HISTORY OF PYROLYSIS GAS CHROMATOGRAPHY

Pyrolytic Gasification is by no means new. The principals were first brought forth in 1958 at
Bell Laboratories within the United States of America. Thereafter, a number of universities and
organizations around the world started R&D programs. The word Pyrolysis meaning, chemical
change brought about by heat is widely used, even by incineration technologies, which have tried to
escape their roots in oxidation and combustion because of the problems prevalent with both.
Gasification is a term being used to describe the chemical reaction and molecular break down, or
degradation of materials.
The first Pyrolytic Gasification systems were brick ovens using indirect heat / low oxygen
that were made of firebrick. Waste was placed into the unit - the unit was sealed and heat applied.
After the process of degradation was completed, the oven was opened and emptied to make room for
the next batch. These systems were known as batch-by-batch systems. This format was first
introduced commercially in the early 70's. They were limited by volume and, after some time in
operation, were also found to have defects that related to the mortar that was used to bind the bricks
together. During the late 70's and early 80's, R&D turned away from batch-by-batch systems, which
at that time, had found some commercial success processing Hospital Waste and continual-flow
systems, which were a form of rotating Auto Clave. This format was later refined into cone shaped
retorts in order to direct the gas stream to a central point for evacuation. This refined cone design
first showed up in England, then the US and Germany, followed by Japan, Canada and the
Netherlands.
It was during this time that manufacturers of incinerator systems started to run into
environmental problems. As environmental laws worldwide became stricter, it became exceedingly
difficult to get permitting. The price and installation of incinerators became extraordinarily
expensive due to the air quality equipment that had to be added in order to pass air quality
regulations. But, whereas, air quality issues could be handled with additional equipment, byproduct
leachability could not. In most cases, the average incineration system was eight to ten times over
limits set for low volatile metals, which are leachable and carcinogenic if ingested through drinking
water.
It was also during this period that the National Aeronautics Space Administration (NASA)
was completing their studies into the effects of zero gravity and zero oxygen environment, which
were conducted at the end of the Apollo missions and were finished within the first few flights of the
space shuttle. The information and technology derived from these studies showed that the oxygen
molecule is a binding molecule, which is why incineration, that makes use of high oxygen, has such
a high degree of low volatile metals, which are bound by the degree of oxygen content within the
retort or firebox and are locked into their byproducts. The binding element of oxygen also causes the
formation of dioxins, which is the combination of two oxygen molecules along with others within the
gas stream. At this point, in the early to mid-80's, the first pilot and then commercial systems using
direct gasification started to show up. These were in the form of Fixed Bed, Entrained Bed and
Fluidized Bed Systems. These systems all had draw backs in the form of their byproducts, which
were tars that were hazardous, or char and ash, that the oxidation within the process, had
consolidated low volatile metals that were leachable. In some cases, the Entrained Bed Systems
created a slag that contained leachable metals, but the major drawback was the operational costs.
The Fixed Bed and Fluidized Bed Systems were still found to, at times, create smaller but
traceable amounts of dioxins due to the continued use / presence of oxygen.
In the mid 80's, the Balboa Pacific Corporation of the United States of America started
testing their new design of an indirect pyrolytic gasification system. This system was patented in
 1988. A 50 ton-per-day pilot plant was refined and constructed over a two-year period from 1993 to
1995, which was partially funded by Southern California Gas Company and private investors. The
plant operated at California Steel for 18 months, during which time, several of the nation’s
environmental engineers such as Dames & Moore did exhaustive studies on the system’s ability to
process, on a continuous feed basis, a wide variety of toxic and nontoxic, liquid or solid organic
waste streams. Studies and testing of emissions, leachate and byproducts were, in every case,
determined to meet or exceed the environmental thresholds and guidelines set forth by the
Environmental Protection Agency (EPA), the Air Quality Management District (AQMD) and the
State of California Air Quality Control Board. And the efficacy of Balboa Pacific’s proprietary
technology of molecular decomposition through pyrolytic gasification was determined to be
superior for waste management. The Balboa Pyrolytic Gasification Process makes use of high tech
patented ceramics and alloys, as well as patented digitized valving, combined with process secrets;
thereby, producing an oxygen-free, high temperature environment within the retort of between
0.05% to a maximum 2.5% oxygen and upwards of 2250 degrees F, resulting in the destruction of
99.999984 percent of any organic toxic or nontoxic feed-stock that is introduced through the system.
Once high-density metals are removed through magnetic separation, the process produces an output
of non-leachablebyproducts.
Currently, and over the past eight years, a number of companies have experimented with
pressurized retorts. Whereas this method can help to maintain an oxygen free environment, it also
creates other problems such as how to maintain continuous throughput of waste material. To date,
most have been unsuccessful. Pressurized retorts have, however, been used within ash-melting
combustion systems. In many respects, these systems are much like blast furnaces. They operate at
high oxygen / high heat and produce a byproduct of slag, which still needs special handling and to
date, has no market value. Also, the amount of energy needed to operate the system effectively is
believedtooffsetpotentialreturns,muchthesameasinPlasmaArchtechnology.
An independent investigation, resulting in a thorough evaluation of Balboa Pacific’s
proprietary continuous feed Pyrolytic Gasification process, determined that there is currently no
technology that can compare to their indirect Pyrolytic Gasification Systems. Most of the
technologies discussed were pyrolytic gasification systems of direct heat formats such as, Fixed Bed,
Entrained Bed and Fluidized Bed. Other technologies mentioned were rotary kiln low oxygen
formats and organic wood digesters/gasifiers, none of which, can handle the waste streams that the
Balboa system can, such as, but not limited to: PCB’s, hazardous solids and liquids, computer
industry waste, plastics, mining industry waste, municipal solid waste (MSW), hospital red-bag
waste, illicit drugs and Treasury Department’s out-of-circulation currency. Furthermore, many of the
burgeoning technologies are just now coming into commercialization, with the exception of
EDL/BSC, which for the most part can only handle organic material in a limited format.

INTRODUCTION

Structural analysis and the study of degradation properties are important in order to understand
and improve performance characteristics of synthetic polymers and copolymers in many industrial
applications. Polymers/copolymers cannot be analyzed in their normal state by traditional gas
chromatography (GC) because of high molecular weight and lack of volatility. However, by heating
these macromolecules to temperatures above 500 °C, they are pyrolyzed into many individual
fragmentation substances, which can be then separated chromatographically and identified by mass
spectrometry. Pyrolysis technique hyphenated to gas chromatography/mass spectrometry (GC/MS) has
extended the range of possible tools for characterization of synthetic polymers/copolymers. Under
controlled conditions at elevated temperature (500 – 1400 °C) in the presence of an inert gas,
reproducible decomposition products characteristic of the original polymer/copolymer sample are
formed. The pyrolysis products are chromatographically separated by using a fused silica capillary
column and subsequently identified by interpretation of the obtained mass spectra or by using mass
spectra libraries (e.g. NIST, Wiley, etc.).
Pyrolysis methods eliminate the need for pre-treatment by performing analyses directly on the
solid polymer/copolymer sample. Most of the thermal degradation results from free radical reactions
initiated by bond breaking and depends on the relative strengths of the bonds that hold the molecules
together. A large molecule will break apart and rearrange in a characteristic way (Moldoveanu, 2005;
Wampler, 2007; Sobeih et al., 2008). If the energy transfer to the sample is controlled by temperature,
heating- rate and time, the fragmentation pattern is reproducible and characteristic for the original
polymer. Another sample of the same composition heated at the same rate to the same temperature for
the same period of time will produce the same decomposition products. Therefore the essential
requirements of the apparatus in analytical pyrolysis are reproducibility of the final pyrolysis
temperature, rapid temperature rise and accurate temperature control. Depending upon the heating
mechanism, pyrolysis systems have been classified into two groups: the continuous-mode pyrolyzer
(furnace pyrolyzer) and pulse-mode pyrolyzer (flash pyrolyzer) such as the heated filament, Curie-
point and laser pyrolyzer. The pyrolysis unit is directly connected to the injector port of a gas
chromatograph. A flow of an inert carrier gas, such as heliu flushes the pyrolyzates into the fused silica
capillary column. The detection technique of the separated compounds is typically mass spectrometry
but other GC detectors have been also used depending on the intentions of the analysis (Sobeih et al.,
2008). The currently commercially available pyrolysis equipment was described in detail in previous
work of the author (Kusch et al., 2005).
The applications of analytical pyrolysis–gas chromatography/mass spectrometry range from
research and development of new materials, quality control, characterization and competitor product
evaluation, medicine, biology and biotechnology, geology, airspace, environmental analysis to forensic
purposes or conservation and restoration of cultural heritage. These applications cover analysis and
identification of polymers/copolymers and additives in components of automobiles, tires, packaging
materials, textile fibers, coatings, half-finished products for electronics, paints or varnishes, lacquers,
leather, paper or wood products, food, pharmaceuticals, surfactants and fragrances. In earlier
publications of the author (Kusch, 1996; Kusch et al., 2005), the analysis and identification of
degradation products of commercially available synthetic polymers and copolymers by using analytical
pyrolysis hyphenated to gas chromatography/FID and gas chromatography/mass spectrometry have
been presented. In this chapter, examples of application of this analytical technique for identification of
different polymeric materials are demonstrated.

Theory
Pyrolysis gas chromatography mass spectrometry (Py/GC/MS) is an instrumental method that
enables a reproducible characterisation of the intractable and involatile macromolecular complexes
found in virtually all materials in the natural environment. It differs from GC/MS in the type of sample
analysed and the method by which it is introduced to the GC/MS system. Instead of the direct injection
of a highly refined organic solution, a few mg (or in the case of materials with a high organic carbon
content, <mg) of the original natural material (e.g. soil, sediment, vegetation, insect cuticle, hair etc.) is
analysed directly.
The analysis is usually preceded by an extraction of the sample with an organic solvent to
remove any free, unbound components with a low molecular mass that would otherwise obscure
analytical data pertaining to the high molecular mass components of interest. Extracted samples are
then inserted into a quartz chamber in a pyrolysis unit (Fig. 1) that is then heated resistively in an
oxygen free enivironment at a pre-set temperature for a number of seconds (e.g. 610 ºC for 10 s). This
results in a heat mediated cleavage of chemical bonds within the macromolecular structures of interest
producing a suite of low molecular weight chemical moieties the composition of which is indicative of
specific types of macromolecule (e.g. lignin, cellulose, chitin etc.). This mixture of compounds is then
swept onto the analytical column of the GC and GC/MS proceeds as normal.
For some macromolecules it is desireable to introduce a chemical reagent that, upon heating, will react
with the macromolecule in a more directed manner, e.g. the preferential cleavage of ester domains, to
produce a mixture of derivatized low molecular weight moieties in a process know as thermally
assisted chemolysis. Typical reagents that are used include tetramethylammonium hydroxide (TMAH)
and trimethylsufonium hydroxide (TMSH).

The Shimadzu GC/GCMS Advanced Flow Technologies (dual oven multi-dimensional, backflush,
heartcut, detector splitting, detector switching) offer effective techniques for enhancing gas
chromatographic analysis.
The detector splitting system introduced here is a system that can provide multiple chromatograms
simultaneously by post-column splitting of the column effluent to multiple detectors. Due to the large
amounts of information that can be obtained in a single analysis, improved analytical productivity and
identification accuracy can be anticipated.
A specialized detector splitting device is connected at the outlet of the analytical column, and the
column outlet pressure is controlled using an Advanced

Pressure Controller (APC). A restrictor tube (capillary column) connects the flow lines to the detectors.
The detector splitting system diagram is shown in Fig. 1, and a picture of the detector splitting device is
shown in Fig. 2. In addition to the hardware, integrated software is provided to enable simple setting of
multiple sets of analytical conditions, allowing simple method development in GCsolution and GCMS
solution software. (See Fig. 3)
Here we introduce an example of analysis focusing on sulfur compounds in rubber by pyrolysis-
GC/MS using a system in which a mass spectrometer (MS) is connected as detector 1, and the high
sensitivity sulfur detector, FPD (S-mode), is connected as detector 2.
Analisis
The vulcanizing agents and vulcanizing accelerators used in rubber products decompose and react
within the rubber during the vulcanization reaction, making it impossible to identify the chemical
structure of the initial raw material. Therefore, pyrolysis-GC/MS, a technique that can detect thermal
decomposition products, is used for these types of qualitative analyses.
Although this method provides for easy analysis without sample pretreatment, detection of the sulfur
compounds becomes difficult due to the appearance of a large quantity of hydrocarbon-derived
substances that are the principal ingredients of rubber. On the other hand, the FPD (S-mode) detector
can selectively detect sulfur compounds with high sensitivity. Here we report an example of qualitative
analysis of sulfur compounds using an FPD and MS simultaneously.
Instantaneous pyrolysis (600 °C) of a 0.5 mg rubber sample was conducted, followed by gas
chromatographic separation using a capillary column, and simultaneousined from the MS is shown in
Fig. 4, and the FPD (S-mode) chromatogram is shown in Fig. 5. Benzothiazole (C7H5NS) is the only
sulfur compound that was detected as a major peak in the total ion chromatogram.

Use of the instrument

For characterization of very complex and challenging samples four powerful analytical techniques are
available:

1. Evolved gas analysis (EGA-MS)

For EGA analysis a short and narrow (2.5 m, 0.15 mm i.d.) deactivated capillary tube without a
stationary phase is used as direct connection between GC-injector and mass-detector. As the sample is
temperature programmed over a given temperature range (i.e. 40 - 800 °C) , the evolved gases flow to
the detector without chromatographic separation. The result shows the simple thermogram such as a
differential thermogravimetric curve for a given sample.

2. Single-shot analysis (Py-GCMS)

The sample cup free-falls into the preheated pyrolyzer furnace. The sample temperature goes from
ambient to the pyrolysis temperature in less than 20 msec. Pyrolysis occurs instantly and the
pyrolyzates are introduced into a capillary column for separation without second reaction.

3. Double-Shot analysis (TD/Py-GCMS)

Double Shot analysis provides both: information about volatile compounds e.g. monomers or additives
and the polymeric content of the sample. Therefore the sample analysis is divided into two steps:

Step 1: during the thermal desorption step the sample is heated over a temperature range and the
volatile compounds evolve from the sample. The evaporated compounds are trapped at the beginning
of the GC column and analyzed via GCMS after the temperature program of the pyrolyzer is finished.

Step 2: the residual sample is pyrolyzed at a temperature determined by EGA data. The program
facilitates the identification of the polymeric composition of the sample.

4. Heart-cut analysis (Heart-cut EGA-GCMS)

In cases where highly complex samples demand a detailed analysis, Heart-cut EGA-GCMS is the
most useful technique to determine the composition of the sample. In this technique, the evolved gas
analysis (EGA) is used to obtain a thermogram and each temperature zone of interest can be analyzed
separately. By heart cutting components evaporated in this interesting temperature zones are selectively
introduced to a GC column, temporarily trapped at the beginning of the column and finally analyzed by
GCMS. This technique allows a detailed characterization of a polymer as well as target compound
analysis in complex matrix, e.g. additive analysis in mineral oil.

Working principle
Pyrolysis is the thermal decomposition of materials in an inert atmosphere or a vacuum. The
sample is put into direct contact with a platinum wire, or placed in a quartz sample tube, and rapidly
heated to 600–1000 °C. Depending on the application even higher temperatures are used. Three
different heating techniques are used in actual pyrolyzers: Isothermal furnace, inductive heating (Curie
Point filament), and resistive heating using platinum filaments. Large molecules cleave at their weakest
points and produce smaller, more volatile fragments. These fragments can be separated by gas
chromatography. Pyrolysis GC chromatograms are typically complex because a wide range of different
decomposition products is formed. The data can either be used as fingerprint to prove material identity
or the GC/MS data is used to identify individual fragments to obtain structural information.
To increase the volatility of polar fragments, various methylating reagents can be added to a sample
before pyrolysis.
Besides the usage of dedicated pyrolyzers, pyrolysis GC of solid and liquid samples can be
performed directly inside Programmable Temperature Vaporizer (PTV) injectors that provide quick
heating (up to 60 °C/s) and high maximum temperatures of 600-650 °C. This is sufficient for many
pyrolysis applications. The main advantage is that no dedicated instrument has to be purchased and
pyrolysis can be performed as part of routine GC analysis. In this case quartz GC inlet liners can be
used. Quantitative data can be acquired, and good results of derivatization inside the PTV injector are
published as well.
 Pyrolysis gas chromatography is useful for the identification of involatilecompounds[4] and
synthetic polymeric media, such as acrylics or alkyds, and synthetic varnishes. The way in which the
polymer fragments before it is separated in the GC can help in identifying the way that the sample
polymer assembled itself (step growth v. chain growth, for example). The method of pyrolysis gas
chromatography can also be used for environmental samples, including fossils.Trace evidence
scientists in forensic laboratories use Pyroylsis GC to compare and identify paint or finish found at
crime scenes or victims.

Schematic diagram of instrument

Instrument pyrolisis for bacterium detection
Discrimination of bacteria was investigated using pyrolysis-gas chromatography-differential
mobility spectrometry (Py-GC-DMS). Three strains belonging to the genus Bacillus were investigated
and these included two strains of Bacillus subtilis and a single Bacillus megaterium. These were
chosen so as to evaluate the possibility of bacterial strain discrimination using Py-GC-DMS. The
instrument was constructed in-house and the long-term reproducibility of the instrument was
evaluated over a period of 60 days using a Scotch whisky quality control. To assess the reproducibility
further each bacterium was cultured six times and each culture was analysed in replicate to give three
analytical replicates. The DMS data were generated in both positive and negative modes, and the data
in each mode were analysed independently of each other. The Py-GC-DMS data were pre-processed
via correlation optimised warping (COW) and asymmetric least square (ALS) to align the DMS
chromatograms and to remove any unavoidable baseline shifts, prior to normalisation. Processed
chromatograms were analysed using principal component analysis (PCA) followed by supervised
learning methodology using partial least squares for discriminant analysis (PLS-DA). It was found that
the separations between B. subtilis and B. megaterium can be readily observed by PCA; however,
strain discrimination within the two B. subtilis was only possible using supervised learning. As multiple
biological replicates were analysed an exhaustive splitting of the training and test sets was
undertaken and this allowed correct classification rates (CCRs) to be assessed for the 3375 test sets. It
was found that with PLS-DA the negative ion mode DMS data were more discriminatory than the
positive mode data.

Adavantages and Disadvantages

Advantages

 Polymer can be identificated by comparison of pyrograms and mass spectra with known
references.
 Optimal for qualitative analysis and structural characterization of copolymers, sequence statistics of
copolymers, differentiation between statistical and block polymers,
 Determination of the (micro) structure of polymers (degree of branching and crosslinking,
compositional analysis of copolymers and blends, co-monomer ratios, sequence distributions, analysis
of end-groups),
 determination of the polymers steric structure (stereoregularity, tacticity, steric block length, and
chemical inversions.
 Iinvestigation of thermal stability, degradation kinetics and oxidative thermal decomposition of
polymers and copolymers.
 Good quality control,

Disadvanatges

 Hard to learn for uses

 Expensive tools
 High specification device
Comercial Instrument

Features of the Multi-Shot Pyrolyzer EGA/PY-3030D

- Rapid heating (600 °C/min) and cooling (100 °C/min)

- High temperature pyrolysis up to 1050 °C
- Superior performance due to exact temperature control, inert sample pathway, no dead volumes, no
cold spots
- Dedicated samplers for sample introduction e.g. Micro Reaction Sampler, UV Sampler
- Special F-Search SW and various libraries (Additive-, Pyrogram-, Pyrolyzate-, EGA-Library)
- Valuable accessories:Auto-Shot sampler (capacity: 48 sample cups)
Cryo Trap (Micro Jet Cryo Trap), Vent-free GCMS adaptor
Carrier Gas Selector (for pyrolysis under air atmosphere)
High temperature capillary columns (Ultra Alloy)