HYDROGENATION

Group#3
Muhammad Bilal 2017-CH-738
Awais Muazzam 2017-CH-734
Mahwish Ismail 2017-CH-704
Junaid Anwar 2017-CH-716
Rana Abu Bakar 2017-CH-729
Contents
 Introduction
 Components of Hydrogenation
 Behavior with Different Functional Groups
 Types of Catalysts
 Hydrogenation of gas oil
 Synthesis of methanol
 Applications
 Advantages and disadvantages
 HYDROGENATION

Generally, It is
Specifically refers to a chemical reaction of an
unsaturated element or compound with molecular
Hydrogen, in the presence of a catalyst.
In terms of Reduction,
Hydrogenation is synonymous to Reduction, in which
mostly Oxygen or some other element(N, S, C etc.) is
withdrawn OR Hydrogen is added to the molecule.
Catalytic Hydrogenation

The addition of Hydrogen to an unsaturated system

in the presence of a catalyst OR addition of molecular
Hydrogen as a reduction on metal.

Almost all Alkenes can be saturated in a very high

yield by treatment with Hydrogen and a metal catalyst. It
is an exothermic reaction.
 Components

Hydrogen Catalyst
Source
Substrate
Hydrogen Sources

 From Hydrocarbons & Steam

 From Steam & Iron
 From steam & Methanol
 From Ammonia
 Behavior with Different Functional
Groups
 Alkenes Alkanes
 Alkynes Alkanes
 Aldehydes Primary Alcohols
 Ketones Secondary Alcohols
 Carboxylic Acid Primary Alcohols
 Esters Alcohols
 Nitro Alkenes Primary Amines
 Nitriles Primary Amines
 Acyl Halides Alcohols
 Types of Catalyst
 Homogeneous Catalysts
Reaction Mixture
and the catalyst are of same phase,
That we dissolve in our substrate as
a homogeneous solution e.g.
Wilkinson’s Catalyst
 The reaction occurs in liquid or
gaseous phase
 The catalyst is involved in
chemical reaction
 Heterogeneous Catalysts
Reaction Mixture
and the catalyst are of different
phases, That we actually suspend in
our substrate solution e.g. Pt. metal
plate
 The reaction occurs on the surface
of solid.
 The catalyst absorbs the reactant
molecules forming chemical bond.
Examples of Catalysts
 Wilkinson’s Catalyst
 Raney Nickel
 Palladium
 Adam’s Catalyst
 Chromium Oxide
 Cobalt Oxide
 Alumina
 Copper Chromite
 Rhodium
 Triethylamine
 Thermodynamics & Kinetics of hydrogenation

Factors affecting the hydrogenation reaction are:

 Temperature
 Pressure
 Catalyst surface
 Time
 Ratio of hydrogen to substance being hydrogenated
 Temperature Effect

 Most hydrogenation temp is below 400°c

 But some cases it exceeds to 500°c (pyrolytic decomposition)
 Direction can be reversed by increasing temperature
 So the reaction necessarily occur at low temperature ,where
the reaction is satisfactory.
 Catalyst effect the speed and course of reaction while
temperature affects the equilibrium.
 Increase in temperature adversely affect the equilibrium
position which affect the maximum ultimate yield
 But it affect the speed of reactions ,so that in given time
greater quantity of product can be obtained.
 In some case the increase in temperature cause the
sintering effect in which the catalyst activity decreased
,rate of reaction decreased.
 Pressure Effect

 Rate of reaction increased by increasing pressure for

gaseous reaction ,concentration increased by increasing
pressure
 Phenol is hydrogenated very slowly at 150 °c and
atmospheric pressure but at 15 atm and same temperature
the reaction rapidly complete
 Catalyst Surface
 Hydrogenation affected at the surface of the catalyst
 Honey womb like porous catalyst is prepared chemically
 Promoters is added to the surface of catalyst to increase the
activity of the catalyst
 It can cause sintering effect which is the lowering of
activity of catalyst when coating is fused in the pores of
catalyst hence the rate of reaction is decreased
 The speed of hydrogenation depend upon the type and
active surface available
 Time

 The time is necessarily for hydrogenation

 It varies from seconds to several hours
 In general the more active the compound ,the faster the
hydrogenation take place
 Aldehydes is hydrogenated readily while hydrogenation of
aromatic ring or ester is slower reaction
 Ratio Of Hydrogen To The Substance

 Ratio of hydrogen to the substance being hydrogenated is

expressed in terms of partial pressure
 Speed and path of a certain hydrogenation can be affected by
the proportion of hydrogen to the substance
 It has been found that ethyl lactate and malonate are reduced
to their corresponding alcohol in good yield in a flow
systems at pressure of about 1300 psig ,practically the entire
pressure is hydrogen and partial pressure of esters is about
centimeters
 Hydrogenation Of Gas Oil
 Raw material:
Gas Oil
Hydrogen
Catalyst
 Reaction condition:
100-250 atm pressure
400-500◦ C temperature
 Catalyst
 the catalyst employed in the reaction chamber are very
stable physically and chemically and are not harmed by
the normal constituents of oils including sulfur
compounds.
 It is evident that molybdenum and the tungsten sulfides
are effective catalyst for converting gas oil into the lower
molecular weight and more saturated products. Such
catalyst are affected by sulfur compounds in the oil.
 When the oil is sulfur free, the nickel type catalysts are
frequently used.
 Otherwise metal sulfide or oxide types that are sulfur
resistant have to be employed.
 The life of catalyst may be extended to a year or more.
 Process description

 The oil is fed to the system by the high pressure pumps,

and the oil is brought to the reaction temperature by
specially designed heat exchanger and by heating in a
direct fired high pressure coil or heater.
 It is mixed with fresh hydrogen that has been separately
compressed to the operating pressure.
 The hydrogenation take place in a high pressure reaction
chamber containing the catalyst.
 There is a net evolution of heat as the reaction is
exothermic.
 To control the temperature, the intermediate cooling is
sometimes effected by adding the cold recycle gas at
suitable points in the reactor.
 After exchanging its heat with the entering mixture of oil
and hydrogen, the reaction product passes through the
cooler to a high pressure gas separator where the recycle
gas consisting mainly of hydrogen is removed.
 Synthesis of methanol
 Raw material:
Carbon monoxide
Hydrogen
Catalyst
 Reaction condition:
300◦ - 400 ◦ temperature
1000 psig pressure
 Catalyst

 The catalyst usually consist of the metal and metallic

mixtures, the most common constituents being copper
with oxides of zinc, chromium, magnesium, and
aluminum.
 Zinc chromate is the typical of the catalyst used.
 Reaction kinetics

Co + 2H2 CH3OH
 This is a reversible reaction.
 The equilibrium constant for this small and decrease
rapidly with the temperature.
 The temperature below 300◦ the rate of reaction is very
slow.
 The temperature above 400 ◦ becomes unfavorable.
 Pressure shift the reaction to the right direction or higher
conversion.
 Thus at the 300◦ and 3500 psig using one volume of
carbon monoxide to the two volume of the hydrogen the
equilibrium yield is 60%
 Process description
 Preparation of carbon and hydrogen mixture
 Tradionally it was prepared from the coke,
steam and air by using the water gas method.
 Now this method has been replaced by the
partial oxidation of natural gas and by the steam
hydrocarbon reforming.
 The cost of synthesis gas is a major item. It is generally
believed that the gas is compressed to several hundred
pound of pressure than atmospheric pressure
 Cont.……
 catalyst is contained in a special reactor to withstand the
temperature and pressure conditions.
 By a heat inter-change either in a reactor or in a special heat
exchanger the heat of reaction absorbed.
 Some of this is used to heat the gas to its reaction
temperature.
 And the gas is passed into the reactor containing the catalyst.
 Reaction take place and the methanol containing gases
leaves the reactor and after passing trough a heat
exchanger and finally to the condenser where methanol is
condensed usually at full operating pressure of 3000-4000
psig.
 Any drop in the pressure of the rector and the cooler is
repressured by the booster compressor.
 If mixture other than ratio 1:2 is used, the composition of
the gases must be continually adjusted as it is recycled.
 For the synthesis of methanol alone the contact of hot
gases with the iron must be prevented. in this case the
reactor are usually lined with copper or other material not
affecting the catalyst.
 With the proper catalyst and the exclusion of the sulfur
and iron, the methanol of 99 per cent purity or better can
be produced.
Applications of Hydrogenation
 Hydrogenation is done at laboratory or industrial level.
 In laboratory it is used in chemical synthesis, as a basis
for many analytical procedures and as a research tool in
the identification and determination of the structure of
organic compounds.
 Applications of Hydrogenation

 In industry, large quantities of hydrogen consumed in the

manufacturing of Ammonia, methanol, liquid fuels,
hydrogenated vegetable oils.
 It is also used in the petroleum processing.
 Further, coal hydrogenation is use in the manufacturing of
fuels and chemicals.
 In food industry, it is used in the manufacturing of vegetable
oil from unsaturated
 Applications of Hydrogenation
 The Commercialization of hydrogenation developed over
the years with the work of:
 Haber in ammonia synthesis.
 Bergius in coal and heavy oil hydrogenation.
 Fischer and Tropsch in fuel synthesis.
 Advantages of hydrogenation
 Hydrogenation changes a liquid oil to semi-solid or solid,
to make the melting point of an unsaturated fat more like
that of a saturated fat(increase the melting point).
 Decrease the rate of oxidation (stability increases with
increasing saturation).
 Increases hardness.
 Disadvantages of hydrogenation
 Mono and poly-unsaturated fats are healthier for the heart
than saturated fats.
 In the partial hydrogenation ,trans fats can form.
 Trans fat are hard to metabolize, accumulate in fatty
tissue, and are more difficult to excrete from the body.
 Trans fats also increase levels of cholesterol and are a low
quality energy source.