CAPROLACTAM

Caprolactam is an intermediate primarily used in the production of nylon 6 fibres and resins.
Around 68% of caprolactam is consumed in the production of nylon fibres for textile, carpet and
industrial yarns with the rest used in engineering resins and films.

Physical and Chemical Properties

Physical Properties
Caprolactam [105-60-2], C6H11ON, is a white, hygroscopic, crystalline solid with a characteristic odor. Its
basic properties are summarized below:

Caprolactam is soluble in polar and aromatic solvents and slightly soluble in high molecular mass aliphatic
hydrocarbons.

Chemical Properties
Polymerization is caprolactams most important chemical property. The ring is hydrolyzed at 260
270C. Linear polymer chains are formed by polycondensation. Caprolactam also reacts directly by
polyaddition with the polymer chains. These reactions lead to an equilibrium between the polymer and
caprolactam favoring a 90 % conversion to polymer. Caprolactam can also be polymerized by anionic
polymerization at low moisture contents, preferably less than 100 ppm. A catalyst and cocatalyst system is
necessary. The reaction temperature is lower than in hydrolytic polymerization.
Caprolactam can undergo all cyclic amide reactions, such as oxidation, hydrolysis, N-alkylation,
phosphogenation, and nitration.

Production Methods
Caprolactam Production from Toluene via Cyclohexanone Carboxylic Acid by Oxidation,
Hydrogenation, Nitrosation, and Rearrangement

Caprolactam is obtained in three steps:

1.

Catalytic oxidation of toluene with air to benzoic acid:

2.

Hydrogenation of benzoic acid to cyclohexanecarboxylic acid:

3.

Nitrosodecarboxylation of cyclohexanecarboxylic acid to caprolactam in the presence of oleum:

Process Description:
The oxidation of toluene with air is carried out in liquid phase using a cobalt catalyst at 160 170C
and 0.81MPa (810bar) pressure. The yield is well above 90 % of theory. The gases from the oxidation
reactor contain mainly nitrogen with small amounts of oxygen, carbon dioxide and carbon monoxide. They
are cooled to 7 8C in order to recover unreacted toluene. The water accumulated during the reaction is
removed in a separator drum and toluene is recycled to the reactor. In addition to toluene and cobalt catalyst,
the liquid reaction product contains about 30 % benzoic acid and also various intermediates and byproducts.
Most of the toluene is removed by distillation, and the remaining concentrated solution is given into
a rectication column. The lower boiling intermediates and the remaining toluene are removed at the top and
reused. Benzoic acid in vapor form is removed from the rectication column as a side stream. The highboiling byproducts leave the column as a residue. They include the cobalt salt, which is reprocessed. The
benzoic acid obtained is suitable for hydrogenation without any further purication.
Hydrogenation of benzoic acid to cyclohexanecarboxylic acid is carried out in liquid phase in the
presence of a palladium on graphite catalyst. A series of stirred reactors are used with a temperature of about
170C and pressure of 1 1.7 MPa (10 17 bar). Conversion is 99.9 % with a commensurate yield. The
catalyst is centrifugally separated from the liquid reaction product, mixed with benzoic acid, and reused in
hydrogenation. Cyclohexanecarboxylic acid is distilled under reduced pressure. Any catalyst still present
remains in the residue. A 73 % nitrosylsulfuric acid solution in sulfuric acid is used for the nitrosation of
cyclohexanecarboxylic acid. It is obtained by absorption of nitrous gases (from ammonia combustion) in
concentrated sulfuric acid or oleum. Cyclohexanecarboxylic acid is premixed with oleum at ambient
temperature and fed into a multistage nitrosation reactor. Exactly dened amounts of cyclohexanecarboxylic
acid and nitrosylsulfuric acid are reacted at each stage, ensuring the complete reaction of the nitrosating
agent. The conversion rate of the cyclohexanecarboxylic acid is maintained at about 50 %. One mole of
carbon dioxide per mole of caprolactam is set free along with small amounts of other gases such as nitric

oxide, carbon monoxide, sulfur dioxide, and nitrogen. In order to maintain the reaction and remove the
reaction heat, this process is carried out in boiling cyclohexane under atmospheric pressure. Depending on
the organic acid, less than 10 % of the yield is lost.
Sulfonic acids are byproducts. During the reaction, 3.3 moles of sulfuric acid per mole of caprolactam
are consumed. Nitrosation with subsequent rearrangement is the most important part of the process.
Products from the nitrosation/rearrangement step are hydrolyzed with water at low temperatures.
Cyclohexane extracts unreacted cyclohexanecarboxylic acid. The nal residues are extracted from the
sulfuric acid solution, which has been diluted with water, by countercurrent extraction using cyclohexane as
the solvent. The recovered cyclohexanecarboxylic acid is freed from the solvent and recycled to the process.
The acidic caprolactam solution containing excess sulfuric acid is then fed into the neutralization stage, where
it is neutralized with ammonia.Neutralization is carried out directly in a crystallizer under reduced pressure.
Two liquid layers are formed, a saturated ammonium sulfate solution and a concentrated aqueous
caprolactam solution. The caprolactam solution is puried in several stages. It is rst separated from the
water-soluble byproducts by toluene extraction. An aqueous caprolactam solution is then obtained by
countercurrent extraction of the caprolactam toluene solution with water. The toluene-soluble byproducts
remain in the organic layer. Water is removed from the aqueous caprolactam solution and the product distilled
to give pure caprolactam. Crystallization of the separated saturated ammonium sulfate solution gives 4.1 tons
of ammonium sulfate per ton of caprolactam.

Caprolactam Production from Cyclohexane via Cyclohexanone by Oxidation, Oximation, and

Beckmann Rearrangement
Cyclohexanone from Cyclohexane:

Process Description:
I.

Cyclohexanone from Cyclohexane

Cyclohexane is first oxidized to a cyclohexanol or cyclohexanone mixture, which is then
dehydrogenated. This mixture is first fractionated in a series of three distillation colums operating
under vaccum, of which the first two (20 trays each) separate the light and heavy compounds.
Cyclohexanone is collected at the top of the last colum (40 trays). The withdrawal, consisting
essentially of cyclohexanol, is vaporized and superheated, and then sent to the dehydrogenation
reactor. The endothermic reaction tales place around 400 degC, in the presence of a zinc catalys
and at atmospheric pressure, with heating provided by the circulation of a molten salt. 84 percent
cyclohexanone and 1 percent of light compounds are formed. Unconverted cyclohexanol and
the cyclohexanone produced are recycled to the fractionating colum of the Ol/One mixture, after
separation of the hydrogen produced and removal of the light compounds.

II.

Caprolactam from Cyclohexanone

The reaction of cyclohexanone with hydroxylamine is the best known method for the
production of cyclohexanone oxime.

Hydroxylamine is used in its sulfate or phosphate form. Some manufacturers produce

hydroxylamine by the modied Raschig process using ammonium salts as starting materials.
Oximation is then carried out with aqueous hydroxylammonium sulfate solution containing
ammonium sulfate. The sulfuric acid liberated is neutralized with ammonia to form ammonium
sulfate. The amount of ammonium sulfate formed during oximation is about 2.7 tons per ton of
cyclohexanone oxime.
The BASF process (Fig. 2) for the production of hydroxylammonium sulfate solution
generates about 0.7 tons of ammonium sulfate per ton of cyclohexanone oxime during the
oximation step. A similar process has been developed by Inventa [17]. BASF and Inventa obtain
the hydroxylammonium sulfate solution by hydrogenation of nitric oxide over a platinum catalyst
in the presence of dilute sulfuric acid. The hydroxylammonium sulfate solution is reacted with
cyclohexanone and ammonia in an oxime reactor. This reaction is conducted with thorough
mixing at 85 90 degC in a weak acidic solution.
Cyclohexanone oxime is obtained as a moist melt. It is separated from the aqueous
ammonium sulfate solution in a separator drum. The puried aqueous ammonium sulfate
solution is free of substances that would be undesirable in fertilizer- or technical-grade salt uses.
The rearrangement, which includes opening of the cyclohexyl ring, is a very rapid, highly
exothermic reaction.

Since the Beckmann rearrangement is highly exothermic, molten cyclohexanone oxime and
concentrated oleum (27 %) are introduced simultaneously into a relatively large amount of
already rearranged product. Molar ratios of cyclohexanone oxime and oleum may range from 1
to 1.05 [19]. Sulfur trioxide binds the water in the moist cyclohexanone oxime to form sulfuric
acid and catalyzes the rearrangement. Cooling reduces the heat of reaction. The reaction gives
the sulfate of caprolactam in excess sulfuric acid. It is hydrolyzed by neutralization with ammonia
or ammonia water. The reactions take place according to the following equations:
The rearrangement mixture is removed from the reactor at the rate it is formed. It is
neutralized in ammonia and water to prevent precipitation of solid ammonium sulfate. The
reaction product is then separated from the lighter phase above the concentrated ammonium
sulfate solution as 70 % aqueous crude caprolactam. The crude caprolactam is removed in a
separator drum and fed to an extractor.
Caprolactam is extracted with solvents such as benzene, toluene, or chlorinated
hydrocarbons. The virtually caprolactam-free aqueous solution is discharged into a waste

treatment plant or incinerated. Concentrated ammonium sulfate solution is further evaporated

and crystallized.
The caprolactam-containing solvent is fed into a distillation column. Solvent-free
caprolactam is further distilled under reduced pressure. Very pure caprolactam is obtained in
molten form. It is either used as such or solidied in a aker. A total of 4.5 tons of ammonium
sulfate per ton of caprolactam is obtained from both oximation and neutralization with the
Raschig process. The BASF or Inventa process produces a total of 2.5 tons of ammonium sulfate
per ton of caprolactam in oximation and neutralization.
Caprolactam yields can be improved and undesirable byproduct formation reduced by
multistage rearrangement and the adjustment of reactionconditions in each stage. Acid
concentration, free sulfur trioxide concentration, amount of oxime added, reaction temperature,
and degree of mixing are critical variables at each stage.

Caprolactam Production from Phenol via Cyclohexanone by Hydrogenation, Oximation, and

Beckmann Rearrangement

Process Description:
III.

Cyclohexanone from Phenol

Phenol is first placed at 180 degC, in two reactors in series and in the presence of caustic
soda, with a sequentering agent (EDTA) to remove the metallic impurities that are detrimental to
the hydrogenation catalyst. It is then sent to a first distillation column (15 trays), where a fraction
corresponding to the requisite quality is collected at the top. A large share remains in withdrawal.
This stream is sent to a second column (20 trays) operating under vacuum. The distillate is
recycled to the initial distillation, and the botton, which contains 30 ppm of free or combined
phenol, is removed.
The purified phenol is hydrogenated at 175 degC, in a series of three reactors operating at
1.3x106 Pa absolute. The catalyst, used at the level of 0.5 percent weight of the feed is 5 percent
palladium deposited on coal. 95 percent volume hydrogen is employed in a 20 percent excess
in relation to stoichiometry. The heat generated by the transformation is removed by internal
circulation of cooling water, to limit the temperature at the outlet of the last reactor to 200 degC.
The hydrogenated effluent is cooled to 90 degC and centrifuged to recover the catalyst, which is
then recycled. Molar selectivity is 97 percent for cyclohexanone and 2.5 percent for
cyclohexanol. The cyclohexanone is then purified by distillation (35 trays).

IV.

Caprolactam from Cyclohexanol (same as in the second process)