Analysis of Waxes
by Arthur D. Barker
INTRODUC~ON
PETROLEUM WAXES are the solid hydrocarbon residues re-
maining at the end of the refining process either in the lube
stream (as mainly paraffin and intermediate waxes) or in the
residual lube stock "tank bottoms" (as higher melting micro-
crystalline waxes). The waxy oil is fractionated to produce an
oily wax, called slackwax. This is separated by solvent extrac-
tion and fractionated into different melting point ranges to
give waxes with a variety of physical characteristics. Paraffin
waxes consist mainly of straight chain alkanes (also called
normal alkanes), with small amounts (3 to 15%) of branched
chain alkanes (or iso-alkanes), cycloalkanes, and aromatics.
Microcrystalline waxes contain high levels of branched chain
alkanes (up to 50%) and cycloalkanes, particularly in the
upper end of the molecular weight distribution. Paraffin
waxes contain alkanes up to approximately 600 molecular
weight, whereas microcrystalline waxes can contain alkanes
up to 1100 molecular weight.
Today refinery crude oils tend to be purchased from a
variety of sources, which leads to variations in the wax prod-
ucts from the lube stream. Also paraffin and microcrystalline
waxes have a large range of uses, either singly or as blends, or
blended with other polymers. Therefore there is a need to
characterize the refinery waxes, blended waxes, and end-user
products. The main problems in characterizing waxes arise
from the solid nature of the material and the difficulty in
separating the material into its components, particularly in
the case of microcrystalline waxes.
CURRENT PRACTICES
Analytical methods for waxes were originally based on
physical tests, which are clearly explained in the ASTM Man-
ual on Significance of Tests for Petroleum Products [1 ].1 Waxes
are traded on the basis of the melting point range (e.g., 130 to
135°F melting point) as defined by ASTM Test Methods D87,
Melting Point of Petroleum Wax (Cooling Curve), 2 or D127,
Drop Melting Point of Petroleum Wax Including Petrolatum. 2
The growth in the reliability of sophisticated instrumentation
has coincided with the need by wax blenders and users for
more detailed "fingerprinting" of materials to obtain more
precise quality control and detailed information.
~The italic numbers in brackets refer to references at the end of this
chapter.
2Appears in this publication.
31
ASTM Test Method D4419, Measurement of Transition
Temperatures of Petroleum Waxes by Differential Scanning
Calorimetry, 2 was produced in 1984 as a more accurate
means of evaluating the melt characteristics of a wax. In the
1980s, ASTM D02.04 developed a gas chromatographic
method, originally intended for the analysis of wax blends
used in the rubber industry'. However, by the time the method
was published, in 1993, the scope of the method had changed
to ASTM Test Method D5442, Analysis of Petroleum Waxes
by Gas Chromatography. 2 More recent innovations in nuclear
magnetic resonance (NMR) instrumentation for measuring
the oil content of waxes has led to the possibility of an
alternative test to replace the lengthy ASTM Test Methods
D721, Oil Content of Petroleum Waxes, 2 and D3235, Solvent
Extractables in Petroleum Waxes. 2
Gas Liquid Chromatography
The separation of waxes on packed columns has been car-
ried out since the 1960s [2,3 ], and capillary column chroma-
tography was used in 1970 to separate a microcrystalline wax
up to carbon chain length (also known as carbon number)
n-Csa [4]. In the early 1980s, tire manufacturers requested
ASTM D02.04 to produce a capillary column gas chromatog-
raphy method to analyze rubber waxes (with oil content of
less than 10%) from carbon number n-C~7 to n-C44. ASTM
D02.10, the Subcommittee on Petroleum Wax, was asked by
D02.04 to carry out the development of the method.
By the time ASTM D5442 was issued, the scope of the
method had been changed to encompass all petroleum-
derived waxes, including blends of waxes, from n-C17 to n-C44
using an n-Cl~ internal standard. The sample is diluted in a
suitable solvent (cyclohexane is suggested), containing the
n-C~6 internal standard. It is then injected into a capillary
column, meeting a specified resolution, and the components
are detected using a flame ionization detector. The eluted
components are identified by comparison to a standard mix-
ture containing every fourth alkane from n-Ct6 to n-C44. The
resulting chromatogram is complex, and the area of each
straight chain and branched chain alkane must be measured
using a programmable integrator or computer chromatogra-
phy software. ASTM Method D5442 outlines a complex pro-
cedure for measuring the amount of each n-alkane and asso-
ciated iso-alkanes, which is difficult to carry out in an
accurate manner.
Immediately after the issuance of D5442, it was realized
that the Scope of the method (alkanes from n-CI 7 to n-C44)
was applicable only to the analysis of paraffin waxes, exclud-
32 MANUAL ON H Y D R O C A R B O N A N A L Y S I S
ing h i g h e r c a r b o n n u m b e r waxes. The availability of n-Cs0
a n d n-C60 s t a n d a r d s enables the m e t h o d to be extended to
m i c r o c r y s t a l l i n e waxes. Also, the existing m e t h o d does not
(1) take into account r e s e a r c h w o r k c a r r i e d out in the later
p a r t of the 1980s on the effect of different integration meth-
ods that w o u l d result in i m p r o v e d a c c u r a c y of wax c h r o m a -
t o g r a p h y results a n d (2) include the use of p r o g r a m m a b l e
t e m p e r a t u r e v a p o r i z e r (PTV) injectors [5,6]. The accurate
quantitative analysis of microcrystalline waxes up to n-CT0
using the PTV injector was further amplified by Ludwig [7 ] in
1995 (30 years after his original p a p e r on w a x c h r o m a t o g r a -
p h y [3 ]).
A review of the m e t h o d has t a k e n place, a n d it is h o p e d that
a new r o u n d - r o b i n evaluation can be c a r r i e d out before the
next revision of D5442 to validate (1) the use of the PTV
injector, (2) use of the n-Cs0 a n d n-C60 standards, a n d (3)
substitution of a new s i m p l e r calculation methodology.
Oil Content Analysis
During wax refining, increasing a m o u n t s of oil are re-
moved, a n d this process needs to be controlled. Also, the oil
content of slackwaxes, petrolatum, a n d waxes m u s t be as-
sessed for end user specification. F o r high oil content waxes
(i.e., greater t h a n 15%), ASTM Test M e t h o d D3235 was de-
vised. This m e t h o d involves a lengthy p r o c e d u r e of dissolving
a weighed a m o u n t of wax in a mixture of methyl ethyl ketone
(MEK) a n d toluene, followed b y cooling to - 32°C to precipi-
tate the wax. The oil a n d solvent are removed; then the
solvent is e v a p o r a t e d off to p r o d u c e a weighable a m o u n t of
oil. GLC analysis of the solvent-extracted m a t e r i a l has shown
that the d e t e r m i n e d "oil" contains a small a m o u n t of addi-
tional wax, Y/-CI7to r/-C22 alkanes, t h e r e b y p r o d u c i n g a small
error. ASTM Test M e t h o d D721 was devised for waxes con-
taining less t h a n 15% oil. It is used in the specification of
food-contact a p p r o v e d waxes a n d for waxes used in explo-
sives. This m e t h o d is similar to ASTM D3235, b u t uses only
M E K as the solvent.
Both m e t h o d s take over half a day to complete, are l a b o r
intensive, p r o d u c e variable results, a n d c a n n o t easily be used
to analyze the oil content of microcrystalline waxes. This is
not very useful for refinery process control, n o r for the analy-
sis of wax m a t e r i a l s used in food-contact applications, etc.
Refineries have o v e r c o m e this lengthy p r o c e d u r e by using
various n u c l e a r m a g n e t i c r e s o n a n c e (NMR) techniques, cali-
b r a t e d using waxes analyzed by either ASTM D721 o r D3235.
In 1997 the UK L a b o r a t o r y of the G o v e r n m e n t Chemist
(LGC) p r o d u c e d a wax certified reference m a t e r i a l with an oil
content of 0.54% (Reference CRM:LGC 3004) [8]. This is
useful as a n analytical quality control s t a n d a r d a n d over-
comes the p r o b l e m of i n t e r l a b o r a t o r y disputes.
Over the p a s t three years there has been a growing interest
in the use of pulse NMR for the analysis of waxes for oil
content. This technique relies on the fact that, after a wax has
experienced a pulse of r a d i o - f r e q u e n c y radiation, the signals
received f r o m the solid a n d liquid phases decay at different
rates a n d that the a m p l i t u d e of each signal is p r o p o r t i o n a l to
each p h a s e present. The solid signal decays r a p i d l y whereas
the liqu!d signal lasts m u c h longer. The s a m p l e is cooled so
that the wax is totally solid a n d the liquid signal is p r o p o r -
tional to the oil content.
An N M R m e t h o d has n o w b e e n developed, in conjunction
with Oxford I n s t r u m e n t s , as a suitable alternative to ASTM
Methods D721 a n d D3235. The N M R m e t h o d provides a
r a p i d d e t e r m i n a t i o n of oil content, a unified m e t h o d for all
wax oil content/solvent extractables analysis (covering the
r a n g e 0.2 to 35% oil content), the exclusion of hot solvents,
a n d it is easy to analyze the oil c o n t e n t of microcrystalline
waxes. The c a l i b r a t i o n for this m e t h o d can n o w be c o m p a r e d
with the present ASTM D721 b y using the LGC3004, 0.54%
oil in wax s t a n d a r d CRM. A p r o p o s e d draft ASTM m e t h o d is
being written for circulation a m o n g i n s t r u m e n t m a n u f a c t u r -
ers a n d users. It is h o p e d that the final draft will be jointed
with the Institute of P e t r o l e u m a n d other s t a n d a r d i z a t i o n
bodies so that a n i n t e r n a t i o n a l r o u n d r o b i n test can be car-
ried out with sufficient participants.
FUTURE TRENDS
In the next five years the p r o b l e m s associated w i t h the GLC
analysis of waxes should be resolved, a n d there should be a
n e w ASTM m e t h o d using N M R to m e a s u r e the oil content/
solvent extractables. Also, ASTM Test Method D4419 needs to
be u p d a t e d a n d e x p a n d e d to i n c o r p o r a t e the m e a s u r e m e n t of
wax enthalpy so t h a t the degree of crystallinity can be esti-
mated.
There also needs to be i m p r o v e m e n t s to ASTM Test
M e t h o d D1833, Test M e t h o d for O d o r of Petroleum Wax, a
w h i c h requires at least five people examining the o d o r of a
wax u n d e r rigorous conditions. It is not a very practical test
for small, m o d e r n laboratories. Solvent odors can be quanti-
fied by h e a d s p a c e GLC, but o t h e r odors, such as those due to
oxidation, are m o r e complex a n d difficult to detect. F o r sev-
eral years the possibility has b e e n explored of using a new
type of i n s t r u m e n t a t i o n that consists of up of 32 sensors
acting as an "electronic nose" to analyze h e a d s p a c e emis-
sions. The responses from the multi-elements of the detector
are complex a n d variable. Therefore, the electronic signals
m u s t be processed as a neural network, a n d each a r o m a has
to be "learned" by the software. These i n s t r u m e n t s are capa-
ble of m e a s u r i n g odors from individual waxes b u t will need
further d e v e l o p m e n t to be of practical use for analyzing a
variety of waxes. This example illustrates that there is still
plenty of scope for the d e v e l o p m e n t of new m e t h o d s for the
analysis of h y d r o c a r b o n s in waxes.
REFERENCES
[1 ] Dyroff, G. V., Ed., Manual on Significance of Tests for Petroleum
Products, Chap. 10, ASTM Manual Series MNL1, 6th ed., 1993.
[2 ] Scott, C. G. and Rowel1, D. A., Nature, Vol. 187, 1960, p. 143.
[3 ] Ludwig, F. J., Analytical Chemistry, Vol. 37, 1965, p. 1732.
[4 ] Gouw, T. H., Whittemore, I. M., and Rentoft, R. E., Analytical
Chemistry, Vol. 42, 1970, p. 1394.
[5 ] Barker, A. D. in "Wax Chromatography--The 80's Crossroads,"
Petroanalysis '87, G. B. Crump, Ed., John Wiley & Sons Ltd., New
York, 1988.
[6 ] Barker, A. D., "The Chromatographic Analysis of Refined and
Synthetic Waxes," Journal Chromatography Library, Vol. 56,
aAnnual Book of ASTM Standards, Vol. 05.01.
 C H A P T E R 5 - - A N A L Y S I S OF W A X E S 33

Chromatography in the Petroleum Indust~, E. R. Adlard, Ed., [8 ] Petroleum Wax Oil Content CRM: Reference No. LGC 3004; Of-
Elsevier Science B.V., New York, 1995. fice of Reference Materials, Laboratory of the Government
[7 ] Ludwig, Sr., F. J., Journal of Chromatography A., Vol. 718, 1995, Chemist, Queens Road, Teddington, Middlesex, TW11 0LY, En-
p. 119. gland.