5.

2 Feedstock and Feedstock Pretreatment

Feedstock for a catalytic steam reforming process can vary widely in composition. The
simplest, methane, occurs as natural gas and will probably contain other saturated hydrocarbon
for low molecular weight, as well as nitrogen, carbon dioxide, and organic and inorganic
sulphur compounds. Chloride can also be present, arising from storage in brine well cavities.
Liquid feedstock can vary from pure distillates such as propane and other compounds with a
general formula CnH2n+2 to more-complex compounds having empirical formulae witch lie
between CH1.9 and CH2.4. They may contain sulphur or chlorine compounds, which arise as a
result of contamination in shared storage tanks or transport vessels.
5.2.1 Natural Gas
Typical analyses of natural gas from four location are given in Table 5.1 (Page 227).
Before being used as a feedstock for steam reforming, liquid condensates must be removed in
order to ensure a constant gas composition, and any solid suspension must be removed by
filtration. As was discussed in Chapter 4. Sulphur compound, both inorganic and organic, must
be removed by hydrogenolysis and absorption in a bed of zinc oxide. Chloride, if present in
concentrations greater than 1 ppm, must be removed by using, for example, an alkalized
absorbent such as ICI-59-3, usually placed in the same vessel but as a separate bed above the
desulphurization catalyst. Gas in normally supplied to a site at pressure and at ambient
temperature. Expansion across valves result in a reduction in temperature and, as there is often
a small quantity of moisture present in the gas, there is the possibility of forming hydrates on
pressure let-down. It is therefore advisable to heat the gas by 50-100oC before passing it into
the process.
Carbon dioxide present in the gas supplied to an ammonia or hydrogen plant is a diluent
and decreases the efficiency of the reforming process. It is heated in the reforming process,
participant in the shift reaction in the reformer, but subsequently must be removed from the gas
steam. Also, there is a possibility that it will methanate in the presence of hydrogen in the
desulphurization process. This could cause an unacceptably high temperature rise in the vessel,
and also reduce the quantity of hydrogen available for sulphide hydrogenolysis and reduce the
rate of desulphurization. To avoid methanation the concentration of carbon dioxide prenet
should be less than 5%. Nitrogen present in natural gas is an inactive diluent in the reforming
process and remains with the hydrogen produced. If the hydrogen is required for the production
of ammonia it can contribute towards establishing the required nitrogen/hydrogen ratio.
However, if the hydrogen is required for methanol synthesis nitrogen will eventually have to
be purge from the synthesis loop.
5.2.1 Naphtha
5.4 Design of Steam Reforming Catalysts
In designing a practical catalyst for a steam reforming duty it is necessary to keep a
number of objectives in view, and these are discussed in this section
5.4.1 Selectivity
The catalyst must promote the desired reaction and be as inactive as possible toward
unwanted side-reactions, particularly to the formation of carbon. The catalyst should also be as
resistant as possible to poisons.
5.4.2 Thermal Stability
The catalyst must be able to maintain its activity under the demanding process condition
necessary to promote the desired reaction. With impregnated catalyst (see below) an important
parameter in maintaining activity over prolonged periods is the nature of the support material
and its pore structure.
5.4.3 Physical Properties
The catalyst must be strong enough to withstand the handling it receives, from
manufacture to charging into the reformer, as well as the stresses generated by the process
condition and the thermal cycles arising from plant start-up and shutdown. The catalyst also
must be of a suitable physical shape to provide an appropriate geometric surface area to give
an acceptably low pressure-drop characteristics. The support must not be affected by water
condensing on it, nor must produce an unacceptable quantity of dust and material carryover,
which could foul heat exchanger and other catalyst downstream.
5.4.4 Nickel as a Steam Reforming Catalyst
For many years nickel has been recognized as the most suitable metal for steam
reforming of hydrocarbons. Other metals can be used; for example colbat, platinum, palladium,
iridium, ruthenium and rhodium. Although some precious metals are considerably more active
per unit weight than nickel, nickel is mush cheaper and sufficiently active to enable suitable
catalyst to be produced economically. The reforming reaction takes place on the nickel surface,
so the catalyst must be manufactured in a from which produces the maximum stable nickel
surface area available to the reactants. This is done by dispersing the nickel as small crystallites
on a refractory support which must be sufficiently porous to allow access by the gas to the
nickel surface. This is usually achieved by precipitating nickel as an insoluble compound,
mixtures of aluminium oxide, magnesium oxide, calcium oxide and calcium aluminate cement.
Alternatively, the nickel can be alumina or an aluminate, with a solution of a nickel salt which
is subsequently decomposed by heating to the oxide. In either case the plant, or by cracking a
suitable reactant gas over the catalyst as the reformer is being started up. In some instances
process gas itself is used to reduce the nickel oxide to metal as the reformer is gradually brought
on-line.
Catalytic performance and strength are determined by the catalyst formulation.
Impregnated catalysts are generally stronger than precipitated catalyst, and this is one of reason
for their widespread use. When comparing the activity of different catalyst types it is necessary
to take into account their nickel contents. Table 5.5 demonstrates the variation of strength and
nickel surface are for typical natural gas reforming catalyst with varying nickel content. The
activity of a steam reforming catalysts in service is closely related to the available surface area
of the nickel metal and the access the reactant have to it. Most commercial natural gas catalyst
are now of the impregnated type and give a relatively high nickel surface area when first
reduced, but under normal reforming conditions the surface are falls as sintering of nickel
crystallites occurs. The higher the temperature is, the more rapidly the sintering proceeds. This
effect can be seen from Table 5.6 which gives the nickel surface are for a precipitated and an
impregnated catalyst before and after use. It is not surprising that activity is a function of the
overall nickel content. However, it has been demonstrated that with both impregnated and
precipitated catalyst there is an optimum beyond which an increase in activity. Typically these
optima area approximately 20% for precipitated and up to about 15% for impregnated catalyst.
But this does depend on the nature and physical properties of the actual support. Table 5.7
show the result of two series of experiments with precipitated catalyst where this effect is
clearly demonstrared. A graphic representation of the relationship between nickel content,
surface area, crystallite size and activity for one particular precipitated catalyst is given in
Figure 5.8.
Steam reforming catalyst differ in the case with which they reduce, and the extent of
reduction is influenced by the chemical mature of the catalyst support, the reduction
temperature and time, and the composition of the reducing gas. The highest initial nickel
surface area is obtained when the reduction is done using pure hydrogen and when the reduction
temperature is 600oC. Below this temperature reduction can be slow and incomplete. Above
600oC some sintering may take place, which lowers the nickel surface area. When steam is
present lower surface area can result, because sintering is enhanced, and this process proceeds
further to give even lower surface areas if excessive reduction period are employed.
Nevertheless, for some catalyst, particularly precipitated catalyst for naphtha reforming,
reduction period up to twenty four hours are recommended. Some of these effects are illustrated
in figure 5.9 and 5.10 for particular precipitated and impregnated catalysts.
If a reduced nickel steam reforming catalyst is subject to normal reforming condition
of temperature and pressure in the presence of steam but no hydrogen, the nickel may become
re-oxidized-a situation that probably exist at the top of tubes in reformers which operate with
no hydrogen recycle. Reducing conditions are maintained if a H2O/H2 ratio of 8:1 or less is
sustained. Full reduction procedures are detailed in section 5.8.7.
5.4.5 Sopport for Nickel Steam Reforming Catalyst
The design of steam reforming catalyst support must reflect the need for it to be robust
at high temperature and pressure. It must also be suitable foe the dispersion of nickel crystallites
and allow access of the reacting species, but in must not interfere with their activity. If possible
it should promote or at least sustain the activity of the nickel, but it must not catalyse side-
reaction, particularly those which produce carbon deposits. Good physical properties can be
obtained by using a simple support of alumina that is calcined at a temperature around 1500oC.
A particularly useful range of catalyst ate produced from a support which is derivers from
mixture of alumina and an hydraulic cement that is processed to a porous calcium aluminate.
This support is less acidic than alumina, and is therefore less susceptible to carbon formation
initiated by hydrocarbon-cracking reaction. The presence of silica would further increase the
already adequate strength of the support, but as silica is volatile in the presence of steam at
high temperature only very small quantities can be used, except in in naphtha steam reforming
catalyst when it is combined with potassium which significantly reduces its partial pressure
under reforming conditions. Magnesia can also be included in some formulation, but has to
used with caution and understanding, however, as under certain condition it can hydrate and
markedly weaken the catalyst. Table 5.8 shows the relationship between temperature and
partial pressure of water in equilibrium with Mg(OH)2. Thus, at about 425oC the partial
pressure of water in equilibrium with Mg(OH)2 is about that commonly used in reforming.
Therefore during start-up or shutdown in the presence of reaction steam only, hydration of the
magnesia can take place below 425oC and, since the molar volume of the Mg(OH)2 is almost
twice that of MgO, a dramatis weakening of the support may result unless the MgO is
formulated in such a way that it is chemically associated with other refractory oxides. If this is
not done reformer start up and shutdown must ensure that the catalyst is in a dry atmosphere
whilst temperatures are below the critical hydration temperature.
5.4.6 Carbon Formation On Reforming Catalyst
All hydrocarbons will spontaneously decompose into carbon and hydrogen as
illustrated in equation (10), at the elevated temperature experienced in a steam reformer if
steam is not present.
CCH4 C + 2H2 ( thermal cracking)
For naphta the decompositions is more complex, being represented in figure 5.11,
where carbon can be formed by direct thermal cracking and also from various intermediates,
particularly unsaturated species. In the presence of steam, and in particular with less than the
stoichiometric quantity of steam, other carbon forming reactions become possible. These are
the disproportionation and reduction of carbon monoxide, reaction (11) and (12) respectively
2CO C + CO2 (disproportionation)
CO + H2 C + H2O (CO reduction)
When methane or naphthas are reformed the formation of carbon within the nickel
catalyst can be prevented by ensuring the steam/hydrocarbon ratio exceeds a certain minimum
ratio. This minimum varies with pressure and temperature, and thermodynamic data derived
by Dent et al. can be used to calculated the minimum steam ratio under different conditions,
as illustrated in figure 5.12. the exact values calculated depend on the thermodynamic
parameters assumed for “carbons”, and a considerable amount of research has shown that
different forms of carbon can be produced, depending on the prevailing conditions.
Accordingly, graphs of the kind shown in figure 5.12 should only be taken as being indicative,
rather than definitive.
There is a greater tendency for higher hydrocarbons than for methane to from carbon,
because on pyrolysis the readily formed initial intermediates is an important factor, and is
critical in influencing the delicate balance between carbon-forming and carbon-removing
reactions. Both the nockel and the support play dual roles, contributing to the reforming process
and also to the formation of carbon.