Petroleum Waxes
G. Ali Mansoori, 1 H. Lindsey Barnes, 2 and
Glenn M. Webster3
Chapter 19 (Pages 525-556) of:
"Manual 37 - Fuels and Lubricants Handbook: Technology,
Properties, Performance, and Testing"
ASTM Manual Series: MNL37WCD
P.O. Box C700, ASTM International, West Conshohocken, PA
19428-2959
WAXES ARE USUALLY SOLID AT ROOM TEMPERATURE because they
contain linear paraffinic hydrocarbons with carbon chains of
various lengths. Waxes can vary in consistency from easily
kneadable to brittle. They exhibit relatively low viscosity at
temperatures slightly above their melting point. The ap­
pearance of waxes Can vary from translucent. to opaque, but
they are not glassy. The consistency (i.e., hardness) and solu­
bility of waxes depends on the temperature at which they are
observed.
The use of waxes dates back more than 5000 years. As early
as 4200 B.C. the Egyptians extracted a waxy �ubstance from
the honeycomb of bees and used it to satw:ite · linen wrap­
pings of mummies [!]. The spulptured porittaffof the de­
ceased decorating a coffin cover was often modeled in
beeswax and painted with pigmented beeswax. Another use
of wax was in the preparation of erasable writing tablets. Fas­
tening together several tablets with fiber produced forerun­
ners. of the modern book [2].
Waxes are classified by the matter from which they are de­
rived: insect, vegetable, synthetic, and mineral [3]. Beeswax
is an example of insect wax. The chemical composition of
beeswax is. unique and its characteristics vary with the
species of the honeybee. Apis mellifera is the most common
cultured bee in the world and will provide a chemical gener­
alization of composition of wax for this species [4]. Beeswax
is secreted in eight glands on the underside of the worker bee.
Bees are believed to secrete one pound of wax £Or every eight
pounds of honey they produce. Since secreted beeswax read­
ily absorbs color, the final color of the beeswax is influenced
by the source of the pollen. A typical composition analysis of
beeswax is provided in Table I. Beeswax is extracted by melt­
ing or boiling the honeycomb in water and has applications
in pharmaceuticals and cosmetics, and is the primary com­
ponent of religious candles.
Vegetable waxes are extracted from the leaves, bark, and
berries (seeds) of plants and trees. Abnost all multi-cellular
plants are covered by a layer of wax [5]. Only a few species
grown in semiarid climates produce enough wax to be com­
mercially viable for recovery. Carnauba and candelilla wax
are two of the most common vegetable waxes that are com­
mercially marketed [6]. Carnauba wax is removed from the
dried leaves (fronds) of palm trees grown in the northeast re­
gion of Brazil. Carnauba is utilized in the polish paste indus-
1 Department of Chemical Engineering, University of Illinois at
Chicago, 810 S. Clinton Street, Chicago, IL 60607-7000.
2 CITGO Petroleum Corporation, Highway 108 South, P.O. Box
1578, Lake Charles, LA 70602.
3 63 Rocklege Rd., Hartsdale, NY 10530.
525
try as a gelling agent for organic solvents·and as a raw mate­
rial used. in lipstick formulations for the cosmetic market.
Carnauba wax is recognized generally as safe by the United
States Food and Drug Administration.
Candelilla wax is harvested from the shrubs Eurplwrbiea
antisiphilitica, E. cerifera, and Pedilanthus pavonis in Mexico
and southwest Texas. The candelilla wax is recovered after
the entire mature plant is uprooted and immersed in acidi­
fied boiling water. During the immersion, the candelilla wax
floats to the surface and is skimmed off. The primary market
for candelilla wax is cosmetics where it is a component in lip­
stick formulations. The chemical composition of carnauba
and candelilla wax is listed in Table 2.
Synthetic waxes are derived from either the Fischer-Trop­
sch process [7] or by ethylene based polymerization pro­
cesses [8]. The Fischer-Tropsch (F-T) process originated in
Germany in the 1920s and is illustrated schematically in Eq
I. The F-T process was developed to synthesize hydrocarbons
and oxygenated compounds from a mixture of hydrogen and
carbon monoxide. During World War II, the F-T process was
· used by Germany to produce fuels from coal-derived gas. The
first commercial plant in South Africa started in 1955 at
Sasolburg, using coal as a feedstock. The so-called Sasol pro­
cess is illustrated in Fig. I [9]. This plant produces waxes, fu­
els, pipeline gases (i.e., ethylene, methane), and other prod­
ucts using a fixed bed catalyst F-T process. During the F-T
process, carbon monoxide, which is generated from coal
gasification, is reacted under fixed-bed conditions using
high-pressure at approximately 220°C in the presence of an
iron catalyst to produce synthetic hydrocarbon waxes, as
shown in Eq 1. Typical reaction products that may be derived
from the F-T process are listed in Table 3.
2nH2 + nCO -> Cn H2n + nHzO (1)
Poly(ethylene) waxes may be prodticed by the industrial
polymerization of ethylene using high or low pressure ethy­
lene polymerization technology [10], or as thermal decompo­
sition products of the polyethylene polymers. The molecular
weights and melting points of the synthetic waxes as com­
pared with the Fischer-Tropsch waxes are listed in Table 4.
The market stability of pricing and availability of insect
and vegetable waxes is affected by climate conditions and
natural disasters. With the advent of the petroleum industry,
the waxes from mineral and synthetic sources surpassed the
annual production of the combined total of the other two wax
categories. Waxes from insect and vegetable sources are mix­
tures of long chain fatty acids, esters of aliphatic alcohols,
and hydrocarbons. Waxes from mineral origins are chemi-
526 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

TABLE I-Compositional analysis of beeswax. TABLE 3-Products derived from the Fischer-Tropsch process.
Component Amount in wt. % Approx. Typical
Product Yield (wt.%)
Monoesters, C1sli.31COOC3oH61; C2sHs1COOC30�1 55-65
Diesters, triesters, hydroxy diesters 8-12 Paraffins (i.e., methane, ethane, propane, 7.2
Free fatty acids, C23COOH-C31COOH 9.5-10.5 and butane)
Free fatty alcohols, C340H-C 360H 1-2 Olefins (i.e., methylene, ethylene, propylene, 5.6
Hydroxy-monoesters, C 14H29CH(OH)COOC26H6 1 8-10 and butylene)
Hydrocarbonsa, C2sHs2-C31H64 12-15 Gasoline (Cs-Cu) 18.0
Moisture and mineral impurities 1-2 Diesel (C,2-C") 14.0
aHydrocarbons most commonly found in beeswax include nonacosane
C19 to C23 7.0
(C2�) and nentriacontane (C31H64). Medium Wax (C24-C3s) 20.0
Hard Wax (>C,s) 25.0
Water soluble non-acid chemicals 3.0
Water soluble acids 0.2

¢-,
TABLE 2--Chem.ical composition of camauba and candelilla wax.
Component Carnauba (wt.%) Candelilla (wt.%)
TABLE 4-Comparison of Fischer-TroJ)Sch waxes with other
Monoesters 83-88% 28-30% synthetic waxes.
Fatty alcohols 2-3 2-3 Type of Wax Molecular Weight Melting �oints; °C
Free fatty acids 3-4 7-9
Hydrocarbons a 1.5-3.0 49-57 Fischer-Tropsch wax 500-1200 85-110
Resins 4--6 4--6 Low Pressure polyethylene 900-3000 90-125
Moisture and inorganic residue 0.5-1 2-3 wax
High Pressure polyethylene 500-4000 85-130
aHydrocarbons commonly found in camauba and candelilla wax are prin­
cipally hentriacontane (C 31 l¼) and tritriacontane (C33f4s).
wax
Pyrolysisa waxes 1000-3000 90-130
aPyrolysis waxes are derive<J from thermo-cracking of polyethylene.

P0WER cally inert and are primarily composed of straighfchain

COAL PLANT
WATER (paraffinic) hydrocarbons.
STEAM Petroleum wax may vary compositionally over a wide
range of molecular weight, up to hydrocarbon chain lengths
AIR of approximately CS0-C60. It is typically a solid at room
temperature and is derived from relatively high boiling
petroleum fractions during the refining process. Petroleum
NH,
waxes are a class of mineral waxes that are naturally occur­
MWCAS
TARACID PIJBI1'JCAIION ring in various fractions of crude petroleum. They have a
COz+lfiS wide range of applications that include: coating of drinking
1lREGAS
cups; an adhesives additive; production of candles and rub­
ber; as components of hot melts, inks, and coatings for paper;
and they can be used in asphalt, caulks, and binders. This
chapter will provide a review of petroleum waxes including
history, production, types, chemical composition, molecular
structure, and property testing.

0 w:
DISCUSSION
f---+CO,

C, C,IC, Classification of Crude Oils and Chemical

.-------, Structure of Ingredients
OILS
Petroleum crude oil, commonly referred to as crude oil, is a
complex mixture of hundreds of compounds including
solids, liquids, and gases that are separated by the refining
process. Solid. components at room temperature iriclude
asphalt / bitumen and inorganics. Liquids of increasing vis­
C,, cosity vary from gasoline, kerosene, diesel oil, and light and
heavy lubricating stock oils. Also included are the major com­
FIG. 1-Generalized Sasol Plant for hydrocarbon synthesis . ponents of natural gas, which include methane, ethane,
by the_ Fischer-Tropsch Process.
propane, and butane (11).
An elemental analysis of crude oil shows that it consists of
primarily two elements: hydrogen (11-14%) and carbon
 CHAPTER 19: PETROLEUM WAXES 527
TABLE 5-Crude oil content.
Crude Type Solvent Neutral Oil Base Oil Wax.Content Sulfur and Nitrogen Asphalt API Gravity" ASTM Test Method
Paraffinic base Yes Yes <10% Low No >40 E-1519
Naphthenic base No Yes No Low No <33 D-2864
Intermediate base No Yes <6% Low Yes 33-40 D-8
Asphaltic base No Yes 0% High Yes <10 D-1079
aAmerican Petroleum Institute gravity is an arbitrary scale expressing the density of liquid petroleum products. The measuring scale is calibrated in terms of
degree API (0API) and can be calculated in terms of the formula: 0AP[= 141.5/(SGL[60°F)) - 131.5 where SGL stands for liquid specific gravity with respect to wa­
ter. The higher the value of API gravity, the more fluid the liquid.

(83-87%). Crude oil hydrocarbons contain long hydrocarbon
chains (saturated and unsaturated), branch structures, and
ring structures, with each having specific physical and chem­
ical properties. Small quantities of other compounds con­
taining sulfur, oxygen, nitrogen, carbon, and hydrogen are
frequently present in crude oils.
Crude oils are generally classified based on their predomi­
nant hydrocarbon structure type, as shown in Table 5. The
types are :['.eferred to as paraffi.nic, naphthenic, intennediate
(mixture of paraffinic and naphthenic crude), and asphaltic
base crude (12].
Paraffinic hydrocarbon fractions are saturated linear or
branched alkanes. Naphthenic fractions contain five and six
carbon cyclic alkane (alicyclic) structures. Naphthenes are
monocyclic in the lower-boiling fractions (i.e., gasoline) and
polycyclic in the higher-boiling fractions (i.e., lubricating oils)
(13]. The asphaltic crudes contain unsaturated aromatic
structures containing rings of five and six member carbon
atoms. Aromatics are defined as those classes of organic com­
pounds that behave chemically like benzene. They are cyclic,
unsaturated organic compounds that can sustain an induced
electronic ring current due to delocalization of electrons
around the ring. Aromatic base oils contain 20-25% aromatic
compounds. A constituent of asphaltic crudes is asphaltene.
Asphaltenes are defined as the high molecular weight non­
hydrocarbon fraction of crude oil precipitated by a designated
paraffinic naphtha solvent at a specified temperature and sol­
vent-oil ratio (14]. Like the naphthenic crude, the aromatic
rings are monocyclic in the lower boiling fractions and poly­
cyclic in the higher boiling fractions. Various ASTM test
methods listed in Table. 6 are used for sampling, separation,
and characterization of petroleum fractions.
Petroleum waxes are derived from both paraffinic and in­
termediate crude oils and are composed of three basic carbon
structures (i.e., linear, branched, and ring) that are charac­
teristic of the crude oil.
Production, Transportation, and Refining of Waxy
Petrolenm Crndes]
The majority of crude oils produced around the world contain
substantial amounts of paraffin wax. These compounds,
sparingly soluble in solution components of the crude oils,
crystallize at lower temperatures and are the major contribu­
tors to petroleum wax deposits [IS]. The wax present in
petroleum crudes primarily consists of paraffin hydrocarbons
(C18-C36), known as paraffin wax, and naphtenic hydrocar­
bons (C30-C60). Hydrocarbon components of wax can exist
in various states of matter (gas, liquid, or solid) depending on
their temperature and pressure. When these hydrocarbons
freeze, they form crystals, which are known as macrocrys-
TABLE 6-ASTM test methods used for sampling, separation, and
classification of various oil samples and the procedures used.
Test Method Procedure and Application
D4057 Practice for manual sampling of petroleum and
petroleum products
D270 Sampling of petroleum and petroleum products
D4007 Centrifuge method for determination of water and
sediment in crude oil
D86 Distillation of petroleum products
D2007 Clay-gel absorption chromatography for oil- samples
of initial boiling point of at least 260°C (500 °F} into
the hydrocarbon types of polar compounds, aro­
matics and saturates, and recovery of representa­
tive fractions of these types
D2425 Mass· spectrometry for classification of hydrocarbon
typ'es-in middle-distillate
D2549 Elution chromatography for separation of represen­
tative aromatics and non-aromatics fractions of
high-boiling oils, between 232 aod 538°C (450 aod
1000°F)
D2786 High ionizing voltage mass spectrometry for hydro­
carbon types analysis of gas-oil saturate fractions
D2887 Gas chromatography for boiling range distribution
ofpetroleum fractions
D3239 High ionizing voltage mass spectrometry for aro­
matic types analysis of gas-oil aromatic fractions
D3279 Titration for determination of the weight percent of
asphaltenes as defined by insolubility in normal
heptane solvent
talline wax. Those formed from naphtenes are known as mi­
crocrystalline wax. A hydrocarbon in pure state has definite
boiling and freezing (or melting) points, which can be mea­
sured in the laboratory (16]. Knowing the intermolecular en­
ergy parameters or critical properties and acentric factor
and/or refractive index of hydrocarbons, one can predict their
boiling point using vapor pressure correlations or equations
of state as discussed in Section I of this report. However, such
methods are not capable· of predicting pure hydrocarbon
freezing points. There are other methods that can be used to
predict hydrocarbon and wax freezing (melting) point, which
include but are not limited to variational statistical mechani­
cal theory (17] and cell-lattice theories (18].
Waxy Crude Oil
A waxy crude usually consists of: (a) a variety of light and in­
termediate hydrocarbons (paraffins, aromatics, naphtenic,
etc.); (b) wax as defined above; and (c) a variety of other
heavy organic (non-hydrocarbon) compounds, even though
at very low concentrations they include resins, asphaltenes,
diamondoids, organometallics, etc. When the temperature of
a waxy crude oil is lowered to its cloud point, first the heav­
ier fractions of its wax content start to freeze out. ,Upon low­
ering of the temperature of a crude oil to its pour point al-
---;,_;:_ - -
528 MANUAL 37: FUEI.S AND LUBRICANTS HANDBOOK
most all the fractions of its wax content will freeze out. A
waxy crude is characterized by its cloud point and pour
point, which are measured according to ASTM Test Methods
D 2500 and D 97, respectively, as they are dis.cussed later in
this report.
A clean waxy crude is defined as a crude oil in which there
exists only hydrocarbons and wax as its only heavy organic
constituent. As the clean waxy crude flows through a cold
·pipe or conduit (with a wall temperature below the cloud
· point of the crude) wax crystals may be formed on the wall,
which could then grow until possibly the whole inner wall is
covered with the encapsulating oil �ide the wax layers. As
the wax thickness increases, pressure drop across the pipe
needs to be increased to maintain a constant flow rate. As a
result, the power requirement for the crude transport will in­
crease. The arterial blockage problems of clean waxy crude
can be efficiently controlled by insulation and heating of the
pipe to a temperature above its cloud point. Most of the ex­
isting wax deposition problems of the clean waxy crudes are
due to the lack of proper insulation and heating systems. As
a result, application of chemical anti-foulants and frequent
use of pigging operations have become necessary [15]. Regu­
lar paraffinic or waxy crudes are widespread. The major com­
plex systems problems related to the production, processing,
and transportation of these medium-gravity fluids is not just
crystallization of their wax content at low temperatures, but
the formation of deposits that do not disappear upon heating,
and will not be completely removed by pigging.
Regular waxy crudes are not clean and, in addition to wax,
they contain other heavy organics such as asphaltene, resin,
etc. [1 SJ. Asphaltenes do not generally crystallize upori cooling
and, for the most part, they may not have definite freezing
points. Depending on their natures, these other heavy organics
will have different interactions with wax, which could either
prevent wax crystal formation or enhance it. Existence of
branched paraffins, aromatics, naphtenes, and resins in
petroleum, however, contribute less to µtese deposits, but mod­
ify their crystallization behavior. However, asphaltene pres­
ence in the crude oil could prevent or erihance wax deposition
depending in the microscopic nature of asphaltene [19 ,20].
The precipitation of wax from petroleum fluids during pro­
duction and transportation may give rise to a variety of prob­
lems [17]. One ofthe main problems observed is deposition of
solid material on well and pipe walls as demonstrated in Fig.
2. This happens if (a} the temperature of the wall is below the
cloud point of the oil, {b) a negative radial temperature gradi­
ent is present in the flow, (c} the wall friction is high enough
for wax crystals to stick to the wall, and (d} asphaltene present
in the crude oil has already deposited and has increased the
friction of the wall (changed of wettability) and acting as mor­
tar for the sticking together of wax crystals. Wax crystalliza­
tion may cause three problems: (a} higher viscosity, which
leads to pressure losses, (b) high yield stress for restartability
of flow, and (c} fouling of petroleum flow arteries [15].
To predict wax deposition tendency of a crude oil it is im­
portant to know its composition for paraffin wax and the other
components present in, or added to, the crude oil; their com­
position distributions; and the pressure and temperature of the
system. Thermodynamics and statistical mechanics of phase
transitions in polydisperse mixtures can be utilized to develop
predictive models for wax deposition in petroleum fluids [17].
FIG. 2-Pipeline petroleum transport plugging due to
wax and other heavy organics depositions (Courtesy of
Phillips Petroleum Company).
To predict the deposition as a function of time, principles of en­
ergy and mass conservation, the Jaws of diffusion, and the prin­
ciples,of phase transitions need to be considered [21,22]. In or­
der to prevent or remediate arterial blockage/fouling and
facilitate the production of regular waxy crudes, many issues
must be undertaken: (a} detailed fluid properties characteriza­
tion, (b} production scheme alternatives, (c} retrograde con­
densation and deposition behavior prediction, (d) onsets of de­
position studies, (e) equipment and facility options, (f) design
and use of chemical anti-foulants and/or pour-point depres­
sants and blending alternatives, (g} performance specification
and maintenance planning, and (h) transportation, storage,
and blending studies [23,24].
Petroleum Refining .
Crude oil is first desalted if salty, deasphalted if asphaltenic,
and dewaxed if highly waxy, before it is distilled in an atmo­
spheric distillation unit to separate light ends (gases}, naph­
tha, gasoline, jet, kerosene, gas oil distillate, and residuum
(resid) (see Fig. 3). The residuum (resid) remaining after the
atmospheric distillation is then further fractionated in a vac­
uum distillation unit into fractions that are distinguishable
by viscosity for further processing into lubricating oil base
stocks. Wax is concentrated in the distillate stream and the
residuum fraction is used to produce the base oils for lubri­
cant formulation. Both the distillate and residual lube frac­
tions (stock) contain unde.sirable constituents such as aro­
matics that must be removed by extraction to yield base oils
that are thermally stable with a sufficiently high viscosity in­
dex• product. The distillate fraction is extracted with a sol-
4
Viscosity Index is defined as V.I. = (µL - µx)/(µL - µH), where µL
is the viscosity at 100°F of the zero-V.I. oil, µH is the viscosity at
100°F of thel00 V.I. oil, and µxis the viscosity at-100°F of the un­
known (test) oil. See ASTM D 567 and D 2270 for further detail. A
measure of the magnitude of viscosity changes in lubricating oils
with changes in temperature. The higher the viscosity index number,
the more resistant the oil is to change in viscosity.

vent (such as furlural) that has a greater solubility (selective
solvent) for the components having a low viscosity index. The
residuum fraction is extracted with propane to remove bitu­
men (asphalt) and resinous material. The desirable oil and
wax component is solubilized for further processing.
The nonsoluble portion of the distillate extraction and the
soluble portion of the residuum fraction are referred to as the
raffinate phase and both contain the more paraffinic oil.
Wax, which typically exhibits a hlgh viscosity index, remains
in the raffinate phase for further processing. Because the raf­
finate produced from the extraction process contains wax,
whlch crystallizes at relatively hlgh temperatures (> IS °F =
-9.4° C), the fluidity of the base oil that exhibits a hlgh pour
CHAPTER 19: PETROLEUM WAXES 529
point (i.e., the temperature where the oil ceases to be fluid) is
reduced.
Solvent Dewaxing Process
The solvent dewaxing process can be divided into three dis­
tinct sections: (a) crystallization of the wax components by di­
lution and chllling, (b) filtration of the wax from the solution
of dewaxed oil and solvent, and (c) recovery of the solvent
from the dewaxed oil and wax products [25]. To overcome the
hlgh pour point, a solvent dewaxing process has been devel­
oped to remove the wax from lubricating oil basestocks, as
shown in Fig. 4. The most widely used solvent dewaxing pro-

Water

Desaldng Naplrta

Nater
Gasoline,
Jet,
Kerosene
Crude
Storage
Tank Distillate
Dewaxed
Oil
v&ccum
Dis�on

FIG. 3-Schematlc Illustration of various possible locations of wax production in

petroleum refining.

Oily Wax
Receiving Product Shipped

mended
Product

.......
--
Oily Wax 1----..-C.,,stallization
Storage
..........
Wu:
a
.Fliall sai...t
Oil
S!an,p

Stop W.XIB' Faall 01 Prailllc!Wu:

FIG. 4-Solvent dewaxing process for the removal of wax from lubri­
cating oil slackwax basestocks.
530 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

90 dewaxing process. The major process variables include: 1)

80 solvent composition, 2) feedstock composition, 3) solvent di­

--
70 lution procedure, 4) filtration temperature, 5) filtration pro­
00 cedure, and 6) solvent recovery method.
50 1. Ketone based solvents are excellent solvents for oils at low
� 40
temperatures necessary to remove the wax by filtering. Di­

""
'S 30 luting the raffinate with too much ketone-based solvent can
·15 20 cause the oil to separate into a distinct l ayer. Oil phase sep­
1
s
10
aration will adversely affect the yield of wax and result in
0 Oil Phase
u •IO Sepa�tion the wax portion having an undesirable higher oil content.
The likelihood of oil phase separation can be determined
-20
-30
experimentally by maintaining a constant solvent dilution
ratio and changing the percentage of ketone content.
-40
2. If the raffinate feedstock contains a high proportion of
.50
paraffinic content, it will have a high viscosity or viscosity
30 40 50 00 W 80 90 � index. An oil phase separation can occur when a ketone­
% MEK Content In Dewu Solvent based dilution solvent is mixed with the raffinate.
FIG. 5-lllustration of the effect of the ratio of MEK to the 3. The amount of dilution with the solvent can affect the oil
petroleum fraction being dewaxed on the resulting cloud point content of the wax. Using a solvent dilution greater than 2
of the mixture. parts solvent to 1 part raffinate will result in a re.duction of
the oil content of the wax.
4. The cooling temperature used to crystallize the wax during
the filtration process can affect the oil content of the wax
cesses are based on solvent mixtures of methyl ethyl ketone and the desired physical properties such as melting point
. and toluene, methyl ethyl ketone and methyl isobutyl ketone, and hardness. If the dilution solvent is too cold or low cool­
or methyl isobutyl ketone itself. Figure 5 illustrates the effect ing temperatures are used, the crystal size of the wax formed
of the ratio of MEK to the petroleum fraction being dewaxed on the surface of the rotary filter will be small and will re­
on the resulting cloud point of the mixture. In the dewaxing tain more oil. As the dewaxing temperature is reduced,
process, the raffinate (feedstock) is diluted with solvent and , softer and lower melting point wax fractions will increase
heated 15-20°F (-8-11 ° C), above the cloud point of the raffi­ the overall production yield. As illustrated in Table 7, as a
nate/solvent mixture (or slurry) and chilled at controlled rates
in double-pipe scraped-surface heat exchangers and chillers.
The slurry is chilled to 5-20 °F (-3-11 °C) below the desired
pour point of the oil. When the wax/solvent solution is cooled,
wax crystals precipitate from the solution, which are then
removed by filtration using a rotary vacuum filter. The crys­ -i 40.

tallized wax forms as a layer (cake) on the surface of the rotary

vacuum filter. The wax cake (filtrate) is washed with a spray
of a cold solvent to remove any residual oil before being dis­
I
a 30

charged from the primary filters. At this point, the wax 6M

I
contains 10--40% oil and is referred to as "slack wax" if it is de­ '20
rived from the distillate lube fraction, or "petrolatum" if it is

--
derived from the residual lube fraction. Figure 6 illustrates the
effect of solvent dilution ratio on the amount of residual oil 10

�·
content in the slack wax.
To produce waxes with lower oil contents ( <5%), an addi­
tional dewaxing process is performed. The wax cake from the 0
primary filter is diluted with additional solvent and filtered in 2;I 3'I 4:1 5;1 6;1
a second (repulp) rotary vacuum filter using the same oper­
ating conditions as the primary filters to obtain the desired
FIG. 6-lllustration of the effect of solvent dilution ratio on
wax oil content. the amount of residual oil content in the slack wax.
The solvent is recovered from the dewaxed oil filtrate by
flash vaporization and distillation. The solvent is recycled for
future use in the dewaxing process. Residual solvent in the
TABLE 7-Effect of dewax temperature on wax.
wax is recovered by flash vaporization and is recycled for fu­
ture process use. Wax Needle
Dewax Wax Wax Melt.Point Penetration
Temperature Yield (ASTM D 127) @ 77°F (25°C)
("F) ("C) (%) ("F) ("C) (ASTM D 1321)
Dewaxing Process Variables
60 15.6 62 141 60.6 11
Wax production yield, oil content of the wax, and the pour 55 12.8 67 139 59.4 13
point of base oil are directly affected by variables of the so 10.0 72 137 58.3 16

lower dewaxing temperature is used, wax yield increases
and the melting point and softness change.
5. The dewaxing process is performed to maximize the re­
covery of the wax with the desired oil content and physical
properties such as melting point and hardness. This re­
quires maintaining a uniform thickness (less than 2.5 cm)
of the wax cake on the rotary filter by controlling the pro­
cess temperatures and rotational speed of the filter. Apply­
ing wash solvents (for reducing oil content) uniformly pre­
vents cracking of the wax cake. Diluting with adequate
repulp solvent is necessary to provide a sufficiently fluid
raffinate.
The Wax Finishing Process
The last step in producing petroleum waxes is the finishing
process. This process involves the removal of odor and ques­
tionable color. In addition, the finishing process may involve
steps to reduce the polycyclic hydrocarbons to a level that
meets the Food and Drug Administration regulations for food
contact.5
Wax color removal may be performed by flowing wax
through a static bed of activated clay or bauxite. There is a
production loss in the amount of wax after completing the
clay or bauxite contact process. ThiS loss is attributed tO ab­
sorption of the wax on the clay or bauxite medium and the
production loss is greater for darker colored waxes. Newer
finishing process technology is based on hydrofinishing
(fixed bed catalytic process using hydrogen) and doesn't re­
quire any filtering medium. Hydrofinishing has the advan­
tage of processing waxes with negligible product loss [26].
If the wax exhibits a questionable odor (such as extraction
or dewaxing solvent odor), the wax may be steam stripped
(distilled) to remove traces of processing solvent. Hydrofin­
ishing may also be used to produce odor free waxes. After the
wax has completed the finishing process step, it can be
shipped to consumers; either in solid form (i.e., 22 kg car­
tons) or as a molten liquid (in specialized tanks with electri­
cal heaters or steam coils).
Types of Petroleum Waxes
There are two general types of petroleum waxes that are pro­
duced during the dewaxing process. Wax that is obtained
from the distillate lubricating oil fractions is known as
macrocrystalline wax (paraffin wax), and wax derived from
the residual distillate lubricating oil fraction is referred to as
microcrystalline wax (microwax). This nomenclature is
based on the crystal structure of the wax as seen through a
microscope (microstructure). A paraffin wax can be distin­
guished from a microwax by its larger c:rystal structure.
Paraffin waxes usually exhibit plate-like crystal structures
while microwaxes exhibit needle-like crystal structures.
The composition, nomenclature, and physical properties of
petroleum are related to the refinery process used in their
production. Slack wax is a refinery term for distillate-derived
waxes that have oil contents ranging from 3-40% by weight
oil. Scale wax is a distillate wax that has an oil content be-
5 FDA regulations for waxes, 21 CFR 172.886 and 21 CFR 178.3710.
CHAPTER 19: PETROLEUM WAXES 531
tween 1 and 3%. Petrolatums are derived from the residual
lubricant fractions with oil contents between 10 and 30%
Compositional and Molecular Characteristics of
Petroleum Wax
Paraffin waxes consist predominately of a mixture of straight
chain saturated hydrocarbon molecules (normal-alkanes)
with the chemical formula C,,H20+2 with n e: 16 [27,28]. In
order to demonstrate the physical properties of straight chain
saturated hydrocarbon molecules, Table 8 is reported as
taken from Ref 28. In this table the molecular weights, melt­
ing points, latent heats of fusion, densities (at 20°C), specific
heats in solid and liquid states, and boiling points of the nor­
mal alkanes from C 1 to C 100, all at atmospheric conditions,
are reported. According to this table, the first four alkanes of
the series, (from methane, CH., up to butane, C4H10) are
gaseous at room temperature and atmospheric pressure. The
alkanes between Cs and C 17 are liquids and alkanes with
more than 17 carbon atoms are waxy solids at room temper­
ature. The melting points and heats of fusion of alkanes in­
crease with their number of carbon atoms. In addition to the
n-alkanes, paraffin waxes may contain varying amounts of
iso- and cyclo-alkanes (i.e., branched chains and aliphatic
rings). Typically, paraffin waxes contain carbon atom chains___
of C 18 to C44. Their macrocrystalline structure is illustrated in
Fig. 7. Their plate-like crystal structures are illustrated by an
atomic force microscope image given in Fig. 8. Their molec­
ular weights are usually less than 450 and their kinematic vis­
cosity at 100°C (212 °F) will usually be less than six centis­
tokes. Being derived from distillate fractions, paraffin waxes
have distinct boiling point curves that consist of a minimum
and maximum value.
Microcrystalline waxes contain higher proportions of iso­
and cyclo-alkanes (naphthenic) than paraffin waxes. Micro­
rystallline waxes exhibit molecular weights between 500 and
700 with carbon atom chains ranging typically from C23 to
C85 in length. Their microcrystalline structure is illustrated
in Fig. 9. Microcrystalline waxes (microwaxes) exhibit kine­
matic viscosities greater than 10 centistokes at 100° C
(212 °F). Because microcrystalline waxes are derived from
residual fractions, they do not have a distinct boiling range.
Physical properties of microcrystalline waxes vary with the
type of crude oil and processing conditions used to produce
the wax. Typically, m.icrocrystalline, naphthenic waxes ex­
hibit needle-like microstructures.
Intermediate wax properties are intermediate between
those exhibited by paraffin and microcrystalline waxes. They
generally exhibit viscosities between 6 and 10 centistokes at
100°c (212° F) and a melting point between 155-165 °F
( -68-74°C). Intermediate waxes are derived from the highest
boiling distillate lubricating oil fraction and like paraffin
waxes, they exhibit a distinct boiling point range.
Petrolatums are soft, unctuous products having a melting
point between !00--149 °F (-38-o5 ° C). The term "unctuous"
means "smooth and greasy" in texture. Petrolatums are gener­
ally produced from the same residual oil fraction as micro­
crystalline waxes and can be prepared by controlled blending
of microcrystalline wax with mineral oil. Petrolatums generally
exhibit oil contents greater than 10% and are marketed with
colors that vary from dark brown to white..Table 9 lists the gen­
eral physical properties of the different petroleum waxes.
532 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

TABLE 8---Physical properties of n-Alkanes (28].

Specific Heat (/mol K)
Latent Heat
No.of Melting Pt of Fusion Density at 20°C Solid at Liquid at Boiling Pt
AlkaneS CAtoms Mol. Wt (K) (kJ/kg) (kg/m3) 298K 353K (K)
Methane 1 16 90.68 58 0.658 (g) 116.6
Ethane 2 30 90.38 95 0.124 (g) 184.6
Propane 3 44 85.47 80 1.834 (g) 231.1
Butane 4 58 134.79 105 2.455 (g) 272.7
Pentane 5 72 143.45 117 621 (I) 0167.2 309.0
Hexane 6 86 177.83 152 655 (I) 195.4 341.9
Heptane 7 100 182.55 141 679 (I) 225.0 371.6
Octane 8 114 216.37 181 699 (I) 254.2 398.8
Nonane 9 128 219.65 170 714 (I) 284.5 424.0
Decane 10 142 243.50 202 726 (I) 314.5 447.3
Undecane 11 156 247.55 177 737 (I) 345.0 469.1
Dodecane 12 170 263.55 216 745 (I) 376.0 489.5
Tridecane 13 184 267.75 196 753 (!) 406.9 508.6
Tetradecane 14 198 278.95 227 759 (I) 438.5 526.7
Pentadecane 15 212 283.05 207 765 (!) 470.0 543.8
Hexadecane 16 226 291.25. 236 770 (!) ---,__ 501.5 560.0
Heptadecane 17. 240 295.05 214 775 (s) 534.3 575.2
Octadecane 18 254 301.25 244 779 (s) 485.4 564.4 589.5
Nonadecane 19 268 305.15 222 782 (s) • 514.6* 618* 603.1
Eicosane 20 282 309.75 248 785 (s) 544.3 658* 617.0
Heneicosane 21 296 313.35 213 788 (s) 570.7* 698* 629.7
Docosane 22 310 317.15 252 791 (s) 598.1* 739.0 641.8
Tricosane 23 324 320.65 234 793 (s) 625.0* 772.0 653.4
Tetracosane 24 338 323.75 255 796 (s) 651.4* 805.0 664.5
Pentacosane 25 352 326.65 238 798 (s) 670.4* 815.9 675.1
Hexacosane 26 366 329.45 250 800 (s) 677.8 870.0 685.4
Heptacosane 27 380 331.95 235 802 (s) 728.1* 928* 695.3
Octacosane 28 394 334.35 254 803 (s) 752.8* 937.0 704.8
Nonacosane 29 408 336.35 239 805 (s) 777.2* 1001* 714.0
Triacontane 30 422 338.55 252 806 (s) 801.2* 1037* 722.9
Hentriacontane 31 436 341.05 242 808 (s) 824.5* 1073* 731.2
Dotriacontane 32 450 342.85 266 809 (s) 867.4 1095 740.2
Tritriacontane 33 464 344.55 256 810 (s) 871.0* 1113 748.2
Tetratriacontane 34 478 346.25 268 811 (s) 887.4 1149 755.2
Pentatriacontane 35 492 347.85 257 812 (s) 916.0 1210* 763.2
Hexatriacontane 36 506 349.35 269 814 (s) 937.5* 1206 770.2
Heptatriacontane 37 520 350.85 259 815 (s) 959.1* 1276* 777.2
Octatriacontane 38 534 352.15 271 815 (s) 980.4* 1305* 784.2
Nonatriacontane 39 548 353.45 271* 816 (s) 1001* 1341* 791.2
Tetracontane 40 562 354.65 272 817 (s) 1022* 1411 795.2
Dotetracontane 42 590 357.32 273 817 (s) 1062* 1435 804.2
Tritetracontane 43 604 358.65 273* 819* (s) 1085* 1465* 813.2
Tetrateracontane 44 618 359.55 274 820* (s) 1102* 1495* 818.2
Hextetracontane 46 646 361.45 276 822* (s) 1140* 1553* 829.2
Octatetracontane 48 674 363.45 276 823 (s) 1177 1595 838.2
Pentacontane 50 702 365.15 276 825* (s) 1213* 1665* 848.2
Hexacontane 60 842 372.15 279 831*(s) 1380* 1916* 888.2
Heptacontane 70 982 378.65 281* 836* (s) 1526* 2131* 919.2
Hectane 100 1402 388.40 285* 846* (s) 1869* 2598* 935.2
(*)Predicted value.

(a) X'200
(b)
FIG. 7-A scanning electron microscopic illustration of a macrocrystalline structure wax
(a= 200 X; b = 1000 X).
 CHAPTER 19: PETROLEUM WAXES 533

FIG. 8-An atomic force microscope image of the spiral growth of paraffin crys­
tal (measuring approximately 15 microns across). Inset shows orthorhombic ar­
rangement (0A9 nm x 0.84 nm) of chain ends of one of the crystal terraces (cour­
tesy of Professor M.J. Miles).

(a) X 200 X 1000 (b)

FIG. 9-A scanning electron microscopic illustration of a microstructural characteriza­
tion of a refined paraffin wax (a. = 200 X; b = 1000 X).

TABLE 9-Physical properties of petroleum waxes.

Property Paraffin Wax Intermediate Microcrystalline Petrolatum
0
Melt. Point ( F) 110-155 150-165 14Q..a195 110-180
Molecular Wt. 320--450 450-550 450-700 450-700
Crystal Structure Plates Needles Needles Needles
Color White White-Yellow White-Dark Brown White-Dark Brown

Crystal Structure
Paraffin waxes exhibit several crystalline structures depend­
ing on their carbon chain length. Odd number carbon chains
between C, 9 and C29 exhibit an orthorhombic type crystal
structure. Even numbered carbon chains between C 18 and
C26 exhibit a triclinic structure. Even numbered carbon
chains between C28 and C36 exhibit a monoclinic structure.
All paraffins with carbon chains between C20 and C3• have a
distinct transition point (change in crystal form) lower than
the temperature at which they solidify. The transition point
occurs when the wax crystal structure rotates from a hexag­
onal to orthorhombic form as the wax solidifies from a
molten state. Paraffins with carbon atom chains above C37 do
not exhibit a transition point due to the wax solidifying di­
rectly into an orthorhombic crystal structure. Microcrys­
talline and intermediate type waxes do not exhibit any tran­
sition pOiht because they contain higher amounts of
branched alkanes.
Because of the steric effects caused by the arrangement of
atoms in the molecule there is a difference between alkanes
with odd and even numbers of carbon atoms. The even-num-
534 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

bered homologs have higher latent heat than the odd-num­
bered homologs. Humphries [29] showed that alkanes with an
even number of carbon atoms (between 20 and 32) and alka­
nes with odd number of carbon atoms (higher than 7) exhibit
a lattice transition in the solid state. The even-numbered car­
bon atom alkanes exhibit this transition closer to their melt­
ing point than the odd-numbered alkanes, as demonstrated in
Fig. 10. The boiling point of normal-alkanes for the tempera­
ture range on the figure are also shown in Fig. 10.
The lattice transition in alkanes is accompanied by the re­
lease of heat of transition. Generally, lattice transition occurs
in the solid state at about 2-S'K below the melting point. The
difference between the transition temperature and melting
temperature becomes smaller with increasing molecular
weight and finally disappears for alkanes with more than 36
carbon atoms [25,28] as demonstrated in Fig. 10. The heat as­
sociated with this solid-solid transition is subtracted from the
lattice heat of melting. Figures 11 and 12 show variations of
the latent heat of melting, melting point, and density of nor­
mal alkanes versus increasing number of carbon atoms in
their structure. According to these figures, while the melting
point and density versus the number of carbon atoms have
_

500

2"
MP
-450
TrT

I! 400 BP
"&
� 350

300

250

- 200

150

100
5 10 15 20 25 30 35 40
Number of carbon atoins
FIG. 10-Variation of melting point (MP), transition temperature (TrT), and boiling point
(BP) of normal alkanes with their number of carbon atoms [28].

-300

�
250
:

�200

150

100
0 20 40 60 . 80 100
Number of carbon atoms
FIG. 11-Variation of the latent heat of melting of normal alkanes with the number of car­
bon atoms in alkanes and exhibition of the steric effect [28].

l
 CHAPTER 19: PETROLEUM WAXES 535

a
4 n
, -r------------�1000 it is necessary to be able to predict thermodynamic proper­
Q' 0

j..
ties of wax. In this section we present five equations of state,
which are used for prediction of molar volumes, vapor pres­
0
p..
:--------------7800 -�,.Q"' sures, and supercritical solubilities of alkanes [32].
The simplest and one of the most widely known equations
::I

-]
o.0 300 of state is that of van der Waals. However, this equation of
-� state is not accurate enough to predict thermodynamic prop­

-_e,�
� erties of most fluids. Inspired by the van der Waals model, in­
::E · 600
vestigators have proposed several equations of state through
200
400
! the years. Almost every equation of state has been claimed. to

Table 10-Chemical composition and

thennophysical properties of Suntech P1!6
100 Paraffin Wax (30].
200 Hydrocarbon Weight�%
-0-MP
_._ DENSITY n-C-20 2.0
n-C-21 5.5
n-C-22 14.0
0 0 n-C-23 23.0
0 20 40 60 80 .. 100 n-C-24 22.0
Number of carbon atoms n-C-25
n-C-26
14.0
6.5
FIG. 12-Variation of the melling point and densily (@ 20'C) n-C-27 3.0
of normal alkanes with the number of carbon atoms in alkanes n-C-28 2.5
[28]. n-C-29 2.0
n-C-30 1.7
n-C-31 1.5
n-C-32 1.3
Melting range 316-329K
smooth variations, the latent heat of melting goes through Heat of fusion 266 kJ/kg
fluctuations. Because of the steric effects (the solid-solid Liquid specific heat 2.51 kJ/kgK
Solid specific heat 2.95 kJ/kgK
phase transitions mentioned above) the latent heats of melt­ Liquid thennal conductivity 0.24W/mK
ing of two consecutive alkanes do not always increase with in­ Solid thermal conductivity 0.24 W/mK
creasing number ofcarbon atoms, as demonstrated in Fig. 11. Liquid density 760 kg/m3
Each even-numbered alkane (with eight carbon atoms or Solid density 818kg/m3
Liquid viscosity J.90kg/ms
more) exhibit a lower latent heat than the odd numbered Molecular weight 332 g/mol
alkane having one carbon atom less than it. This fluctuation
of the latent heat of melting vanishes as the number of carbon
atoms approaches 40, and after that the latent heat increases

••
smoothly with increase of the number of carbon atoms. 2"
As an example, the composition and thermophysical data
of a paraffin wax sample (Suntech Pll6) [30], which contains
almost 100% normal alkanes, is reported in Table 1_0. Ac­ �
0
20
cording to this table, the hydrocarbons with 20--32 carbon
atoms constitute 99% of the mixture and the ones with more
than 32 carbon atoms constitute the remaining 1 %. Paraffin
waxes are generally polydisperse compounds for which poly­
disperse solution (continuous ntixture) theories may be used
15 • •
for characterization [31]. Figure 13 is the graphic represen­
tation of the composition data of Suntech Pl16 paraffin wax 10_
reported in Table 10.
Wax can be crystallized out of a solution by lowering its
• •
• •• • • •
temperature. Varying the temperature gradient causes a tran­ 5
sition between the growth of wax plates and growth of a tree­
like structure with regular branches as it is shown on Fig. 14.
Also shown on Fig. 14 is the banded growth of wax due to ad­
• . •

dition of a crystallization inhibitor. 20 21 .22 23 24 25 26 27 28 29 30 31 32

Equations of State
In order to characterize the petroleum wax and perform var­
ious operations on wax mixtures, such as.wax fractionation,
Number of carbon atoms
FIG. 13-The distribution of n-alkanes in Suntech P116
paraffin wax as a function of the number of carbon-atoms
(28].
 CHAPTER 19: PETROLEUM WAXES 535

�.s
400------------1000 it is necessary to be able to predict thermodynamic proper­

a....
$2' ties of wax. In this section we present five equations of state,
which are used for prediction of mol:tr volumes, vapor pres­
0 - sures, and supercritical solubilities of alkanes [32].
p.. 800 ,.Q- The simplest and one of the most widely known equations
=

-:E
300
-�
01)
of state is that of van der Waals. However, this equation of
state is not accurate enough to predict thermodynamic prop­
�
600 _e, erties ofmost fluids. Inspired by the van der Waals model, in­
�-
200
.... vestigators have proposed several equations of state through
the years. Almost every equation of state has been claimed to
�
400 �
Table 10---Chemical composition and
thermophysical properties of Suntech Pl16
100 Paraffin Wax [30].
200 Hydrocarbon Weight�%
-0-- MP
_._ DENSITY n-C-20 2.0
n-C-21 5.5
n-C-22 14.0
0 0 n-C-23 23.0
0 20. 40 60 80 . .100 n-C-24 22.0
Number of carbon atoms n-C-25 14.0
n-C-26 6.5
FIG. 12-Variation of the melting point and density (@ 20°C) n-C-27 3.0
of normal alkanes with the number of carbon atoms in alkanes n-C-28 2.5
(28]. n-C-29 2.0
n-C-30 1.7
n-C-31 1.5
n-C-32 1.3
Melting range 316-329 K
smooth variations, the latent heat of melting goes through Heat of fusion 266 kJ/kg
fluctuations. Because of the steric effects (the solid-solid Liquid specific heat 2.51 kJ/kgK
Solid specific heat 2.95 kJ/kgK
phase transitions mentioned above) the latent heats of melt­ Liquid thermal conductivity 0.24 W/rriK
ing oftwo consecutive alkanes do not always increase with in� Solid thermal conductivity 0.24 W/rriK
creasing number ofcarbon atoms, as demonstrated in Fig. 11. Liquid density 760kg/m3
Each even-numbered alkane (with eight carbon atoms or Solid density 818 kg/m3
Liquid viscosity 1.90kg/ms
more) exhibit a lower latent heat than the odd numbered Molecular weight 332 g/mol
alkane having one carbon atom less than it. This fluctuation
ofthe latent heat ofmelting vanishes as the number ofcarbon
atoms approaches 40, and after that the latent heat increases
smoothly with increase of the number of carbon atoms.
As an example, the composition and thermophysical data
ofa paraffin wax sample (SuntechP116) [30], which contains
25
,, ••
almost 100% normal alkanes, is reported in Table 10. Ac­ �
20
cording to this table, the hydrocarbons with 20-32 carbon
atoms constitute 99% of the mixture and the ones with more 'iii
than 32 carbon atoms constitute the remaining I%. Paraffin
waxes are generally polydisperse compounds for which poly­
disperse solution (continuous mixture) theories may be used
3:: 15
• •
for characterization [31]. Figure 13 is the graphic represen­
tation of the composition data of Suntech Pl 16 paraffin wax 1C
reported in Table 10.
Wax can be crystallized out of a solution by lowering its
temperature. Varying the temperature gradient causes a tran­ • •
• • • ••
5
sition between the growth ofwax plates and growth of a tree­
like structure with regular branches as it is shown on Fig. 14. • J.•

Also shown on Fig. 14 is the banded growth of wax due to ad­ •

dition of a crystallization inhibitor. 20 21 .22 23 24 25 26 27 28 29 30 31 32

)

Number of carbon atoms

Equations of State
FIG. 13-The distribution of n-<>lkanes in Suntech P116
In order to characterize the petroleum wax and perform var­ paraffin wax as a function of the number of carbon-atoms
ious operations on wax mixtures, such as wax fractionation, (28].
536 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

PR, and SRK are three-constant-parameter equations. All the

above-mentioned five equations of state can be written in the
following generalized form [32]:
Z = v+ -yb _ av/RT
(2)
v-b T"(v+1JC)(v+Ac)
where a = lJ,, a R2 T/2+•) IP, and b = c = 0,,, f3 RT, IP,.
Parameters nw {Jb, 11 'l, and A are component-independent
constants, while a and f3 are component-dependent con­
stants, and their numerical values for various equations of
states are given in Table I I. In extending the equations of
state to mixtures, parameters a, b, and c are replaced with arm
b= and Cm with the following expressions (mixing rules):

(a) RK, PR, SRK, RM-I: llm = LLYiY;ll;;

i j
(3)
bm = Cm = LYibii
i

3M: llm = LLYiY;llij

i i
(4)
bm = (3LI,y,y;b.;; + iy,b,,)14 Cm = L,yibii
� i J . i i

For the RM equation there is another alternative in extend­

ing it to mixtures by replacing T, and P, with Tern and Pcm as
given below:

(b)
RM-2: Tcm = (:ff Yi)l;T;,; P cj)I(
f't'Y;Y;Tcij P cj),
FIG. 14-(a) An atomic force microscope image of wax Pcm = (tfY;Y;T;;; Pc1;)i(tfYiY; T,,; Pc1;)
2
(5)
"trees" growth in a lowering temperature solidification of wax _
from solution. Varying the temperature gradient causes a tran­
sition between the growth of wax plates and growth of a
tree-like structure with regular branches; (b) An atomic force R'/:i = LLYiY;Rij
i j
microscope image of banded growth of wax due to addition of
crystallization inhibitors (courtesy of Prof. J.L. Hutter). These equations of state can be used to calculate properties
of wax, its components, i.e., vapor pressure, and molar volumes
of liquid at saturated-, sub--cooled and supercritical-conditions
as well as the solubility of wax in supercritical solvents.
be superior in some respects to the earlier ones. The Redlich­ To perform phase equilibrium and other saturated prop­
Kwong (RK) equation that is a modification of the van der erty calculations for wax in liquid and vapor states , we need
Waals equation, was a considerable improvement over other to perform equality of pressures and fugacity calculations
equations of relatively simple forms at the time of its intro­ [32]. The fugacity coefficient of a component of the wax in a
duction. In the Soave-Redlich-Kwong (SRK) equation, the mixture (4>l')?derived from the generalized Eq I is in the fol-
temperature-dependent term of aJT 0·5 of the RK equation is
replaced by a function denoted by a that depends on the
acentric factor of the compound and temperature. The Peng­
Robinson (PR) equation is another cubic equation of state in­
volving acentric factor. Riazi and Mansoori [33] modified the TABLE It-Parameters of the generalized equation of state.
parameter b of the RK equation by introducing a function, Eq. ofState-+
RK MMM RM PR
denoted by?, that depends on the refractive index of the com­
P.µ-ameters -1. SRK

pound. They showed that the resulting equation is quite ac­ 1' 0 1.3191 0 0 0
curate in the prediction of hydrocarbon densities. Mohsen­ 1J 1 1 1 1 +../2 0
.\ 0 0 0 1-../2 0
Nia et al. [34] proposed that the 3M equation in which the e 0.5 0.5 0.5 0 0
repulsive part of the RK equation is modified based on the n. 0.42748 0.487480 0.42748 0.45724 0.42748
statistical mechanics improved the thermodynamic predic­ !ls
"
0.08664 0.064462 0.08664 0.07780 0.08664
tions appreciably. This equation is shown to be more accu­ 1 1 1 "PR "SRK
f3RM
rate for heavy hydrocarbon phase behavior calculation than {3 1 1 1 1
apR = [1 + (0.37464 + 1.524226w - 0.26992w2)(1 - �·5)]2
most of the other equations of state. RK and 3M equations aSRK = [1 + (0.48508 + 1.55171w - 0.15613.:J)(l - �-5 )]2
are two-constant-parameter equations of state, while the RM, (/3RM)-• - I+ [0.02(1 - 0.92 exp(-J,OOOIT0 - 11)] - 0.035 (Tc - l)}(R* - I)
 CHAP'I'ER 19: PETROLEUM WAXES 537

lowing form [32): erence system, SG = specific gravity, Tb = normal boiling

point, in degrees Rankine, a = 1 - Tb I Tg, <iSG = specific
In ef>Y = (I + 'l'i[ a(:�t�n, - ln(v - bmlv)] gravity correction and f = correction factor.
The critical volume (in cubic feet per pound mole) is given
by the following expressions [37)
a,,, v a(nc,,,)
- In z -
CmRT(l+e) [ (v + 'f/Cm)(v + ACm) ] � = l/g [(1 + 2fv)f(1 - 2fv)J2 (8)
Ve

where

fv = <iSGv [0.466590!Tt'2
+ (-0.182421 + 3.0172!Tt'2)<i5Gv]
<iSG v = exp [4(SG 02 - SG2)) - 1
where for RK, PR, SRK, RM-1:
vg = [(0.419869 - 0.505839a - 1.5643a3 - 9481.70a14)]-•
1 a(n am) 2
The critical pressure (in psia) is given by the following ex­
pression [37):
for 3M: + 2fp)!(1 - 2fp))2 (9)
Pc= Pg (TJT;;)(V"JVc)[(I
where
fp = <iSGp [(2.53262 - 46.1955/T,\'2 - 0.00127885 Tb)
+ (-11.4277 + 252.1401Tt'2 + 0.00230535 Tb),iSGp]
<iSGp = exp [0.S(SG0 - SG)] - 1
Pg = (3.83354 + 1.19629a112
+ 34.8888a
+ 36.1952a2 + 104.193a4)2
and where V = molar volume, in ft3/lbmole, P = pressure, in
psia and subscripts V and Prefer to the volume and pressure.
The acentric factor can be estimated with the use of the
generalized Edalat et al. vapor pressure equation [38):
Jn PR = (aT + hT312 + CT + d.f')/(1 - T)
3
(10)
where
To calculate liquid molar volume and vapor pressure us­ T= 1-T!Tc, (11)
ing equations of state, the data of critical temperature and w = (-log PR)rR-0.1 - 1
pressure, acentric factor, and molar refraction are needed.
The experimental critical properties of n-alkanes up to.C2• and
are available in the literature [35,36), while those of n-alka­ a(w) = -6.1559 - 4.0855w
nes higher than C24 can be estimated using correlations. b(w) = 1.5737 - 1.0540w - 4.4365x10-3 d(w)
The critical temperature (in degrees Rankine) can be writ­ c(w) = -0.8747 - 7.8874w
ten as [37): d(w) = (-0.4893 - 0.9912w + 3.1551w2)- 1
Tc= T;[(l + 2fr)/(1 - 2fr)]2 (7) The above equation is quite accurate for calculation of va­
por pressure-provided the acentdc factor and critical proper­
where ties of a fluid are available. The molar refractions of wax
compounds needed in the RM equation of state are available
fr = l!,.SGr [-0.362456/Tt'2 in Ref. 36.
· + (0.0398285 - 0.948125/I'612)<iSGrJ The accuracy of molar volumes of saturated liquid wax
components, molar volumes in sub-cooled and supercritical
<iSGr = exp [5(SG 0 - SG)] - 1
conditions and vapor pressures calculated using various
T;; = Tb(0.533272 + 0.191017 X 10-3 Tb + 0.77968 equations of state are reported in Tables 12-14, respectively.
10 - 10 rt According to these tables the three-constant RM equation of
X 10-1 rt -0.284376 X + 0.959468 X 1028 T,; 13) state is quite satisfactory for molar volume prediction while
SG0 = 0.843593 - 0.128624a - 3.3615a3 - 13749.5a12 the SRK is accurate for vapor pressure prediction of wax.
In Fig. 15 the solubility ofn-tritriacontane (n-C33H68) in su­
and where subscript T refers to temperature, subscript c percritical carbon dioxide is depicted along with the predic­
refers to the critical conditions, superscript o refers to the ref- tions obtained from various equations of state. According to
 538 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

TABLE 12-The average deviations of various equations of state in predicting saturated liquid molar volumes of pl.lre
compounds compared with those calculated using the hankinson and thomson (1979) correlation.
AAD%
Compound T,. Range RK 3M RM PR SRK
co, 0.71-1.00 19.5 8.8 19.5 4.7 14.7
CR, 0.48-0.99 4.5 13.9 4.5 8.6 4.5
C2H6 0.33-0.99 10.3 11.8 6.4 6.0 9.2
C3Hs 0.35-0.98 11.2 10.8 3.9 5.3 9.2
n-C4H10 0.36-0.96 13.3 9.0 3.0 3.6 10.3
n-CsH12 0.47-0.99 16.8 7.5 2.4 3.4 12.5
n-C6H14 0.39-0.99 19.9 6.9 2.2 2.2 14.8
n-C1H16 0.41-0.99 22.3 7.4 1.4 2.7 16.0
n-CsH1s 0.41-0.99 24.7 6.9 1.2 4.2 17.7
n-C,,H,o 0.42-0.98 26.8 7.8 0.8 5.1 18.7
n-C10H22 0.43-0.98 29.9 10.5 0.7 7.0 20.8
n-C11H24 0.55-0.78 31.1 10.5 0.3 7.4 21.3
n-C12H26 0.54-0.89 35.3 14.7 0.4 10.1 24.3
n-C 13H28 0.56-0.80 37.6 16.5 0.2 11.4 25.8
n-C1�30 0.54-0.85 42.8 21.4 1.2 15.0 29.9
n-C1sH32 0.58-0.82 45.8 24.1 1.2 16.7 31.8
n-C 16H34 0.56-0.81 49.7 26.9 1.8 19.7 35.1
n-C11H36 0.59-0.83 56.2 32.9 3.9 24.3 40.3
n-C1sH3s 0.55-0.84 59.5 35.5 4.0 26.9 43.1
n-C19Rw 0.56-0.85 63.5 39.0 4.4 29.6 46,1
n-C20�2 0.57-0.85 67.9 42.9 4.8 32.2 49.0
n-C22Ri6 0.55-0.81 57.6 31.8 4.5 25.1 40.6
n-C24Hso 0.56-0.82 66.2 39.2 2.9 31.1 47.2
n-C2sHss 0.58-0.84 62.9 36.4 l!.2 27.7 43.1
Overall 36.5 19.7 3.6 13.8 26.1

TABLE 13-The average deviations of various equation of state in predicting molar volumes of liquids in sub-cooled and
supercritical conditions compared with experimental data.
AAD% Experimental Data
Compound T,. Range P,. Range RK 3M RM PR SRK No. of Data Pts. Ref
co, 0.7-2.2 1.0-13.6 5.0 4.8 5.0 2.9 6.1 447 a
CR, 0.5-2.6 0.0-15.2 2.0 11.1 2.0 7.4 2.4 459 b
C2H6 0.3-2.3 0.0-14.3 3.8 11.2 1.7 5.6 4.1 474 C
C3Hs 0.2-1.9 0.0-16.5 5.9 9.6 1.8 4.2 5.9 533 d
n-C4H10 0.3-1.7 0.0-18.5 8.4 8.4 1.6 3.8 7.9 638 e
n-CsH12 0.4-0.7 0.0-71.3 11.2 7.6 0.8 2.5 9.4 880 f
n-C6H14 0.4-0.7 0.0-332 14.7 5.8 2.0 2.5 12.6 510 f
n-�H16 0.6-1.1 1.8-183 14.5 5.6 2.3 3.3 13.5 70 f, g
n- C9H20 0.5-1.0 2.2-218 18.8 3.1 2.2 5.1 17.1 66 g
n-C11H24 0.5-0.9 2.6-259 25.1 3.1 2.6 10.4 23.1 70 g
n-CnH2s 0.4-0.9 3.0-303 32.3 7.9 3.2 16.7 30.1 70 g
n-C11H36 0.4-0.8 4.1-410 48.5 19.8 7.2 31.0 45.9 60 g
n-C2olf42 0.4-0.8 5.0-500 59.9 28.6 9.9 41.1 57.1 so g
n-C3oH62
· Overall
0.4-0.8 6.8-682 62.7 28.9 6.8 43.5 59.8 so g
22.3 11.1 3.5 12.8 21.0 4377
a Angus et al., 1976.
1,Goodwin, 1974.
c Goodwin and Roder, 1976.
d Goodwin and Haynes, 1982.
eHaynesandGoodwin, 1976.
f Frenkel et al., 1997a.
8 Doolittle, 1964.
 CHAPTER 19: PETROLEUM WAXES 539

TABLE 14-The average deviations of various equations of state in predicting vapor pressures of pure com pounds
com pared with the experimental data.
AAD% Experimental Data
Compound g
Tr Ran e RK 3M RM PR SRK No. of Data Pts. Ref
co, 0.71-1.00 19.1 4.0 19.1 0.8 0.5 47 a
CH, 0.48-0.99 17.2 50.0 17.2 0.7 2.9 84 b,c
C,H,; 0.33-0.99 11.5 36.3 11.9 3.0 2.6 114 b,d
C3Hs 0.35--0.98 19.8 39.5 8.3 3.0 1.9 101 b,e
n-C.JI1 0 0.36--0.96 43.2 32.4 7.0 5.6 1.9 130 b,f
n-CsH12 0.47--0.99 63.4 19.2 9.9 0.8 1.5 91 b,h
n-C6H14 0.39--0.99 >100 15.8 16.5 3.1 1.9 88 b,h
n-C1H16 0.41--0.99 >100 11.0 20.7 2.4 1.2 80 b,h
n-CsH1a 0.41--0.99 >100 18.5 28.9 2.7 1.2 87 b,h
n-CgH20 0.42--0.98 >100 33.2 33.3 2.1 1.5 82 c,h
n-C10H22 0.43--0.98 >100 51.4 37.4 3.1 1.2 86 b,g,h
n-C11H24 0.55--0.78 >100 81.7 37.7 6.6 4.4 27 b
n-C12H26 0.54--0.89 >100 89.9 31.7 2.9 0.4 40 b,g,h
n-C13H2s 0.56--0.80 >100 >100 28.8 3.3 0.5 27 b
n-C1.µl30 0.54--0.85 >100 >100 30.3 5.8 2.5 42 b,g,h
n-C1sH32 0.58-0.82 >100 >100 23.4 4.0 0.6 27 b
n-C1�34 0.56--0.81 >100 >100 29.3 5.6 0.9 45 b,g,h
n-C11H36 0.59--0.83 >100 >100 23.9 6.2 1.6 43 b
n-C1sH3s 0.55--0.84 >100 >100 30.2 9.2 3.0 44 b,g
n-C19llio 0.56--0.85 >100 >100 30.4 10.4 3.6 42 b,g
n-C20H42 0.57--0.85 >100 >100 33.0 8.8 2.4 42 b ,g
n-C22l46 0.55--0.81 >100 >100 69.1 18.6 1.2 21 b,g
n-Cz.µ!50 0.56--0.82 >100 >100 79.4 24.7 1.5 22 b ,g
n-CzsHss 0.58-0.84 >100 >100 57.9 33.9 1.7 23 b,g
n-C29H60 0.54--0.84 >100 >100 82.5 42.S 2.7 12 b
n-C3off62 0.54--0.84 >100 >100 75.8 44.5 2.7 12 b
n-C32H66 0.55-0.85 >100 >100 61.5 48.9 3.2 12 b
n-C3�6s 0.55--0.85 >100 >100 56.9 51.8 3.9 12 b
Overall -2100 -650 35.4 12.7 2.0 1483
a Angus et al., 1979.
b Frenkel et al., 1997a.
c Goodwin, 1974.
d Goodwin and Roder, 1976.
e Goodwin and Haynes, 1982.
£Haynes and Goodwin, 1976.
8 Morgan and Kob ashi, 1994.
ay
h Salemo et al., 1986.

this figure, the 3M and RM equations are capable of predict­
ing supercritical solubilities accurately. In all these cases the
unlike-interaction parameter, kti, is best fitted to experimen­
tal data Table 15 shows the interaction parameters of vari­
ous equations of state for a number of systems at various
temperatures along with the AAD%. According to this table,
the 3M equation of state gives the least value of AAD%.
Differential Scanning Calorimetry
When a solid is heated, it may absorb heat resulting in a tem­
perature increase or a structural change (phase transition)
such as a solid to liquid or a transition from one crystalline
form to another. These transitions may be endothermic (ab­
sorb heat) or exothermic (emit heat) depending on the ther­
mal process that is occurring. These thermal processes may
be quantitatively measured by differential scanning
calorimetry (DSC).
DSC analysis is performed by heating two small sample
pans, one containing the material being analyzed and the
other empty and used as a reference. The analysis concept is
that the two sample pans are maintruned at a very small tem­
perature difference(:!: 0.01 °C). Each pan is heated with two
heaters; 3: main heater and an aUX11iary heater. After· begin-
ning the experiment by supplying heat with the main heaters,
while heating the temperature difference (<iT) between the
sample and reference pans is sensed using a thermopile (set
of thermocouples) which produces a small (0-SµV) off-set­
ting voltage. The auxiliary heater is then used to heat the
sample pan to keep the off-balance voltage close to zero. The
instrument displays the differential power (<iP) between the
two pans as a function of temperature. The area under the
peak of differential power (<iP) versus temperature(T) pro­
vides an experimental measure of the energy or total enthalpy
change (<iH) of the entire process [39,40].
As described in ASTM Test Method D 4419, the melting
point can readily be determined by DSC analysis, as can heat
of fusion, which is also an important characterization pa­
rameter for waxes. Heat of fusion is defined as the increase in
enthalpy accompanying the conversion of one mole, or a unit
mass, of a solid to a liquid at its melting point at constant
pressure and temperature [43]. The heat of fusion(/JJi,) is ob­
tained from the melting transition peak illustrated in Fig. 16,
by measuring the total area under the peak that is propor­
tional to the heat flow per mass of material. Heat flow is the
heat emitted per second, therefore the area under the peak is
given in units of(heat · temperature · time -1) for the mass of
the sample used. As a result the area per unit mass (APUM)
540 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

-4 .---------'-----�
-5
-<�----------�
.5
-6 -6
-7 -7
S.a
·:&»..g
�-9
"!10 -10
-11 -11
-12 RK -12 SRK
-13 ......__.,___.,___ _,__..-.J -13 .___.,___.,___.,____,
0 2 3 4 . I 2 Pr 3 4
Pr

-4��C57
-st
-6
OO 0 ; r---=:;e::e�;::=o:::�
-6
-7 -7
Ss
�9
':lo -t
-11
·11
-12 MMM
-12 PR -13 ,___.,___...____,____,
-13 ,___.,____,___...____,
0 2
Pr 3 4
0 I 4

�r---;;:;;::o:e::e==o===i
-6
� r---�::o:e;:e==o===i
-6
-7 -7
Ss S.a
J9 �-9
-10 �10
-11 -11
-12 �----' RM-1 :12 �-'--' RM-2
-13 ._____,.____,_____.____J -13 .___,____,___,____,
0 2 Pr 3 4 0 2 Pr 3 4

FIG. 15-Solubility of n-tritriacontane (n-C.3H68) in supercritical carbon dioxide at 308

K as predicted by various equations of state and compared with the experimental solubil­
ity data [32].

of the sample will be trace shown by Fig. 17 demonstrates the decrease in crys­
Heat x Temperature Q.T
tallinity as the melting point of the wax increases. The ther­
APUM = Ttime X Mass (12) mal analysis procedure for this work was started at -50°C for
0.M
optimum crystallization of the wax. The wax sample was
Typically, the actual units of !J.Hr are (joules · Kelvin · sec­ heated at a controlled rate to + 150°C. The point at which
onds_, · grams-1). Typically, the APUM is divided by the there is a deflection in the base line is the temperature that
heating rate (K/s) of the DCS experiment used to collect the the wax begins to melt. The point at which the peak scan re­
data. This will simplify the expression to yield the specific turned to the base line is the temperature the wax sample is
heat.of melting: completely melted. The peak area represents the amount of
energy used to melt the wax sample and is calculated as de­
Q.T scribed above. In addition, an estimate on the expected melt­
APUM 0.M Q
(13) ing point can be distinguished. The experienced technologist
Heating Rate = T = M
e could tell by looking at the shape of a DSC trace if the wax is
a paraffin, intermediate, or microwax. Paraffin waxes typi­
Since the mass of the sample that was analyzed is known, it cally exhibit sharp peaks as shown in Fig. 16a, DSC peak
is then multiplied by the heat emitted/gram of sample to yield shapes for intermediate waxes are less sharp as shown in Fig.
the amount of heat given off (Q) during the melting process. 16b, and microwaxes exhibit even less sharp peaks, typically
like the peak shown in Fig. 16c.
QXM=M (14)
M It should be noted that there is a characteristic small tran­
Figure 16 illustrates the DSC traces for three different sition peak in the DSC trace for a macrocrystalline paraffinic
petroleum waxes; one for each wax type - paraffin (Fig. 16a), wax as illustrated in Fig. 16a. The transition that is indicated
intermediate (Fig. 16b), and microwax (Fig. 16c). The DSC is a solid-solid phase ch;mge (orthorhombic to hexagonal
 TABLE 15-Interaction parameter (k12) of some systems.
T p k ,, AAD%
System [K] [bar] RK 3M RM-2 PR SRK RM-1 RK 3M RM-2 PR
Cz� - n-C2sHss 308.2 56-240 -0.4638 -0.2099 0.0807 -0.0553 -0.0189 -0.1283 46.2 27.0 14.4 38.
C2� - n-C291¾0 308.2 65-240 -0.4146 -0.1618 0.1215 -0.0131 0.0260 -0.0701 53.1 29.9 23.9 48.
C,H6 - n-C,oH.2 308.2 66-200 -0.4777 -0.2066 0.1025 -0.0571 -0.0206 -0.1121 25.0 22.8 57.2 22.
313.2 66-136 -0.4738 -0.2137 0.0901 -0.0517 -0.0139 -0.1233 13.9 30.8 29.7 18.
C2H6 - n-C32�6 308.2 66-240 -0.5124 -0.2259 0.1020 -0.0707 -0.0297 -0.1214 46. 43.0 56.2 41.
313.2 66-200 -0.5011 -0.2264 0.1050 -0.0658 -0.0263 -0.1131 24.4 34.5 40.2 20.
318.2 80-240 -0.5248 -0.2438 0.0966 -0.0762 -0.0347 -0.1142 45.2 17.7 22.8 32.
319.2 80-136 -0.4872 -0.2241 0.1087 -0.0565 -0.0157 -0.1219 23.6 37.4 39.3 28.
C,H,; - n-C33H,;8 308.2 65-240 -0.4632 -0.1933 0.1100 -0.0286 0.0137 -0.0779 50.2 34.4 50.7 43.
313.2 65-202 -0.4459 -0.1845 0.1433 -0.0240 0.0193 -0.0580 39.6 21.5 28.9 25.
318.2 65-240 -0.4506 -0.1918 0.1433 -0.0203 0.0228 -0.0530 45.7 24.2 28.0 42.
CO2 - n-CzsHss 307.2 123-181 -0.3458 -0.0936 0.2487 0.0110 0.0507 0.0211 51.0 7.5 34.4 45.
308.2 80-240 -0.3161 -0.0901 0.2477 0.0296 0.0708 0.0194 52.3 18.3 35.0 49.
313.2 90-275 -0.2910 -0.0835 0.2532 0.0365 0.0765 0.0286 46.7 25.0 44.5 39.
318.2 100-250 -0.2915 -0.0867 0.2504 0.0359 0.0746 0.0232 64.7 13.4 31.0 47.
318.6 119-284 -0.3067 -0.0859 0.2531 0.0347 0.0736 0.0278 53.7 8.2 33.2 45.
323.4 125-327 -0.2973 -0.0869 0.2552 0.0385 0.0764 0.0314 62.5 5.8 28.9 53.
325.2 121-284 -0.2946 -0.0867 0.2540 0.0321 0.0690 0.0287 64.2 7.3 22.6 45.
CO2 - n-C2 9H60 308.2 100-240 -0.2751 -0.0530 0.2782 0.0645 0.1075 0.0670 71.8 21.5 12.9 67.
318.2 100-240 -0.1961 -0.0540 0.2789 0.0818 0.1451 0.0672 81.2 22.2 6.9 76.
CO2 - n-C3oH62 308.2 90-250 -0.3254 -0.1141 0.2481 0.0327 0.0779 0.0084 69.6 17.1 28.8 66.
318.2 105-250 -0.3125 -0.1197 0.2439 0.0273 0.0700 -0.0005 67.5 8.3 28.7 57.
C O2 - n-C32H66 308.2 120-240 -0.4140 -0.1500 0.2448 -0.0162 0.0316 c-0.0139 59.5 8.1 24.1 54.
318.2 140-240 -0.3913 -0.1462 0.2483 -0.0035 0.0426 -0.0092 67.3 6.7 22.3 55.
328.2 140-240 -0.3777 -0.1345 0.2596 0.0044 0.0477 0.0104 57.5 9.2 27.1 40.
CO2 - n-C33H6s 308.2 120-240 -0.3461 -0.1051 0.2825 0.0262 0.0754 0.0496 68.4 25.0 11.3 64.
318.2 140-240 -0.3384 -0.1043 0.2832 0.0280 0.0872 0.0494 65.0 22.9 4.8 61.
328.2 140-240 -0.3057 -0.0990 0.2878 0.0428 0.0876 0.0557 67.4 18.5 3.5 60.
Overall 60.0 20.3 28.3 46.
a Kalaga and Trebble, 1997.
b Moradinia and Teja, 1986.
c Suleiman and Eckert, 1995.
d Moradinia and Teja, 1988.
"McHugh et al., 1984
fReverchonetal., 1993.
8 Chandler et al., 1996.

...."'"' "--·-=-
i,
gu
,..
...
---
n
�

"'l-...
I::"'
,..
... .......
-('(:)
"-'
,..
..... .,.. " "' "' ""

-·-----�-,� ----------
... n=

{ ...
� uw
- w

j
j ,..
,.. 3--�-.,__----j
,..,-'1-----------------'--I ...,-1----------------'
45.G 0.0 2!.G 50,0 .'1511 llU nu . WQ

FIG. 16-The heat of fusion (Mt,) calculation from the DSC melting transition peak by
measuring the total area under the peak, (a) paraffin, (b) intermediate, (c) microwax.
542 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK
85.0
80.0
r'!
I
75.0 l of the wax. The wax sample is heated at a controlled rate to
{- fo.O
70.0
,I,.
65.0
I"
ss.o 1·
so.o I area represents the amount of energy used to melt the wax
i .. 45;0 I I
f, �
4M
35.0
30.0
25.0
-so.o -25.0 0.0 25.0 SO.0 75.0
Temperature ('CJ
FIG. 17-The heat of fusion (AH,) calculation from the DSC
melting transition peak by measuring the total area under the
peak of several paraffins demonstrating the decrease in crys­
tallinity as the melting point of the wax increases.
crystal structure). As the wax crystal continues to absorb en­
ergy, a larger peak is recorded and then actual melting occurs
with a return to the base line as the temperature continues to
increase.
In addition, there is a bimodality indicated in the DSC
trace peak shapes for intermediate (Fig. 16b) and microcrys­
talline (Fig. 16c) waxes. Bi-modal shape is related to the
breadth of the wax composition. Bimodal peak shape is not
related to transition. The apparent bimodality indicates that
as
the wax has not been made a narrow distillation cut. The
melting point of wax is in the DSC area that the curve begins
to return to the base line (downward slope) as the tempera­
ture increases. The squat DSC peak shape of the microwax
shown in Fig. 16c indicates that it is less crystalline and has
a broader melting. The apparent bimodality of the microwax
is related to the different melting fractions that appear in this
particular wax.
Determination of the heat of fusion of a wax is of practical
significance for a number of reasons. For example, the
changes of shape of a DSC trace to that of known waxes may
indicate that a wax has been contaminated or altered. This
may be confirmed by comparing the heat of fusion of a pre­
viously purchased paraffin wax with the suspect wax. For ex­
ample, a historical value for heat of fusion of a wax may be
200 Jig and a newly purchased paraffin wax may have a heat
of fusion of 180 Jig. This variation confirms that the two
waxes exhibit different properties.
Another application of the heat of fusion could be for the
comparison of properties of nominally similar waxes offered
by two different suppliers. The higher the heat of fusion, the
more crystalline the wax is. For some applications, like can­
dles, high crystallinity is desirable to aid in the mold release
properties due to shrinkage upon cooling. Low crystalline
waxes do not shrink as much as high crystalline products.
ASTM Test Method D 4419 has been developed to char­
acterize petroleum waxes and measurement of their transi­
tion temperatures by Differential Scanning Calorimetry
(DSC). Figures 16a, 16b, and 16c are DSC endothermic
scans of a paraffin, intermediate, and microcrystalline wax,
respectively. Referring again to Fig. 16a (paraffin wax), the
endotherm is started at - 50°C for optimum crystallization
+ 1 S0'C. The point at which there is a deflection in the base
line is the temperature that the wax begins to melt. The
point at which the peak scan returned to the base line is the
temperature the wax sample is completely melted. The peak
sample as discussed above. Figure 17 illustrates that as the
melting point of paraffin wax increases, the heat of fusion
decreases because of the higher content of less crystalline
branched alkane structures. Microcrystalline waxes have a
lower heat of fusion than paraffin wax that is directly re­
lated to the greater amount of branched alkanes (less crys­
100.0 125.0 tso.0 talline microstrucfure). Listed in Table 16 are the typical
heats of fusion data for both paraffin and microcrystalline
waxes.
Effect of Additives
In the petroleum wax industry; it is often necessary to use ad­
ditives to improve the processability of wax or wax mixtures
by modifying their physical properties. This may be accom­
plished by the addition of additives that may include stearic
acid, polyethylene, ethylene-vinyl acetate copolymer or a Fis­
cher-Tropsch wax. For example, stearic acid may be added to
a paraffin wax to increase firmness, reduce melting point, aid
in mold release, prevent candles from losing their shape in
warm weather, etc. Polyethylene is another additive that may
be used. Polyethylene may be added to a paraffin wax to
harden the wax structure, modify burning rate, and improve
strength and gloss. In addition to physical property modifi­
cation, additives also could alter the microstructure of waxes
as demonstrated by Fig. 14.
Test Procedures for Petroleum Wax
Characterization
There are three properties used to characterize petroleum
waxes: (I) physical properties, (2) chemical properties, and
(3) functional properties.
Physical Property Determination
Melting Point - Test Methods ASTM D -87, D 3944, and D 127-
Melting point is a wax property that is of interest to the con­
sumer and can be an indication of the perlormance proper­
ties of the wax being tested. The melting point of a wax is
defined as the temperature at which the melted petroleum
wax first shows a minimum rate of temperature change when
allowed to cool under prescribed conditions.
Test Method D 87 is one of the most commonly utilized
tests for melting point determination for petroleum waxes.
Paraffin waxes are often marketed based on melting point
data produced by D 87. This test method is performed by
placing a specimen of molten wax in a test tube equipped
with a thermometer as illustrated in Fig. !Sa. The test tube is
TABLE 16--Typical heats of fusion (Jig).
Fully Refined Paraffin wax 180-210
Microcrystalline wax 140-190
 CHAPTER 19: PETROLEUM WAXES 543

. �·

..
..-,. ::
'c !!

(a)
I 1
51' ID
d30) .I
Dimensions in inches (millimeters)

..

a
K.
�

r
(b) Time-+ (c)

FIG. 18-{a) Apparatus for ASTM Test Method D 87. Cooling curve for: (b) a paraffin wax,
(c) for intermediate wax, microwax, petrolatum, or waxes containing a high percentage
(>50%) of branched alkanes
544 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

then placed in an air bath that is immersed in a water bath
and held at 16-28°C (-61-82 °F). Temperature readings are
taken periodically until the wax, solidifies under specified
conditions. During solidification, the rate of temperature de­
creases and produces a plateau in the cooling CUIVe, which is
obtained by plotting the temperature versus elapsed time as,
illustrated in Fig. 18b. The temperature where the plateau oc­
curs is defined as the melting point. (Note: The thermometer
used for this work shall conform to ASTM Specification E-1.)
Test Method D 87 is not applicable for microcrystalline
wax, intermediate wax, petrolatum, or waxes containing a
high percentage (> 50%) of branched alkanes, because a tem­
perature plateau will not occur with such type of waxes as il­
lustrated in Fig. 18c and because these type of waxes have a
much broader melting distribution (characterized by DSC)
than paraffin waxes. For non-paraffin type waxes, Test
Method D 3944, which is a "solidification point" method (Fig.
19a), can be used for melting point determination. The solid­
ification point of a petroleum wax is: the temperature in the
cooling curve of the wax where the slope of the curve first
changes significantly as the wax sample changes from a liq­
uid to a solid state. This is illustrated in Fig. 19b, which is a
typical cooling curve for solidification point measurement of
a petroleum wax.
Test Method D 3944 is performed by heating 50 mg of sam­
ple in a test tube above the solidification temperature. Once
the wax is melted, Fig. 20a, a thermocouple (connected to a
recorder) is placed in the sample, as illustrated in Fig. 20b,
and allowed to cool to ambient temperature. As the sample
cools, a plot of temperature versus time (Fig. 18a) is ob­
tained. This test method is based on the same methodology
as D 87 with the exception that automated test equipment is

'i'o Jli!:c:ordcr

I
'I'B'E-nuorocarbon
HoldOl" Adapter A].uminUllll'BeatiAg
Block
6x50 111111. 'lest 'l'ube 50x50x50 111111
(2x2x2 in)
0.020 .in OD
Metal Sheathed Autotransformer
'lheEmDCOuple Prabe <:onnecti1;19'
;c.eaa
TFE-Fl.uorocarbon TO 110
Disk CMt..ing ---+-...q, AC
Guide out:let

so mg
(a) wax sample

t
· Temperatw:e Heat turned ot.l

. I
Sol.idification
Point

(b)

FIG. 19-(a) Apparatus for determination of melting (solidification) point (cooling curve)
of non-paraffin type waxes used in ASTM Test Method D 3944; (b) A typical cooling curve
for melting (solidificat ion) point measurement of non-paraffin type waxes.
548 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

Sample
Reference
Resistance
Thermometer
Heater

Nitrogen��� AT-Signal
(a)

First-Order Transition:
Apex - TlA
onset. - -r20
.tnd - 'r2E
Second Order-Transition:
Apex - Tu l I
Onset - T10 I I
End - TlE II

�
l '2A
(b)
FIG. 24-(a) Differential scanning calorimetry (DSC) experimental set up; {b) Schematic
of petroleum wax DSC curve {heating cycle) sample determined to have solid-liquid and
solid-solid transitions. This figure is similar to Fig. 16a.

method for petrolatum, which may also be used for softer
waxes. The cone penetration value is more of a measure of
finnness or consistency rather than hardness.)
Transition Temperatures by Differential Scanning Calorime­
try (DSC)-Test Method D 4419-Test Method D 4419 is a rapid
and convenient method for determining the temperature lim..:
its governing the change a wax undergoes from solid to liquid
or as a solid-solid transition. This test method measures the
transition temperatures of petroleum waxes, including mi­
crocrystalline waxes, by differential scanning calorimetry
(DSC) as shown in Fig. 24a. The normal operating tempera­
ture range extends from 1Sc-150° C. DSC is a technique that
measures the difference in energy inputs into a substance
and a reference material using a controlled-temperature pro-
gram. DSC can differentiate the type of petroleum wax being
evaluated by its melting and crystallization property. Figure
24b (which is similar to Fig. 16a) is the schematic of a
petroleum wax DSC curve exhibiting solid-liquid and solid­
solid transitions (Heating Cycle) and the calculation of such
temperatures. Paraffin waxes being derived from the distilla­
tion process have sharp peak shapes, while microcrystalline
waxes being derived from residual fractions have broader
peak shapes. This is shown in Fig. 16 (Note: Refer to Stan­
dard Terminology E 473 for additional information).
I
Chemical Property Detennination
Petroleum waxes being composed of hydrocarbons are rela­
tively inert but they can undergo compositional chemical

changes when exposed to elevated temperatures in the pres­
ence of oxygen due to oxidation. Waxes can degrade in the
presence of heat and oxygen. The degradation process in­
volves breaking a bond between a carbon and a hydrogen
atom to make a free radical. The free radicals quickly form
peroxides initially and further react to form acids. The
changes in composition can possibly be detected by testing
for color and odor. Antioxidants are added to petroleum
waxes to chemically stabilize them from the heat degradation
process [41].
Color - Test Methods D 156 and D 1500-The color of
petroleum waxes can indicate the degree of refinement or
possible contamination. Color is not always a reliable pa­
rameter for determining quality and should be used judi­
ciously as a specification. There are two methods for deter­
mining the color of petroleum waxes: Test Methods D 156
and D 1500, and both are subjective and measure the empir­
ical value based on visual observation of the wax in the
molten state.
Test Method D 156 is the Saybolt Chronometer Method for
quantifying the color of petroleum products such as a
petroleum wax. Saybolt color is an empirical definition of the
color of a clear petroleum liquid based on a scale of -16
(darkest) to + 30 (lightest). The number is derived by finding
the height of a column that visually matches the appropriate
one of three glass standards and referring to Table 1 of Test
Method D 156. Tiris is done using a Saybolt chronometer (see
Fig. 25), which consists of a sample and standard tubes, op­
tical system, light source, and ASTM color standards.
While Test Method D 156 is used to determine the degree
of whiteness of a wax, Test MethodD 1500 is used to measure
the color of waxes that have a tint darker than off-white. Test
Method D 1500 is conducted using a standard light source,
with liquid sample placed into a standard glass container
(sample jar) (see Fig. 26) and compared with colored glass
disks ranging in value from 0.5--8.0 with 0.5 increments.
Carbonizable Substances - Test Method D 612-Test Method
D 612 is applicaj,le to paraffin waxes for pharmaceutical use
as defined in the United States National Formulary. Molten
wax is treated with sulfuric acid and the acidic layer is com­
pared visually with a colorimetric reference standard to de­
termine if it passes the conformance criteria for refined wax
using the color comparator shown in Fig. 27.
Peroxide Number - Test Method D 1832-Waxes are heat
sensitive and they are susceptible to the action of the oxida­
tion process. The detection of peroxides is the first indication
that a wax has begun to deteriorate in terms of oxidation sta­
bility. Petroleum waxes should not have any measurable per­
oxide values. Deterioration of petroleum wax results in the
formation of peroxides and other oxygen-carrying com­
pounds that will oxidize potassium iodide. Peroxide content
is reflected by the peroxide number that is defined as the mil­
liequivalents of constituents per 1000 g of wax that will oxi­
dize potassium iodide.
Odor - Test Method D 1833-In some end-use applications,
such as food packaging, the intensity of the odor is an impor­
tant characteristic. Odors can be an indication of the degree
of refining, contamination, or oxidation. Test Method D 1833
describes how to rate the odor intensity based on a subjective
evaluation using a multiple-member test panel. This test is
conducted by preparing odor test specimens from petroleum
CHAPTER 19: PETROLEUM WAXES 549
wax and placing approximately 10 g of thi n shavings on odor­
free paper or glassine. Individual test specimens are then eval­
uated for odor by each panel member and assigned a number
according to the odor scale shown in Table 18 that best fits the
intensity of the odor. As an alternative procedure, the wax
shavings are placed in bottles with each panel member mak­
ing an odor determination between 10 and 60 min after the
shavings are placed into the bottles. The average of the panel
ranking is reported as the odor rating of the sample.
Composition by Gas Chromatography-Test MethodD 5442-
Test MethodD 5442 is applicable to petroleum derived waxes,
including blends of waxes. This test method covers the quan­
titative determination of the carbon number distribution of
petroleum waxes in the range of n-Cl 7 through n-C44 by gas
chromatography using internal standardization. In addition,
the content of normal and non-normal hydrocarbons for each
carbon number is also determined. Material with a carbon
number above n-C44 is determined by difference from 100
mass % and reported as C 45 +. (Note: Standard Practice E 260
provides further information on gas chromatography and
Standard Practice E 355 provides information relating to gas
chromatography terms and relationships.)
Test Method D 5442 is not applicable to oxygenated waxes,
such as synthetic polyethylene glycols (i.e., Carbowax), or
natural products such as beeswax or carnauba. This test
method is not directly applicable to waxes with oil content
greater than 10% as determined by Test Method D 721.
Functional Property Determination
The following methods are for the evaluation of wax base
coatings intended for paper and paperboard. The methods
were developed in concert with the Technical Association of
Pulp and Paper Industries.
Specular Gloss - Test Method D 1834-Specular gloss is
defined as the degree to which a swface simulates a mirror
in its capacity to reflect incident light. Test Method D 1834
is a method designed to determine the capacity of a wax
coated surface to simulate a mirror in its ability to reflect an
incident light beam using a glossmeter such as that illus­
trated in Fig. 28. Surface gloss is desirable for some waxed
paper applications. For determining the gloss of book pa­
per, reference should be made to Test Method D 1223. For
very high gloss paper refer to Wink et al. [42].
Gloss Retention - Test Method D 2895-This test is intended
to correlate with the conditions that are likely to occur in the
storage and handling of wax-coated paper and paperboard.
Test Method D 2895 is intended primarily to measure the
gloss retention, which is defined as the percent of original
gloss retained by a test specimen after aging under specified
conditions. It is calculated as the final gloss divided by the
initial gloss multiplied by 100. The initial gloss of waxed pa­
per or paperboard is measured in accordance with Test
Method D 1834, then remeasured after aging the sample in
an oven at 40° C (104°F) for 1 and 7 days. The !-day test is
conducted to observe trends while the 7-day test is the stan­
dard test duration.
Surface Wax - Test Methods D 2423, D 3521, and D 3522-
Wax coatings are applied to provide a better moisture bar­
rier, appearance, and abrasion resistance. These perlor­
mance features are influenced by the amount of wax present
on the surface. Test Method D 2423 is used to determine the
550 MANUAL 37: FUELS AND LUBRICANTfiHANDBOOK

. ....·=-+
F½
NOTI!• HAJIQLC II PAtram TO"o•

@ bu•
® oou.u:
@ -­
® lttNIOLAV
@-­
© .....
@ flTOOl:K
@,.........
(D JtlTAININI RUN
© AXU:
® IPfUH
© co wan OOIL H!Affl

Saybolt Chromometer Tube Heater Adapter

FIG. 25-ASTM Standard Test Method D 156 Saybolt Chromometer and artificial daylight
lamp.
 CHAPTER 19: PETROLEUM WAXES 551

amount of wax present on the surface of the substrate, but
not the absorbed wax. Test methods that determine the ap­
plied wax by solvent extraction (such as Test Method D 3344)
do not clifferentiate between the wax present at the surface
and to that which penetrated the substrate.
.
Test Method D 3521 also determines the amount of wax that
is present on the surface of corrugated paperboard. This
method is applicable to a board on which wax has been ap­
plied by curtain coating, roll coating, or other methods. The
substrate board may or may not contain impregnating (satu­
ration) wax within its structure. If it is known that the speci­
men has coating wax only, with no internal saturating wax,

I
,'
I
then Test Method D 3344 may determine the total coating wax
applied. Determination of the total amount of wax present by
I
I
I ASTM D 3521 involves delamination of the coated facing to
I
obtain a ripple-free sheet, then scraping off the wax using a ra­
' '
I
zor blade and calculating the amount of wax removed.
'
I I

-....,..._, ••
I Test Method D 3522 is used to determine the amount of
I

••
•I wax that has been applied to the inclividual layers of the cor­
0
rugated paperboard and the amount of the impregnating
(saturation) wax in the same facing. This is accomplished by
0
• U2-'·3U ••-a peeling the coated facing from the meclium and then splitting

•'. .,
0 it into two layers; one bearing the coating on waxed fibers
� only and the other containing waxed fibers only. The layers
I are extracted separately, collecting both fibers and wax. This
' will permit the calculation of the applied surface coating and
I I
' the amount of impregnating wax.
• •I
I
' -, <--
•' •I
..______ ... i
TABLE 18-0dor intensity scale.
Numerical Rating Odor Description
FIG. 26-Standard 0 None
glass sample jar used 1 Slight
2 Moderate
3 Strong
in Test Method D 1500
4 Very strong
to measure the color of
waxes.

f
�:
I , ,,_
�
'-..:!:-_;!=--.:::..-i---l-1 �· Ti
{:t

r
. . . . .
' !'
'f13 STOPPER

I : I ' I ! ! !· I
i, 7' T '
: 1· ·1
l l 1! l
I. " .I!l
' I I • I
f, I I I I '.
, jl l

1+ +-�I1· I-.I ,I1· !�!�

I ! I I:

iJ.
7!I !;i I! i·1 ' i . !
1
'l'

I
,__ I

.f- i i I 'I , 1·. 1'

I : 1
--, • �• .1· rl!illlj ,,11 ,'
:
111,

:_-J-JW- -l�
A
.__ -' L-t-" .1 t-ti ]t-!... I

.,_l'°>
.I. ,+-,iiL . ...,..
',,
End ElevjStion
I •
Elevation

TEST TUBE
FIG. 27-Color comparator used in Standard Test Method D 612 for measurement of car­
bonizable substances in paraffin waxes for pharmaceutical use.
552 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK
Specimen
I a calibrated temperature gradient plate for 17 h and re­
I
I second coated surface. This is done experimentally by
\-
FIG. 28-Diagram of relative positions of essential elements
of Glossmeter used in Standard Test Method D 1834.
Total Wax Content - Test Method D 3344--Many of the func­
tional properties ofa wax-treated paperboard are dependent on
the amount of wax that is present. Test Method D 3344 deter­
mines the total amount of wax in a sample of wax-treated cor­
rugated paperboard by extraction. It is applicable to specimens
that have been waxed by either impregnation (saturation) op­
erations or coating operations, or combinations of the two.
Weight of Wax Applied During Coating - Test Method D
3708-Test Method D 3708 is used to determine the weight of
a hot melt coating applied to corrugated board by curtain
coating. This method is intended for use as a routine process
control in the plant. The amount of wax applied is deter­
mined by attaching a folded sheet of paper to production cor­
rugated board, running the combination through the curtain
coater, and subsequently determining the applied weight of
wax on the sheet of paper.
Blocking Point - Test Method D 1465-The blocking point of
a wax is defined as the lowest temperature at which a film
disruption occurs across 50% of the waxed paper surface
when the test strips are separated. The temperature at which
the first film disruption occurs on the waxed paper when the
test strips are separated is the wax picking point. Test
Method D 1465 is used to determine the temperature at
which two strips of wax-coated paper will adhere to each
other. Surface disruption of wax coatings at relatively low
ambient temperatures is a performance problem for low
melting point waxes. If the surface of a waxed paper is
blocked together, then surface gloss and barrier properties
will be altered. Two strips of wax-coated paper are placed on
moved, cooled, and peeled apart to determine the block point
temperature. Figure 29 illustrates a Type A and a Type B
blocking plate used for these measurements.
Coefficient of Kinetic Friction - Test Method D 2534-A
coated surface under load is pulled at a uniform rate over a
preparing a "sled" with a weight and then pulling it over the
surface to be tested using a horizontal plane and pulley as­
sembly. The force required to move the load is measured, and
the coefficient of kinetic friction ( JL0 is calculated as follows:
(15)
Where A = the average scale reading from the electronic
load cell-type tension tester for 1 SO mm (6 in) of uniform slid­
ing and B = sled weight (g). The value obtained is related to
the slip property of the wax coating. High slip property val­
ues may not be desirable for many commercial articles that
have been coated with petroleum wax.
Abrasion Resistance - Test Method D 3234-This test
method is designed to help predict the resistance in change of
gloss that coatings may be subject to during the normal han­
dling of coated paper and paperboard products. Abrasion re­
sistance is the resistance to change in gloss when that coat­
ing has been subjected to an abrading action by an external
object. Test Method D 3234 is conducted by dropping 60 g of
sand on a very small area of a coating under fixed conditions.
The abrasion resistance test apparatus is illustrated in Fig.
30. Gloss is measured with a 20° specular glossmeter illus­
trated in Fig. 28 before and after the abrading action by the
falling sand.
Hot Tack - Test Method D 3706-Hot tack is defined as the
cohesive strength during the cooling stage before solidifica­
tion of a heat seal bond formed by a wax-polymer blend. Flex­
ible packaging materials are formed into finished packages by
joining surfaces with heat sealed bonds. The bonding process
is performed on high-speed packaging lines and the applica­
tion pressure used to hold the surfaces together is released be­
fore the bond has completely solidified. The wax-polymer
blend must have enough hot tack while still in a molten stage
to hold the sealed areas together until the blend has cooled.
In Test Method D 3706, flexible packaging specimens are
heat-sealed together over a series of temperatures and dwell
times. Immediately after each seal is formed and before it has
started to cool, a force tending to separate the specimens is
applied by a calibrated spring. If the hot tack of the blend is
strong enough, the seal remains closed until it has solidified;
if not, the seal separates. Thus each spring force and test con­
dition either passes or fails. The pattern of pass/fail results is
plotted to the blend characteristics.
 CHAPTER 19: PETROLEUM WAXES 553

ll(loyltoc;i,�""'*'ir;-,.25-(1•at'1.
1$...,.;,.ISlt- Hi"lhirlforlMqolltt,I
762-QO") ......

•111.--......
·-�------.......
nqli..t
a-••-·-­
tt"'•1W',...,_

•-es-i111111.w..,__

--­
....... MI-S-$") ....
molpWi.ffols1_.,,-,

....... """'"·-·1D-•71Z-
...... ___ D'1 ...

Me"'><Slfr"- ... ___ _

_
....... ..........._,,_
"*"-".._. .. ,..._.Im�
........, ...... , ....... _ID.WI

....,
_,.....,.,._"'"

...,,
WU.T

Type A Blocking Plates

ll

.... .......
"' .............
..__....
--­
._._151_12-t ........
.............. flit

....
,_.._.�1-
n,rthb-�
...... 11-

....,..�-....
CZ-,ti..lll'l ....

·:-�:.-
,,...,... ...,,
Type B Blocking Plate
FIG. 29-The two types of blocking plates used in Standard Test Method D-1465 to mea­
sure the blocking point of wax.
 554 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK

Spotl lght
Source 500 111
Separatory funnel

80 g of Sand
Stopeoc:k
Sizeri II-

!!'!
Blass
Tuba I Stell Cut Off fro11
I ie Separatory funnel

.
3:
l;

U.S. standard Sieve

ll l!
Ko. 12

l!'ll
25 • (I") l,D,

-.
I

Specimen Specimen

For tocating Exact Position for For Drop_plng 80 g .of S�d

Making GlossHter ReadlJJgS

FIG. 30--Apparatus for measuring abrasion resistance of wax coat­

ings in Standard Test Method D 3234.

Acknowledgments D721 Test Method for Oil Content of Petroleum Waxes

D937 Test Method for Cone Penetration of Petrolatum
The authors thank Dr. George Totten for his helpful advice D938 Test Method for Congealing Point of Petroleum
and guidance in the preparation of this chapter and Dr. Sony Waxes, including Petrolatum
Oyekan, Dr. Chen-Hwa Chiu, Dr. Sang J. Park. and Mr. D 1168 Test Method for Hydrocarbon Waxes Used for
Adrian D'Sousa for their technical assistance. Electrical Insulation
D 1298 Test Method for Density, Relative (Specific Grav­
ity) or API Gravity of Crude Petroleum and Liquid
ASTM STANDARDS Petroleum Products by Hydrometer Method
D 1223 Test Method for Specular Gloss of Paper and Pa­
No. Title perboard
D87 Test Method for Melting Point of Petroleum Wax D 1321 Test Method for Needle Penetration of Petroleum
I
I D97
D 127
Test Method for Pour Point of Petroleum Products
Test Method for Drop Melting Point of Petroleum D 1465
Waxes
Test Method for Blocking and Picking Points of
Wax Including Petrolatum Petroleum Wax
D 156 Test Method for Color, Saybolt, of Petroleum D 1500 Test Method for Color, ASTM, of Petroleum Prod­
Products ucts (ASTM Color Scale)
D287 Test Method for Gravity, API, of Crude Petroleum D 1832 Test Method for Peroxide Number of Petroleum
and Petroleum Products (Hydrometer Method) Wax
D445 Test Method for Kinematic Viscosity of Transpar- D1833 Test Method for Odor of Petroleum Wax
ent and Opaque Liquids D 1834 Test Method for20 ° Specular Gloss of Wax Paper
D612 Test Method for Carbonizable Substances in D2423 Test Method for Surface Wax on Waxed Coated
Paraffin Wax Paper
 CHAPTER 19: PETROIEUM WAXES 555

D2500 Test Method for Cloud Point of Petroleum ISO 1392 Determination of crystallizing point­
Products General method
D2534 Test Method for Coefficient of Kinetic Friction ISO 2207 Petroleum waxes-Determination of
for Wax Coating congealing point
D2669 Test Method for Apparent Viscosity of Petroleum ISO 3016 Petroleum products-Determination of
Waxes Compounded with Additives (Hot Melts) pour point
D2895 Test Method for Gloss Retention of Waxed Paper ISO 3841 Method for determination of melting
and Paperboard after Storage at40 ° C (104 ° F) point of petroleum wax ( cooling curve)
D3234 Test Method for Abrasion Resistance of nsKo0-64 Testing methods for melting points of
Petroleum Wax Coatings chemical products
D3235 Test Method for Solvent Extractables in nsKo0-65 Test methods for freezing point of chem­
Petroleum Waxes ical products
D3236 Test Method for Apparent Viscosity of Hot Melt NFT60-114 Petroleum products-Melting point of
Adhesives and Coatings Materials paraffins
D3344 Test Method for Total Wax Content of Corrugated NFT20-051 Chemical products for industrial use.
Paperboard Determination of melting point. Method
D3451 Standard Practices for Testing Polymeric Pow­ for the determination of crystallizing
ders and Powder Coatings point (freezing point).
D3521 Test Method for Surface Wax Coating on Corru­
gated Board
D3522 Test Method for Applied Wax Coating and Im­ REFERENCES
pregnating (Saturating) Wax in Corrugated
Board Facing [1] Hackett,W. J., Maintenance Chemical Specialties, Chemical Pllb­
D3706 Test Method for Hot Tack of Wax-Polymer Blends lishing Co.,Inc.,NY,1972.
by Flat Spring Test [2) Warth,A.H.,Chemistry and Technology ofWaxes, Reinhold Pub­
D3708 Test Method for Weight of Wax Applied During lishing Corp.,NY, 1956.
Curtain Coating Operation [3) Bennet, H., Industrial Waxes, Vol. 1, Chemical Publishing Com­
D4419 Test Method for Transition Temperatures of pany,Inc., NY, 1963.
Petroleum Waxes by Differential Scanning [4] Puleo, S. L., "Beeswax," Cosmetics and Toiletries, Vol. 102, Al-
Calorimetry lured Publishing Company, Inc., Chicago, 1987.
D 5442 Test Method for Analysis of Petroleum Waxes by [5] Warth,A. H., Chemistry and Technology ofWaxes, Reinhold Pub­
lishing Corp., NY, 1956.
Gas Chromatography [6) Letcher,C. S., 'Waxes," Kirk-Othmer: Encyclopedia of Chemical
El Specification for ASTM Thermometers Technology, Vol. 24,3"' ed.,1984, pp. 466-481.
E260 Practice for Packed Column Gas Chromatogra­ [7] Dcy, M. E., "Sasol's Fischer-Tropsch_Experience," Hydrocarbon
phy Processing, August,1982,pp. 121-124.
E355 Practice for Gas Chromatography Terms and [8] Erchak, Jr., M., "Process for the Oxidation of High Molecular
Relationships Weight Aliphatic Waxes and Product 880kb, U. S. Patent
E473 Standard Terminology Relating to Thermal 2,504,400, Washington DC, April 18, 1950.
Analysis [9) Haggin, J., "Fischer-Tropsch: New Life for Old Technology,"
E537 Test Method for Assessing the Thermal Stability Chemical and Engineering News, October 1981, pp. 22-32.
[10] Caraculacu,A., Vasile, C., Caraculacu, G., "Polyethylene Waxes,
of Chemicals by Methods of Thermal Analysis Structure, and Thermal Characteristics," Acta P olymerica, Vol.
35,No. 2, 1984,pp. 130-134.
[11) Brooks, B. T.,Boord, C. E.,Kurtz, S.S.,and Schmerling, L., The
OTHER STANDARDS Chemistry of Petroleum Hydrocarbons, Vol. 1, Reinhold Publish­
ing Corp., NY, 1954.
No. [12) Gruse, W. A., Chemical Technology of Petroleum, 2nd ed., Mc­
Title
Graw-Hill Company, NY, 1942.
BS4633 &4634 Method for the determination of crystal­ [13] Mazee,w. M.,"Petroleum Waxes," Modern Petroleum Technol­
lizing point. Method for the determina­ ogy, 4"' ed., 1973,pp. 782-803.
tion of melting point and/or melting [14] Vasquez, D. and Mansoori,G. A.,"Identification and Measure­
range ment of Petroleum Precipitates," Journal of Pe troleum &ience
BS4695 Method for determination of melting and Engineering, Vol. 26,Nos. 1-4,2000,pp. 49-56.
point of petroleum wax (cooling curve) [15] Misra. S.,Baruah,S., and Singh,K, Paraffin Problems in Crude
DIN53175 Binders for paints, varnishes and similar Oil Production and Transportation: A Review, SPE Production
coating materials; determination of the and Facilities,Society of Petroleum Engineers,Richardson, TX,
solidification point (titer) of fatty acids Feb. 1995,pp.50-54.
(method according to Dalican) [16) Holder, G. A. and Winkler, J.,'Wax Crystallization from Distil­
late Fuels," Journal ofthe Institute ofPetroleum, Vol. 51,No. 499,
DIN 53181 Binders for paints, varnishes and similar 1965,pp. 228-243.
coating materials; determination of the [17) Mansoori, G. A. and Canfield, F. B., "Variational Approach to
melting interval of resins by the capil­ Melting," Journal of Chemical Physics, Vol. 51,No. 11, 1969, pp.
lary method 4967-4972.
556 MANUAL 37: FUELS AND LUBRICANTS HANDBOOK
[18] Pourgheysar,P., Mansoori,G. A., and Modarress,H., "A Single­
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Alkanes And Paraffin Waxes for Application as Phase Change En­
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[31] Du, P. C. and Mansoori, G. A., "Phase Equilibrium of Multi­
component Mixtures: Continuous Mixture Gibbs Free Energy
Minimization and Phase Rule," Chemical Engin.eeri.ng Commu­
nication, Vol. 54, 1987, pp. 139-148.
[32] Hartono, R., Mansoori, G. A., and Suwono, A., "Prediction of
Molar Volumes, Vapor Pressures and Supercritical Solubilities
of Alkanes by Equations of 5-tate," Chemical Engin.eeri.ng Com­
munications, Vol. 173, 1999. pp.23--42.
[33] Riazi, M. R. and Mansoori, G. A. "Simple Equation of State Ac­
curately Predicts Hydrocarbon Densities," Oil & Gas Journal,
1993,pp. 108-111. J
[34] Mohsen-Nia, M., Modarress, H., and Ml\fisoori,G. A., "A Simple
Cubic Equation of State for Hydrocarbons and Other Com­
pounds," SPE Paper No. 26667, Proceedings of the 1993 Annual
SPE Meeting, Society of Petroleum Engineers, Ric/>ardson, TX,
1��
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[36] Frenkel, M., Gadalla, N. M., Hall,K. R., Hong,X.,and Marsh, K.
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bon, R. C. Wilhoit, Ed., ThermodYilamic Research Center, The
Texas A & M University System, College Station,TX, 1997.
[37] Twu, C.H., "An Internally Consistent Correlation for Predicting
the Critical Properties and Molecular Weights of Petroleum and
Coal-Tar Liquids," Fluid Phase Equlibrium, Vol. 16, 1984, pp.
137-150.
[38] Edalat, M., Mansoori, G. A., and Bozar-Jomehri, R. B., ''Vapor
Pressure of Hydrocarbons, Generalized Equation," Encyclope­
dia of Chemical Processing and Design - 61, Marcel Dekker, Inc.,
NY, 1997,pp.362-365.
[39] Letoffe, J. M., Claudy, P., Garcin, M., and Volle, J. L., ''Evalua­
tion of Crystallized Fractions of Crude Oils by Differential Scan­
ning Calorimetry, Correlation With Gas Chromatography,''
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[40] Braun, R., '!Limits in Differential Thermoanalysis of Waxes,"
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[41] Handbook on Anti.oxidants and Anti.ozonants, Goodyear Chemi­
cals, Akron, OH, 1977.
[42] Wink, W. A., Delevanti, C.H.,and Van den Akker, J. A.,Instru­
mentation Studies IXXVII, Study on Gloss I, A Goni.ophotomet­
ric Study ofHigh Gloss Papers, TAPPI, Technical Association of
the Pulp and Paper Industry, Vol. 35, December 1953, p. 163A.
[43] Tomsic,J., Dictionary of Materials and Testing, 2'"' ed., SAE In­
ternational, Warrendale, PA, 2000, p. 205.