GAS-CHROMATOGRAPHIC ANALYSIS OF H Y D R O C A R B O N

COMPOSITION OF PARAFFIN WAXES

V. V. Postnov, I. A. Mikhailov, UDC 543.544:665.521.62

and N. I. Lulova

The solid paraffin waxes recovered from various petroleum products are the main type of raw material being
used in processes of petrochemical synthesis to produce synthetic fatty acids and detergents; these waxes are also
used in a number of branches of the food industry. In order to process these waxes under optimum conditions, their
hydrocarbon composition must be known. Usually, the most detailed information on the chemical and hydrocarbon
group composition of paraffin waxes is obtained by mass spectrometry [1, 2]. However, mass spectrometry is not
suitable for general use in plant control laboratories. Gas chromatography, which is already in widespread use in
refineries shows considerable promise in this area. It has been used to study the hydrocarbon composition of a num-
ber of paraffin waxes recovered from USSR and foreign crude oils [3-5].
Here, we used gas-liquid chromatography to investigate the individual chemical composition of mlid paraffin
waxes. The analysis was performed with a chromatograph equipped with a flame ionization detector, with a
column 1 m in length and 2 m m in diameter, packed with Chromosorb W (80-100 mesh)with 15%oSE-30 (poly-
methylsiloxane). Since the paraffins had a wide boiling range, the analysis was performed with the temperature pro-
grammed from 180 to 320~C at a rate of 3~ Under these conditions, since the thermal stability of the liqnid
phase was inadequate, a slight drift of the zero Une is observed. The position of the zero line is determined by a
"blank" experiment without any sample injection, using the same regime of temperature programming. The wax
sample was injected into the evaporator of the chromatograph in chloroform solution. Such solutions were prepared
from 20-30 mg samples of the melted wax with 2 to 5 parts by weight of chloroform. Such mixtures are liquid at
room temperature and thus can be handled easily in a syringe; handling the sample in this form also favors rapid
evaporation in the chromatograph. The sensitivity of the flame ionization detector to chloroform is many times
less than its sensitivity to hydrocarbons; hence, with a comparatively large amount of chloroform in the sample,
the chloroform registers on the chromatogram as a small symmetrical peak that is well removed from the peaks of
the sample being analyzed.
The n-paraffin hydrocarbons were identified by addition of standards and also by the use of a graph showing
the retention temperature as a linear function of the number of carbon atoms in the n-paraffin molecule (with
programmed temperature) [6]. Quantitative calculation of the chromatograms was carried out by an internal cali-
bration m e t h o d - the "marker" method [7]. The "marker" was a chromatographically pure n-paraffin hydrocarbon
that was not present in the mixture being analyzed (C19 or C20). The peak areas were obtained by multiplying the
peak height by the peak width at half-height.
The materials taken for investigation were waxes obtained in various processes from paraffinic sweet and sour
crudes. A l l of the wax samples can be divided into three groups on the basis of production method: Group I
(samples 1-3) was obtained by sweating with subsequent sulfuric acid and percolation treating, Group II (samples
4-6) by selective deoiling of slack wax with supplementary treatment with a moving bed of adsorbent, and Group
III (samples 7 - 9 ) b y selective deoiling with subsequent percolation treating.
The physicochemical characteristics of the waxes are shown in Table 1. It will be noted that all of the
samples are well-deoiled products, white in color, with oil contents of 0.2-0.6%, melting points of 52-62~ and
average molecular weights on the order of 365-400. For the waxes produced from sweet crudes by sweating, the
n-peraffin content is 91-94%. For the waxes produced from sweet or sour crudes by selective deoiling of slack wax,
All-Union Scientific-Research Institute for Petroleum Processing (VNII NP). Translated from Khimiya i
Tekhnologiya Topliv i Masel, No. 4, pp. 9-12, April, 1973.

9 1974 Consultants Bureau, a division of Plenum Publishing Corporation, 227 West 17th Street, New York, N. Y. 10011. No part
of this publication may be reproduced, stored in a retrieval system, or transmitted, in any form or by any means, electronic, me-
chanical, photocopying, microfilming, recording or otherwise, without written permission of the publisher. A copy of this article
is available from the publisher for $15.00.

258
TABLE I. Physicochemical Characteristics of Petroleum Waxes

PhysicochemicaI characteristics of Content of n-paraffins

(wt. %), determined by
wax
Wax
Crude source Crude type
melting oil con- average average gas chro- mas~ spec-
point, ~ tent, wt, I moleeu- Icarbon mato- trometry
% lar i number graphy
weight

Stavropol Sweet 52,0 0,60 371 26,3 90,9 94,0

II
West- Ukrainian 55,0 0,45 372 26,4 94,2 95,6
w
55,0 0,58 365 25,9 92,3 93,7
Mangyshlak 62,0 0,30 437 31 79,0
57,0 0,53 392 27,8 79,6
It gl 56,0 0,20 389 27,6 86,6
Tnimazy S our 56,6 0,60 398 28,1 84,2 81,6
Romashkino
iI 54, 1 0,60 372 26,2 75,4 78,3
Samotlor 60,0 0,40 432 30,4 83,7

D b
/3 a 12
/2 11
3 6

9
"" I
7
7
/#
U 5

3
g
1
2o zz 24 2~ 2a 3o 32 3~ 3# 20 22 2~ 25 28 30 52 ,74 38 30
Carbon number Carbon number

/3
c
1,7

10

/\\\
II /-3 .o.. .,. x.,
co af- ;l f N "".%

t I I
gO gZ z~ 2u $0 oo 32 3~ #g 3o
Carbon number
Fig. 1. Distribution of n-paraffin hydrocarbons by carbon number in fractions of paraffin wax. a)
Samples 1, 2, a; b) samples 4, 5, 6; e) samples 7, 8, 9.

the n-paraffin content is 75- 86%. The n-paraffin contents obtained by ~as chromatography on certain samples were
compared with resuits from mass-spectrometric analysis [2]. As can be seen from Table 1, the agreement is entirely
satisfactory. Also checked was the repeatability of the chromatographic results. The deviation from the mean value
for the total n-paraffin hydrocarbons as determined in experiments 5 and 6 is =~3 % relative.
Data on the distribution of n-paraffins by carbon number are shown in Fig. 1. It can be seen that the molecular
composition of the waxes varies over wide limits. In samples 1, 2, 3, 5, 6, and 8, n-paraffins with 20 to 35 carbon

259