KATALCOJM 89-6GQ catalyst in excellent condition

Small number of broken pellets but OK for reuse

There was no alumina condensed on the 89-6GQ

This remained in as new condition

KATALCOJM 28-4Q catalyst in good condition

Very top of bed slightly fouled with alumina

Replaced with KATALCOJM 28-4EQ catalyst Larger holes so less easy to foul in the future

Rest of bed in excellent condition and reused

KATALCOJM 89-6 charge in July 2010

KATALCOJM 94-1 tiles

KATALCOJM 28-4Q catalyst

KATALCOJM 94-1 lumps

KATALCOJM 89-6GQ catalyst

KATALCOJM 28-4EQ catalyst

Pressure drop 0 6 years

Findings after 6 years service

KATALCOJM 94-1 tiles and lumps in excellent condition

Minor spalling, no evaporation, no discolouring

Described as good as new

KATALCOJM 89-6GQ catalyst in excellent condition

No sign of vaporization

No ruby formation

Some pellet breakage observed

KATALCOJM 28-4Q catalyst

Only very top of bed inspected

Vaporization of pellets seen in mixed layer of KATALCOJM 89-6GQ and KATALCOJM 28-4Q from 2010 reload

ATR inspection June 2013

KATALCOJM 94-1 Tiles

Top of bed

ATR inspection June 2013

KATALCOJM 89-6GQ and KATALCOJM 94-1 lumps

Operation through till end of run

Findings after 7 years service

KATALCOJM 94-1 tiles and lumps in excellent condition

Minor spalling, no evaporation, no discolouring

Findings after 7 years service

KATALCOJM 89-6GQ catalyst in excellent condition

No sign of vaporization

No ruby formation

Some pellet breakage observed

Findings after 7 years service

KATALCOJM 28-4Q catalyst

Vaporization of pellets seen in mixed layer of KATALCOJM 89-6GQ and KATALCOJM 28-4Q from

2010 reload

alumina based supports are not as thermally stable as high density stabilized ceramics

Conclusions

Johnson Matthey have extensive experience in the technology of autothermal reforming

Johnson Matthey have demonstrated a range of superior target tiles and catalysts for autothermal reformers

These catalysts operated successfully with less pressure drop build-up for 7 years in a large combined reforming

methanol plant

Johnson Matthey catalysts and inert materials loaded again in 2014.