Unit – II

Process in organic chemical manufacture-II

Hydrogenation

The term hydrogenation refers to the chemical reaction of a substance with molecular

hydrogen in the presence of a catalyst. This process includes reactions in which hydrogen

simply adds to a molecule (hydrogenation), reactions in which molecules are cleaved by

hydrogen (hydrogenolysis of destructive hydrogenation) and also reactions such as

isomerisation, crystallization and like which occur in presence of molecular hydrogen and

catalyst.

Hydrogenation is synonymous with reduction, which is the term usually applied to a

reaction in which oxygen or some other element is withdrawn or hydrogen is added to a

molecule. A number of methods have been used for this purpose. Catalytic hydrogenation is

the simplest one with high yield. Examples of important method of reduction other than

catalytic hydrogenation are: (i) by metals in acids or basic solution, (ii) by alkali metals in

alcoholic solution, (iii) by electrolysis, (iv) by alkali metals and hydrazine, (v) by complex

metal hydrides and (vi) by hydrogen transfer.

Of the above method catalytic hydrogenation is confused with hydrogen transfer,

which involves the saturation of ethylenic double bonds by the direct exchange of hydrogen

generally from one substance to another with no participation of free molecular hydrogen.

Hydrogen transfer reaction is important in petroleum industry, especially in exchanging

hydrogen from naphthenes to olefins to prepare aromatics and isoparaffins.

Alcohol also undergoes a similar hydrogen-exchange reaction with ethylene as the

acceptor to give aldehydes or ketones in yields of 40-75%. The reaction takes place at

atmospheric pressure, at a temperature of about 280 ºC with copper-zinc-nickel-barium

chromate as catalyst.

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Survey of hydrogenation

Catalytic hydrogenation is used extensively both in laboratory and in industrial

processes. In laboratory, it is used in chemical synthesis, as a research tool in the

identification and determination of structure of organic compounds. In industry, large

quantity of hydrogen are used in the manufacturing of ammonia, methanol, liquid fuels,

oxygenated compounds, hydrogenated vegetable oils and a variety of organic chemicals.

Increasing quantities of hydrogen are being used for petroleum processing and in future

additional quantities may be demanded for coal hydrogenation to produce fuel and chemicals.

The earliest technical application of hydrogenation was in the reduction of double

bonds between two carbon atoms for the purpose of converting liquid fats into solid fats also

known as fat hardening. The commercialization of hydrogenation developed over the years

with the work of Haber in ammonia synthesis, Bergius in coal and heavy oil hydrogenation

and Fischer and Tropsch in fuel synthesis.

Coal hydrogenation

The destructive hydrogenation of coal to produce gasoline has been undertaken at

various times. Initial work of Bergius, brown coal was first hydrogenated commercially in

Germany in 1927 followed by the first plant processing bituminous coal in Great Britain in

1935. Bituminous coals having lower hydrogen content than brown coals are more difficult.

Coal or hydrogenation of coal involves raising the atomic hydrogen to carbon ratio.

Coal can be converted to liquid and gaseous fuels by direct and indirect processing.

Hydrogenation of coal is also called liquefaction of coal. The source of coal is from various

coal mines.

Hydrogenation reaction:

4(C3H4)n + nH2 nC6H6 + 5nC + nCH4

Powdered coal Aromatic liquid Hydrocarbon

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This is highly exothermic reaction.

Process flow sheet: Illustrated in Figure.

Functional role of each unit:

(a) Coal storage vessel:

 Here pulverized coal is stored.

 Produced coal is fed to the preheater by a screw conveyor.

 Hydrogen gas stream is added to the fed.

 Hydrogen is obtained from any dehydrogenation process or any other hydrogen synthesis

process.

 Pressure equalizing line is used to maintain pressure of reaction mixture stream with the

help of valve.

(b) Preheater:

 Powdered coal and hydrogen are the raw material fed to the preheater.

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 Optimum temperature is required for reaction so reaction mixture is preheated instead of

feeding it in reactor directly.

 Heat required for preheating is supplied by furnace.

 In furnace, combustion of fuel gases is occurring and all hot gases from furnace are passed

from preheater.

(c) Reactor:

 Temperature is maintained at 400-1000˚C and pressure of about 500 to 3000psi.

 The residence time is about 1 to 10 minutes.

 Since reaction is highly exothermic, so cooling jackets are used to control temperature of

reactor.

 Catalyst used is 1% tungsten or molybdenum oxide.

 Catalyst solution is made for reaction.

 The products from the reactor then pass to cyclone.

 There will be liquid aromatics along with unreacted coal and hydrogen in stream leaving

the reactor.

(d) Cyclone:

 Solids as bottom product are removed.

 Hot reaction mixture from the reactor is fed to the cyclone for separation of solids and

gases.

 Gaseous mixture leaving cyclone contain aromatics, unused hydrogen and small amounts

of light hydrocarbon and carbon dust.

 Temperature of the leaving stream is about 700˚C.

(e) Scrub quenching tower:

 The gases from cyclone are at very high temperature.

 Sudden cooling of gases or quenching of gases is done in this tower.

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 Quenching and absorption both are done simultaneously.

 Water scrub carbon dust from gaseous mixture.

 Stream leaving mainly contain aromatics, hydrogen and other hydrocarbons.

(f) Condenser:

 All the gaseous mixture from the scrubber is fed to the condenser to condense aromatic

liquids.

 The stream leaving the condenser, the aromatics are in liquid form, whereas, hydrogen and

other hydrocarbons are in gaseous form.

(g) Separator:

 This unit separate aromatic liquids from other gaseous impurities.

 Hydrogen and other lighter hydrocarbons (gaseous form) are obtained as top product and

aromatic liquids are obtained as bottom product.

(h) Distillation tower:

 Light oil and heavy oils are separated by distillation tower as top and bottom product

respectively.

 The process occurs at high pressure. So at first, pressure is reduced before distillation by

pressure reducing valve.

 Reduction in pressure increases relative volatility of heavy oils and light oils.

 Lower temperature and less residence time reduces thermal degradation of aromatic oils.

Because the relative price of coal and oil have changed so that the coal hydrogenation

is no longer economical. Coal hydrogenation to produce motor fuel is not yet economical,

even various by-product chemicals such as phenols, cresols, xylenols, toluene, xylenes,

naphthalene and liquefied hydrocarbons gases.

Petroleum hydrogenation

Before 1950, hydrogenation played only minor role in petroleum technology because

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of preventive cost of hydrogen. The outstanding exception was the hydrogenation of high-

octane olefinic fractions for the production of aviation naphthas during World War-II.

However, with the advent of catalytic reforming processes by which heavy naphthas are

upgraded in octane value, large quantities of by-product hydrogen became available to

petroleum industry and this hydrogen is being used for the improvement of wide range of

products. At the end of 1956 about 70,000 tons per year of hydrogen was consumed for this

purpose. At present large portion of this hydrogen is being diverted to ammonia synthesis.

Mild 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.

The mild hydrogenation process is more advantageous and replaces many other less efficient

methods for removing sulphur compounds improving color and odour and increasing the

storage stability of the products.

The synthetic ammonia process represent at present the largest single demand for

hydrogen followed by petroleum processing, fat hydrogenation and synthetic methanol.

Fat hydrogenation

Fat hydrogenation is the addition of hydrogen to fatty acids particularly edible oil

such as cottonseed and soybean. In 1956, in United States the output of hydrogenated fat

amounted to about 1.5 million tons. The fats resulting from the hardening of whale oil, fish

oil and vegetable oil such as linseed, soybean and cottonseed oil by addition of hydrogen

under pressure are of two types:- edible oil and nonedible oil. The edible oils are used as lard,

butter substitute and shortening composition in the baking industry and for the manufacturing

of creams and coatings for confections. The soap industry is the largest consumer of

nonedible oils. Minor uses of nonedible oil are in leather dressings, electrical insulations,

candle making, paint industry and pharmaceutical ointments.

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Other hydrogenation

Synthetic methanol consumes much hydrogen, in 1956 the rate of synthesis of

methanol was about 800,000 tons per year and hydrogen consumption rate was about 100,000

tons. The hydrogenation and hydrogenolysis of carbohydrates such as glucose, sucrose, starch

and other saccharides have been treated with hydrogen at 100-250 ºC and about 80-300 atm

pressure using Ni, Fe and Cu catalyst to produce propylene glycol and glycerol. By a two

stage hydrogenation of hexose, 1530 tons of glycerogen containing 40% propylene glycol,

40% glycerol and 20% hexyl alcohol was produced during World War II.

In the manufacture of many chemicals there are many examples in which hydrogen is

required. Most important use of hydrogenation in aldol process for producing alcohols having

chain of four to eight carbons. Other organic chemical being hydrogenated are glycolic acid

to make ethylene glycol, adiponitrile to hexamethylenediamine, dextrose to sorbitol, phenol

to cyclohxanol and cyclohexanone and naphthalene to tetralin and decalin.

Hydrogen is also used in the conversion of benzene to cyclohexane and of acetylene

derivatives to butanediols. In food industry, hydrogen is used to remove acids from fatty oils.

Catalytic hydrogenation has been applied to materials of widely varying molecular weight

and structure. Thus, materials such as wood, rubber, vitamins, protein, steroid, elastomers,

cotton linter and nylon are such typical compounds undergoes to reaction. Nitric oxide on

hydrogenation over a platinum carbon catalyst yields hydroxylamine.

Catalyst used in hydrogenation

Number of catalyst capable of effecting hydrogenation is large, in addition many

types of hydrogenation are possible. Any type of unsaturation can be hydrogenated

catalytically. Hydrogenation may involve the saturation of a carbon to carbon linkage or the

reduction of carbonyl or carboxyl or hydroxyl group and may involve the breaking of carbon

to carbon linkage as in hydrogenation of coal and mineral oils.

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Hydrogenation catalyst may be classified as:

1. Vigorous hydrogenation catalysts

2. Mild hydrogenation catalysts

3. Catalyst with properties other than hydrogenation

4. Sulphide catalysts

Vigorous hydrogenation catalysts

These types of catalyst carried the hydrogenation process to the greatest extent so that

the maximum addition of hydrogen to the compound occurs under the particular operating

condition. Cracking tendencies (breaking of bond such as carbon to carbon) are usually

associated with this class of catalyst, although cracking can be suppressed by controlling

temperature and pressure. Common catalyst belongs under this category are nickel, iron,

cobalt as well as molybdenum and tungsten oxide or sulphides. Raney nickel is generally

used catalyst for the hydrogenation of alkyne and alkene linkage, aldehyde, ketone, nitro

compounds, nitriles, oximes and phenyl.

Mild hydrogenation catalysts

These catalysts affect the hydrogenation process as rapidly as vigorous hydrogenation

catalyst, but these catalysts are able to carry out only one step at a time in hydrogenation or

do not permit the reaction to proceed the hydrocarbon stage. These catalysts easily reduce an

aldehyde or ketone to alcohol, ester, or an acid. Large number of catalyst is developed for the

direct synthesis of methanol from water gas. Catalyst belongs to this categories are copper,

zinc oxide, chromium oxide, manganese oxide and noble metal catalyst such as platinum or

palladium or their oxides. Vanadium oxide is widely used as oxidation catalyst (also reported

as sulphur resistant catalyst) for hydrogenation of unsaturated hydrocarbon (high temperature

around 400 ºC is required).

Catalysts with properties other than hydrogenation

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 Synthesis of higher alcohol form water gas involves condensation as well as

hydrogenation reaction. These higher alcohol catalyst are usually of the mild hydrogenation

type but contain some more alkaline materials, such as sodium, calcium, barium carbonates,

aluminium or magnesium oxides. Other types of catalysts are capable of splitting out water

from a molecule along with the hydrogenation but do not posses any appreciable cracking

tendencies. These are usually vigorous hydrogenating catalyst but sometimes preponderating

quantities of dehydrating catalyst such as alumina, thoria, tungstic oxide or chromium oxide.

They can effect the reductions such as phenol to benzene, cresol to aromatic hydrocarbon and

also convert various hydroxyl compounds to hydrocarbons with little or no change in

molecular structure.

Sulphide catalyst

Molybdenum sulphide and tungsten disulfide are active catalyst for hydrogenation at

pressure in the range of 3000 psi. The hydrogenation reaction catalyzed by molybdenum

compounds are:

 Reduction of unsaturates

 Cleavage of C – C, C – S, C – O, C – N linkage

 Reduction of nitro compounds to amines

 Dehydroisomerisation

Metal sulphide catalysts also have a remarkable activity and selectivity or hydrogenating

certain polyolefines to monoolefins. Such catalysts are active at low temperature.

Hydrogenation of oil

Purpose of hydrogenation of oil is to produce a hard fat or one of the greater

consistency than the original liquid oil and also to remove certain impurities that are not

removable by other means. This process involves the conversion of glycerides of unsaturated

fatty acids to glycerides of saturated fatty acids.

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 (C17H33.CO.O)3C3H5 + 3H2 (C17H35.CO.O)3C3H5

Reaction condition

Temperature – 100-250 ºC

Pressure – 200 psi

Catalyst – nickel

Lower temperature is favourable in order to minimize the undesirable side reaction.

Importance of hydrogenation

Conversion of low melting oleic acid which has the cis form to elaidic acid or other

high melting trans form generally referred as iso-oleic acid.

When oils are completely hydrogenated solid product obtained and when oils are

partially hydrogenated fats of various melting points are obtained. Degree of hydrogenation

can be determined by melting point, iodine absorption number, refractive index.

In case of hydrogenation of more highly unsaturated oils, the reaction mixture passes

through a stage where it is practically equivalent to an oleic oil before it proceeds to complete

saturation.

There are number of apparatus available for hydrogenation of oil, these are mainly

categorised into three types:

(i) A vessel nearly full of oil containing the catalyst in suspension through which the

hydrogen is circulated by mechanical means, possibly also with the circulation of

the oil to maintain the suspension of the catalyst.

(ii) A vessel full of hydrogen and oil in which an intimate mixture is attained without

moving parts or stirrer.

(iii) Continuous process in which the catalyst is maintained stationary and through

which oil and hydrogen are continuously circulated.

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Apparatus belongs to second category is shown in the figure. Here no moving agitator is

used. The catalyst is suspended in the oil in finely divided state. The oil and gas flow counter-

currently through the tall mixing column, intimate contact being caused by the action of fixed

propeller like baffle plates, causing the oil and gas mixture to rotate alternately in opposite

direction.

In operation the column is filled with oil it enters at the top and is recirculated by the

pump. The enlarged section at the top serves to effect a separation of the intimate hydrogen-

oil mixture so that hydrogen may be withdrawn at the top of the apparatus, repressured by the

gas compressor and then returned at the bottom of the column. The degree of mixing of

hydrogen and oil may be varied by the rate at which the gas compressor and oil pump

operate. A steam jacket serves to heat the charge and maintained suitable temperature.

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 This process is said to effect very rapid hydrogenation for instant of peanut oil or

cottonseed oil in 15-25 min. with an initial temperature of 130 ºC. Because of the rapid

reaction at low temperature this process is particularly applicable for hardening of oils for

edible purposes where the product must possess a good flavour. `1

Synthesis of methanol from hydrogen and CO

Carbon monoxide may be hydrogenated to produce either alcohol or hydrocarbons

depending on the catalyst used and the reaction condition. Synthesis of methanol from CO

and H2 is a reversible reaction, at temperature lower than 300 ºC, the rate of reaction is slow.

CO + 2H2 CH3OH

At 300 ºC and 3500 psi pressure, 1 vol of CO and 2 vol of H2, the yield of product is about 60

%. While at 150 lb pressure yield is only 2%. Hence pressure used in the synthesis of

methanol is usually 3000-4000 psi.

CO and H2 mixture traditionally generated from coke, steam and air by water-gas

method, but this process has been supplanted by steam-hydrocarbon reforming and by partial

oxidation of natural gas.

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 For the synthesis of methanol, catalyst is contained in special reactor designed to

withstand the pressure and temperature used. By heat interchange either in the reactor or in

special heat exchanger, the heat of reaction (24620 cal per g mole of methanol) is absorbed.

Temperature of the catalyst must be constant. Amount of methanol produce depends on the,

per volume of catalyst per hour and the amount of heat removed in heat exchangers. This

amount of heat removed in heat exchanger is used for maintaining constant temperature of

catalyst.

The methanol containing gases leave the reactor and after passing through heat

exchanger are finely led through condenser where the methanol is condensed under high

operating pressure (3000-4000 psig). This process frees the gases more completely of

methanol than if the condensation took place at lower pressure. Any drop in pressure in

reactor and cooling system is represented by booster compressor. If a gas mixture other then

1:2 ratio of CO : H2 is used, the composition of the gases must be continually adjusted as it is

recycled and provision must also be made for venting inert or other gaseous side products.

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 Catalyst usually consists of metal and metallic oxide mixture, the most common

constituents being copper with oxides of zinc, chromium, manganese and aluminium. Zinc

chromate is typical catalyst used. For the synthesis of methanol alone, contact of hot gases

with iron should be avoided. For this reactors are lined with copper or some other material

not affecting the catalyst. Methanol synthesis is a striking case of selectivity or preferential

character of catalysts. Methanol catalyst readily reduces CO to methanol with only traces of

methane at 375 ºC and high pressure 4000 psig. With proper catalyst and the extraction of

sulphur and iron, methanol of 99% purity can be produced.

Hydrogenation of acid or ester to alcohol

Direct reduction of carboxyl group to alcohol by means of molecular hydrogen and

catalyst occur at temperature usually from 300 – 400 ºC and with hydrogen pressure about

3000 psig. The acid or ester may be of long straight chain or may be of shorter chain with

branching. The oil hardening processes use long chain acid and ester and only saturate

olefinic linkage in the carbon chain.

Reduction of acid or ester to alcohol involved the use of metallic sodium with

anhydrous alcohol. Acid derivatives such as acid chloride could be reduced by direct

hydrogenation to an aldehyde by palladium catalyst. The direct reduction, using molecular

hydrogen at high pressure involves 2 moles of hydrogen per mole of acid reduced.

RCOOH + 2H2 RCH2OH + H2O

A secondary reaction consists of the esterification of a portion of a alcohol formed

with a portion of the unchanged acid. The proportion of ester present in the product depends

chiefly on the completeness of the hydrogenation. When the reaction is conducted under

conditions that yield only partial reduction of the acid, the process may be altered to give

esters as the main products, according to the reaction:

2RCOOH + 2H2 RCH2COOR + 2H2O

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 R represents the unsaturated or olefinic bond, partial reduction of C – C unsaturation

may occur. Sometimes reaction favours the formation of alcohol or ester and then further

reduced the olefinic bond at lower pressure and temperature with nickel catalyst. This brings

all the reaction products to the same completeness of hydrogenation, yielding new

compositions usually solids from which alcohol and ester may be separated.

The reduction may be carried out in a batch system or in a flow system. Flow system

is more preferable. The catalyst in the granular form is held in place in a heated tube capable

of withstanding the pressure and temperature. The acid or ester may be melted if solid and

dissolve in a solvent such as butyl alcohol or ethyl alcohol and then pumped into the reactor

over the catalyst. The acids or esters pumped through the reactor at the rate of 2-8 vol of the

material per volume of the catalyst per hour, a considerable excess of hydrogen being passed

along with the material over the catalyst. From 2-10 moles of hydrogen is used per mole of

acid hydrogenated. The proportion of ester to alcohol produced in the hydrogenation will

depend on the ratio of hydrogen to acid being reduced.

An active catalyst for hydrogenating the lauryl ester of coconut oil fatty acid is made

by decomposing copper ammonium chromate at 350- 400 ºC. 90% hydrogenation is obtained

in 2 hour by operating at 275 ºC and 3000lb hydrogen pressure.

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