Hydrotreating Unit

PGS.TS. Trương Hữu Trì

 CONTENTS

1 Impurities: Origins and effects

2 Objectives of hydrotreating

3 Hydrotreating reaction

4 Hydrotreating catalyst

5 Operating variables

6 Process technology
2
 Operating Variables
 The main thermodynamic and kinetic operating variables for
hydrotreating processes are:
• the hydrogen partial pressure (PH2 in bar);
• the weight average reactor temperature (Tm in oC):
• the liquid hourly space velocity (LHSV in m3 of feed/m3 of catalyst
per hour, m3/m3.h).
 Two secondary variables are also important:
• the recycle ratio and purity of the recycled hydrogen:
• the H2 partial pressure,
 The choice of these variables leads to determination of:
• the operating pressure;
• the process flow scheme;
• the investments and operating costs.
 Operating Variables
 Hydrogen partial pressure (ppH2)
 Higher H2 partial pressure is, higher the catalyst activity is and lower
coke deposit and polymerization are on the catalyst;
 An adequate level of hydrogen partial pressure must be kept at each
point in the reactor;

 Hydrogen partial
pressure is linked to
the H2/HC ratio and
total system pressure
and reactors
temperatures.

Influence of hydrogen partial pressure PH2

on hydrodesulfurization performance on a
middle gas oil.
 Operating Variables
 Hydrogen partial pressure (ppH2)
 Hydrogen pressure therefore aims to shift reactions in the right
direction and minimize side reactions such as gas production
and coke deposit on the catalyst surface. In this way-it
promotes long-lasting stable catalyst operation.
 The heavier the feed, the higher the hydrogen pressure needed:
for a given feed (for example straight run gas oil) it varies
according to the performance required:
• hydrodesulfurizalion 15-25 bar.
• hydrostabilization (mild hydrogenation) 25-35 bar.
• hydrodearomatizatlon (deep - hydrogenation) 35-60 bar.
 Operating Variables
 Hydrogen partial pressure (ppH2)
An improved cetane number and reduced aromatics content demand
particularly high hydrogen partial pressures.
Chemical hydrogen consumption, which depends on the performance
required is also important as indicated in table below

Hydrogenation of a primary distillation gas oil containing

26.79%wt of aromotics and 1.3% wt of sulfur
 Operating Variables
 Temperature
 Temperature is a key parameter for the chemical reactions
equilibrium (Kinetics aspect).

 Temperature is adjusted to obtain expected results, is increased

to compensate for the deactivation until the Maximum
possible.
 Increase temperature is favorable to:
• Hydrotreating (HDS, HDN);
• Promote deactivation rate and Coke deposit;
• Increase gas yields.
 Operating Variables
 Weight Average Catalytic Bed Temperature (WABT)
 Hydrotreating units are operated at constant performance and pressure.
Given the gradual deactivation of the catalyst, the performance level is
maintained by increasing the reaction temperature. A start-of-run and
end-of-run temperature are defined (TSOR and TEOR)
 Additionally, since nydrotreatiog reactions are exothermic, a rising
temperature gradient is established in the catalyst bed. Even though the
temperature can not be known at every point in the catalytic bed,
installing thermocouples allows the temperature of several portions of
the catalyst bed to be measured.
 In this way a weight average temperature of the catalytic bed (WABT)
can be defined by:
 Operating Variables
 Weight Average Catalytic Bed Temperature (WABT)

 Several other temperatures can be measured for a

hydrotreatiog unit reactor, particularly:
• the outlet temperature of the feed heating furnace;
• the reactor inlet temperature (te):
• the reactor outlet temperature (ts).
 More simply the weight average temperature can be defined
roughly for a catalyst bed by:
 Operating Variables
 Weight Average End-of-Run Temperature
 The weight average end-of-run temperature (TmEOR) is the maxinum
temperature that the catalyst can with stand and is generally between
400 and 410oC depending on the feed.
 When the temperature is in excess of 410oC thermal cracking becomes
severe and can no longer be moderated by increasing the hydrogen
partial pressure.
 At high temperature, hydrogenation of polyaromatic coke precursors
becomes limited thermodynamically and furthermore unsaturated
compounds tend to condensate. This leads to accelerated catalyst
deactivation by coke deposit.
 The maximum temperature defines the temperature for the end of
the catalyst run. It depends on the type of feed and the required product
quality (sulfur content, thermal stability, aromatics content, etc.).
 Operating Variables
 Weight Average Start-of-Run Temperature
 The weight average start-of-run temperature (TmSOR) is selected in
order to insure stable operation of the unit for one to three years.
 In general, taking the weight average end-of-run temperature into
account, a run duration of two years is chosen. This requires a
minimum variation in weight average temperature of 30oC during the
run, i.e.:

 The Weight Average Start-of-Run Temperature depends on the physic-

chemical characteristics off the feed.
 The higher the average molecular weight of feed, the more sulfur
compounds there are and the more difficult desulfurization is.
 Operating Variables
 Liquid Hourly Space Velocity (LHSV)

 Amount of Liquid feed, expressed in volume (at 15°C),

processed in one hour, divided by the volume of catalyst;

 The LHSV affects directly the progress of the reactions through

the reactor (Kinetic aspect).

 Liquid hourly space velocity is used to define the amount of

catalyst needed to get a specified performance. It is expressed
in m3 of fresh feed (at 15oC) per m3 of catalyst per hour.

 The inverse of LHSV is generally called residence time.

 Operating Variables
 Liquid Hourly Space Velocity (LHSV)

 The LHSV
depends on
the catalyst
activity, the
type of feed
and the
hydrogen
partial
pressure

Influence of residence time on performance

for light gas oil (230-360oC)
 Operating Variables
 Hydrogen Ratio or Recycle Ratio (Hydrogen on hydrocarbon ratio (H2/HC))

 Optimum catalyst use demands relatively high hydrogen partial

pressures. It is therefore necessary to let the feed in with a much larger
amount of hydrogen than that required for chemical consumption.
 In order to minimize hydrogen requirements, gas is recycled - from the
separator drum which is supplemented by make up.
 The hydrogen partial pressure therefore depends on the relationship
among:
• the hydrogen recycle flow rate,
• the hydrogen purity, and
• the hydrocarbon flow rate,
 For a total fixed pressure and a given make up gas purity and hydrogen
consumption.
 Operating Variables
 Hydrogen Ratio or Recycle Ratio (Hydrogen on hydrocarbon ratio (H2/HC))
 When reactions are highly exothermic, it is also necessary to control the
thermal gradient in the reactor by distributing the catalyst onto several
beds and by injecting enough cold gas between each bed to cool down
the hydrocarbon by quenching.
 This allows operation as close as possible to the isotherm and minimizes
premature catalyst aging by reducing the high temperatures in the bottom
of each catalytic bed - particularly in the first one.

Figure beside
illustrates the
effect of
injecting
hydrogen
between two
catalyst beds.
Temperature gradient controlled by hydrogen quenching
 Operating Variables
 Hydrogen on hydrocarbon ratio (H2/HC)

 The ratio of pure hydrogen flow in recycle gas (standard m3/hour),

quench and make-up excluded, to feed flow rate (m3/h at 15°C).
 H2/HC typical has few influences on HDX or yields
 H2/HC impacts the deactivation rate
 H2/HC affects several parameters:
 Lower H2/HC increases the coke formation;
 Lower H2/HC increases ppH2S (HDS inhibition).
 Operating Variables
 H2S concentration in recycle gas

 The recycle gas also contains hydrogen sulfide which has an

inhibiting effect on desulfurization and hydrogenation
reactions.
 Depending on the performance required (deep
desulfurizatlon, aromatics reduction) the recycle gas can be
partially or totally washed with amines.
 However, it is useful to retain some H2S partial pressure to
keep the catalytic phase sulfurized.
 Operating Variables
 Operating parameters
 Operating Variables
 Operating parameters
BSR
NHT LCO-HDT
Feed Naphtha LCO from FRCC
Sulfur in feed 100 ppm max 500 ppm
Nitrogen in feed 1 wt.ppm 800 - 1000 ppm

Sulfur in product 0.1 ppm in LN, 0.5 ppm in HN 50 ppm

Nitrogen in product 0.1 ppm in LN, 0.5 ppm in HN 200 ppm

Feed filter
1 Rx 1 Rx
PFD 1 tripper H2 quench
1 splitter 1 Stripper

Pressure 30 bar 50 bar

Licensor UOP Axen
Catalyst Co-Mo Ni-Mo
 Operating Variables
 Operating parameters
NSRP
NHDS KHDS GHDS RHDS
Feed Naphtha Kerosene GO, LCO
Sulfur in feed 500 wt.ppm 4.3 wt.%
Nitrogen in
1 wt.ppm 2500 wt.ppm
feed
Sulfur in 0.1 ppm in LN, 0.5
50 ppm 50 ppm 0.4 wt.%
product ppm in HN
Nitrogen in 0.1 ppm in LN, 0.5
1100 wt.ppm
product ppm in HN
Feed filter
2 Rx in series, 3 Rx in series,
H2 quench H2 quench
Cold HP Separator Hot HP Separator
1 Rx HP Amin absorber Cold HP Separator
1 Rx
PFD 1 tripper Cold MP Separator Cold HP Absorber
1 tripper
1 splitter MP Amin absorber Hot LP Separator
Stripper Cold LP Separator
CLPS, CLPFD Absorbers
Fractionator: Wild Naphtha,
Diesel, Residue
Pressure 30 bar 50 bar 100 bar 180 bar
Licensor UOP Axen Axen Chevron
Catalyst Co-Mo Ni-Mo Ni-Mo Ni-Mo (Co, V, P…)
 Operating Variables
 Summary
 CONTENTS

1 Impurities: Origins and effects

2 Objectives of hydrotreating

3 Hydrotreating reaction

4 Hydrotreating catalyst

5 Operating variables

6 Process technology
22
 Process Technology
 The process technology and catalyst are adapted to the performance
required for the different feeds sent to hydrotreating.
 In the range of equipment that makes up hydrotreating processes
(reactors, furnaces, compressors, separators, heat exchangers), the
reactors and their internals are the heart of the technology.

 Reactors
Fixed bed reactors are used in distillate hydrotreating units. There are
two types:
• reactors operating in the gaseous phase, used with light feeds such
as naphthas and kerosenes;
• reactors operating in combined liquid and gas phase, used with
heavier feeds such as light and heavy gas oils, vacuum gas oils,
lube oils and deasphalted oils.
Process Technology
 Reactors
Process Technology
 Reactors
 Process Technology
 Reactors
 Process Technology
 Reactors
Process Technology
 Reactors
 Process Technology
 Process flow schemes
Reaction section Separation section
 Process Technology
 Process flow schemes: Reaction section

 The section comprises the reactor, the furnace, the heat

exchange train, the booster pump, the compressors and the
separator drum. If need be, there is also water and
hydrocarbon washing and an amine H2S absorber.
 Two types of reaction sections are used, the cold and the hot
separator process.
 The criteria for choosing between the two are based on the
type of feed, the feed temperature, the risks of foaming and
the problems of water-hydrocarbon separation.
 Process Technology
 Process flow schemes: Reaction section: Cold process

Cold separator hydrodesulfurization process

 Process Technology
 Process flow schemes: Reaction section: Cold process
The advantages of the cold process are:
• purer recycle gas and therefore lower operating pressure and less
hydrogen loss;
• greater simplicity;
• the possibility of treating light feeds.

The drawbacks are:

• a larger heat exchange surface area:
• a greater heating load on the stripper furnace;
• a large settling drum (separator).
 Process Technology
 Process flow schemes: Reaction section: Hot process

Hot separator hydrodesulfurization process

 Process Technology
 Process flow schemes: Reaction section: Hot process
The advantages of the hot process are:
• a great reduction in the heat exchange surface area;
• the possibility of treating hot feeds;
• a lower heating load on the stripper furnace;
• the possibility of feeding direCtlyinto the stripper.
The drawbacks are:
• use limited to heavy feeds;
• greater hydrogen loss and lower hydrogen partial pressure;
• the need to purify the recycle gas by washing with amines
or hydro carbons.
 Process Technology
 Process flow schemes: Naphtha hydrotreating
 Process Technology
 Process flow schemes: Naphtha hydrotreating
 Process Technology
 Process flow schemes: Naphtha hydrotreating

Characteristics of feed for naphtha pretreatment by hydrorreating and

of resulting effluents for isomerization and refonning processes
 Process Technology
 Process flow schemes: Kerosene hydrotreating
 Process Technology
 Process flow schemes: Gas oil hydrotreating
Process Technology

 Process flow schemes:

Kerosene and Gas oil
hydrotreating

Hydrotreating kerosene
and gas oil. Feed and
product properties
 Process Technology
 Process flow schemes: Atmospheric Residue hydrotreating
 Process Technology
 Process flow schemes: Atmospheric Residue hydrotreating

Typical properties of vacuum distillates

 Process Technology
 Process flow schemes: Atmospheric Residue hydrotreating

Hydrotreating vacuum
distillates. Yields and
hydrogen
consumption for two
types of operation:
hydrodesulturization
(HDS) and mild
hydrocracking (HDC).
Process Technology

 Process flow schemes:

Atmospheric Residue
hydrotreating

Hydrotreating vacuum
distillates. Product
properties for two
types ofoperation:
hydrodesulturization
(HDS) and mild
hydrocracking (HDC).
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