Hydrogen is an essential component of many industrial processes.

It is used in oil
refinery processes including hydrotreating, hydrocracking, dearomatization and
isomerization. On downstream chemical plant it is used in polymer production and
for chemical intermediates such as aldehydes, alcohols, cyclohexane and
polyurethanes. Hydrogen rich gas is also required in processes such as glass making,
direct reduction of metals and town gas manufacture.
In oil refineries and integrated petrochemical sites, hydrogen often comes as a by-
product from other processes. Howeer, when this source is insufficient or
unaailable, dedicated or !on-purpose! hydrogen production is needed. Indeed, !on-
purpose! hydrogen capacity is increasing as site hydrogen demand reaches limits due
to tighter fuel specifications, the processing of heaier and sourer crudes, increasing
need for lighter crude oil products and strong demand for chemical intermediates.
"his section describes the steam reforming hydrogen process and how it can be
designed or modified to suit your needs. #n oeriew of the catalytic steps inoled
is also included and the type of catalysts used.
The Steam Reforming Process
"he most common method of !on-purpose! hydrogen production is the steam
reforming process. "he main process step inoles the reaction of steam with a
hydrocarbon oer a catalyst at around $%&-'&&&( )*+'&-*,$&-./ to form hydrogen
and carbon oxides. Howeer, there are seeral other steps to remoe impurities and
maximize hydrogen production. "he main steps inoled are as follows0
feedstock purification - remoal of poisons such as sulphur and chloride to
maximize the life of the downstream steam reforming and other catalysts
steam reforming - the main hydrogen-producing reaction
shift conersion - carbon monoxide reacts with steam to produce carbon
dioxide and additional hydrogen. "his often done in two stages0 High
"emperature 1hift )H"1/ and 2ow "emperature 1hift )2"1/.
product purification - in older designs, carbon dioxide is remoed in a liquid
absorption system and finally the product gas goes through a methanation
step to remoe residual traces of carbon oxides. In most new plants, a
3ressure 1wing #bsorption unit )31#/ is used instead, producing 44.445
product hydrogen and an-offgas used in the fuel system.
Feedstock Purification
"he catalysts used in the steam reforming process are poisoned by trace components
in the hydrocarbon feed, particularly sulphur, chlorine and metal compounds. 1ulphur
is the commonest problem, the nature and leel of sulphur species being dependent
on the source, pre-treatment and molecular weight of the hydrocarbon. (hlorine
compounds are less common and metal compounds are typically found in some
heaier 236 and naphtha feeds.
"he best way to remoe sulphur compounds is to conert the organic sulphur species
to H71 oer a hydrodesulphurization catalyst. "he next step is sulphur remoal with
an absorbent. "he same catalyst similarly conerts any organo-chloride species to
gie H(l and also acts as an absorbent for most problematic metal species. # second
absorbent is used for chloride remoal.
1ynetix supplies products for the three steps. #lso, our many decades of experience
in the design and operation these flowsheets hae proided an understanding of the
key product features for high performance. (ommon flowsheets are shown below.
(lick on any section for more information.
Steam Reforming
"his is the heart of the hydrogen generation process. "he main steam reforming
reactions are0
(H, 8 H7O 9:; (O 8 + H7
(xHy 8 H7O 9:; x (O 8 )x 8 &.%y/ H7
and
(O 8 H7O 9:; (O78H7
"he reaction takes place across a nickel catalyst packed in tubes in a fired furnace.
#n excess of steam is used to promote the reforming reaction and aoid carbon
deposition on the catalyst.
1ome flowsheets may hae pre or post-reforming in addition to the conentional
steam reformer.
<ewer plants tend to be 31#-based, with typically only a High "emperature 1hift bed
rather than both High and 2ow "emperature 1hift.
Steam Reforming Catalysts
1ynetix can adise on the most appropriate combination to meet your needs. "his
selection considers the feedstock types and operating conditions. "he selection is
usually dictated by the heaiest hydrocarbon feed and may inole two or three
catalyst types in order to obtain optimum performance. "he main categories of
catalyst are as follows.
Light duty reforming:
.or light feeds )most natural gas, refinery offgas and pre-reformed feeds/, 1ynetix
will select from a range of nickel based catalysts using either alpha-alumina or
calcium aluminate support media. "he use of specialized shapes such as !,-hole! and
!fluted ring! optimizes the properties of actiity, heat transfer and pressure drop
when using the KATALCO 7+-1eries, KATALCO %$-1eries and DCAT '$&-1eries
catalysts.
!ntermediate duty reforming:
Intermediate duties comprise hydrocarbon feeds with a significant (78 content up to
236. "he heaier feedstock increases the tendency for catalyst deactiation through
carbon laydown and requires a specialist catalyst in the top +&-%& 5 of the reformer
tubes. "his tendency also occurs with light feeds run at low steam0carbon ratio
and=or high heat flux. 1ynetix offers the KATALCO 7%-1eries and DCAT '4&-1eries
catalysts which retain the adantages of the light duty catalysts but also contain
complex alkali or rare earth promoters principally potash and lanthana which
augment carbon gasification. 1ynetix light duty catalyst fills the remainder of the
tubes.
"ea#y duty reforming:
Heay duty primarily means naphtha feeds which hae yet more tendency for carbon
deposition. Highly specialized catalysts are required and 1ynetix is the world leader
in naphtha reforming catalysts. "he co-precipitated KATALCO ,>-1eries of nickel
based catalysts contain complex stabilized alkali phases and other promoters to
maximize carbon gasification actiity.
1ynetix uses its expertise to tailor the catalyst to the optimum combination for your
duty. ?orderline heay duty applications use catalysts combined from the heay and
intermediate ranges. 2ow pressure drop limits are met by using larger pellet sizes.
High actiity requirements are met with smaller pellet sizes. "herefore, the approach
taken is always flexible and 1ynetix is uniquely placed to proide the optimum
catalyst combination for any duty.
1ynetix has also deeloped highly actie precious metal based steam reforming
catalysts, KATALCO '4-1eries. "hese promise to extend the boundaries of operation
to ery low steam0carbon ratio and to more difficult hydrocarbon feed types.

"igh Tem$erature Shift Con#ersion
"he high temperature shift section increases the hydrogen yield by driing the water-
gas shift reaction, shown below, to the right.
(O 8 H7O 9:; (O7 8 H7
@ost H"1 reactors operate at about +%&-( )>>7-./ inlet temperature and lower the
(O leel from *&-*% mol 5 )dry/ to *-7 mol 5 )dry/. Ideally, the catalyst takes the
reaction to equilibrium at as low a temperature as possible as this faours the H7
make. "he catalyst must retain a high actiity and also resist breakage and poisoning
to gie an extended operational life.
"he KATALCO $*-1eries H"1 catalysts hae been deeloped to delier these
requirements. .or some years, copper has been added to the iron-chrome
formulation to augment actiity. In our most recent deelopment, a structural
promoter has been introduced and this unique patented formulation has significantly
increased actiity and in-serice strength compared with older catalyst types.
"he high actiity allows enhanced performance through lower temperature operation
with inlet temperatures as low as 74&-( )%%,-./ leading to less (O slip and slower
sintering. "his allows new plants to be designed with smaller catalyst olumes saing
both capital and inentory costs.#lso essels on existing plants can be short loaded
to achiee the same performance as older catalyst types using less of the new
1ynetix catalyst formulation. "he increased in-serice strength proides more
resistance to breakage and a lower tendency for increasing pressure drop. "hus,
recoery is possible from upsets such as boiler leaks when deposition of condensate
and solids would usually result in catalyst breakup. .or plants susceptible to boiler
leaks, 1ynetix also offers high surface area shaped alumina hold-down materials to
protect the H"1 catalyst by stopping condensate and solids from reaching the H"1
catalyst. "he high surface area shape traps particulates and the strong alumina
substrate resists breakage from condensate impingement
Lo% Tem$erature Shift Con#ersion
@any newer flowsheets use a 31# unit downstream of the H"1 essel to produce
high purity product hydrogen. #lternatie flowsheets feature an 2"1 conerter before
the 31# unit or an 2"1 conerter followed by (O7 remoal and methanation. "he 2"1
conerter enables increased hydrogen yield by further moing the water-gas shift
equilibrium in faour of H7.
"he 2"1 reactor operates at about *4&-7*&-( )+$,-,*&-./ inlet temperature and
lowers the (O leel from *-7 mol 5 )dry/ to &.*-&.7 mol 5 )dry/. #s for the H"1
catalyst, the 2"1 catalyst ideally takes the reaction to equilibrium at as low a
temperature as possible to faour H7 make. #gain, the catalyst must retain a high
actiity and also resist breakage and poisoning to gie an extended operational life.
"he copper based 2"1 catalyst has operational limits. .irstly, the inlet gas
temperature must be aboe its dew-point by a reasonable margin as water
condensation damages the catalyst. "his limits the minimum inlet temperature to
around *4&-( )+$,-./. 1econdly, the 2"1 catalyst is affected by traces of poisons
such a sulphur and chloride which hae little effect on, and pass through the
upstream reforming and H"1 sections at sub-ppm leels.
1ynetix has focused on designing 2"1 catalysts to oercome these limitations. "he
KATALCO '+-1eries combine high copper surface area with robustness to do this.
"he actiity results from a high and stable actie copper surface area which 1ynetix
has achieed by maximizing copper dispersion throughout the structure without
compromising strength.
#nother feature of the KATALCO '+-1eries 2"1 catalysts is a high degree of !self-
guarding! capacity against trace poisons. "he catalysts hae a high capacity and
demonstrate a sharp absorption profile for typical poisons, which continue to
accumulate at the top of the bed well beyond the point at which this catalyst is
deactiated. #daptations of the catalyst further improe this self-guarding feature for
situations where poisoning has been a noted problem.
&ethanation
In flowsheets featuring a methanation step, this remoes traces of carbon oxides
which may affect downstream H7 user plants. #n exit specification in the order of %
ppm is usual. "he methanation reactor conerts any residual carbon oxides back to
methane using a small part of the hydrogen product to effect the reactions -
(O 8 +H7 9:; (H, 8H7O
(O7 8 , H7 9:; 7(H, 8 7H7O
1ynetix catalysts are formulated on a calcium aluminate base with the actie nickel
incorporated in a <iO=@gO solid solution. "his results in negligible nickel sintering
during operation. Aeactiation mostly results from solent carry oer from the
upstream (O7 remoal section.