TOPSBE SECONDARY REFORMING CATALYST RKS-2-7H

HALDOR TOPBEJE AlB

TOPSf(JE SECONDARY REFORMING CATALYST RKS-2-7H

In a traditional ammonia plant, secondary reforming involves continuation of the methane reforming reaction that began in the primary reformer, via the introduction of air to the reactor. The combustion of the oxygen in the air produces temperatures in the area of 1250°C (2300°F) which result in further reforming of methane, while the nitrogen is required for the eventual synthesis of ammonia product.

In methanol plants, secondary reforming is performed using pure oxygen, while in some synthesis gas (H2/CO) plants, natural gas is heated in a fired heater, mixed with steam and oxygen or enriched air, and reformed in a reactor similar to a secondary reformer (autothermal reforming).

Obtaining a long and satisfactory run life at the high operating temperatures in a secondary reformer requires a catalyst with outstanding thermal stability and mechanical integrity. Such features are found in Topsee's secondary reforming catalyst, RKS-2-7H.

Features of RKS-2-7H

No Heat Shield Required RKS-2-7H catalyst is based on a magnesia alumina spinel (ceramic

type) carrier with a fusion point in excess of 2000°C (3600°F), well beyond the highest temperatures typically observed in secondary reformers. Consequently, there is no need for a special heat shield material on top of the catalyst bed. RKS-2-7H may be loaded in the entire reactor, topped off by target bricks or alumina lumps, which serve as a hold-down material to prevent agitation of the catalyst by the incoming process gas streams.

Long Catalyst Life

The superior thermal stability of RKS-2-7H catalyst has been well proven in the industry, as plants worldwide have operated the catalyst in excess of 10 years with fully satisfactory performance. Frequently, catalyst unloading only takes place when an inspection of the reactor internals is required, and it is often possible to screen the catalyst and reload the majority of the material into the reactor, where it operates sucessfully for many more years.

Excellent Resistance to Temperature Excursions

High thermal stability in a secondary reforming catalyst is critical, because of the potential for temperature excursions in the reactor. Mishaps such as

Designation RKS-2-7H RKS-2-7H RKS-2-7H RKS-2P-1H
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Shape Cylinders w/7 Cylinders w/7 Cylinders w/7 Cylinders w/7 I
axial holes axial holes axial holes axial holes
Dimensions:
Outer diameter, mm 16 20 30 30
Hole diameter, mm (7x)3 (7x)4 (7x)6 (7x)6
Height, mm 11 18 20 20
Chemical composition:
NiO, % by weight 9 9 9 0.5-1.0
MgAI204, by weight balance balance balance balance
Impurities: less than 100 ppm
S
K-t:·i"J;;l. less 'the:n ~ 000 Pltllfl
S1 max..·O:j% Table 1: Properties of Secondary Reforming Catalysts RKS-2-7HIRKS-2P-7H

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the interruption of process gas flow can result in very high temperatures. One such case is illustrated in Figure 1 below. A malfunctioning burner in this facility's secondary reformer resulted in extremely high localized temperatures which caused the burner tip to melt and fall into the catalyst bed. Despite these high temperatures, which almost certainly exceeded 1500°C, the RKS-2-7H catalyst remained intact. The plant performed a skim of the top layer to remove the burner debris, and the catalyst was put back into service, where it continued to operate fully satisfactorily.

Low Pressure Drop and Reactor Short-loading Potential

RKS-2-7H is a shape-optimized VEr sion of Topsee's original secondary

Figure 1: Melted burner tiP wnt: lIll(iillllil'lf'(/ secondary reforming catalyst RKS2 /H

reforming catalyst, RKS-2. It is formed as a cylinder with seven axial holes and dished ends. This shape is unique amongst secondary reforming catalysts and provides a higher surface area and therefore a higher catalyst activity per unit volume than ordinary ring-shaped catalysts, as well as a substantially lower catalyst pressure drop. The high activity permits the short-loading of most reactors while maintaining fully satisfactory performance for the lifetime of the charge. Short-loading of the reactor often improves the performance of the secondary reformer by allowing a more

uniform mixing of the reactants above the catalyst bed. Short-loading also reduces the initial catalyst costs, and the savings can be substantial.

Table 1 gives the chemical composition of RKS-2-7H. The catalyst is manufactured from very pure raw materials and is fired at a temperature 200-300DC higher than normal operating temperatures, producing a very stable pore system. The catalyst will not shrink during operation, not even in the top layer. The catalyst contains less than 0.1 wt% silica, eliminating the potential of silica migration and downstream deposition. Likewise, the concentrations of sulphur and chlorine are virtually nil, thus avoiding poisoning of downstream catalysts.

RKS-2-7H. 20 x 18 mm

Catalyst Operation

Activation of RKS-2-7H

RKS-2-7H may be started up using any normal reformer system start-up procedure, such as preheating in circulating nitrogen or heating of the primary reformer in stagnant atmosphere followed by exposure to condensing steam. Reduction of the catalyst will occur following the introduction of feed gas or hydrogen to the primary reformer; no special actions are required. Air is generally introduced to the secondary reformer once the primary reformer outlet temperature has reached 700°C (1300°F).

Normal Operation

of RKS-2-7H Catalyst

In most ammonia plants, the secondary reformer operation is adjusted to achieve the required stoichiometric ratio of nitrogen and hydrogen necessary for ammonia production. Typical catalyst bed inlet temperature is about 1250°C (2300°F) in a secondary reformer, and up to 1400cC (2550DF) in autothermal reformers.

Shut-down of RKS-2-7H Catalyst The shut -down of the secondary reformer is normally dependent on the process constraints of the primary reformer shut-down. The catalyst may be maintained in the reduced state during the down period, or may be oxidized by steam or steam-air iniection during the shut-down procedure. If access to the reactor is required during the down-period, oxidation of the catalyst is recommended.

Catalyst Poisons

The high operating temperatures in the secondary reformer make the catalyst resistant to poisoning. Consequently, poisoning of the secondary reforming catalyst is rarely of concern in the industry.

Autothermal Reformers:

RKS-2P-7H Catalyst

Because autothermal retorrners 11mmally operate at higher temperatures than air-blown secondary reformers. they are often subject to depositron 01 foreign material (usually evaporated calcium aluminate from transfer 111'es or refractory material) onto the Ci del' Iyst, causing an increase In pressure drop. In order to minimize this pi It)lem, Topsoe offers a special refoll'lln'j catalyst. RKS-2P 7H

RKS-2P-7H is a larger size catalvst with a lower nickel COil tent than I~KS 2-7H (see Table 1) These teaturs ~ combine to give the catalyst il re ctlVE Iy low reforming activity comparee 10 RKS-2-7H, which retards the dell lsi tion of the foreign matte: onto till) tOl' of the catalyst. We recommend t -at iI 30-centimeter (one- foot) layer 01 ::'IK~ 2P-7H catalyst be loaded 011 top I)j RKS-2-7H in autotherrnal re10WH; S any secondary reformer expellell _11', : frequent pressure drop I JUIlel ,11= caused by the deposit 1011 01 feJlfil ell matter onto the catalyst

Technical Assistance

Detailed written procedures tor C It; I Iyst loading. start-up. operatron c:lel shut-down are provided upon 01il'31 '" Topsoe secondary reforrrunq catalystTopsoe also offers onqoinq "UI'VICE) II the form of performance chocks III! I trouble-shooting, if requlreeJ. Ihrouqh out the catalyst lifetime.

Packing

RKS-2-7H and F~KS ~)F) iH .dtillIS!' are shipped in polyethvlene-vneo drums, each containing 1 ()O kg I )() Ibs) of catalyst. As lonq as tllE?Y C:I·; kept sealed and sheltered fl' »u tI,~ weather, the drums Ina) [)e ·;tl JIE I I '( , many years before IISI;

Topsee Burner Technology Optimal Process Gas Mixing

A critical parameter for satisfactory secondary or autothermal reformer performance is efficient mixing of the process gas and air or oxygen. Uneven mixing can result in large temperature variations above and into the catalyst bed, causing variations in the degree of methane reforming achieved and often yielding a poor overall approach to reforming equilibrium, even with a highly active secondary reforming catalyst. The efficiency of gas mixing is primarily a function of the burner design. In addition to causing inefficient gas mixing, a poorly designed burner can damage the vessel walls, refractory or even the burner itself, when there is impingement of hot gas and/or flame in these areas.

Traditional Nozzle Design

Velocity Vectors

Temperature

Haldor Topsoe AlS has done extensive research to optimize burner design to eliminate the problems described above, and offers two special burners. For air-blown secondary reformers in ammonia plants, we offer a ring-type burner with a specialized nozzle shape that eliminates back-flow of hot gas onto the nozzles themselves, thereby reducing mechanical wear and damage to the burner. Figure 2 illustrates a Computational Fluid Dynamics (CFD) model of a conventional burner nozzle and the Topsoe design. The Topsoe nozzle does not experience impingement of hot gas back-flow and therefore is able to operate for much longer periods without need for repair or replacement.

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In autothermal and oxyqen-blown secondary reformers, the ennched air or oxygen is typically supplied at high pressures, thereby allowing tor the pos sibility of a higher pressure drop across the reactor burner. For these services. Topsoe offers the CTS burner

Figure 3 illustrates CFD profiles ot a CTS burner, illustrating the maintenance of low temperatures at the ve~; sel walls and an efficient gas circula tion pattern, thereby producinq opt I mal mixing and minimizing reactor damage.

For more information on Iousoe IJlIIl1 er technology and rnodellinq capabih ties, please contact your TOPS08 rf'p resentative.

Improved Topsee Design

Velocity Vectors

Temperature

High

Low

Figure 2: CFD Comparison of Traditional Nozzle and Topsoe DeSign

fi9vre 03 .. em 9rrrHiJrrnP,1 01 11m lempEr"lum di~llihujiD!'rn an Ill/ibttrtJrTmllrola,mill' u5iil.f/ i1 fO/'iSrIfI GTS ~.

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