Sie sind auf Seite 1von 4

Pre-reformer catalyst in a hydrogen plant

Good operation following recommended practice with technical support


highlight the successful performance of a pre-reformer catalyst

K R Ramakumar Johnson Matthey


Sultan Orman and Ismail Bahadir Kara Tüpraş

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-

www.digitalrefining.com/article/1002420 Catalysis 2020 1


Step 1: Step 2: Step 3: Step 4: Preheated
Hydro- Chloride H2S removal Ultra-
feed gas
desulphurisation removal purification
(HDS)

Organic sulphur HCL removal H2S absorbed H2S < 50 ppbv


converted to H2S using chloride in ZnO For sensitive
Organic chloride guard bed absorbers downstream
converted to HCL HCL < 0.1 ppmv H2S < 0.1 ppmv reformer (pre-
Absorption of reformers or HDS ZnO ZnO
lead/arsine highly stressed
Olefin reformers)
hydrogenation
CL guard UP layer UP layer

Figure 1 Functions of various sections in a purification system

Gradual deactivation from top

Process
Temperature

2 3 4 steam in
EOR profile
SOR profile Pre-
reformer

Bed depth Figure 2 Simplified flow diagram of the


purification system in PLT-147
Figure 3 Typical temperature profile across the pre-reformer for natural gas
feed A simplified sketch of the purifi-
cation system in PLT-147 is shown
in Figure 2.
Gradual deactivation
from top
Understanding the mechanism of
pre-reformer catalyst deactivation
Temperature

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-

2 Catalysis 2020 www.digitalrefining.com/article/1002420


tored by drawing a Z-90 plot. A
Z-90 plot is a method to moni-
Poisoning (growing flat profile)
tor and trend the temperature
profile movement throughout
the pre-reformer catalyst bed,
whereby the 90% point of total Sintering

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

reducing the effective surface 1 04 Nov 15

area and therefore relative activ- 10 Nov 16


0.8 21 Feb 17
ity. The effect of sintering can be 19 Sept 17
known by monitoring the bed 0.6 18 Dec 17

temperature profile. The slope 19 Mar 18


0.4 25 Dec 18
of the bed temperature profile
is slightly different for catalyst 0.2
subjected to sintering (see Figure
5). This difference in bed profile 0
0 500 1000 1500 2000 2500 3000 3500
assumes that the plant is at the Bad depth, mm
same rate.
Figure 6 Normalised bed temperature plot along bed depth
Pre-reformer performance in
PLT-147 the catalyst has been performing exceptionally
The PLT-147 hydrogen manufacturing unit of well for more than four years from the time it
the residue upgradation project has a design was taken in-line. The bed temperature profile
capacity of 160 kNm3/h and was commissioned has not exhibited any significant change since
in 2015. The unit supplies H2 for the integrated SOR, which is evident from a very low Z-90
hydrocracker and diesel hydrotreater units and point.
is designed to operate with flexible feeds rang- The normalised bed temperature profile along
ing from heavy naphtha to natural gas. The plant the bed depth is shown in Figure 6.
runs close to design feed rate most of the time. The Z-90 point is still at 12% of bed depth after
PLT-147’s pre-reformer catalyst is a pre-re- 1400 days of operation, which indicates that the
duced, high-Ni based catalyst and is operated catalyst’s performance is still good. There has
with the objective of minimising C2+ slip. The been no sign of any deactivation by poisoning or
pre-reformer catalyst was loaded in February sintering.
2015. There are about 40 temperature measure- The key reasons contributing to the perfor-
ment points, of three sets, within the catalyst bed; mance of pre-reformer catalyst at Tüpraş Izmit
these are placed equally round the circumference refinery are:
of the reactor shell. The three thermowell sets are • Robust upstream purification system: sulphur in
installed vertically down the reactor length. the feed has always been minimal and the over-
With a steam to carbon ratio at the inlet of the all purification system with an ultra-purification
pre-reformer of normally less than 2.5 mol/mol, layer ensured that the pre-reformer catalyst life

www.digitalrefining.com/article/1002420 Catalysis 2020 3


was greatly enhanced due to very low levels of the standard operating procedure was followed.
sulphur in the inlet stream to the pre-reformer. This meant that, despite plant upsets, the pre-re-
• Monitoring of key parameters: the inlet temper- former catalyst was not affected and its perfor-
ature to the pre- reformer was maintained low mance remained robust.
and steady, below 450°C, without any excursion This case study of excellent catalyst perfor-
during upsets. This greatly decreased the rate mance in a critical pre-reformer duty is an
of catalyst sintering. The steam to carbon ratio example of how good operation following rec-
was also maintained steady at 2.5 mol/mol. ommended practice with technical expertise can
Our timely evaluation of operational datasets help realise the true potential of assets.
helped Tüpraş keep track of the plant’s overall
performance. K R Ramakumar is a Technical Service Engineer with Johnson
• Smooth changeover of feed: Normally, the Matthey. A chartered chemical engineer with more than
pre-reformer catalyst is subjected to a ‘shock’ 14 years’ overall experience in downstream oil and gas, his
when feeds are switched over (for instance, from main areas of expertise are hydrogen and hydroprocessing
technologies. He holds a BS degree in chemical engineering
natural gas to naphtha, or vice versa), as differ-
from Sardar Vallabhbhai National Institute of Technology, Surat,
ent feeds have significantly different tempera-
Gujarat, India.
ture profiles and sudden switching of the feed Sultan Orman is a Process Superintendent at Tüpraş
may stress the catalyst, resulting in loss of activ- headquarters where she is responsible for the hydrogen
ity. The operations team of Tüpraş has always manufacturing units. She has experience in building a
ensured that the feed changeover was smooth management information systems to monitor the performances
and have followed our recommendations. of refining process units, holds MS and BS degrees in chemical
• Clean source of steam: steam may also con- engineering from Middle East Technical University, and a MBA
tain contaminants such as sulphides, metals, degree from Koç University.
chlorides, and silica which are poisons to the Ismail Bahadir Kara is a Process Superintendent at Tüpras¸Izmit
downstream pre-reforming catalyst. From the refinery. He is responsible for hydroprocessing units including
hydrocracker, DHP and hydrogen manufacturing units. He
temperature profiles, it is evident that the steam
previously worked as operation/process supervisor and holds
source was free from all such contaminants.
an MS degree in chemical engineering from Boğaziçi University.
• Use of appropriate support/hold-down balls:
high purity alumina balls (for hold-down and
support layers) are always recommended for pre- LINKS
reformer service. The high purity of the supports
is required to avoid leaching of the silica from More articles from: Johnson Matthey
standard inert supports, which may lead to cata- More articles from the following categories:
lyst poisoning and weaken the support itself. Catalysts & Additives Hydrogen Technologies
• Following the correct procedure: during upsets,

4 Catalysis 2020 www.digitalrefining.com/article/1002420