Katalco

Steam reforming catalysts for naphtha containing feeds

KATALCOJM 46-series catalysts

Contents
Page The naphtha steam reforming process KATALCOJM 46-series steam reforming catalysts Features, benefits and applications of KATALCOJM 46-series Typical reformer loadings with KATALCOJM 46-series 1 2 3 4

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The naphtha steam reforming process

Tube inlet
Thermal dissociation of the most easily cracked components of heavy naphtha occurs on all hot surfaces within the reformer. This process can produce the carbon on the external surface of catalyst pellets and on the metal surfaces of the reformer tube: CXHY CX+ (y/2)H2 The middle zone of the reformer is dominated by the steam reforming reactions, which transform the methane and olefins produced at the inlet of the reformer into carbon monoxide and hydrogen. CH4 + H20 CX-1 H2X-2 + (x-1) H2O CO + 3H2 (x-1)CO + (2x-2) H2

Catalytic induced cracking of naphtha produces a variety of olefins together with methane and hydrogen: CXHY CH4 + Cx-1 H2X-2 + H2

It is important that these reactions occur rapidly since the build up of high concentrations of olefins in the lower, higher temperature, zones of the reformer can cause carbon deposition. Catalysts for this zone of the reformer must have a propensity to resist carbon deposition, which matches the carbon forming potential of the hydrocarbon feedstock. That is, high levels of promoters will be required on duties involving heavy naphthas while lower levels of such materials will be required for lighter naphthas or mixed feeds.

Polymerisation of these intermediate olefins can lead to the formation of carbon rich deposits. The most important feature of the naphtha steam reforming process at the inlet of the reformer is the potential for carbon deposition. With very heavy naphtha feeds this zone of heavy carbon deposition can stretch down to the middle of the reformer tube. With lighter naphtha feeds the cracking reactions only occur near the inlet of the tube. Catalysts for this zone of the reformer must be designed to prevent carbon deposition. However, the catalysts must also have great strength in order to resist the impact of a process upset which could cause gross carbon deposition and to allow the catalysts to be steamed for prolonged periods in order to remove the carbon deposits.

Tube exit
At the exit of the reformer the methane and olefin steam reforming reactions are carried out until the system reaches close to equilibrium conversation. CH4 + H20 CO + 3H2

The water-gas shift reaction is also brought to equilibrium in this zone of the reformer tube: CO + H20 C02 + H2

Tube middle
With heavy naphtha feedstocks a small amount of thermal cracking can still be found within the middle zone of the reformer. This does not occur with lighter naphtha feeds. Catalytic induced cracking of hydrocarbons is usually completed within the middle zone of the reformer.

This zone of the reformer is generally at very low risk of carbon deposition but high activity catalysts are required to bring the system close to equilibrium. However, olefin slip from the middle zone of the reformer, which is most likely during process upsets, can provide the potential for carbon formation.

KATALCOJM 46-Series steam reforming catalysts

The KATALCOJM 46-Series catalyst range consists of three distinctive catalysts, which are used in different combinations depending on the nature of the hydrocarbon feedstock. - Heavy naphtha feedstocks require a combination of KATALCOJM 46-3Q and KATALCOJM 46-6Q - Light naphtha feedstocks permit the use of KATALCOJM 46-3Q, KATALCOJM 46-5Q and KATALCOJM 46-6Q - Mixed feedstocks, which involve the occasional use of light naphthas, also use KATALCOJM 46-3Q, KATALCOJM 46-5Q and KATALCOJM 46-6Q All of the catalysts are manufactured with a distinctive QUADRALOBE design Two types of QUADRALOBE design are used in the KATALCOJM 46-Series catalysts - KATALCOJM 46-3Q is produced as a high strength QUADRALOBE pellet - KATALCOJM 46-5Q and KATALCOJM 46-6Q are produced as high activity QUADRALOBE pellets The chemical composition of each catalyst is individually tailored to meet the different demands of the inlet (KATALCOJM 46-3Q), middle (KATALCOJM 46-5Q) and exit zones (KATALCOJM 46-6Q) of a naphtha steam reformer.

Summary of typical catalyst physical properties 46-3Q 46-5Q High Strength QUADRALOBE High Activity QUADRALOBE 15.0 16.5 3.7 1.05 1 7.0 13.0 3.5 0.89 60 46-6Q High Activity QUADRALOBE 1 7.0 13.0 3.5 0.89 60

Form Pellet length (mm) Pellet O.D. (mm) Hole diameter (mm) Typical loaded density (kg/l)

Typical average crush strength (kg) 100 (radial)

Summary of typical catalyst chemical properties 46-3Q Form NiO% K2O% ZrO2% Support 46-5Q 46-6Q High Activity QUADRALOBE 16 0 Proprietary Balance

High Strength QUADRALOBE High Activity QUADRALOBE 23 7 0 Balance 20 2 0 Balance

Features, benefits and applications of KATALCOJM 46-Series

Tube inlet
Catalyst features
KATALCOJM 46-3Q Produced in a large, high strength (average crush strength > 100kg), version of the QUADRALOBE pellet shape. The catalyst contains 7wt% of a potash promoter in the form of a complex mineral phase. This unique ingredient provides a mobile form of potash, which ensures that carbon removal reactions are promoted across the catalyst surface, within pores and on the internal walls of the reformer tube.

Tube middle

Tube exit
Operational benefits
KATALCOJM 46-3Q The high strength QUADRALOBE shape provides an assurance of robust and durable performance at the inlet of the reformer when operating on naphtha feeds. Potash is the best available promoter to ensure carbon free operation when naphtha feedstocks are to be processed. The unique, mobile potash promoter within KATALCOJM 46-3Q ensures that carbon deposition is prevented on every hot surface within the reformer tube.

Plant applications
KATALCOJM 46-3Q If carbon deposition occurs during a process trip then KATALCOJM 46-3Q will remain physically intact. A prolonged steaming process can then be used to remove the carbon deposits. At the end of this procedure the KATALCOJM 46-3Q pellets will be physically intact and the pressure drop through the reformer will not have increased. The potash promoter will allow a heavy naphtha, with a final boiling point of 180C, to be processed at a steam/carbon ratio of only 3.5 without risk of carbon formation. The potash promoter will allow a light naphtha, such as a pentane rich feed, to be processed at a steam ratio of only 2.6 without risk of carbon formation.

KATALCOJM 46-5Q Produced in a smaller, higher activity, version of the QUADRALOBE pellet shape. This shape ensures that a large catalyst surface area is made available for reaction within the reformer tube. The catalyst contains 2wt% of a potash promoter intimately bonded as a mineral within the support material. The catalyst contains an elevated concentration of nickel (20% NiO)

KATALCOJM 46-5Q With lighter naphtha feeds, where the potential for carbon deposition is reduced, KATALCOJM 46-5Q can be substituted for KATALCOJM 46-3Q in the middle zone of the reformer tube. The lower concentration of potash in KATALCOJM 46-5 is sufficient to resist carbon deposition from light naphthas while the high activity QUADRALOBE shape provides a higher catalytic activity than is achievable with KATALCOJM 46-3Q. Higher plant through puts are therefore achievable if KATALCOJM 46-5 can be used in the middle of the reformer tube. In plants with variable feedstocks, in which a heavy naphtha will never be processed, KATALCOJM 46-5Q will often be substituted for KATALCOJM 46-3Q in the middle zone of the reformer tube. The high nickel and lower potash concentrations within KATALCOJM 46-5Q ensure high activity for gaseous feeds while maintaining resistance to carbon deposition if light naphtha feeds are processed.

KATALCOJM 46-5Q With a pentane rich feedstock, the use of KATALCOJM 46-5Q in the middle section of a reformer tube will provide a 20% increase in throughput above that which is attainable by using KATALCOJM 46-3Q throughout the inlet of the reformer. The improved throughput will be obtained with no increased risk of carbon formation. When the lighter, gaseous, component of a mixed hydrocarbon feedstock is being processed then high tube wall temperatures can be encountered. However, by using KATALCOJM 46-5Q in the middle section of the reformer the high activity of this product ensures that the high tube wall temperatures are reduced to acceptably low levels. The use of KATALCOJM 46-5Q therefore prolongs tube life on plants which process mixed hydrocarbon feeds.

KATALCOJM 46-6Q Produced in the small, high activity, version of the QUADRALOBE pellet shape. This shape ensures that a large catalyst surface area is made available for reaction within the reformer tube. The catalyst contains a small concentration of a special zirconia promoter. However, olefin slip from the middle zone of the reformer, which is most likely during process upsets, can provide the potential for carbon formation.

KATALCOJM 46-6Q This high activity catalyst minimizes methane slip from the reformer when operating on heavy naphtha, light naphtha or on variable feedstocks. The catalyst maximizes hydrogen production from the reformer while making certain that any threat of carbon deposition in the lower zones of the reformer tube is minimized.

KATALCOJM 46-6Q Any plant that processes naphtha-containing feedstocks runs the risk of experiencing a trip or process upset, which could force heavy hydrocarbons towards the exit of the reformer. By using KATALCOJM 46-6Q in this zone of the reformer the risk of carbon deposition from such an event is minimised.

Typical reformer loadings with KATALCOJM 46-Series

KATALCOJM 46-series catalysts should be used whenever a plant desires the flexibility to process a naphtha feedstock at some time during its operations. This range of catalysts is uniquely designed to provide the combination of carbon resistance, strength and activity which is required for the steam reforming of naphtha. No other catalysts will deliver the benefits associated with KATALCOJM 46-series products and, even if naphtha is no more than an occasional feed material, then only the 46-Series catalysts should be considered for these type of duties.

Catalysts for heavy naphtha duties

The catalyst combination which delivers premium performance when heavy naphtha is the only plant feedstock is a 50:50 loading of KATALCOJM 46-3Q and KATALCOJM 46-6Q. Catalysts for duties involving light naphthas If a heavy naphtha will never be used as the process feedstock then the risk of carbon formation in the middle zone of the reformer tube is significantly reduced. Therefore, if a light naphtha feedstock (such as a pentane rich material) is to be processed then it is possible to substitute KATALCOJM 46-5Q instead of KATALCOJM 46-3Q in the middle section of the reformer tube. Hence, the catalysts which deliver premium performance when a light naphtha is the heaviest hydrocarbon feedstock is a triple-decker loading of KATALCOJM 46-3Q, 46-5Q and 46-6Q.

Tube 46-3Q

Tube Inlet 46-3Q Tube Middle 46-5Q

Tube 46-6Q

Tube Exit 46-6Q

For further information on Johnson Matthey Catalysts, contact your local sales office or visit our website at www.jmcatalysts.com KATALCO and QUADRALOBE are trademarks of the Johnson Matthey group of companies.. PO Box 1 Belasis Avenue Billingham Cleveland TS23 1LB UK Tel +44 (0)1642 553601 Fax +44 (0)1642 522542 Oakbrook Terrace Two Transam Plaza Drive Chicago Illinois 60181 USA Tel +1 630 268 6300 Fax +1 630 268 9797

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928JM/0406/1/AMOG