Vous êtes sur la page 1sur 57

HYDROGENATION

HYDROGENATION

A chemical reaction between molecular


hydrogen (H2) and another compound or
element, usually in the presence of a catalyst.

A form of chemical reduction


HYDROGENATION

o The process is commonly employed to reduce or


saturate organic compounds .
o Hydrogenation typically constitutes the addition
of pairs of hydrogen atoms to a molecule,
generally an alkene.
o Catalysts are required for the reaction to be usable;
non-catalytic hydrogenation takes place only at very
high temperatures.
o Hydrogen adds to double and triple bonds in
hydrocarbons
HYDROGENATION

A reaction where bonds are broken while


hydrogen is added is called HYDROGENOLYSIS
, a reaction that may occur to carbon-carbon
and carbon-heteroatom ( O , N , X ) bonds.

Hydrogenation differs from protonation or


hydride addition: in hydrogenation, the
products have the same charge as the
reactants.
HYDROGENATION

Hydrogenation has three components,


1. the unsaturated substrate,

2. the hydrogen (or hydrogen source) and,

3. invariably, a catalyst.

The reaction is carried out at different


temperatures and pressures depending upon the
substrate and the activity of the catalyst.

RCH=CH 2 + H 2 RCH2CH3 (R = alkyl, aryl)


HYDROGENATION
APPLICATIONS

Numerous important applications are found in


1. PETROCHEMICAL,

2. PHARMACEUTICAL AND

3. FOOD INDUSTRIES.
HYDROGENATION

Hydrogen can be obtained from


1. Hydrocarbons (thermal decomposition, steam
reforming etc.)
2. Water gas and steam

3. Electrolysis of water

4. Steam & iron


HYDROGENATION

THERMODYNAIMCS
Effect of Temperature
o Hydrogenation is a strongly exothermic reaction. In
the hydrogenation of vegetable oils and fatty acids,
for example, the heat released is about 105
kJ/mol
o At temperatures of about 100 C, small chain
hydrocarbons can be easily hydrogenated but as
the temperature is increased ( 400 C ) cracking of
hydrocarbons starts which yields lower
hydrocarbons and reverse reaction may proceed
with a reasonable speed.
HYDROGENATION

o Temperature is the most important variable


affecting the reaction
o The temperature for most of the hydrogenation
reactions is usually below 400 C
o Practically every hydrogenation reaction can be
reversed by increasing temperature
o Temperature must as low possible where the
rate of reaction will still be satisfactory.
o High temperature may also lower the efficiency
of the catalyst because of sintering
HYDROGENATION

o Catalyst affect only speed and course of a reaction


o Temperature affects the equilibrium position, the
speed and the path of the reaction
o Increasing temperature in hydrogenation adversely
affects the equilibrium position, so the ultimate
yield is decreased; but it affects favorably the
speed of reaction, so that in a given time greater
quantity of product can be obtained
o It is necessary to balance the less favorable
equilibrium position with faster rate of reaction
HYDROGENATION

Effect of Pressure
o Pressure, like temperature can affect the rate
of reaction as well as the equilibrium position
o The rate of reaction in generally increased with
increase in pressure, because a gas phase is
usually present and an increased in pressure
increase the concentration, and in creased
concentration speed up a reaction
HYDROGENATION

o Pressure increases the equilibrium yield in a


hydrogenation reaction where there is decrease
in volume of the reaction as it proceeds.
CO + 2 H2 CH3OH

CH2O + H2 CH3OH
HYDROGENATION

Effect of Time
o Time necessary for a hydrogenation reaction
may vary from a few seconds to several hours,
depending on the materials being
hydrogenated, the catalyst, the temperature,
and the pressure
o In general, the more reactive is the compound,
the faster the hydrogenation reaction
HYDROGENATION

Effect of Ratio of Hydrogen to the substance


o It is generally expressed by the partial pressure
of hydrogen to the partial pressure of the
substance.
o Yield will generally increase if the partial
pressure of hydrogen is much more larger then
the partial pressure of the substance
HYDROGENATION

Liquid or Gas phase reaction


o The hydrogen, the substance being hydrogenated
& the product may exist entirely in the gas phase
or the substance & product may exist in liquid
phase.
o Intimate contact between hydrogen, substance
and the catalyst is necessary.
o Different product may be obtained if the phases
are not the same.
o In liquid-vapor reactions, to get intimate contact,
agitation, stirring or circulation of hydrogen
through the liquid is done
HYDROGENATION

Solubility of hydrogen
o In liquid-vapor reactions, solubility of hydrogen
will increase with the increase in pressure.
o This will lead to more contact between
hydrogen and the substance
HYDROGENATION

MECHANISM
Catalysis
1. Heterogeneous
Processes that use bulk metal or metal on a
solid support, which are examples of
Heterogeneous catalysis
2. Homogeneous
Processes that utilize soluble organometallic
compounds as catalysts fall under the category
of Homogeneous catalysis
HYDROGENATION

How the heterogeneous catalyst works


1. One or more of the reactants are adsorbed on to the
surface of the catalyst at active sites.
2. There is some sort of interaction between the surface
of the catalyst and the reactant molecules which
makes them more reactive.
3. At this stage, both of the reactant molecules might be
attached to the surface, or one might be attached and
hit by the other one moving freely in the gas or liquid.
4. The product molecules are desorbed.
5. Desorption simply means that the product molecules
break away. This leaves the active site available for a
new set of molecules to attach to and react.
HYDROGENATION

Example: The hydrogenation of a carbon-carbon


double bond
CH2 =CH2 + H2 Ni CH3CH3

Ethene molecules are adsorbed on the surface


of the nickel. The double bond between the
carbon atoms breaks and the electrons are
used to bond it to the nickel surface.
HYDROGENATION

Ethene molecules adsorbed on the surface of the catalyst


Hydrogen molecule

Nickel catalyst
HYDROGENATION

Ethene molecules adsorbed on the surface of the catalyst

Hydrogen molecules
adsorbed on the
surface of the catalyst

Nickel catalyst
HYDROGENATION

Hydrogen atom forms


bond with one of the
carbon atom

Nickel catalyst
HYDROGENATION

Another
Hydrogen
molecules
adsorbed on the
surface of the
catalyst

Nickel catalyst
HYDROGENATION

The product
molecule is now
free

Leaving space on the


surface to adsorb more
ethene and hydrogen
molecule
Nickel catalyst
HYDROGENATION

Mechanism of Catalytic Hydrogenation:

H H
B Y
H H
C C
A
X
HYDROGENATION

Hydrogen molecules adsorbed on the surface


of the catalyst
B Y
C C
A
X

H H
H

H
HYDROGENATION

Ethene molecules adsorbed on the surface of


the catalyst

B
Y
A X
H H
H
C C

H
HYDROGENATION

Hydrogen atom forms bond with


one of the carbon atom

B
Y
A X
H H
H
C C

H
HYDROGENATION

Another Hydrogen molecules forms bond


with the other carbon atom

B
Y
A X
H H
C C

H H
HYDROGENATION

The product molecule is now free


B
Y
A X
Leaving space on the surface to
adsorb more ethene and hydrogen
C C
molecule

H H
H H
HYDROGENATION

CATALSYTS
o Hydrogenation catalysts are solids consisting of
metal & metal oxides.
o Hydrogenation is effected at the surface of the
catalyst, so a highly extended surface is essential.
o Usually, the preparation of catalyst is associated
with some chemical reactions whereby a highly
extended, porous, and honeycombed surface is
produced so that the density of the surface metal
is far less than that of the bulk metal.
o Contd.
HYDROGENATION

o Catalyst support or carriers greatly increase the


effective surface area of catalysts.
o The speed of hydrogenation will depend on the
type and amount of active surface available.
o Increasing the ratio of catalyst to the substance
undergoing hydrogenation usually increases
the speed of hydrogenation.
o Contd.
HYDROGENATION

Classification of Hydrogenation Catalysts


1. Vigorous Hydrogenation Catalysts e.g Nickel,
cobalt, or iron type as well as molybdenum and
tungsten oxides or sulfides
2. Mild Hydrogenation Catalysts e.g copper, zinc
oxide, chromium oxide, manganese oxide,
platinum, palladium or their oxides.

Contd.
HYDROGENATION

3. Catalysts with properties other than


hydrogenation e.g sodium. Calcium or barium
carbonates or aluminum or magnesium oxides
4. Sulfides catalysts e.g Molybdenum sulfide and
tungsten sulfide
HYDROGENATION

HOMOGENEOUS CATALYSIS
Strictly speaking, homogeneous catalysis are
catalytic reactions where the catalyst is in the
same phase as the reactants, so homogeneous
catalysis applies to reactions in the gas phase
HYDROGENATION

How the homogeneous catalyst works

1. Binding of the hydrogen to give a dihydride


complex ("oxidative addition"):
Ln M + H2 L n MH2
HYDROGENATION

2. Binding of alkene: The metal binds to both


components to give an intermediate alkene-
metal(H) 2 complex.

Ln M H2 + CH2 =CHR L n-1 MH 2 (CH2 =CHR) + L


HYDROGENATION

3. Transfer of one hydrogen atom from the


metal to carbon (migratory insertion)

L n-1 MH2 (CH2 =CHR) L n-1 M(H)(CH 2 -CH2 R)


HYDROGENATION

4. Transfer of the second hydrogen atom from the


metal to the alkyl group with simultaneous
dissociation of the alkane ("reductive
elimination")
L n-1 M(H) (CH2 -CH2 R) L n-1 M + CH3 -CH2 R
HYDROGENATION
HYDROGENATION

Examples of Homogeneous Catalysts


o Acid catalysis, Organometallic catalysis, and
Enzymatic catalysis are examples of homogeneous
catalysis.
o Most often, homogeneous catalysis involves the
introduction of an aqueous phase catalyst into an
aqueous solution of reactants.
o In such cases, acids and bases are often very
effective catalysts, as they can speed up reactions
by affecting bond polarization.
HYDROGENATION

o An advantage of homogeneous catalysis is that


the catalyst mixes into the reaction mixture,
allowing a very high degree of interaction between
catalyst and reactant molecules.
o However, unlike with heterogeneous catalysis, the
homogeneous catalyst is often irrecoverable after
the reaction has run to completion.
o Homogeneous catalysts are used in variety of
industrial applications, as they allow for an
increase in reaction rate without an increase
in temperature
HYDROGENATION

Equipment used for hydrogenation


Most of the hydrogenation reactions are done at
high pressure where reactor is smaller. Under
such conditions:
1. The reaction velocity is increased
2. Equilibrium positions are made more favorable
3. The reaction path is better defined
4. Side reactions are very few
5. Heating & cooling and heat exchange is easy
HYDROGENATION

INDUSTRIAL REACTORS
o Catalytic hydrogenation is done in a tubular plug-flow
reactor (PFR) packed with a supported catalyst. The pressures
and temperatures are typically high, although this depends on
the catalyst. Catalyst loading is typically much lower than in
laboratory batch hydrogenation, and various promoters are
added to the metal, or mixed metals are used, to improve
activity, selectivity and catalyst stability. The use of nickel is
common despite its low activity, due to its low cost compared to
precious metals.
o Gas Liquid Induction Reactors (Hydrogenator) are also used
for carrying out catalytic hydrogenation.
HYDROGENATION

Substrate Product of hydrogenation

Alkene R2C=CR2 Alkane R2CHCHR2

Alkyne RCCR Alkene cis- RCH=CHR

Aldehyde RCHO Primary Alcohol RCH2OH

Ketone R2CO Secondary Alcohol R2CHOH

Esters RCO2R Two alcohols RCH2OH, ROH

Imine RRCNR Amine RRCHNHR

Amide RC(O)NR2 Amine RCH2NR2

Nitrile RCN Imine RHCNH Easily hydrogenated further

Nitro RNO2 Amine RNH2


HYDROGENATION

Two Ways to Add Hydrogen:


H H
Hydrogenation:
A Y A Y
Addition across Pi bonds
Hydrogenolysis:
Cleavage of Sigma bonds A X A X
H H
HYDROGENATION

Discrimination dependent upon:


Metal
Support
Solvent
Temperature
Presence or absence of poisons
Promoters
Catalyst Inhibitors and Poisons
o Inhibitors diminish the rate , but the effect can be
reversed by washing it away.
o Poisons exert an appreciable inhibitory effect when
present in small amounts.
o Both can be used to fine-tune the selectivity of a catalyst
HYDROGENATION

Rate of reduction dependent upon:


Catalyst preparation
Time (in hours) since prep. of catalyst

Pressure

Temperature

Loading of catalyst
FACTORS AFFECTING HYDROGENATION

Selectivity Ratio Trans Content Reaction Rate

Temperature

Pressure

Agitation

Catalyst
HYDROGENATION

SELECTIVITY IN HYDROGENATION
Selective hydrogenations are done either by
1. Making the proper choice of catalyst,
temperature, pressure & solvent ( and thereby
a difference in reaction rate)
2. By interrupting the reaction when the desired
amount of hydrogen has been absorbed
HYDROGENATION

HYDROGENATION REACTIONS
Acetylene:
2 moles of hydrogen can easily be added to such
compounds under catalytic conditions to give
corresponding saturated derivatives.
RCCR + H2 RCH=CHR + H2
Olefin
RCH2CH2 R
Alkane
where R & R may be aliphatic, aromatic or other groups

Under proper conditions reaction can be stopped at


intermediate olefin stage
HYDROGENATION

Acetylene cntd.

Selective hydrogenation of the acetylene to


ethylene is done by passing the mixture of
acetylene and hydrogen( 10 to 35 % ) over a
catalyst at a temperature ranging from 200 to
315 C and at pressures of 45 155 psig
HYDROGENATION

Olefins:

Olefins undergo catalytic hydrogenation readily . The


catalysts used are nickel or nickel containing catalyst
and some time platinum or palladium
HYDROGENATION

Aromatics:
Such compounds generally require temperatures
above 180 C for complete hydrogenation over
nickel catalyst.
Since olefins readily hydrogenate at a much lower
temperature so that it can easily be differentiated
between the olefinic double bond or aromatic
double bond hydrogenation
HYDROGENATION

Carbonyls (Aldehydes & Ketones):


They can be easily reduced by catalytic
hydrogenation in the presence of mild catalysts
The product of the reduction of an aldehyde is
a primary alcohol
The product of the reduction of a ketone
a secondary alcohol.
RCOR + H2 RCHOHR
Where R is an aliphatic or aromatic group and R
may be the same or H
HYDROGENATION

Esters & Acids:


Such chemicals react with hydrogen in the
presence of a catalyst according to the general
equation:
RCOOR + H2 RC H2 OH + ROH
HYDROGENATION