To reduce the air pollutants SOx and NOx that are formed by internal combustion

engines, most countries strictly limit the sulfur and nitrogen content of motor
fuels. The primary process refineries use for removing these contaminants from
gasoline, diesel, and jet fuel is referred to as hydrotreating or hydroprocessing.

The hydrotreating process involves mixing hydrogen with sour hydrocarbon feed
inside a reactor filled with Cobalt/Molybdenum (CoMo) or Nickel/Molybdenum (NiMo)
catalysts. In their active form, CoMo and NiMo catalyze the reactions that convert
sulfur and nitrogen contaminants into H2S and NH3. These compounds can then be
easily removed from the hydrogen off-gas stream in subsequent processing
steps. After hydrotreating, the hydrocarbon product leaving the reactor is an
extremely clean motor fuel.

Hydrotreating catalysts are produced by coating alumina extrudates with potentially

active metals such as cobalt, nickel, molybdenum, and/or tungsten. In the catalyst
production process, these metals are deposited on the alumina substrate in their
benign oxide form and must be converted to the corresponding sulfide before they
will catalyze hydrodesulfurization (HDS) and hydrodenitrification (HDN) reactions.

After a hydrotreater or hydrocracker reactor is loaded with fresh catalyst, the

activation step, referred to as “sulfiding”, is accomplished by reacting the metal
oxides with hydrogen sulfide (H2S) in the presence of hydrogen. This process is
often referred to as “presulfiding” since the sulfiding process is carried out prior to
resuming operation of the hydrotreating unit.

Catalyst sulfiding involves the following chemical reactions:

The Sulfiding Process

The sulfiding process involves passing feed spiked with a sulfiding agent over the
catalyst bed in a carefully controlled procedure that includes several temperature
holds. As the feed and spiking agent are heated in the presence of hydrogen, the
sulfur compound will readily decompose to form the H2S required to complete the
sulfiding reactions.

Sulfiding Agents
The sulfiding agents most commonly used by refiners today are dimethyl sulfide
(DMDS) and tertiary-butyl polysulfide (TBPS). DMDS is used in the majority of
sulfiding applications due to its higher sulfur content (68% vs. 54%) and lower
cost. It also decomposes in two steps, reducing the chance of reactor exotherms
that can result from sulfiding reactions. TBPS is used in some cases where a lower
decomposition temperature is desirable. Note that these decompostion
temperatures only apply when the chemical is in the presence of a hydrotreating
catalyst. Without a catalyst present, thermal decomposition of DMDS to H 2S will not
occur unitl the temperature exceeds 900F. The table below compares the two most
commonly used sulfiding agents.

Sulfiding Agents
The Sulfiding Process

Each catalyst manufacturer has their own procedure for achieving maximum
performance from their catalysts, but in general they all follow a process similar to
the profile shown in Figure 1. This illustration represents a sulfiding regimen with
DMDS as the sulfiding agent.

Figure 1 – Temperature Profile for Sulfiding Hydrotreating Catalysts

The initial phase involves a drying step to remove any water that may remain in the
system from cleaning during the turnaround, as well as moisture entrained within the
catalyst pores. Hydrotreating catalysts are hygroscopic and can easily absorb 2-4%
water when exposed to humid air during the loading process. If the catalyst bed is
heated too quickly while moisture remains in the catalyst pores, steam will rapidly
form that can cause physical damage to the catalyst particles. This phenomenon is
commonly referred to as the “popcorn effect”, since rapid steam formation can
fracture the catalyst in a phenomena similar to the way popcorn is formed by
heating.

After the bed is thoroughly dried (typically 2-4 hours in the range of 200-250F), the
“wetting step” can begin. This may seem counter-intuitive since the catalyst was just
dried in the previous step, but in this case we are referring to wetting the catalyst
with warm hydrocarbon feed. Only straight run feedstocks should be used for
sulfiding because cracked stocks contain reactive olefinic compounds. Freshly
sulfided catalysts tend to be hyperactive at start up, and will quickly transform the
constituents in cracked stocks into activity harming coke and gums.
A heat wave will normally be seen during the wetting step that results from the heat
of absorption that is released as hydrocarbon wicks into the pores of the extremely
dry catalyst. Wetting ensures that all of the catalyst particles are evenly coated with
hydrocarbon, leading to improved distribution once the sulfiding step begins. If
possible, high flow rates should be utilized to improve liquid distribution and to help
flush catalyst fines from the bed that are generated during loading. High throughput
will also ensure that that there is a sufficient heat sink in place to absorb the heat
that is released.

Once wetting is complete, the temperature of the reactor can be ramped up to the
level at which the sulfiding agent will be injected. This temperature range varies
from 360-420F depending on the catalyst manufacturer, the type of catalyst, and the
reactor pressure. After injection begins, catalyst bed temperatures must be
monitored closely since DMDS decomposition and the sulfiding reaction are both
exothermic. A typical guideline will limit the delta T across each catalyst bed to
50F. Again, this will vary depending on the size and type of unit being sulfided and
the mass flux through the bed.

The H2S level of the gas effluent from the reactor also needs to be closely monitored
once injection begins. This is normally handled by sampling the gas stream from
open sample ports with draeger tubes. However, H2S is a poisonous gas, forcing
operators to equip themselves with breathing air (SCBA) during the sampling
operation. Three years ago, the concept of an online H2S analyzer was introduced
by Reactor Resources in order to reduce the risks of H2S sampling. The online
analyzer system offers a continuous stream of data in real-time and eliminates the
hazardous operation of sampling with draeger tubes.

The reactor temperature is normally held below 450F for 10-12 hours until H2S
“breakthrough” occurs. This step is often referred to as the “first sulfiding
plateau”. Breakthrough is determined when the H2S concentration of the gas exiting
the reactor reaches 3000-5000 ppm. Prior to breakthrough, very little H2S will be
seen in the gas effluent since the oxide catalyst is reacting with and consuming all of
the sulfur injected into the feed. Breakthrough is a signal that the catalyst particles in
the reactor are saturated with sulfur and indicates that the reactor temperature can
be raised without harming the oxide catalyst. If bed temperatures are raised
prematurely (> 450F), reduction of the metal oxides will occur, preventing formation
of the active sulfide form of the catalytic metals.

It should be noted that water is a by-product of the sulfiding reaction and its
formation signifies that the active sulfide form of the catalyst is being produced. The
amount of byproduct water produced will be approximately 8-10 wt% of the catalyst
weight. In addition, ~2 SCF of hydrogen will be consumed per pound of catalyst
loaded in the reactor.

Once the catalyst bed reaches 600-660F (the final hold temperature varies with
catalyst manufacturer), the second sulfiding plateau can begin. This phase will
normally last for 4-8 hours. During the second temperature hold, sulfiding reaction
kinetics will initially accelerate, leading to an increased consumption of H2S in the
recycle gas. To compensate, the injection rate of the sulfiding agent is increased
while the H2S content is closely monitored. Completion of the sulfiding process is
normally indicated by the H2S content of the recycle gas quickly rising to levels
exceeding 20,000 ppm (2.0%). Once the calculated amount of sulfur being injected
to the unit equals the amount of sulfur exiting the reactor, sulfiding is complete and
chemical injection should cease.

Catalyst manufacturers typically recommend that cracked stocks should not be

introduced to the unit for at least three days after sulfiding. This delay allows a layer
of soft coke to form on the catalyst surface, tempering the hyper-activity associated
with freshly sulfided catalysts. Once catalyst activity moderates, cracked stocks can
be gradually added to the feed without affecting catalytic activity.

Summary

Proper sulfiding of hydrotreating catalysts is critical for obtaining optimum HDS and
HDN activity from a hydroprocessing unit. The sulfiding process must be carefully
monitored to avoid reduction of the metal oxides prior to the formation of the active
sulfides and to ensure that the active metal sites are properly and completely
formed. Having adequate information, such as sulfiding agent injection rates and the
H2S content of the reactor gas effluent, allows precise control of the sulfiding process
and avoids problems caused by excessively sour gas overloading the recycle
compressor.

For more information on the optimum procedure and techniques for sulfiding your
particular hydrotreating or hydrocracking unit, please do not hesitate to contact the
pros at Reactor Resources. Sulfiding is our business, and we would love to help you
out.