Hydrogenation

Learning Objectives
 After completion of this section, you will be able to:

 Understand the fundamentals of hydrogenation

 Explain the commercialization of hydrogenation

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 Introduction
 “Hydrogenation is a fundamental process in organic chemistry and
has been used for centuries to add elemental hydrogen across
unsaturated bonds”.
 The unit process hydrogenation (as contrasted with the general term
reduction) specifically refers to the chemical reaction
of a substance with molecular hydrogen in the presence of a catalyst.
 The process includes reactions in which hydrogen simply adds to a
molecule (hydrogenation), reactions in which molecules are cleaved
by hydrogen (hydrogenolysis or destructive hydrogenation), and also
reactions such as isomerization, cyclization, and the like which occur
in the presence of molecular hydrogen and catalysts.
 Other reactions which involve molecular hydrogen and catalysts are
reductive amination (hydroammonolysis), hydroformylation (Oxo and
Oxoyl reactions), and the synthesis of ammonia. These processes,
however, will not be considered in this course.
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 Introduction
 Hydrogenation, in the exact usage of the designation, is
synonymous with reduction, which is the term usually applied to a
reaction in which oxygen or some other element (most commonly
nitrogen, sulfur, carbon, or halogen) is withdrawn from or hydrogen
is added to a molecule.

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5
 Commercialization of hydrogenation
 Hydrogenation reactions are extensively used to create commercial
goods.
 Hydrogenation is used in the food industry to make a large variety
of manufactured goods, like spreads and shortenings, from liquid
oils.
 This process also increases the chemical stability of products and
yields semi-solid products like margarine.
 Hydrogenation is also used in coal processing.
 Solid coal is converted to a liquid through the addition of hydrogen.
 Liquefying coal makes it available to be used as fuel.

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 Coal Hydrogenation
 The destructive hydrogenation of coal to produce gasoline has been
undertaken at various times in countries where the existence of
petroleum had not, at the time, been proved
 Direct coal liquefaction technology developed from work on
hydrogenating coal tar by Bergius in Germany in the 1920s.
 Second generation technology came along in the late 1970s and
early 1980s.

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 Coal Hydrogenation
 Coal hydrogenation is a type of direct coal liquefaction process in
converting coal to gaseous or liquid hydrocarbon products.
 Coal hydrogenation serves as an alternative to coal combustion and
offers lower temperatures, more reduced conditions, and longer
residence times while producing a more crystalline product with
reduced ash.
 Direct liquefaction involves the addition of hydrogen to coal in a
solvent slurry at elevated temperature and pressure.
 Catalysts are normally used to increase the rates of the desirable
reactions which include cracking, hydrogenation, and removal of
oxygen, nitrogen, and sulfur.
 Common types of catalysts used are supported metal-containing
catalysts such as cobalt molybdate on alumina, and molybdenum
oxide or sulphide on alumina silica support.

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 A reducing atmosphere is an atmospheric condition in which
oxidation is prevented by removal of oxygen and other oxidizing
gases or vapours, and which may contain actively reducing gases
such as hydrogen, carbon monoxide, and gases such as hydrogen
sulfide that would be oxidized by any present oxygen.

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 Coal Hydrogenation
 Process Description
 Direct coal liquefaction refers to the direct reaction of coal with
hydrogen to form liquids.
 The hydrogen reacts with oxygen, sulfur, and nitrogen in coal to
remove them as water, hydrogen sulfide, and ammonia.
 The hydrogen is also required to hydrogenate the donor solvent
which in turn transfers hydrogen to the dissolved coal thereby
substantially increasing the H/C ratio of the coal as it is liquefied.

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 Coal Hydrogenation
 Process Description
 The ideal technology for direct coal liquefaction for gasoline
production would:
 1. Produce only C5-400 °F products which contain no nitrogen,
oxygen, or sulfur hydrocarbon gases.
 2. Produce no light since these gases consume large amounts of
hydrogen.
 3. Produce aromatic liquid for octane requirements to reduce
hydrogen consumption.
 4. Remove oxygen from coal by carbon rejection to carbon oxides
rather than hydrogenation.

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Coal Hydrogenation

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 Petroleum Hydrogenation
 Hydrogenation, or adding hydrogen to unsaturated hydrocarbons, is
used for stabilization of petroleum products and aromatic reduction
 One particular application of hydrogenation is to saturate unstable
olefins and di-olefins that are implicated in producing gums (high-
molecular-weight sticky semi-solid material) during the storage of
fuels, such as gasoline and jet fuel.
 Gum formation is detrimental, particularly, to the operation of fuel
injectors in combustion engines.
 Narrow passages found in fuel injectors can be partially or
completely plugged with deposition/accumulation of gums on flow
surfaces causing engine failures.
 The objective of hydrogenation is just adding hydrogen to
unsaturated hydrocarbons using precious metal (Pt, Pd) or Ni
catalysts at low temperatures to avoid cracking or other chemical
changes.

https://www.e-education.psu.edu/fsc432/content/hydrogenation 13
 Petroleum Hydrogenation
 Mild hydrogenation is being used extensively in petroleum
processing, especially in product finishing of naphtha, kerosene,
diesel fuel, heating oil, and distillate lubricating oils.
 This mild hydrogen treatment serves primarily to replace other less
efficient methods for removing sulfur compounds, improving color
and odor, and increasing the storage stability of the products.

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 Fat Hydrogenation
 The hydrogenation of fats and oils and their oleochemical derivatives
such as fatty acids, fatty acid esters and fatty nitriles has proven to be
a very useful and versatile way to modify these starting materials.
 * Olechemical: A chemical compound derived industrially from
animal or vegetable oils or fats.
 * Fatty acids are the building blocks of the fat in our bodies and in
the food we eat. During digestion, the body breaks down fats into
fatty acids, which can then be absorbed into the blood. Fatty acid
molecules are usually joined together in groups of three, forming a
molecule called a triglyceride.
 * Examples would be fats, oils, cholesterols, and steroids. Fatty acids
are in fact carboxylic acids with long aliphatic chain, which can be
saturated (containing only C-C single bonds) or unsaturated
(containing multiple bonds between carbon atoms). Examples of
saturated fatty acids are Palmitic acid, stearic acid etc.
https://lipidlibrary.aocs.org/edible-oil-processing/hydrogenation-in-practice 15
 *Fatty acid esters (FAEs) are a type of ester that result from the
combination of a fatty acid with an alcohol. When the alcohol
component is glycerol, the fatty acid esters produced can be
monoglycerides, diglycerides, or triglycerides. Dietary fats are
chemically triglycerides.

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 Purpose of hydrogenation
 In general, hydrogenation serves any or several of the following
purposes:
 1. To convert a liquid oil into a solid fat.
When solid fats of the right consistency are expensive or not
available, hydrogenation, sometimes in combination with other
processes such as inter-esterification or fractionation, may provide
a way to produce the desired fat.
 2. To change the consistency of a fat.
The melting point of a hydrogenated fat can be controlled by the
degree of hydrogenation.
 Vegetable oils contain practically exclusively cis isomers of fatty
acids.
 Hydrogenation will also convert some of the cis isomers into trans
isomers, which give the triglycerides different melting
characteristics.

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 Purpose of hydrogenation
 Furthermore, by using specific catalysts and/or hydrogenation
conditions (such as temperature and hydrogen pressure), the
composition of the fatty acids and the level of cis and trans isomers
occurring at a particular iodine value (IV) can be controlled.
 Consequently, the melting behavior of the fat at a particular IV can be
influenced by the processor.
 3. To stabilize an oil or a fat.
In general, saturated fatty acids are chemically more stable than
unsaturated fatty acids.
 By converting unsaturated fatty acids to less unsaturated ones, the
shelf life of the product will be improved and also the product may
become more suitable for heavy-duty functions, such as frying.
 To broaden the availability of edible oils and fats. Whale oil and later
fish oil are too ‘fishy’ for consumption.
 By hydrogenating these oils, palatable* hard stocks were made
available. (* pleasant to taste)
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 Requirements for hydrogenation: raw materials,
equipment
 Raw materials
 The oil
 The catalyst used for the hydrogenation is sensitive to various
contaminants that may be present in the oil.
 These contaminants may either decrease the activity of the catalyst
reversibly or poison the catalyst permanently.
 When the catalyst is poisoned, its change cannot be reversed and it
must be replaced by fresh catalyst.
 This means that the oil should be refined to such low residual levels
of contaminants that the catalyst consumption is reduced to an
economically acceptable level.

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 Requirements for hydrogenation: raw materials,
equipment
 Generally, (apart from other choices made in refining) the choice in
favor of more thorough refining with consequently lower catalyst
consumption and better predictable catalyst performance, has to
be weighed against its higher costs.
 The level of the individual contaminants varies for each type of oil.
 The choice on which contaminant to focus in refining will therefore
differ for each type of oil.
 Hence it is impossible to give general guidelines for the desired
purity covering all types of oils but it is good practice to try and
attain the following levels of some common potential
contaminants:
Acidity: < 0.1 % free fatty acids by Sulphur: 5 mg/kg max
weight
Phosphorus: 5 mg/kg max. Moisture: < 0.05 % by weight
Soap: < 0,05 % by weight Oxidation products: peroxide value =
0 (meq/kg) 20
 Requirements for hydrogenation: raw materials, equipment
 The hydrogen
 Hydrogen may be obtained from various sources: bottled hydrogen
or supply by pipeline from a major producer of gasses, electrolysis
(usually on site) or gas reforming (usually on site).
 The designer of the hydrogenation plant is supposed to know what
quality the hydrogen should have.
 The quality of the hydrogen is therefore rarely an issue.
 Hydrogen can contain three groups of contaminants which may
affect the hydrogenation: inerts, inhibitors and poisons.
 Inerts are other gasses than hydrogen, such as methane, water or
nitrogen which lower the partial pressure of the hydrogen, thus
reducing the rate of the hydrogenation.

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 Requirements for hydrogenation: raw materials, equipment
 This is particularly problematic in batch hydrogenation because as
the hydrogen is being consumed during the hydrogenation, the
inerts accumulate in the headspace of the reactor.
 As the total pressure is usually kept constant, the partial pressure of
the hydrogen will therefore decrease.
 Inhibitors are substances that temporarily interact with the catalyst
and lower its activity.
 When conditions change and desorption takes place, the original
catalyst activity is restored.
 An example would be carbon monoxide.
 A catalyst poison is a substance that reacts with the catalyst and
that affects its performance in an irreversible manner.

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 Requirements for hydrogenation: raw materials, equipment
 The most common type of poison occurring in hydrogen are
sulphur containing gases.
 Below the levels of contaminants in hydrogen gas are specified:
Sulphur: < 200 mg/kg
Inerts: < 0.2 % by volume
Moisture: < 0.1 % by volume
Carbon monoxide: < 0.03 %

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 Requirements for hydrogenation: raw materials, equipment
 The catalyst.
 In the hydrogenation of fats and oils the only catalysts used industrially
are the so-called supported nickel catalysts, whereby the nickel metal is
mounted on an inert support material.
 In the past, other catalysts have also been used, e.g. Ni-formate, Raney-
type nickel, nickel-copper and copper-chrome.
 In addition, the use of precious metal (supported palladium and
platinum) catalysts has been explored.
 Ni-formate and Raney-type catalysts needed to be activated in situ.
 They were in use until the 1940s and 1950s, when pre-reduced
supported Ni-catalysts that were easy to handle, became generally
available.
 The current supported Ni-catalysts are vastly superior in performance to
Ni-formate and Raney-types.
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 Requirements for hydrogenation: raw materials, equipment
 The catalyst.
 In the hydrogenation of fats and oils the only catalysts used industrially
are the so-called supported nickel catalysts, whereby the nickel metal is
mounted on an inert support material.
 The supported Ni-catalysts used industrially for slurry phase processes
consist of extremely finely dispersed nickel on an inert support that is
suspended in a protective medium.
 It is present as very small crystallites to create a high surface area (up to
c. 100 m2/g Ni), which results in a high activity.
 Along with a high surface area, the Ni must also be well accessible.
 In order for the catalyst to be filtered with relative ease, the Ni is
deposited on a porous support powder (e.g. alumina or silica) with good
filtration properties.

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 Requirements for hydrogenation: raw materials, equipment
 There are several technical criteria that play a role in the
characterization of a catalyst:
 The activity. The activity should be high because it not only
determines the time needed to hydrogenate a batch of oil (production
capacity) but also it determines to a great extent how much catalyst
must be added to achieve a reasonable batch time (i.e. catalyst cost
related).
 The resistance against deactivation, the so-called ‘poison resistance’.
This property only plays an important role if the feedstock contains
relatively high amounts of contaminants that could deactivate the
catalyst or if the catalyst is re-used many times so that catalyst poisons
build up as the catalyst is reused.

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 Requirements for hydrogenation: raw materials, equipment
 The selectivity. In those cases where the feedstock is partially
hydrogenated, selectivity always plays a role of some importance. It
describes e.g. to which extent the catalyst has a preference to
hydrogenate polyunsaturated fatty acids over monounsaturated fatty
acids and whether it produces higher or lower amounts of trans-
isomers than other catalysts.
 The filtration properties. Generally, a plant should be designed to
filter any type of catalyst available on the market but plant
modifications such as capacity increase realized at a later stage,
sometimes result in filtration becoming a critical item. In a batch-type
of operation, filtration should be fast enough to enable to start the
next filtration cycle as soon as hydrogenation of the next batch of oil is
finished. Looking for even faster filtration is of no relevance. The time
to filter a batch of oil depends on many factors, one of which is the
particle size and particle size distribution of the catalyst.

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 Equipment, The reactor
 Batch autoclaves
 In general, the autoclave is provided with two upstream pieces of
equipment that prepare the oil for the hydrogenation: heating
equipment and drying equipment.
 The catalyst has a minimum temperature at which it will become
active. Usually this ‘light-off’ temperature is higher than the
temperature of the oil coming from storage.
 Hydrogenation is an exothermic process so for reasons of heat-
efficiency, the incoming oil is generally heated up in a heat
exchanger, using the exothermic heat generated by the previous
batch of hydrogenated oil.
 In order to make sure that the oil is dry enough, the incoming oil is
either dried prior to or after entering into the autoclave.

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 Equipment, The reactor
 Batch autoclaves
 In the batch process, the oil is filled into the autoclave, oxygen is
removed by evacuating the reactor several times, the oil is
hydrogenated, then drained form the autoclave, usually into an
intermediate vessel (drop tank), from where it is sent to filtration to
remove the catalyst.
 As soon as the autoclave is emptied, it can be filled with the next
batch of oil.

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 Equipment, The reactor
 Batch autoclaves
 The autoclave has to ensure that the hydrogen is dissolved
efficiently into the oil.
 The conventional type of autoclave is a stirred tank, in which the
hydrogen is introduced through a sparger ring at the bottom of the
tank (see figure 1).
 The hydrogen bubbles are dispersed into tiny bubbles by means of
a central vertical agitator device.
 Baffles are attached to the internal wall of the autoclave, and
cooling and heating coils are fitted as well.
 The baffles ensure that the oil does not swirl around without
achieving much mixing with the gas bubbles and the catalyst.

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 Equipment, The reactor
 Batch autoclaves
 Once the undissolved H2 gas bubbles have reached the headspace
of the autoclave, the rate at which the H2 can be made to dissolve
in the oil becomes much lower because the H2 can only enter into
the oil at the upper surface.

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 Equipment, The reactor
 Continuous reactors
 Particularly in the oleochemical industry, there are several plants
that run in a continuous way while using powdered catalysts.
 These reactors are essentially a vertical reactor tube in which the
catalyst/feedstock mixture flows downward and into which
hydrogen is injected at different stages.
 For fatty acid hydrogenation this works well but these reactors are
less suited for triglyceride oils than the so-called fixed bed reactors.
 Fixed bed reactors are very common in the chemical and in the
petroleum industry but are surprisingly rare in the fats and oils
industry.
 They basically consist of a cylindrical, vertically mounted reactor
which contains a bed of catalyst in the form of extrudates or
tablets, supported by a grid at the bottom of the reactor.
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 Equipment, The reactor
 Continuous reactors
 The best way to operate such a reactor is in “trickle phase
downflow” mode.
 The feedstock goes through a distributer plate on top of the
catalyst bed, which distributes the liquid evenly over the bed.
 By design, the flow of liquid is limited in such a way that the liquid
trickles down through the bed while coating the catalyst particles
with a thin layer.
 This allows the hydrogen, also entering from the top and occupying
the void spaces between the catalyst particles, to dissolve into the
liquid effectively. Consequently, the hydrogen concentration in the
oil is higher than in the commonly used dead-end batch autoclave.


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 Equipment, The reactor
 The advantages of fixed bed vs. batch hardening are:
 Low investment cost
 Low running costs
 Large production volumes are easily achievable
 No filtration needed
 24x7 hr. production with a high level of automation and little
supervision
 Uniform product
 Long catalyst life: a life of 5 years is no exception
 Infrequent spent catalyst handling, often outsourced to
specialised companies

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 Equipment, The reactor
 There are also disadvantages:
 Selective (partial) hydrogenation not possible, but quite suitable
for full hydrogenation
 Unsuited for frequent feedstock or product changes because
there will always be a considerable changeover volume
 Frequent shut-downs and start-ups are not very practicable
 Unsuitable for contaminated feed stocks

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Hydrogen
Production

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 Hydrogen Production
 Hydrogen is the simplest element on earth—it consists of only one
proton and one electron—and it is an energy carrier, not an energy
source.
 Hydrogen can store and deliver usable energy, but it doesn't
typically exist by itself in nature and must be produced from
compounds that contain it.

https://www.energy.gov/eere/fuelcells/hydrogen-production 37
 Why Study Hydrogen Production
 With approximately 10 million metric tons (MMT) hydrogen
currently produced in the United States each year, the primary
demand for hydrogen today is for petroleum refining and ammonia
production.
 However, hydrogen can be used across multiple sectors to enable
zero or near-zero emissions in other chemical and industrial
processes, integrated clean energy systems, and transportation.
 Emerging hydrogen markets within these sectors include data
centers, ports, steel manufacturing, and medium- and heavy-duty
trucks.

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 How Hydrogen Production Works
 Hydrogen can be produced through low-carbon pathways using
diverse, domestic resources—including fossil fuels, such as natural
gas and coal, coupled with carbon capture and storage; through
splitting of water using nuclear energy and renewable energy
sources, such as wind, solar, geothermal, and hydro-electric power;
and from biomass through biological processes.

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 Hydrogen Production Processes
 Hydrogen can be produced using a number of different processes.
Thermochemical processes use heat and chemical reactions to
release hydrogen from organic materials, such as fossil fuels and
biomass, or from materials like water.
 Water (H2O) can also be split into hydrogen (H2) and oxygen (O2)
using electrolysis or solar energy.
 Microorganisms such as bacteria and algae can produce hydrogen
through biological processes.

https://www.energy.gov/eere/fuelcells/hydrogen-production-processes 40
 Thermochemical Processes
 Some thermal processes use the energy in various resources, such
as natural gas, coal, or biomass, to release hydrogen from their
molecular structure.
 In other processes, heat, in combination with closed-chemical
cycles, produces hydrogen from feedstocks such as water.
 Natural gas reforming (also called steam methane reforming or
SMR)
 Biomass gasification
 Biomass-derived liquid reforming
 Solar thermochemical hydrogen (STCH)

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 Electrolytic Processes
 Electrolyzers use electricity to split water into hydrogen and
oxygen.
 This technology is well developed and available commercially, and
systems that can efficiently use intermittent renewable power are
being developed.

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 Direct Solar Water Splitting Processes
 Direct solar water splitting, or photolytic, processes use light energy
to split water into hydrogen and oxygen.
 These processes are currently in various early stages of research
but offer long-term potential for sustainable hydrogen production
with low environmental impact.
 Photoelectrochemical (PEC)
 Photobiological.

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 Biological Processes
 Microbes such as bacteria and microalgae can produce hydrogen
through biological reactions, using sunlight or organic matter.
 These technology pathways are in the research and development
stage, with pilot demonstrations occurring, but in the long term
have the potential for sustainable, low-carbon hydrogen
production.
 Microbial biomass conversion
 Photobiological.

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