TECHNICAL SPECIFICATION

CAPROLACTAM

WT-2013/ZA-5/1

1. SUBJECT OF THE SPECIFICATION

The technical specification concerns caprolactam obtained from benzene and sold in liquid form or as solid
flakes.
2.

REQUIREMENTS
2.1 GENERAL REQUIREMENTS

Liquid caprolactam is colorless, clear and free of any suspended matter. Solid caprolactam is white,
hygroscopic, crystalline substance with slight characteristic odour.
2.2. DETAILED REQUIREMENTS
Detailed requirements are shown in Table 1.
Table 1
No.

3.

Requirements

Units

Limits

28 000

mmol/kg

0.3

1.

Permanganate number, at least

2.

Volatile bases content, not more than

3.

Water content, not more than

0.05

4.

Crystallizing point, at least

69.0

5.

Colour of 50% aqueous solution, not more than

Hazen units

6.

Alkalinity, not more than

mmol/kg

0.05

7.

Acidity, not more than

mmol/kg

0.05

8.

Absorbance of 50% aqueous solution, not more than

0.04

9.

Iron content, not more than

mg/kg

0.3

10.

Ash content, not more than

mg/kg

11.

Cyclohexanone oxime content, not more than

mg/kg

LABELLING

Product label shall be located in conspicuous location and shall be permanently affixed to the packing. Label
text and information should be in a size of type large enough to be readily legible.
Labelling must include the following elements:

4.

The commercial product name: CAPROLACTAM

The name, address, logo and telephone number of the manufacturer

The nominal quantity of the product

Index number according to Annex VI of Regulation (EC) No 1272/2008

Hazard pictograms

Signal word

Hazard statements

Precautionary statements

The symbol of recycling - in case of PE bags having capacity of 25 kg

The symbol indicating material of which bag is made of - in case of PE bags having capacity of 25 kg

PACKING

Liquid caprolactam is loaded into thermally isolated, stainless steel tank vehicles or tank wagons provided with
hot water or low pressure steam heating system. The contact zones must be made of acid-resistant steel, free
of any non-ferrous metals and their alloys, additionally seals should be colorless and made of resistant
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materials i.e. PTFE. Tank vehicles and tank wagons should be supplied with properly functioning systems for
controlling caprolactam temperature and nitrogen pressure. To prevent formation of volatile bases, liquid
caprolactam must be loaded under oxygen-free conditions with the use of a dry nitrogen blanket (air content
less than 20 ppm).
Solid caprolactam is packed into polyethylene bags of 25 kg capacity (net weight) closed by welding. These
bags are stacked in pallets and protected by wrapping with stretch film.
5.

STORAGE

Liquid caprolactam shall be stored in thermally isolated, stainless steel containers provided with hot water or
low pressure steam heating system. Storage temperatures should be maintained between 8090C and may
not exceed 95C. Store in oxygen-free conditions, un der a dry nitrogen blanket (air content less than 20 ppm).
Solid caprolactam shall be stored in original packaging i.e. on pallets covered with film and protected by
wrapping with stretch film.
Product must be kept away from incompatibles such as flammables, oxidizing agents, strong acids and strong
bases. Protect from moisture and direct sunlight.
If the above mentioned storage precautions are followed, the product's quality is guaranteed for the period of
six months from the date of shipment.
6.

TRANSPORT

Liquid caprolactam is shipped in thermally isolated, stainless steel tank vehicles or tank wagons intended for
caprolactam carriage, provided with hot water or low pressure steam heating system.
Solid caprolactam is shipped in weather-proof containers or tank wagons
ADR/RID regulations do not apply to this product.
7.

ANALYTICAL METHODS
7.1. TESTING SCHEDULE see Table 2
Table 2

No.

Test description

Limits as per:

Test description as per:

1.

Testing of general requirements.

2.1.

7.4.

2.

Permanganate number, at least

2.2.1.

7.5.

3.

Volatile bases content, not more than

2.2.2.

7.6.

4.

Water content, not more than

2.2.3.

7.7.

5.

Crystallizing point, at least

2.2.4.

7.8.

6.

Colour of 50% aqueous solution, not more than

2.2.5.

7.9.

7.

Alkalinity, not more than

2.2.6.

7.10.

8.

Acidity, not more than

2.2.7.

7.11.

9.

Absorbance of 50% aqueous solution, not more than

2.2.8.

7.12.

10.

Iron content, not more than

2.2.9.

7.13.

11.

Ash content, not more than

2.2.10.

7.14.

12.

Cyclohexanone oxime content, not more than

2.2.11.

7.15.

7.2. BATCH SIZE

Liquid caprolactam: A lot is the content of a single tank intended for shipping.
Solid caprolactam: A batch/lot consist of 1225 tons of final product that can be loaded into a single
container/semi-trailer. A shipment lot is a single consignment per one order.
7.3. SAMPLING
Sampling shall be conducted in accordance with PN-C-04333:2000. During sampling, attention must be paid to
hygroscopicity of caprolactam and build-up of volatile bases which occurs in contact with oxygen. Sampling,
especially for liquid caprolactam, should be performed so as to avoid increase of moisture content and other

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impurities in the sample taken.

Liquid caprolactam: A primary sample of liquid caprolactam is split into a test sample for immediate analysis
and an archive sample which is kept, after labelling for a period of three months from the date of shipment. The
archive sample of caprolactam is kept in the solid form.
Solid caprolactam: A bulk sample of at least 1 kg is taken directly from packaging line. After mixing, the sample
is split into two parts: one for immediate analysis and the other one for archiving purposes. A final bulk sample
of a consignment is prepared from samples of individual batches by mixing 1/3 parts of an archive samples
from individual batches. The final consignment bulk sample is then split into two parts: one for immediate
analysis and the other one as an archive sample. The consignment final bulk sample and archive samples of
each individual batches are stored for a period of 6 months from the date of shipment.
7.4. TESTING OF GENERAL REQUIREMENTS
Transfer liquid caprolactam into a polyamide bag made from sleeve. Compare its appearance with that of water
stored in similar polyamine bag.
Place a solid caprolactam sample in a clear-glass cylinder and check its appearance.
7.5. DETERMINATION OF PERMANGANATE NUMBER
Perform according to guidelines PN-C-45301-03:1993.
7.6. DETERMINATION OF VOLATILE BASES CONTENT
Perform according to guidelines PN-C-45301-06:1993 or ISO 8661:1988.
7.7. DETERMINATION OF WATER CONTENT
Perform according to guidelines PN-C-04959:1981.
7.8. DETERMINATION OF CRYSTALLIZING POINT
Perform according to guidelines PN-C-45301-08:1993 lub ISO 7060:1982.
7.9. DETERMINATION OF COLOUR OF 50% AQUEOUS SOLUTION AT 390NM
Perform according to guidelines PN-C-45301-04:1993 lub ISO 8112:1984.
7.10. DETERMINATION OF ALKALINITY
Perform according to guidelines PN-C-45301-09:1993.
7.11. DETERMINATION OF ACIDITY
Perform according to guidelines PN-C-45301-09:1993.
7.12. DETERMINATION OF ABSORBANCE OF 50% AQUEOUS SOLUTION
Perform according to guidelines PN-C-45301-05:1993 lub ISO 7059:1982.
7.13. DETERMINATION OF IRON CONTENT
Perform according to guidelines PN-C-45301-10:1993.
7.14. DETERMINATION OF ASH CONTENT
7.14.1. Principle of the method
The method consists in determination of ash (residue on ignition) after incineration of a caprolactam sample
followed by heating at 800C.
7.14.2. Apparatus
a) Platinum crucible, approx. 100ml
b) Furnace with a temperature range up to 1000C.
c) Desiccator
d) Beaker
e) Gas burner
7.14.3. Determination procedure
Put a platinum crucible into furnace and heat up to 800C. Hold at this temperate for 30 minutes and af ter that
place the crucible in a desiccator. After cooling to ambient temperature, weigh it on an analytical balance with
precision of 0.0001 g (G1).
Weigh 500 g of caprolactam into a beaker. Transfer approximately 50 g of caprolactam from the beaker into the
previously dried platinum crucible and melt the content over the gas burner. Continue heating until caprolactam
ignites, then remove the burner flame and allow the substance to burn out completely. Repeat this procedure 9
times (each time taking about 50 g) until a whole initial amount of caprolactam (500 g) is incinerated. Next hold
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the crucible for 40 minutes in the furnace at 800C so that all carbonized products are burned out.
Subsequently, place the crucible in a desiccator and after it cools down to room temperature, weigh with
precision of 0.0001 g
Next, place the crucible again in the furnace at 800C and keep it inside for 20 minutes. Remove the c rucible,
cool it to ambient temperature in a desiccator and weigh with precision of 0.0001 g (G2).
Calculate the total ash content (X) as weight percentage (mg/kg) using the following equation:
X = (G2
G1) x 2 x 1000
where:
G1 weight of empty platinum crucible (g);
G2 weight of platinum crucible with residue (g).
7.14.4. Final result
The final results should be an arithmetic mean of the results of at least two consecutive tests, which differ from
each other by not more than 3 mg/kg.
7.15. DETERMINATION OF OXIME CONTENT
7.15.1. Principle of the method
The first step of this method is hydrolysis of cyclohexanone oxime to cyclohexanone and hydroxylamine. Next,
hydroxylamine undergoes oxidation with iodine to nitric acid, which then reacts with sulphanilic acid and naphtylamine to form colour compound. Absorbance of this colour complex is measured at 520 nm wavelength
and corresponds to the content of cyclohexanone oxime.
7.15.2. Reagents and solutions
During the analysis, use only reagents of analytical grade and distilled or deionised water.
3
a) Concentrated Hydrochloric acid, d = 1.19 g/cm
b) Glacial acetic acid, c = 99.5% (w/w)
c) Suplhanilic acid, c = 1% (w/w); solution prepared as follows:
Dissolve 10 g f sulphanilic acid in 750 ml of distilled water and 250 ml of glacial acetic acid. Heat the
mixture until it boils and homogenous liquid is formed. Store obtained solution in a dark glass bottle.
d) Iodine solution, c (I) = 0.1 mol/l; solution prepared as follows:
Transfer 12.7 g iodine into 1 l volumetric flask and dissolve in potassium iodide solution prepared by
dissolving 16 g of potassium iodide in 125 ml of distilled water. Dilute the flask to volume with
distilled water and mix well. Store obtained solution in a dark glass bottle.
e) Sodium acetate, (CH3COONa x 3H2O); solution prepared as follows:
Transfer 225 g of sodium acetate into 1 l volumetric flask, add distilled water to dissolve and dilute to
volume with the same solvent.
f) Sodium thiosulfate solution, c (Na2S2O3) = 0.1 mol/l
g) -naphtylamine, c = 0.3% (w/w); solution prepared as follows:
Dissolve 3.0 g of -naphtylamine in acetic acid solution prepared by mixing 300 ml of glacial acetic
acid with 750 ml of water. Store obtained solution in a dark glass bottle for a period of time no longer
than 1 week.
h) Caprolactam free of cyclohexanone oxime
i) Cyclohexanone oxime
7.15.3. Apparatus
a) Spectrometer with measuring range covering 520 nm wavelength
b) Two absorption cells having optical path of 5 cm
c) Hydrolysis set consisting of a round, flat-bottom 500 ml flask with a reflux condenser (glass joint
connection)
7.15.4. Determination procedure
7.15.4.1. Preparation of standards and the calibration curve
Prepare standard solution of cyclohexanone oxime as follows:
Solution 1: Transfer 0.5000 g cyclohexanone oxime into 500 ml volumetric flask. Add distilled water to
dissolve, dilute to volume with the same solvent and mix well (1 ml of this solution contains 1 mg of
cyclohexanone oxime).
Solution 2: Transfer 50 ml of Solution 1 into 500 ml volumetric flask. Dilute to volume with distilled water and

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mix well (1 ml of this solution contains 0.1 mg of cyclohexanone oxime).

Solution 3: Transfer 50 ml of Solution 2 into 500 ml volumetric flask. Dilute to volume with distilled water and
mix well (1 ml of this solution contains 0.01 mg of cyclohexanone oxime).
Into series of six round-bottom 500 ml volumetric flasks, transfer respectively: 0; 5.0; 10.0; 20.0; 30.0 and 50.0
ml of Solution 3, which corresponds, respectively to 0, 1, 2, 4, 6 and 10 mg/kg of cyclohexanone oxime in
caprolactam.
Add distilled water to each flask to achieve total solution volume of 100 ml per each flask (100, 95, 90, 80, 70
and 50 ml, respectively). Add 50 g of caprolactam free of cyclohexanone oxime to each flask. Further, proceed
3
according to item 7.15.4.2., starting from addition of 37.5 ml of hydrochloric acid (d = 1.19 g/cm ).
Based on the obtained results plot a calibration curve, having absorbance values on Y axis and the content of
cyclohexanone oxime in caprolactam in mg/kg on X axis.
7.15.4.2.

Sample preparation and measurement

Weigh 50 g caprolactam with precision of 0.01 g and transfer quantitatively into 500 ml round-bottom flask. Add
3
100 ml of distilled water and 37.5 ml of hydrochloric acid (d = 1.19 g/cm ). Connect the flask with a reflux
condenser and keep the solution boiling for 1 hour.
Cool the solution to ambient temperature and then transfer quantitatively into 250 ml volumetric flask. Rinse the
condenser and the initial flask with 60 ml distilled water and combine post-rinsing water with the solution being
examined. Dilute to volume with water and mix well. Transfer 25 ml of the resulting solution into 100 ml
volumetric flask. Add 20 ml of sulphanilic acid solution (as per item 7.15.2.c)), 1 ml of iodine solution (as per
item 7.15.2.d)) and mix well. Put the flask in a dark place and keep it there for 15 minutes. Then, add 20 ml of
sodium acetate solution (as per item 7.15.2.e)), 2 ml of sodium thiosulfate solution (as per item 7.15.2.f)) and
10 ml of -naphtylamine solution (as per item 7.15.2.g)). Mix the content of the flask. Dilute to volume with
distilled water and mix well. Put the flask in a dark place and keep it there for 30 minutes. After that measure
absorbance at 520 nm wavelength in 5 cm optical path absorption cells, against blank test (containing
caprolactam free of cyclohexanone oxime). Determine the content of cyclohexanone oxime in caprolactam (in
mg/kg) using previously prepared calibration curve according to item 7.15.4.1.
7.15.4.3. Final result
The final results should be an arithmetic mean of the results of at least two consecutive tests, which differ from
each other by not more than 2 mg/kg.
7.16. DATA ASSESSMENT AND TESTS CERTIFICATE
A batch of caprolactam shall be considered to meet the requirements of this Technical Specification if test
results conform with the requirements indicated in Table 1.
The manufacturer is obliged to send to the customer a certificate stating the compliance of the product with the
requirements of this Technical Specification.
8.

REFERENCES
PN-C-04333:2000 Coal Derivative Products - Sampling And Preparation Of Laboratory Sample
PN-C-04959:1981 Determination of water content in organic and inorganic products by Karl Fischer
method.
PN-C-45301-03:1993 Caprolactam. Test methods. Visual determination of permanganate number in
3% aqueous solution.
PN-C-45301-04:1993 Caprolactam. Test methods. Spectrometric determination of color of 50%
aqueous caprolactam solution in Hazen units.
PN-C-45301-05:1993 Caprolactam. Test methods. Determination of absorbance at 290 nm
wavelength.
PN-C-45301-06:1993 Caprolactam. Test methods. Determination of volatile bases content.
PN-C-45301-08:1993 Caprolactam. Test methods. Determination of crystallizing point.
PN-C-45301-09:1993 Caprolactam. Test methods. Determination of acidity and alkalinity.
PN-C-45301-10:1993 Caprolactam. Test methods. Determination of iron content.
ISO 7059:1982 Caprolactam for industrial use Determination of absorbance at wavelength of
290 nm.
ISO 7060:1982 Caprolactam for industrial use Determination of crystallizing point.
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ISO 8112:1984 Caprolactam for industrial use Determination of color of 50% aqueous
caprolactam solution expressed in Hazen units (platinum cobalt scale). Spectrometric method.
ISO 8661:1988 Caprolactam for industrial use Determination of volatile bases content Titrimetric
method after distillation.
Convention concerning International Carriage by Rail (COTIF), Appendix B - Uniform Rules
concerning the Contract of International Carriage of Goods by Rail (CIM); Appendix C - Regulation
concerning the International Carriage of Dangerous Goods by Rail (RID)
Act dated on 19
position 1367)

th

August 2011 relating to transportation of dangerous goods (Dz.U.2011 No. 227

Regulation (EC) no 1272/2008 (CLP) of the European Parliament and of the Council of 16 December
2008 on classification, labeling and packaging of substances and mixtures, amending and repealing
Directives 67/548/EEC and 1999/45/EC, and amending Regulation (EC) No 1907/2006 (REACH).
9.

ADDITIONAL INFORMATION

WT-2013/ZA-5/1 supersedes WT-2013/ZA-5

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