HYDROTREATING

What Is Hydrotreating?

The term hydrodesulfurization was used to describe processes that removed sulfur

compounds from crude oil fractions by reaction with hydrogen. As the processes evolved to

include nitrogen and oxygen removal, together with the hydrogenation of aromatics and

olefins, the group of processes became known as hydrotreating. Hydrotreatment simply

results in the conversion of organic sulfur, nitrogen, and oxygen compounds to hydrocarbons

and hydrogen sulfide, ammonia, or water, respectively. At the same time olefins and

aromatics may be converted to saturated hydrocarbons without any cracking of the

hydrocarbons. When high-boiling crude oil fractions are hydrotreated under more severe

conditions a proportion of the heavy molecules may crack as impurities are removed.

Hydrotreating:

Sulfur impurities in products manufactured from crude oil products are undesirable because

hydrogen sulfide, sulfur dioxide, etc., formed during product use. It contents in crude oil

which may be categorized in the following groups:

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1. Free elemental sulfur

2. Mercaptans & tiols (R-SH)

3. Hydrogen sulfide

4. Sulfides

5. Disulfides (R-S-S-R')

6. Poly sulfides (R-Sn-R')

7. Thiophenes and their derivatives such as BT (benzothiophene) and DBT (dibenzothiphene)

For many years it was possible to obtain acceptable quality gasoline and kerosene by

selecting low-sulfur, or sweet, crude oils. Sour crude oils contain dissolved hydrogen sulfide,

mercaptans, organic sulfides, thiophenes, and elemental sulfur in varying amounts. These

could be sweetened by a number of chemical processes. High-sulfur crude oils were more

difficult to desulfurize and the chemical and solvent extraction processes were combined with

or replaced by relatively cheap and more efficient catalytic processes that could also remove

gum-forming compounds from cracked gasolines. For a short time from 1946 bauxite or

fuller’s earth was used without the addition of hydrogen. It was found that sulfides and

mercaptans reacted with impurities in the bauxite and that this together with some mild

cracking of hydrocarbons produced sufficient hydrogen to hydrogenate thiophenes. It was

soon realized that the catalytic desulfurization was actually a mild, selective hydrogenation

process that did not saturate aromatics.

During the 1950s, cobalt/ molybdate catalysts supported on bauxite or Fuller’s earth was

used. The new catalysts were most effective when hydrogen was added to the feed. This also

had the effect of reducing the deposition of carbon, and allowed for longer operating cycles

before regeneration was necessary. More effective cobalt/molybdate catalysts were developed

using γ-alumina as support. The activation step for the catalyst involved the formation of

metal sulfides, and when the catalyst was pre-sulfided before use, it was found that light

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distillates, kerosene and even crude oils could be treated effectively with these catalysts.

Operating conditions depended on the boiling range of the fraction being treated. Catalyst

temperature was usually limited to about 400 °C in order to avoid excessive carbon

deposition while total pressure was increased from 300–500 psig for low-boiling distillates

and up to 700–1000 psig for higher-boiling or cracked feeds. Liquid space velocity was

usually up to 8 h-1, with a hydrogen/oil ratio of about 1000 scf of hydrogen per barrel of feed

for low-sulfur distillates. Lower space velocities, in the range from 0.5–3 h-1, with

hydrogen/oil ratios up to 10,000 scf per barrel, needed to be used for higher-boiling residues.

In the hydrotreating of heavy feeds, more carbon was deposited by thermal cracking than in

the hydrotreating of lighter feeds. Catalyst regeneration was required after operation for less

than 24h. The use of hydrodesulfurization became more widespread as catalytic naphtha

reforming processes were introduced. The operation of platinum catalysts needed an

increasingly strict sulfur specification for the naphtha, and as a bonus, the cheap by-product

hydrogen from the reforming process could be used to hydrotreat other refinery product

streams. The use of hydrotreating was extended to kerosene, gas oil, and vacuum gas oils as

government regulations on sulfur emissions became more stringent and as better cobalt

molybdate catalysts became available. By the late 1970s, when atmospheric and vacuum

residues were also being desulfurized.

In the early hydrotreating processes, sulfur compounds were removed from the light

hydrocarbon fractions used in gasoline by hydrogenation over cobalt/ molybdate catalysts to

produce hydrogen sulfide and a saturated hydrocarbon. Around the same time, it was found

that nickel/molybdate catalysts were more active for the hydrogenation of nitrogen

compounds to ammonia and a hydrocarbon while also giving some saturation of olefins and

aromatics. In modern refineries both cobalt/molybdate and nickel/molybdate catalysts are

now widely used in the purification of various crude oil fractions. These include:

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• Straight-run naphthas, used as feedstock for catalytic reforming and steam reforming

processes. They must contain less than 1 ppm of sulfur and nitrogen to avoid poisoning

platinum or nickel catalysts.

• Cracked gasoline, to hydrogenate undesirable sulfur and nitrogen compounds as well as

olefins.

• Middle distillates such as diesel fuel, kerosene, jet fuel, domestic heating oil, and other gas

oils, to remove sulfur for environmental reasons. Hydrotreating is also used to increase the

smoke point or cetane number by hydrogenating aromatic components.

• Vacuum gas oils, used as catalytic cracker or hydrocracker feeds, to remove sulfur,

nitrogen, and metal impurities.

• Atmospheric and vacuum residues, to remove as much sulfur as possible to provide low-

sulfur fuel oils. It is also used to hydrogenate asphaltenes and porphyrins to reduce both

Conradson carbon and metal contents. As the boiling point and the specific gravity of the

fractions increase, more severe hydrotreating operating conditions are needed. A lower space

velocity and more extensive hydrogen recycle are needed to limit deactivation of the catalyst

by deposition of coke. The catalyst must be regenerated after shorter intervals and discarded

more often than when using light fractions.

Process Description of Hydrotreating in ORC-I:

The naphtha hydrotreating process of the ORC-I in BYCO Petroleum Pakistan is a

hydrotreating unit with gas recycles because of high excess hydrogen. A typical

hydrodesulfurization plant has two main sections: reaction section and separation section. At

first, feed straight run naphtha (SRN) mixed with makeup and recycles hydrogen and then

heated up to the reaction temperature (300 – 390°C) in the heat exchanger and furnace. The

hot gases are introduced into the HDS reactor at a pressure of 30 to 130 atm. The reactor is a

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fixed bed type with the flow from top to bottom. The hot reaction products are partially

cooled by flowing through the heat exchanger where the reactor feed was preheated, then flows through

fan cooler and then flows through a trim cooler. The resulting mixture of liquid and gas enters the gas

separatorvessel at about 35°C and3 to5 atmospheres of absolute pressure. Most of the hydrogen-rich gas from the gas

separator vessel is recycle gas which is routed through an amine contactor for removal of the reaction product

H2S that it contains. The pressure of gas is controlled by PCV-235. The H2S-free hydrogen-

rich gas is then recycled back for reuse in the reactor section. Any excess gas from the gas separator vessel

joins the sour gas from the stripping of the reaction product liquid .The liquid from the gas

separator vessel flows to the suction of pump routed through are boiled stripper distillation tower. The bottoms

product from the stripper is the final desulfurized liquid product from hydrodesulfurization unit.

Reaction Mechanism:

The main HDS catalysts are based on molybdenum disulfide (MoS2) together with smaller

amounts of other metals. The nature of the sites of catalytic activity remains an active area of

investigation, but it is generally assumed basal planes of the MoS2 structure are not relevant

to catalysis, rather the edges or rims of these sheets. At the edges of the MoS2 crystallites, the

molybdenum center can stabilize a coordinatively unsaturated site (CUS), also known as an

anion vacancy. Substrates, such as thiophene, bind to this site and undergo a series a reactions

that result in both C-S scission and C=C hydrogenation. Thus, the hydrogen serves multiple

roles—generation of anion vacancy by removal of sulfide, hydrogenation, and

hydrogenolysis. A simplified diagram for the cycle is shown:

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Note that the “direct” removal of a sulfur atom from dibenzothiophene requires 2 molecules

of hydrogen, while the “indirect” removal of sulfur from a hindered dibenzothiophene

requires 5 molecules of hydrogen per sulfur atom. This is important when estimating

hydrogen requirements for deep desulfurization. In sterically hindered compounds, such as

dibenzothiophenes with alkyl groups in the 4- and/or 6-position, HDS rates are low because

the alkyl groups keep the sulfur atom away from the catalyst surface. The benzothiophene

core is planar because it is aromatic. But after saturation removes aromaticity from one or

both of the 6-carbon rings, the molecule can twist, allowing the sulfur atom to reach the

catalyst.

Metal sulfides are "supported" on materials with high surface areas. A typical support for

HDS catalyst is γ-alumina. The support allows the more expensive catalyst to be more widely

distributed, giving rise to a larger fraction of the MoS2 that is catalytically active. The

interaction between the support and the catalyst is an area of intense interest, since the

support is often not fully inert but participates in the catalysis.

The main purpose of the hydrotreater is to clean up a naphtha fraction so that it is suitable as

charge to a platforming unit. There are six basic types of reactions that occurs in

hydrotreating unit.

1. Conversion of organic sulfur compounds to hydrogen sulfide

2. Conversion of organic nitrogen compounds to ammonia

3. Conversion of organic oxygen compounds to water

4. Saturation of olefins

5. Conversion of organic halides to hydrogen halides

6. Removal of organo-metallic compounds

Sulfur Removal

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For bimetallic platforming catalyst, the feed naphtha must contain less than 0.5 weight ppm

sulfur to the selectivity & stability characteristics of the catalyst. Removal of sulfur in

hydrotreating is relatively easy 0.2 weight ppm of sulfur is maintained as standard practice. If

sulfur contents are less the 0.15 wppm then they are injected in the platforming unit for

smooth operation. Typical reactions are:

Generally, operation at 315-340°C (600-645°F) average reactor temperature will give

acceptable rates of the desired hydrogenation reactions and will not result in a significant

amount of olefin/hydrogen sulfide recombination. The sulfur recombination reaction typically

occurs at temperatures greater than 340°C (645°F). This temperature is dependent upon

feedstock composition, operating pressure,

Nitrogen Removal

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Nitrogen removal is considerably more difficult than sulfur removal in naphtha hydrotreating.

The rate of denitrification is only about one-fifth the rate of desulfurization. Most straight run

naphthas contain much less nitrogen than sulfur, but attention must be given to ensure that the

feed naphtha to Platforming catalyst contains a maximum ot 0.5 weight ppm nitrogen and

normally much less. Any organic nitrogen that does enter the Platforming Unit will react to

ammonia and further with the chloride in the recycle gas to form ammonium chloride.

Ammonium chloride will deposit in the recycle gas circuit or stabilizer overhead system.

Denitrification is favored more by pressure than temperature and thus unit design is

important. The ammonia formed in the Denitrification reactions, detailed below, is

subsequently removed in the hydrotreater reactor effluent wash water.

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Oxygen Removal

Organically combined oxygen, such as a phenol or alcohol, is removed in the Naphtha

Hydrotreating Unit by hydrogenation of the carbon-hydroxyl bond, forming water and the

corresponding hydrocarbon. The reaction is detailed below. Oxyegenates are typically not

present in naphtha, but when present they are in very low concentrations. Any oxygenates in

the product will quantalively convert to water in the Platforming Unit. It is important that the

hydrotreater product oxygenate level be reduced sufficiently.

Oxyegenate removal is as difficult, if not more, than nitrogen removal. The specific organic

oxygen species impacts ease or difficulty of removal. Units normally not designed for oxygen

removal may find it difficult to get adequate product quality. Oxygenate removal is favored

by high pressure and high temperatures. For high feed concentrations, lower liquid space

velocities are required. Processing of such compounds should be done with care. Complete

oxygen removal is not normally expected and may only be 50%.

Olefin Saturation

Hydrogenation of olefins is necessary to prevent fouling or coke deposits in downstream

units. Olefins can polymerize at the Platforming combined feed exchanger and thus cause

fouling. These olefins will also polymerize upstream of the naphtha hydrotreating reactor and

cause heat transfer problems. Olefin saturation is almost as rapid as desulfurization. Most

straight run naphthas contain only trace amounts of olefins, but cracked naphthas usually

have high olefin concentrations. Processing high concentrations of olefins in a Naphtha

Hydrotreating Unit must be approached with care because of the high exothermic heat of

reaction associated with the saturation reaction. The increased temperature, from processing

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relatively high amounts of olefins, across the catalyst bed can be sufficient enough to cause

sulfur recombination. The olefin reaction is detailed below

Halide Removal

Organic halides can be decomposed in the Naphtha Hydrotreating Unit to the corresponding

hydrogen halide, which is either absorbed in the reactor eltluent water wash or taken

overhead in the stripper gas. Decomposition of organic halides is much more difficult than

desulfurization. Maximum organic halide removal is thought to be about 90 %, but is much

less at operating conditions set forth for sulfur and nitrogen removal only. A typical organic

chloride decomposition reaction is shown below.

Metal Removal

Normally the metallic impurities in the naphtha feeds are in the part per billion (ppb) range

and these can be completely removed. The Hydrotreating catalysts are capable of removing

these compounds at fairly high concentrations, up to 5 weight ppm or more, on an

intermittent basis at normal operating conditions. The metallic impurities remain on the

Hydrotreating catalyst when removed from the naphtha. Some commonly detected

components found on used Hydrotreating Hydrobon® catalyst are arsenic, iron, catcium,

magnesium, phosphorous, lead, silicon, copper, and sodium.

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LHSV & Residence Time Calculation:

LHSV (liquid hourly space velocity) = Volumetric flow of liquid feed

Volume of catalyst

1bbl(US Oil) = 158.987 liters

1 liters = 0.001 m³

Volumetric flow of liquid feed = 3000 bbl/day(US Oil) = 3000x158.987x0.001

= 476.961 m³/day

= 19.873 m³/hr

Volume of catalyst or reactor = 9.9 m³

LHSV = 19.873/9.9 = 2.0073 hr-1

Residence Time = Volume of catalyst

Volumetric flow of liquid feed

Residence Time = 9.9/19.873 = 0.4981 hr = 29.889 min

Process Equipments Overview:

Reactors

The reactor used in hydrotreating process is fixed bed continuous flow type. This type of

reactors are usually operate at steady state but by the passage of time the steady state

operation is disturbed by the deposition of material on the bed of catalyst & also due to

fouling. Catalyst containment is one of the goals of the design. Process vapors enter through

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the top of the reactor. via an inlet distributor, and flow down through the catalyst bed and out

the bottom of reactor.

Typically the naphtha hydrotreating reactor is constructed of carbon steel with an alloy lining.

The inlet distributor located at the top of the reactor prevents the vapor from disturbing the

catalyst bed and enhances the flow distribution through the catalyst. Usually there are two

layers of graded bed material on top of the catalyst bed. This aids in flow distribution and

minimizes the pressure drop across the reactor. The depth of each layer is a function of the

reactor dimensions and the feed types. The top layer is typically 4 to 6 inches deep (100 mm

to 150 mm) and consists of specially shaped inert ceramic material used to filter larger

particles from the teed. The second layer ranges from 12 to 24 inches (300 mm to 600 mm) in

depth and is another specially shaped material, but includes active metals. At the bottom of

each reactor are ceramic support materials (balls) of different diameters which help in the

flow distribution of the reactor effluent out of the reactor. The varying diameters of the

support material are utilized to prevent catalyst migration. An outlet basket prevents the

ceramic support material from leaving the reactor.

Heaters

The Charge Heater is typically a radiant-convection type with one firing zone, with fuel gas-

fired burners located on the floor of the heater box. It is normally a cylindrical updraft type

having vertical tubes in the radiant section and sometimes horizontal tubes in the convection

section. The combined feed will first flow through the convection section and be preheated.

There are a number of passes in the radiant section and each pass contains skin

thermocouples. These thermocouples can warn of tube plugging from two-phase flow, mainly

during startup. Dampers located in the stack above the convection section control draft

through the heater. Draft gauges (vacuum gauges) are installed in the radiant sections,

convection inlets, and before and after the damper to monitor draft through the heater. A

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negative pressure must be maintained for safe, efficient heater operation. Thus the draft is of

induced type.

Heat Exchangers

Heat exchangers are used to heat and cool! many streams in the Naphtha Hydrotreating Unit.

The shell and tube combined feed exchangers (CFE) allow the hot reactor effluent to add heat

to the hydrotreating feed before the Charge Heater. The reactor effluent is then cooled further

so that hydrogen can be separated from the unit product. The total reactor effluent is

condensed by an air cooler and trim cooler. Heat exchangers are used for the reboiiers of the

Stripper and Splitter Columns. Steam can be used for the Stripper and Splitter Columns.

Compressors

The Naphtha hydrotreating Unit has one or two reciprocating, motor-driven compressors.

One is booster & other is recycling compressor. The Purpose of booster compressor is to

increase the pressure of gas. The recycle compressors circulate hydrogen-rich gas through the

hydrotreating reactor circuit. Without hydrogen circulation, large amounts of coke will form

on the catalyst that will prevent the desired catalytic reactions. It is critical to maintain

recycle gas flow when feed is being charged to the unit.

Pumps

There are many types of pumps used in the Naphtha Hydrotreating Unit. A high~ head multi-

stage pump is usually used to supply feed to the reactor section that is at much higher

pressure than the Feed Surge Drum. Proportioning pumps are used for chemical injection,

such as inhibitor or condensate.

Feed Surge Drum

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The Feed Surge Drum is a pressurized, horizontal killed carbon steel vessel. The naphtha

hydrotreating feeds enter through a baffle distributor located at the bottom of the Feed Surge

Drum and leaves at the opposite end. A level indicator and level glass show the hydrocarbon

level. Maintaining a liquid seal in the bottom of the drum is important. The liquid outlet line

has a vortex breaker. The Feed Surge Drum has a water boot to collect and remove any tree

water that might be present.

Separator

The Separator is designed primarily to separate hydrogen from hydrocarbon. The Separator is

a horizontal carbon steel vessel lined with an alloy, and occasionally concrete, for corrosion

protection. The cooled reactor effluent enters through a slot type distributor at one end of the

vessel to permit proper mixed phase distribution. The hydrogen and liquid separate and both

pass through a vertical mesh blanket. The mesh blanket is used as a demister pad to coalesce,

or helps remove, entrained hydrocarbon droplets from the gas stream. A level indictor shows

the hydrocarbon level and a level controller controls the flow of hydrocarbon from the

separator to the Stripper. Maintaining a liquid seal in the bottom of the separator is important.

The liquid outlet line has a vortex breaker. There is also a water-boot to remove the injected

water.

Over Head Receivers

The Stripper and Splitter columns have receivers to collect condensed overhead vapors. The

Stripper receiver inlet, has a slotted distributor to permit proper mixed phase distribution. A

water boot collects any free water that might be present. A gas outlet nozzle permits non-

condensable gas to go overhead. This valve also acts as the column pressure controller. The

overhead receiver design temperature is much higher than its operating temperature. The

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receiver is designed to withstand temperatures that may develop if the overhead condenser

should fail.

Suction Drum

The Recycle Compressor Suction Drum is a small vertical vessel designed to remove

condensable material from the recycle compressor suction stream and thus protect the

compressor.

Stripper Column

The stripper column is used to remove light ends, H2O and water from the light naphtha

product stream. The stripper is typically fabricated out of killed carbon steel with carbon steel

or stainless steel valve trays. The top part of the column is narrower than the bottom due to

the lower volumes of liquid and vapor in the top section of the column.

Splitter Column

The Splitter is used to separate the light naphtha from the heavy naphtha product. The hexane

(C6) components and heavier will be taken out the bottoms and sent to the Platforming Unit,

tankage or blending system. The pentane (C5) components and lighter will go overhead

where they are condensed and the net liquid will be sent to the tankage or blending. The

Splitter is typically fabricated out of carbon steel with carbon steel valve trays.

Valves

The valves used in NHT are globe, gate & NRV .The NHT unit is totally controlled by DCS

system. The control valves are of pneumatic type with open to failure & close to failure

mechanism.

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Advantages:

Hydrodesulfurization unit have some advantages such as:

- Sulfur & nitrogen removal to less than 10 ppm

- Complete removal of metal compounds from feedstock

- Reduction of environmental pollutants

- Increase in catalysts age and reduction in poisoning of valuable metal catalyst

- Reduction in corrosion of process equipment

- Easy treatment of waste water

- Simple operation of process unit

Conclusion

At the end it is concluded that NHT plays the vital role in cleaning of naphtha before its

further processing. It increase catalyst regeneration cycle time & helps to attain maximum

yield. Thus by the usage of hydrotreating technology we could also meet the specifications

for clean fuel as prescribe by EPA.

Recommendations

 Make sure that reactor temperature could not exceed 340 oC. Because as many time

reactor exceeds that temperature the probability of coke deposition is increased thus

catalyst regeneration cycle time decreases.

 In order to minimize fuel consumption in furnaces use as many heat exchangers as

you can & if possible use reformer furnace as heating source NHT feed to save money

as well as energy

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Bibliography:

http://www.vurup.sk/sites/vurup.sk/archivedsite/www.vurup.sk/pc/vol51_2009/issue1/pdf/pc

_1_2009_mohaddecy.pdf

http://en.wikipedia.org/wiki/Hydrodesulfurization

http://chentserver.uwaterloo.ca/aelkamel/che720/che735/lectures_che735_students/new-book-

practical-advances-refinery/chapter7-hydrotreater-hydrocracker.pdf

http://chentserver.uwaterloo.ca/aelkamel/che720/che735/lectures_che735_students/new-book-

practical-advances-refinery/chapter7-hydrotreater-hydrocracker.pdf

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