Thermal Methods in Petroleum Analysis

by. Heinz Kopsch

CopyrightoVCH Verlagsgesellschaft mbH, 1995

5 Final considerations
5.1 Other applications

The investigations on petroleum and its products described in chapter 4 demonstrate the
suitability of thermal methods such as thermogravimetry, differential thermoanalysis, and
differential scanning calorimetry for analysis of the thermal and oxidative behavior of
these substances but also demonstrate the limitations of the methods. Besides characteriza-
tion of multi-component systems, which is not possible by other methods, interpretation of
the results permits critical examination of the applicability of these substances for part-
cualar processes. Vice versa, processes and process parameters can be selected for the
substances in question. A monograph can only cover certain aspects of the science it deals
with, and this author has set great value on reporting his own experiences. These thermoa-
nalytical procedures may be transferred to other sectors of petroleum technology, which
are connected with thermal strains or which generally use thermal processes. For example,
the investigation of drilling fluids is of rising interest since the increasing depth of
boreholes demands increasing thermal stability of those fluids. Thermal and hydrolytic
stability of surfactants and polymers destined for enhanced oil recovery come into the same
arena. DSC tests have shown, for example, that the thermal stability (pyrolysis stability) of
ethersulphonates containing three to six ethyleneoxide groups in the molecule, is better
than ethoxylated i-octylphenols or ethoxylated monophenylglycols. The thermal and hy-
drolytic stability of organic sulphur compounds has also been investigated. This investiga-
tion contributed to knowledge of the cause of the formation of hydrogen sulphide during
the steam flooding of reservoirs of heavy crudes. In the development of lubricant additives,
the thermal and oxidative stability of single substances can be tested as well as the possible
synergism of blends, in combination with different classes of base oils. This is a classic
case for the investigation of oxidation kinetics, with the possibility of extrapolating the half
life time which was found, towards higher or lower temperatures. Low temperature DSC
may be used for precise measurement of the pour point of lubricants and crude oils, and for
the selection of a suitable pour point depressant. It may even be help the development of
such pour point depressants. The concentration of crystallizing paraffins and possibly
aromatics may also be determined by low temperature DSC.
Both the chemical nature and the concentration of polymeric modifiers in polymer-
modified bitumens can be determined by DSC. The aging behavior of bitumen and
polymer-modified bitumen in road asphalt or of bitumen extracted from road asphalt, may
be analyzed and characterized by thermoanalytical methods. Thermogravimetry in inert
gas has shown, for example, that the concentration of evaporable components decreases as
a consequence of aging whereas the coke residue (residue at 600C or 800C oven
temperature) increases, and that is connected with an increase in the concentration of
asphaltenes.
486 5 Final considerations

Interesting research into the further processing of distillation residues uses thermoanaly-
tical methods. Thermal cracking may be simulated either in inert gas or in a hydrocarbon
atmosphere. The efficiency of catalysts in catalytic cracking, and of hydrocracking in a
hydrogen atmosphere at different pressures may be investigated by both TGA and DSC.
The dependence of the kinetics on temperature and pressure and on the activity of catalysts
may be analyzed and the results transferred to process parameters in the refinery. An
investigation on the residues of such processes using thermogravimetry showed that coke
residues increase (R600 or R800) with increasing crack seventy. As expected the quantity
of crackable residue, CR, and the weight loss rate DTG, which represents the reaction rate,
decrease with increasing crack severity. This is an indication that easily crackable compo-
nents have already been converted.
The sludges in lubrication oils and the deposits in diesel, gasoline, and jet engines may
be characterized and classified using thermoanalytical methods [5-21. The reduction of the
oxidative stability of engine oils may be well quantified using DSC in air, indicating the
necessary oil change intervals [5-3, 5-41.
Thermogravimetry and DSC have the widest field of application of thermoanalytical
methods in investigations on petroleum and its products. Sometimes other methods of
thermoanalysis are preferred. Thus the low temperature viscoelastic behavior of bitumen
and polymer-modified bitumen may be characterized quite completely using a Dynamic
Mechanical Thermal Analyzer (DMTA). This behavior cannot be measured directly by
other analytical methods [5-11. Measurements over a large range of frequencies and the
generation of a master curve from those data, make the extrapolation to both extremly high
and extremly low frequencies feasible, and the resting and rolling of traffic can be
simulated. This method has shown that the temperature of second order transition (glass
transition) clearly depends upon the frequency.
Thermomechanical Analysis, TMA may be used to measure the change of volume of
bitumen, so scratching and crack propagation at low temperatures may be simulated, for
example for asphalt paving material.
The selection of both a suitable instrument and a suitable method for measuring depends
upon the problem. If changes of weight in relation to the temperature are predominantly of
interest, and energetic effects have rarely to be investigated, then a thermobalance is the
optimum choice. Occasionally required energetic measurments should be obtained from a
commercial laboratory. A Simultaneous Thermal Analyzer (TGA/DTA or preferably
TGA/DSC) is very useful if measurements of weight changes and of energetic effects have
frequently to be performed. It is desirable that the instrument can operate from low
temperatures of approximately -80 "C up to 800 "C with the same sample.
For investigation of the kinetics of pyrolysis and oxidation reactions a Simultaneous
Thermal Analyzer is preferred, provided that the incorporated software permits the evalua-
tion according both to ASTME689-79 and Flynn and Wall. In this way the kinetic
parameters can be obtained and at the same time the peak maxima (minima) of the curves
of energy against temperature can be examined to decide whether they really appear at
equal conversion levels independent of the heating rates. All the requirements for the
thermoanalysis of petroleum and its products would be fulfilled if such an instrument could
 5.2 Summary on progress of instrumentation (hard and software) and advice 487

operate in a range of pressures from lo-*up to 250 or 300 bar. Thermobalances complying
with such requirements are only available (with some restrictions) from two suppliers (see
chapter 6). Otherwise the purchase of a Pressure DSC and a Simultaneous Thermal
Analyzer represents a fair compromise.

5.2 Summary on progress of instrumentation (hard

and software) and advice

Progress of the instrumentationhas recently taken a rapid turn. In the sixties the standard
was that thermobalances and differential thermoanalysis instruments were controlled by
electro-mechanical devices and their signals recorded by multipen recorders. In the follo-
wing years the instrumentations for Differential Scanning Calorimetry (Heat Flux DSC)
and Simultanous Thermal Analyzers (STA) comprising thermogravimetry and differential
thermal analysis became commercial, but were still equipped with electromechanical
controls and multipen recorders. The first power compensation DSC was launched by
Perkin-Elmer in 1963 [5-51. Further progress dates to the end of the seventies. At that time
data logging and processing, and computerized control of the instrumentationbecame even
more customary. Analysis of the evolved crack gases or oxidation products from a STA by
mass spectrometry is described relatively early [5-4,5-61. The joint operation of a thermo-
balance together with a Fourier Transformation Infrared Spectrometer (TG-FTIR) was
established to provide identification or at least characterizationof crack gases or oxidation
products [5-21. The coupling of a gas chromatograph to a thermobalance was tried even
earlier [5-71 for the analysis of polymers. Knowledge of the chemical nature of crack gases
evolved from pyrolysis, and the distribution of crack and oxidation products evolved from
experiments in air is certainly of interest, but the experimental difficulties must not be
underestimated. The complete flow of both evolved and carrier gas cannot pass through a
mass spectrometer, gas chromatograph, or FTIR spectrometer, but only a defined partial
stream. The transfer pipe from the thermoanalytical instrument, the gas-flow splitting
device, and the inlet to the analytical instrument, all have to be heated up to relatively high
temperatures (approximately 200 "C). An alternative is the condensation of high boiling
components before the gas stream splitting device by using a cooling trap. Some condensa-
tion of heavy products may not even be avoided by using heated ducts. On this account it
seems impossible to make a quantitative analysis, but adequate evaluations may be
made.
There are as yet so few publications that an opinion can hardly expressed as to whether
this relatively expensive, experimentally difficult, and irritable technique is able to supply
enough information, especially in the petroleum analysis, to satisfy the costs.
Relatively early on the dependence of pyrolysis and oxidation reactions upon the
pressure was investigated by thermogravimetry using devices constructed by the experi-
488 5 Final considerations

mentors themselves [5-81. Thermobalances operating at pressures up to 100 bar became

commercial at the beginning of the eighties. A pressure DSC cell for pressures up to 70 bar
was available earlier [5-91. This type of instrument is suitable for investigation on the
dependence of any reactions upon pressure, such as reaction kinetics, and for measure-
ments on substances possessing relative low atmospheric boiling temperatures.
Thermobalances are available in two different designs, i. e. a horizontal construction
(Fig. 5-1) and vertical construction. For the vertical construction there are two different
versions: the top-loading balance, which has the oven above the balance (Fig. 5-2), and the
thermobalance with the sample tray hanging on a thin hangdown wire into the oven below
the balance (Fig. 2-4). The suppliers claim some advantages for the horizontal arrangement
such as complete lack of buoyancy, the avoidance of condensation in the balance cabinet,
and the reduction of sensitivity to vibration. However the last two points cannot be
confirmed by the authors experience. Despite an efficacious gas flow, a diffusion of
condensates was observed opposite to the flow direction of the gas. The sensitivity to
vibrations seems to be comparable with the vertical design. Of the vertically constructed
balances, the top loader is more convenient to manipulate.
Some suppliers recommend thermobalances in a vertical design which are equipped
with two separate ovens operating with identical heating and gas flow rates for sample and
counterweight. This construction completely compensates any buoyancy effects and gua-
rantees a very high resolution of approximate 0.1 pg (Fig. 5-3).

ELECTROMAGNETIC

r- I
AMPLIFIER

Fig. 5-1 Horizontal Thermobalance

Schematic Diagram of TGA 95 1
(DuPont Instruments, Thermal Analyzers, Leaflet H-16776)
 uurae aas ,
Schematic Diagram STA 409 EP furnace / \
/
t

metallic heater TG sample catmer

TG sample cai'rier
sample carrier

radiation shield
protective tube
/
purge gas - TG sample carrier
thermostat

inductive displacement
transducer

balance system

pig. 5-2 Vertical Thermobalance with Oven in Top Position P

00
Schematic Diagram of the Simultaneous Thermal Analyzer STA 409EP (Netzsch Geratebau GmbH) W
490 5 Final considerations

4
purge gas

Thermo-Microbalance TG 439
Principle of the symmetrical weighing
system with connections for protective
gas, purge gas and vacuum pump
1) thermostat
2) radiation shield
3)water cooling
4) crucible
5) furnace
6)manometer
7) flow meter
8) balance
9) vacuum pump
10) piping
-D$ magnetic valve
control valve

Fig. 5-3 Thermobalance with Symmetrical Weighing System and Two Ovens
Schematic Diagram of the Thermal-Microbalance TG 439
(Netzsch Geratebau GmbH)
 5.2 Summary on progress of instrumentation (hard and software) and advice 491

High P r e s s u r e Thermogravimetry

Fig. 5-4 Magnetic Suspension Thermobalance with High Pressure Oven

(Schematic Diagram: RUBOTHEXM Prazisionsmesstechnik GmbH)

A long-established technique has recently been re-introduced i. e. the principle of

magnetic-suspension balances. In this the balance cabinet and the oven chamber are
completely separated since the sample hangdown is connected to the balance by a magne-
tic-suspension coupling. A construction equipped with a housing made from quartz glass is
suitable for measurements in aggressive gases up to 900C sample temperature. An
instrument made of a chrome-nickel superalloy may be used for pressures up to 450 bar
and for temperatures up to 1 000 "C (Fig. 5-4).
Heat flow DSC instruments are generally equipped with a thermoelectric (constantan)
disc as platform for both sample and reference pan with two thermocouples situated
492 5 Final considerations

underneath the disc. Both sample and reference pan are situated directly above the thermo-
couples (Fig. 2-9). In opposition to this arrangement heat flow detectors introduced by
Tian and Calvet [5-101 are applied in a series of instruments designed by SETARAM. This
type of detector consists of a thermopile each, for sample and reference on the inside. The
thermopiles possess high thermal conductivity combined with high caloric sensitivity. In
the disc DSC arrangement the caloric sensitivity decreases with increasing temperatures,
whereas the caloric sensitivity of the Tian-Calvet system increases. The disc design can
only be calibrated by suitable calibration substances whereas the Tian-Calvet system may
be calibrated with defined amounts of electrical energy (Joule heat), too.
High Resolution Thermogravimetry (HI-RES-TGA) has been developedjust recently in
the late eighties. The principle is based on the adaption of the heating rate to the weight loss
rate. For example any weight loss will be measured isothermally until the weight loss
ceases. Then heating will resume at the pre-set original heating rate until the next weight
loss starts. Applying this mode one will obtain a resolution owing to extremly low linear
heating rates even at normally high heating rates for example 10 K/min. Weak effects,
which will be over-taken at higher heating rates, may be detected in this manner.
Experimental time will be saved, but this principle cannot be applied for measurements on
reaction kinetics.
The latest development (1992) is the Modulated Differential Scanning Calorimetry
(MDSC). Here the linear heating rate is superimposed by a sinoidal modulation. The
following advantages of this mode are claimed:
direct measurement of heat capacity
improved resolution of adjacent or superimposed effects
improved sensitivity for weak transition effects
separation of reversible from irreversible effects
Most suppliers now offer automatic sample loading and unloading devices, which are of
special interest for time consuming investigations such as reaction kinetics requiring
several measurements for each substance, and for quality control laboratiories, which have
to handle a multitude of samples.
The provision of software concerning instrument control, data logging, and data proces-
sing differs less in volume than in quality from the various suppliers. The possibility of
multi-tasking and the option of multimodule operation is standard with regard to the
efficiency of modern computers. But in data logging the first differences in the software are
found from some suppliers concerning the sampling rates. Evaluation of rapid processes or
of processes, which take place within narrow temperature limits (such as oxidation pro-
cesses) require high sampling rates. The recalling of the stored data for evaluation is
me-consumingbecause of the large quantity of data. Therefore the computer should be
ipped with a fast processor. On the other hand medium or slow sampling rates suffice
for some applications, for example to decide whether two samples are identical within
defined limits. Computer programs containing variable sampling rates are resonably pri-
ced.
 5.2 Summary on progress of instrumentation (hard and software) and advice 493

There are some computer programs, which are practically fool proof. In them erroneous
commands can be revoked, the computer indicates if a sufficient number of data is not
stored for an elected operation, intermediate results may be stored and recalled, and
obviously wrong results may be eliminated. In other programs such possibilities are
lacking. In the case of an erroneous command the evaluation must be called off and
restarted or the software crashes displaying something like hit any key to return to
system. This will also happen if the program perceives after prolonged attempts at
calculation, that the number of stored data does not suffice or that an illegal command has
been suggested. In that case the complete evaluation program has to be re-started from the
very beginning including the time-consuming recalling of the stored data. To avoid unplea-
sant surprises it may be advisable to test the instrumentation and the software in the
application laboratory of the supplier, investigating your own substances prior to the
purchase of any instrumentation. Since there are no error-free programs the supplier should
provide adequate software support and regularly update with improvements or correc-
tions.
The manuals for both hardware and software sometimes cause surprise. There are some
excellent as well as some imperfect publications. When buying an instrument worth many
thousands of dollars (marks, yen), it does not seem unreasonable to request the delivery of
manuals in ones own language. One should not presume that the laboratory and mainte-
nance staff who have to operate and maintain the instrumentation are fluent in foreign
technical languages.