Pre-Reformer Catalyst in A Hydrogen Plant
Pre-Reformer Catalyst in A Hydrogen Plant
Pre-Reformer Catalyst in A Hydrogen Plant
P
re-reforming is the process by which meth- opex due to less fuel consumption in the steam
ane and heavier hydrocarbons are steam reformer and less steam requirement
reformed and the products of the heavier • A pre-reformer is also an excellent revamp
hydrocarbon reforming are methanated. The option for increased hydrogen production as it
adiabatic pre-reformer is usually positioned would typically add about 10-15% additional
upstream of the main steam reformer and uses a capacity
catalyst with high nickel content. • The overall excess steam production (steam
Three reactions occur in the pre-reformer and export) with the pre-reformer in the flowsheet
each of them will reach equilibrium: will be less
• The pre-reformer also facilitates operating the
Steam reforming reaction reformer at a higher inlet temperature without
CH4 + H2O ⇌ CO + 3H2 (endothermic) any preheat coil cracking issues as the higher
CnHm + nH2O → nCO + (n+m/2)H2 hydrocarbons are already converted to methane
(endothermic) and hydrogen
• A pre-reformer also acts as a poison buffer,
Water gas shift reaction protecting the downstream reformer catalyst in
CO + H2O ⇌ H2 + CO2 (exothermic) case of any poison slip across the purification
section
Methanation The hydrogen plant in Tüpraş’s residue upgra-
CO + 3H2 ⇌ CH4 + H2O (exothermic) dation project block, PLT-147, supplies hydrogen
for the integrated hydroprocessing unit in Izmit
The overall reaction is endothermic for light refinery. The block consists of vacuum distilla-
(natural gas) feeds while for LPG there is an exo- tion, hydrotreater, and hydrocracker units.
therm. For naphtha, there is an endotherm fol- PLT-147 has a design capacity of 160 kNm3/h
lowed by an exotherm. Overall, for heavier feeds and mainly processes natural gas along with
the reaction is exothermic. hydrogen rich gas from the CCR unit. The unit
The benefits of having a pre- reformer are: also processes naphtha and LPG when there is
• Flexibility to operate with different feeds, a shortage of natural gas, especially during the
especially in refineries where it is important to winter. Natural gas contains up to 3.5 vppm H2S
use the most available and economic feed which and 7.5 vppm of organic sulphur.
might vary at different times of the year The unit consists of a purification section
• When the plant is designed to operate at a (hydrodesulphurisation, H2S absorption, and
very low steam to carbon ratio, such as HyCO ultra-purification), pre-reformer, steam reformer,
units where the main objective is to have more medium temperature shift converter, and a
CO (and also a specific ratio of H2/CO) in the 14-bed PSA system for hydrogen purification.
reformed gas The feed gas first goes through the hydrodes-
• Having a pre-reformer can lead to lower capex ulphurisation reactor. This has a Ni-Mo cata-
due to the smaller size of the steam reformer lyst installed which does all the functions of
• Having a pre-reformer can also lead to lower HDS (see Figure 1). The temperature is nor-
Process
Temperature
2 3 4 steam in
EOR profile
SOR profile Pre-
reformer
depth
EOR
profile
Deactivation by sulphur poisoning
SOR
Even though the ZnO absor-
% bed
profile
bent can remove H2S to below
0.1 vppm, the pre-reformer life
in most natural gas feed cases
Bed depth Onstream days is determined by the gradual
sulphur poisoning rate. This is
Figure 4 Plot of Z90 progression with on-stream days where ultra-purification can help
to improve the pre-reformer run
mally maintained in the range 360-380°C. The length.
HDS reactor also has a small layer of chloride First, let us understand the normal perfor-
guard beneath the Ni-Mo catalyst to absorb mance of pre-reformer catalyst. The typical reac-
HCl. Following this are two H2S absorbers tion temperature profile across the pre- reformer
(ZnO absorbers) which are normally in lead- from start of run (SOR) to end of run (EOR) for
lag arrangement. The ZnO absorbs the bulk the natural gas feed case is shown in Figure 3.
of H2S and reduces its level to less than 0.1 The temperature profiles 1 and 4 in Figure 3
vppm. Below each ZnO, there is a small layer of correspond to the typical profiles at SOR and
ultra-purification (UP) catalyst which polishes EOR respectively. Gradual deactivation of the
the H2S to very low vppb levels. The ultra- puri- catalyst due to poisoning sets in from the top.
fication catalyst is a Cu-Zn formulation. The As the catalyst ages, the bed depth at which
functions of different sections in the purification the reforming reaction begins also increases.
system are highlighted in Figure 1. Deactivation of the pre-reformer can be moni-
Temperature
endotherm is plotted. Typically, (change of gradient)
the Z-90 over time will increase
owing to gradual deactivation
of the bed from top. Figure 4
depicts the gradual increase in
Z-90 for the bed profile repre-
sented in Figure 3. Bed depth
Deactivation by sintering Figure 5 Pre-reformer bed temperature profile differentiating poisoning from
Sintering is deactivation due to sintering
gradual ageing of the catalyst
whereby small crystallites of 1.2
active metal increase in size, thus
Normalised bed temperature