Unit 1 Fundamentals of Process Chemistry

Lesson 4 Reduction
Catalytic Hydrogenation
 reaction of a substrate with molecular hydrogen in the presence of a catalyst.
Advantages
 Higher yield of the desired reduction product
 the simplest in procedure

Types
(1) Hydrogenation
 hydrogen simply adds to a molecule
 Highly exothermic
(2) Hydrogenolysis
 molecules are cleaved by hydrogen
Both of them may overlap depending on the process conditions.
Catalytic hydrogenation is used extensively in industrial processes.
Catalytic Hydrogenation
 Earliest industrial application of hydrogenation was in fat hardening:
Hydrogen is added to the double bonds between carbon atoms in liquid fats to
convert into solid fats.
 Industrially important catalytic hydrogenations
(i) hydrogenation of nitrogen to ammonia.
(ii) petroleum processing
Ex: Hydrotreatment, hydrocracking
(iii) Fat hydrogenation
(iv) hydrogenation of CO to methanol
(v) hydrogenation of fatty acids to fatty alcohols: to prepare sulfuric acid esters
used as high performance surfactants.
(vi) adiponitrile to hexamethylenediamine (used in the synthesis of nylon-6,6)
(vii) benzene to cyclohexane (used in the synthesis of nylon-6)
Catalytic Hydrogenation
Heterogeneous catalysts
 Most of the catalytic hydrogenation employs heterogeneous catalysts.
1. Selective hydrogenation of acetylenes to olefins
 Ethylene feedstock to polyethylene plant must contain less than 10 ppm of
acetylenes [acetylene & methyl acetylene (CH 3C≡CH)] and propadiene (CH=C=CH)]
Catalyst requirement:
 Selectively hydrogenates acetylene to ethylene.
 Does not destroy ethylene by hydrogenation to ethane or oligomerization to oil.
 Ability to withstand sulphur poisoning.
Catalyst: Cobalt molybdate on alumina, Nickel oxide/cobalt oxide/chromia on
Silica-alumina, Pd/Al2O3
 Selectivity of Pd/Al2O3 increased by adding Ag or Cu and by introducing traces of CO
in the feedstock.
 Providing coolers between catalyst bed to control temperature and increase
selectivity.
Catalytic Hydrogenation
2. Partial hydrogenation of diolefins to monoolefins
 Diolefins are highly reactive and hence an undesirable component.
 Diolefins are undesirable to be present in feedstock for alkylation unit of linear
alkyl benzene (LAB) manufacturing.
 Low-temperature selective hydrogenation converts dienes to olefins.
Catalysts
 Palladium supported on γ-alumina and promoted with chromium oxide is active
and selective when sulphur compounds (Mercaptans, organic disulfides) are
minimum.
 Nickel oxide supported on γ-alumina and Nickel oxide/tungsten oxides supported
on alumina are active even in the presence of sulphur compounds.
Catalytic Hydrogenation
3. Hydrogenation of aromatics
Ex: (i) (ii).

 Cyclohexane and cyclohexanol are raw materials for Nylon production.

(iii).
Aniline is the raw material for polyurethane
production.
(iv). Hydrogenation of aromatics to naphthenes in diesel for increasing its cetane
number and to meet the benzene limit (1 Vol%) in petrol.
 Supported nickel is the most widely used catalyst.
 Platinum catalyst (reaction i), palladium supported on a calcium oxide/alumina
(reaction ii), copper chromite (reaction iii) are the other catalysts used for specific
reactions.
Catalytic Hydrogenation
4. Hydrogenation of Oil
 First large scale industrial application of catalytic hydrogenation.
 Hydrogenates unsaturated liquid fats (glyceride esters of unsaturated fatty acids of
C16 – C20) to saturated solid fats and also removes the unpleasant odor.
 Melting point and the resistance of fat to oxidation increases with decrease in
unsaturation and increase of trans isomers.
Catalyst requirement
 High selectivity to convert oil containing three double bonds (Linolenic acid esters)
to two (Linoleic acid esters) and one double bond (Oleic acid esters) but not
completely saturated (Stearic acid esters).
 isomerize cis isomers to trans isomers
Catalyst: Pre-reduced nickel/kieselguhr earth coated with a layer of solid fat.
Catalytic Hydrogenation
5. Production of fatty alcohols
 used as plasticizers or in the production of alkyl hydrogen sulphates used as
detergents.
 Produced by hydrogenation of fatty acid methyl esters (FAME) obtained by
transesterification of fat with methanol (or) fatty alcohol esters of fatty acids
obtained by hydrolysis of fat.

Catalyst:
 Copper chromite (or) Copper oxide/zinc oxide for the hydrogenation of both acid
group and double bonds.
 Selective zinc chromite catalyst is used when an unsaturated fatty alcohol is to be
produced.
Catalytic Hydrogenation
Homogeneous catalysts
 In homogeneous catalysis, all the reactants and catalysts are present in a single fluid
phase and usually in the liquid phase.
 Contribution of homogeneous catalytic hydrogenation in chemical industry is smaller
compared to heterogeneous catalytic hydrogenation.
 Recovery of homogeneous catalyst from the reaction mixture is extremely difficult and
hence its reuse.
 Significance of homogeneous catalysis is growing rapidly particularly in the area of
pharmaceutical industry due to high activity and selectivity.
(i) Chemoselectivity
 selective hydrogenation of one functional group in presence of the other group.

Products II & III

are
chemoselective.
Catalytic Hydrogenation
(ii) Diastereoselectivity: Giving diastereomers and not enantiomers as product.
Diastereomers are stereoisomers
of a compound that are not mirror
images of each other.

(iii) Enantioselectivity: Giving only one of the enantiomer as the product.

Enantiomers are non-

superimposable mirror
images of stereoisomers of a
compound.
Catalytic Hydrogenation
Homogeneous catalysts
 most effective is Wilkinson’s catalyst [RhCl (PPh3)3], where PPh3 is triphenyl phosphine
ligand. Only diastereoselective, since does not contain optically active ligand.
1.Initial dissociation of one of
the triphenylphosphine ligands
to give 14- electron complexes.
2. Oxidative addition of H2 to
the metal.
3. π-complexation of alkene.
4. Intramolecular hydride
transfer (olefin insertion),
forming alkyl complex.
5. Reductive elimination results
in release of the alkane
 product.
Catalytic Hydrogenation
 In pharmaceutical industry, asymmetric hydrogenation by enantioselective catalyst is used
to produce enantiomerically pure compounds having desirable clinical properties.
 Enantioselective catalyst: Metal complexes containing optically active ligand.
Ex: Rhodium complex containing optically active R-prophos as ligand gives L-dopa and S-
prophos gives D-Dopa. Because step 2 and 3 in the catalyst cycle are interchanged.

Hydrolysis

L-dopa, Drug for treating Parkinson’s disease

D-Dopa (inactive)
 Ruthenium complexes containing optically active ligands are effective for ketone
hydrogenation to alcohols.
Hydrogen transfer reactions
 saturation of double bonds by the transfer of hydrogen from one substance to
another without the involvement of free molecular hydrogen.
1. Naphthenes + Olefins → Aromatics + Isoparaffin
 distinct from hydrogenation and proceeds by an ionic mechanism over an acid
catalyst (Ex: silica-alumina containing 60-90% silica )
 important in the petroleum industry for reducing the olefin content of cracked
gasoline.
2. Alcohols + Olefins → Aldehydes or ketones + Paraffin
 Over copper-zinc-nickel-barium chromate as the catalyst
Metal Hydrides
 Most reductions of carbonyl compounds are done with metal hydrides.
 Provide certain chemo- and stereoselectivity.
 Lithium aluminum hydride and Sodium borohydride are the most widely used.
 LiAlH4 is a very powerful and unselective reducing reagent.
 rapidly reduces esters, acids, nitriles, amides, aldehydes and ketones

 Sodium borohydride (NaBH4) is a mild reducing agent that reduces aldehydes and
ketones rapidly but the esters only slowly.
 The difference in the reactivity of these two metal hydrides is due to the
properties of both the cations and the anions.
 Lithium ion is a stronger Lewis acid than sodium ion; AlH 4− is a more reactive
hydride donor than BH4−.
 Neither sodium borohydride nor lithium aluminum hydride reacts with
isolated carbon-carbon double bonds.
 Chemoselectivity of these reagents are improved by replacing some of the
hydrogens of LiAlH4 with alkoxy groups.
Case study on industrial reduction process
Hydrogenation or Hardening of Fats
Hydrogenation of vegetable and animal oils are aimed at
(1) producing a hard fat of greater consistency than the original liquid oil
(2) removing certain impurities that are not removable by any other means, thus
rendering the oil useful.
 It hydrogenates the glycerides of the polyunsaturated fatty acids into glycerides of
less unsaturated acids in stages.
 Carried out at 100-250°C and 200 psi, with nickel as a catalyst.
CH2OOCC 17H29 CH2OOCC 17H31 CH2OOCC17H33 CH2OOCC17H35

| | 3H2 | 3H2 |
CHOOCC 17H29 + 3H2 → CHOOCC 17H31 → CHOOCC17H33 → CH2OOCC17H35
| | | |
CH2OOCC 17H29 CH2OOCC 17H31 CH2OOCC17H33 CH2OOCC17H35
Trilinolenin Trilinolein Triolein Glyceryl tristearate
Hydrogenation or Hardening of Fats
 Degree of hydrogenation is determined by the melting point, iodine-absorption
number, or refractive index.
 Having glycerides of polyunsaturated acid (Ex: linolenic acid and linoleic acid) in diet
is important to avoid health issues like scaly skin, cardiovascular diseases.
 Along with hydrogenation, isomerization of natural low-melting cis form to high
melting trans forms also occurs.
H H
Ex: Triolein | |
CH2OOC(CH2)7CH=CH(CH2)7CH3 M.Pt of Cis form 13oC; - C=C-
| H

CHOOC(CH2)7CH=CH(CH2)7CH3 |
| M.Pt of trans form 45 oC; - C=C-
CH2OOC(CH2)7CH=CH(CH2)7CH3 |
H
Hydrogenation or Hardening of Fats
 Oils must be free from impurities that poison the Ni catalyst.
Ex: Organic sulfur compounds; oxidized unsaturated fatty compounds; colloidal
suspensions of protein; moisture; free higher fatty acids.
 Types of processes
(i) Suspended Catalytic process (ii) Fixed bed continuous catalytic process.
Suspended Catalytic process
 Reactor is a cylindrical vessel of 10 to 20 ft height, fitted with baffle plates ,
 Finely divided nickel obtained by the decomposition of Nickel formate, supported
on inert materials such as clays, kieselguhr, charcoal, or pumice is the catalyst.
 Catalyst suspended in oil enters at the top, and hydrogen gas enters from the bottom
of the reactor and flow counter currently.
 Baffle plates, rotates the oil and gas mixture alternately in opposite directions,
causing their intimate contact and hydrogenation.
 The down flowing oil is recirculated by the pump.
Hydrogenation or Hardening of Fats
Suspended Catalytic process
 Enlarged section at the top effects the
separation of the intimate hydrogen-oil
mixture.
 Hydrogen is withdrawn at the top of the
apparatus, repressurized by the gas
compressor, and returned to the
bottom of the reactor.
 A steam jacket heats the charge to
maintain the temperature.
 Rapid hydrogenation occurs in
15-25 min, for peanut or cottonseed oil.
 Molten hydrogenated fat is filtered to
separate the catalyst, regenerated and
reused.
Hydrogenation or Hardening of Fats
Fixed bed continuous catalytic process
 Rigid nickel catalyst in the form of turnings or wire, prepared by anodic oxidation of
nickel, followed by reduction with hydrogen under carefully controlled conditions.
 Reactor is cylindrical, vertically mounted and the catalyst is packed into the reactor
as fixed bed, supported by a grid at the bottom of the reactor.
 Oil goes through a distributer plate on top of the catalyst bed, which distributes
the liquid evenly over the bed.
 Oil trickles down through the bed.
 Hydrogen also enters from the top and flow in the co-current direction of the oil.
 Both oil and hydrogen get adsorbed on the catalyst surface and hydrogenation
occurs.
Fixed bed continuous catalytic process
Fixed bed continuous catalytic process
Advantages
• Low investment cost.
• No filtration needed to separate the catalyst.
• Low running costs.
• Large production volumes are easily achievable.
• Long catalyst life: 5 years
Disadvantages
• Selective (partial) hydrogenation not possible, but quite suitable for complete
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.
Thank You