Review: Recycling of Nylon From Carpet Waste

COFUNA MIHUT, DINYAR K. CAPTAIN, FRANCIS GADALA-MARIA,

and MICHAEL D. AMIFUDIS*

Department of Chemical Engineering

University of South Carolina
Columbia, sc 29208

Large amounts of post-consumer carpet are discarded every year. Most of this.
waste is currently landfilled, while a small percentage is incinerated. The face car-
pet fibers, consisting primarily of nylon 6 and nylon 6.6, represent the majority
component in the carpet waste. Recent financial incentives and environmental con-
straints have motivated the industrial sector to develop recycling strategies for
these fibers. Depolymerization into their constituent monomers is the most com-
plex recycling route, but at the same time it produces the most valuable product. A
second alternative involves the use of solvents for the extraction of carpet fiber
components in their polymeric form. Finally, a third recycling option yields thermo-.
plastic mixtures by melt blendmg the carpet waste. The recent literature on the re-
cycling of nylon from carpet waste is reviewed in this paper. The paper also in-
cludes a section focusing on the current state of carpet recycling at the industrial
level.

1. INTRODUCTION recycling was published in 1991 by Datye (4),and it

I n the United States alone, approximately 3.3 billion
lbs of carpet fibers, including nylon, polyester,
polypropylene, acrylic, wool and cotton, are produced
annually (1).Of this amount, approximately 65%--0r
2 billion lbs-is composed of nylon 6 and nylon 6,6.
The European annual production of carpet, including
tufted, woven and needed products is approximately
1.5 million tons (3.3 billion lbs) (2). The average life
cycle of a carpet is between 8 and 12 years. Carpet
production also generates a substantial amount of
waste in the form of trimmings and cuts, which typi-
cally amounts to 12%of the total production (3,4).As
a result, an enormous amount of synthetic waste is
generated, most of which is disposed in landfills.
Landfiiling is not an environmentally friendly solution
since carpet fibers, like many other synthetic poly-
mers, are not biodegradable. Furthermore, the cost of
disposal is increasing continuously owing to limited
landfill capacity. Environmental concerns and govem-
mental regulations have spurred efforts in the direc-
tion of recycling all non-biodegradable synthetic poly-
mers, of which carpets and carpet fibers constitute a
significant percentage.
The literature in the area of carpet recycling is rela-
tively sparse. A review paper on the subject of nylon
*Correspondingauthor. Electronic mail: amiridis@engr.sc.edu.
provides a detailed insight into the recycling of post-
production nylon 6 waste. This review, however, does
not focus upon the issue of carpet recycling at both
the post-manufacture and post-consumer levels, as
this concept has emerged only over the last few years
because of the large amounts of non-biodegradable
carpet accumulated in landiUs. Recycling of the entire
carpet poses a significant challenge because of the in-
homogeneous nature of the material. Moreover, it is
even more difficult to recycle post-consumer carpet
waste because of the dirt, cleaning chemicals, and
other materials accumulated in the carpets over the
years. Studies carried out in Europe reveal that post-
consumer carpet is approximately 30% heavier than
new carpet owing to dirt accumulated in the piles (5).
It also contains a signifcant amount of contaminants,
mainly the chemicals used for cleaning purposes. It is
this inhomogeneous nature of carpets that makes ef-
fective recycling a very difficult and costly process.
The recycling of polymers has been broadly classi-
fied into four categories (3):
(a) primary recycling or depolymerization,which con-
verts the waste into products having a quality
equivalent to that of the "virgin" polymer. This
category encompasses methods to break down the
long polymer chains into their original monomers
that can be repolymerized.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9 1457
 Corina Mihut, Dinyar K. Captain, Rancis Gadala-Maria, and Michael D. Amiridis
Secondary recycling, which involves recovering of
the individual components of a polymeric mixture
without necessarily breaking them down to the
monomeric form. This category includes various
extraction and separation methods.
Tertiary recycling, which consists of preparing a
thermoplastic mixture by melt-blending the entire
carpet waste. This recycling route requires no
fiber separation or latex removal, as the carpet
components are mixed by means of reactive ex-
trusion and compatibilization. Products of lower
quality can be manufactured from this blend, by
methods such as injection molding.
Quaternary recycling, which involves only energy
recovery during the incineration of the polymer
waste.
The intention of this review is to provide an insight
into the problem of carpet recycling, along with an
analysis of the different methods being proposed or
commercially utilized. The reviewed literature includes
a limited amount of journal publications, which focus
primarily on fundamental aspects, and a large num-
ber of patents, which describe the available technolo-
gies.
2. CARPETS-A BRIEF BACKGROUND
Artifkial fibers have been created in an effort to im-
prove the quality and availability of textiles, and to re-
duce the cost of several products for the consumer.
Initial attempts were targeted towards the synthesis
of fibers with properties similar to those of the natural
materials. During the industrial revolution of the 19th
century, the first patent for "artificial s i l k was
granted to a Swiss chemist in 1855 in England. It was
not until the end of the 19th century t h a t the
"artificial silk" (rayon) started being produced on a
commercial scale by French chemist Count Hilalre de
Chardonnet.
Discovered in 1931 by chemists at E. I. DuPont de
Nemours and Company, nylon 6,6 quickly became
one of the most used fiber materials. Nylon 6.6 is the
Carpet fibers
Primary backing -
Binder
Secondary backing-
Fig. 1. Carpet construction.
1458 POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
polyamide formed by the reaction between hexameth-
ylene diamine and adipic acid. Each of the monomers
has 6 carbon atoms, thus the designation 6,6. Com-
mercial production of nylon 6.6 by DuPont began in
1939. I t s initial applications were sewing thread,
parachute fabric, and women's hosiery. When the
U.S. entered World War 11, its nylon production was
allocated for military use. In the post-war industry,
nylon became one of the most widely used artificial
materials, with a variety of applications. By the end of
the 1940s, it was already being used for upholstery
and in carpets. During the same period, Paul Schlack
of the infamous I. G. Farben Company in Germany
obtained a different form of polyamide by using capro-
lactam as the monomer, and called it "nylon 6." Most
carpet fiber yarns in production today are either nylon
6 or 6.6, although a small percentage is made of poly-
ester, acrylics, polypropylene and other olefm fibers,
wool or cotton ( 1, 6).
A typical carpet has four main layers (51 as shown
in Rg. 1. The top layer, or face yarn, is composed of
nylon fibers tufted through a primary backing, which
is usually made of polypropylene. Other fibers such as
jute, polyethylene, polyesters and rayon may also be
used. Latex adhesive is applied under the primary
backing in order to secure the face fiber. The adhesive
is usually made of a styrene butadiene co-polymer
(SBR),which is faed with inorganic materials such as
CaCO, or BaSO, (3).The fillers are added for sound-
proofing purposes. Finally, a secondary backing (same
material as the primary backingl may optionally be
added to the primary backing and bonded to it by the
same SBR adhesive. The nylon face fibers, containing
dyes, soil-repellents (to improve the resistance to
stains), and possibly other additives to improve the
quality of the carpet, usually account for about half of
the total carpet weight.
3. CARPET RECYCLING
3.1 Generai Considerations
As mentioned in the Introduction, there are several
recycling approaches, which differ by the type and
quality of the product generated, and consequently by
 Review: Recycling of Nylon From Carpet Waste
the type of process utilized. Depolymerbtion is the
preferred route of carpet recycling, since it breaks
down the carpet fibers (nylon 6 and/or nylon 6,6) into
the corresponding monomers. This allows the recov-
ery of the monomers that can be re-polymerized into
new nylon products of high quality.
Alternatively, the nylon component can be sepa-
rated from the carpet waste by extraction. In this
process, the entire waste carpet material is dissolved
in a solvent at elevated temperatures. During extrac-
tion, the nylon from the fibers is recovered in its poly-
meric form and can be reused in injection molding ap-
plications. The main problem associated with this
approach is the selection of a suitable solvent that se-
lectively dissohres the nylon fibers and does not react
with or dissolve any of the other carpet components.
Use of a partially selective solvent results in the recov-
ery of nylon containing several impurities, and hence,
having limited hrther use.
Melt blending of the entire carpet scrap generates a
thermoplastic mixture that can be used for the manu-
facturing of a lower quality plastic material. Such a
material can be utilized in less “demanding”products.
The method consists of melting the entire carpet
waste, without a previous separation into its compo-
nents, to obtain a blend of different polymeric and
inorganic materials. The low quality and lack of ho-
mogeneity of the resulting mixture are the main draw-
backs of this method, restricting the number of appli-
cations in which its product can be used. Since
carpets consist of several immiscible phases, compati-
bilizers (i.e. interfacial agents that decrease the sur-
face tension and increase the interfacial adhesion be-
tween the different phases in a mixture) often must be
added to the system in order to increase the miscibil-
ity of the various materials. The composition of the
final product depends on the type and composition of
the carpet recycled, varying significantly from one
batch to another. Despite these problems, this recy-
cling approach is still attractive because of its low cost
and the utilization of the entire carpet waste, without
a requirement for any prior separation.
Disassembling the face fibers off the used carpet
material using different mechanical separation meth-
ods provides nylon 6 fibers that can be used in several
applications. One example that has attracted some in-
terest is their use in the reinforcement of concrete (7).
Laboratory studies have shown that adding 1-2 wt%
of short fibers separated from waste carpet to the con-
crete mix improves its properties, such as its tensile
strength and shrinkage.
Used together with landfilling, b u t to a much
smaller extent, incineration is slowly being aban-
doned, mahly because of the air pollution problems it
creates. The main idea behind incinerating this type
of waste is to at least recover some of the energy value
that was input during the manufacturing of the car-
pet. Generally, this approach proves efficient when
the energy needed to make the original material is
less than twice the energy obtained by incinerating it
POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
13).Otherwise, as is the case with polymeric materi-
als, more advanced recycling techniques are pre-
ferred, which make use of the waste in a “smarter”
way by transforming it into useful raw material for
other applications. Hence, incineration of carpet
waste is not regarded as a promising long-term alter-
native for carpet disposal.
In the following sections the technical advantages of
each one of the most promising recycling techniques
(depolymerization,extraction, melt blending, and me-
chanical separation) are reviewed in detail. A n addi-
tional section is devoted to the current state of carpet
recycllng at the industrial level.
3.2 Depolymerization
During depolymerization, polymer chains are bro-
ken down into their monomeric constituents. A de-
tailed description of the chemistry of the depolyrner-
ization of nylon 6 to its caprolactam monomer was
presented by Agrawal in 1975 (8).More recently,
Datye (4) reviewed the depolymerization of waste
nylon generated during the manufacturing of nylon
6 and filament yam. Another review on the topic of
e-caprolactam regeneration from wastes in the manu-
facture of nylon fibers and yams has also been pub-
lished by Dmitrieva et aL (9). In the following para-
graphs we provide a summary of the most important
issues related to the depolymerization process as ap-
plied to the recovery of nylon from carpet waste and
review the more recent developments in this area.
The depolymerization of nylon 6 is a first-order, en-
dothermic reaction, which takes place in initiation
and de-propagation steps. Water is an initiator for the
depolymerization process. This process is endother-
mic and requires high temperatures, achieved by the
use of superheated steam. Steam not only acts as a
heat source and water supply, but also provides a bet-
ter agitation for the reaction system. Temperatures
above the boiling point of caprolactam (around 267°C)
are typically used. Under such conditions a heteroge-
neous system is formed (a liquid polymer melt and a
gas-phase caprolactam product). The caprolactam
monomer is removed from the reactor along with the
steam, resulting in a shift of the equilibrium towards
further monomer formation.
The depolymerizationreaction is thermodynamically
favored at low pressures, since the number of moles
in the system increases as the polymeric chain breaks
into monomeric units. Furthermore, at low pressures
it becomes easier to separate the monomers (which
usually have relatively high boiling points) from the
melt. On the other hand, water solubility in the melt
is favored at high pressures. Consequently, in most
cases, there is an optimum process pressure (usually
above atmospheric value), which maximizes the reac-
tion rate for a given temperature.
Catalysts may also be added to the reaction mixture
to accelerate the process. Both Lewis and Binsted
acidic and basic catalysts have been used for this
application. Each class has certain advantages and
1459
 Corina Mihut, Dinyar K. Captain, Francis Gad&-Maria,
disadvantages that will be discussed later in this sec-
tion. The presence of a catalyst also allows for easier
processing of the polymeric melt by decreasing its vis-
cosity.
Several types of depolymerization processes have
been proposed and patented. All of them result in the
full recycling of the nylon component of a carpet into
recycled nylon that has a quality comparable to the
quality of the original nylon used. Nylon-producing
companies have undertaken most of these efforts in
the past, although carpet manufacturers have re-
cently entered this area as well. The majority of the
available depolymerization processes focus on the re-
covery of caprolactam, the basic monomer of nylon 6.
Companies such as BASF, AUiedSignal (which in 1999
merged with Honeywell under the Honeywell name),
and DSM, which produce nylon 6, have led the efforts
in this area. DuPont, on the other hand, which manu-
factures nylon 6,6, has focused its depolymerization
efforts on the recovery of hexamethylenediamine
(HDM) and adipic acid (the corresponding monomers
of nylon 6,6).
3.2.1 Deplyrnerization With A m n i a (Ammonolysis~
Nylon 6 and/or nylon 6.6 can be converted into a
mixture of the respective monomers through an am-
monolysis process (10). This process involves heating
of a polyamide mixture (such as a mixture of nylon 6
and nylon 6,6) in the presence of ammonia at high
temperatures and pressures. At least one mole of am-
monia (more is preferable) is needed per mole of
amide group in the polymer. The reaction takes place
at temperatures between 300°C and 350°C. In addi-
tion to temperature, the reaction rate also depends on
the reactor pressure, with pressures in the range of
500-2500 psig being preferred. The products gener-
ated during this process include hexamethylene di-
m i n e (HMD), 5-cyanovaleramide (CVAM), adiponitrile
(ADN), caprolactam (CL), 6-aminocaproamide (6-
ACAM) and 6-aminocapronitrile (6-ACN).Water is also
formed during the reaction, and is known to suppress
the complete conversion of the intermediately formed
amides to nitriles by shifting the equilibrium of this
process. This can be avoided by continuous removal
of the water, achieved by flowing excess ammonia
through the reaction zone. The monomers produced
are then fractionally distilled into separate streams
containing HMD/6-ACN, CL and ADN (11). HMD, 6-
ACN and ADN are then hydrogenated to form pure
HMD, the monomer required for the production
of nylon 6,6. Caprolactam can be either purified, or
recycled into the ammonolysis process. Although the
ammonolysis reaction does not require a catalyst, the
addition of a phosphate catalyst (such as phosphoric
acid, ammonium phosphate or boron phosphate) has
been shown to increase its rate.
McKinney, who invented the ammonolysis process,
further explored the effect of Lewis-acid catalyst
precursors on the rate of this process. He reported
that the presence of such precursors makes the
1460 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
and Michael D.Amiridis
ammonolysis process more efficient (12). The term
"catalyst precursors" was used in these studies in-
stead of "catalyst" since the catalyst may or may not
maintain its original structure during the ammonoly-
sis process. These precursors were selected from a
group consisting of SCX,, TR4, M a , , ReX5, FeX3.
C G , CuX, Z e , M q , q, and AX3 (where X can
be C1, Br, or I).
A process patented by Hendrix et aL for DSM (13)
also invokes a method of depolymerizing a polyamide
to its monomer in the presence of "at least one nitro-
gen-containing compound."According to its inventors'
claims, this process can produce monomers with a
higher selectivity as compared to DuPont's ammonoly-
sis process. The nitrogen-containing compounds that
can be used include ammonia, or a primary, sec-
ondary or tertiary mine. Additionally, the nitrogen-
containing compound chosen has to have a boiling
point lower than the boiling point of caprolactam
(267°C).A concentration of two moles of the nitrogen-
containing compound per mole of amide group in the
polymer is recommended, while at least one mole of
nitrogen-containing compound per w i d e group is re-
quired. Additionally, the authors claim that "accelera-
tors" (i.e. catalysts), which increase the reaction rate
and/or improve selectivity towards monomers, can be
also used. Examples of such "accelerators" include
Lewis (such as Al,03)or Br6nsted acids (such as
H,P04 and H3BOJ. Reaction conditions include tem-
peratures between 250°C and 350°C and pressures
between 0.9 and 3 atmospheres.
The DSM process can be carried out in a batch.
semi-batch, or continuous reactor; the continuous
steady state process is preferred, since it improves the
monomer selectivity. The nitrogen-containing com-
pound reacts with the polyamide mixture in a molten
form, and the products are removed from the reactor
through the gas phase. The products are then sepa-
rated by steam and vacuum distillation. The products
include caprolactam and aminocaproic acid (a capro-
lactam precursor), together with small amounts of
aminocaproamide and aminocapronitrile. The desired
monomer in the DSM process is caprolactam. Conse-
quently, the DSM process can be operated in the
presence of water, to minimize nitrile formation, This
is not the case in the DuPont ammonolysis process,
which targets the formation of nitriles, and subse-
quently, HMD. The preferred feed in the DSM process
is nylon that has been separated from the other non-
polyamide components of the post consumer carpet.
However, the DSM patent states that the process can
also be operated without prior separation, but does
not present any performance data in this case. Finally,
mixtures of nylon 6 and nylon 6,6 can be used, al-
though all examples shown in the patent used pure
nylon 6 as the reactor feed.
3.2.2 Acid-CatalyzedDeplymerization
Acid catalysts were utilized in early efforts to de-
polymerize nylon 6 to caprolactam, and several
 Review: Recycling of Nybn From Carpet Waste
processes utilizing such catalysts have emerged from
these efforts. When such processes are applied to the
depolymerization of carpet fibers, however, a separa-
tion of the fibers from the other carpet components
(i.e., "beneficiation")is required, since the CaCO, usu-
ally present in the fillers can consume an equivalent
amount of the acid catalyst used.
Among the several general acid depolymerization
processes, one patented by Crescenthi et aL (14) for
Allied Corporation has several similarities to depoly-
merization processes used for carpet materials. The
Crescentini process was developed for the depolymer-
ization of cyclic oligomers of nylon 6 that are present
in nylon 6 chip wash water, and it involves an initial
separation of unreacted caprolactam from the cyclic
oligomers present in the wash water. This can be
achieved by feeding the aqueous mixture to a wiped-
film evaporator at a temperature of 200°C to 300°C
and a pressure of 10 to 250 Torr (0.013-0.329 atm).
Caprolactam is carried off by steam in the overhead
stream, and the cyclic oligomers are recovered from
the bottoms. The oligomers are then fed to the depoly-
merization kettle. The operating temperature is be-
tween 230°C and 290°C. and the caprolactam formed
is stripped off with superheated steam. A phosphoric
or orthophosphoric catalyst is used at a level of 0.5 to
5 wto/o of the cyclic oligomers fed. More than 75% of
the oligomers can be recovered in the form of capro-
lactam. I t should be pointed out, however, that when
acid catalyzed processes are used, carpet separation
is required, since the CaCO, usually present in the
fillers can consume an equivalent amount of the acid
catalyst used.
Corbin et aL (15) invented a process for BASF Cor-
poration for the continuous recovery of caprolactam
from nylon 6 fibers, as well as carpets made from
such fibers. Corbin et aL claim that beneficiation is
not required in their process and offer an example to
support this claim in the patent. Consequently, the
non-nylon carpet components can either be separated
(via shreddingl before the reaction, or separated from
the caprolactam product after depolymerization. In
the latter case the separation costs are minimized, but
the other carpet components, such as the polypropy-
lene backing, cannot be recovered and recycled. In the
BASF process, pure nylon 6 or a carpet containing
nylon 6 fibers is fed to a continuous depolymerization
reactor unit. Nylon 6 production wastes such as
yarns, chips or extruder slag, along with nylon 6 wash
water, can also be included in the reactor feed. A thin
film evaporator design may be used for the reactor
and in this case the feed is introduced in a molten
form. The process can also be carried out in a batch
reactor, although a continuous process is preferred.
Phosphoric acid at a concentration of 5 to 7 wtYo is
also added as a catalyst. Other active catalysts for
this application include boric acid and phosphate
salts. Superheated steam is also introduced to the re-
actor, preferably at temperatures between 250°C and
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Yo/. 41, No. 9
280°C. The amount of steam added t m vary depend-
ing upon the auxiliary heating requirements of the re-
actor (such as electrical heat to the reactor wall). The
gas phase products are carried out of the reactor by
the steam, and are distilled in order to recover the
caprolactam monomer. The non-volatile wastes and
by-products are directed to a powerhouse for inciner-
ation and heat recovery. I t is also possible to recover
the used phosphoric acid catalyst during heat recov-
ery. Examples are presented in the Corbin et al.
patent, where both nylon 6 fibers and carpet waste
containing nylon 6 fibers were used as the feed. In
both cases, nearly pure caprolactam suitable for
nylon 6 production was recovered. A caprolactam
yield of 56% was reported for the case when only
nylon 6 fibers were fed to the reactor.
BASF Corporation has also developed a semi-con-
tinuous process for the depolymerization of nylon 6 to
caprolactam (16). According to the patent's claims,
this process successfully addresses some of the prob-
lems encountered with the continuous process, such
as low efficiency in the presence of contaminants and
large amounts of catalyst waste. The semi-continuous
process uses acid catalysts such as ortho-phosphoric
or para-toluenesolfonic acid at a loading between 5
and 35 wt% of the polyamide reactant. Polyamides
that have been produced from a single monomer
(nylon 6)are preferred, although mixtures of polymers
can also be depolymerized As claimed by the patent,
this invention is suitable for polymers in various
forms such as molded articles, chips, fibers, films, as
well as polymer wastes containing solid contaminants
(pigments,TiO,, polyethylene, etc.). The primary reac-
tion product is once again caprolactam. The semi-
continuous reactor could be any conventional acid-re-
sistant electrically heated reactor equipped with an
inlet for the addition of the polyamide feed and a con-
denser. Steam, supplied through nozzles, is used as a
carrier to remove the caprolactam product from the
reactive mixture. Usually the reactor is also purged
with an inert gas, such as nitrogen, m order to avoid
the presence of oxygen in the system, which can ad-
versely affect the reaction rate.
A typical run involves adding the polymer and the
acid catalyst in ground or molten form to the semi-
continuous reactor. The reactor is maintained at a
temperature between 260°C and 280°C and super-
heated steam between 100°C and 450°C is added
below the level of the polyamide/catalyst melt. The
steam carries off the caprolactam product to a con-
denser, where the caprolactam-containingdistillate is
collected for further processing. When a sufficient
conversion of the polyamide to the monomer (40% to
goo/) is reached, a new batch of polymer is added and
the process is repeated. No additional catalyst is added
with the new polymer batch. When orthophosphoric
acid is used as the catalyst, a loading of 5 to 25 wt?h
is required. For para-toluenesulfonic acid, the re-
quired loading is 10 to 35 wto/o. According to Kotek,
1461
 Corina Mihut, Dinyar K. Captain, Francis Gadala-Maria, and Michael D.Amiridis
who invented this process, it is these high catalyst
loadings that lead to the effective breakdown of the
polymer into its constituent monomers, and to the
minimization of undesirable by-products. We should
point out, however, that the patent in this case does
not provide quantitative examples to allow us to as-
sess its effectiveness when compared with other avail-
able depolymerization processes.
A process targeting the depolymerization of nylon 6
and/or nylon 6,6 In the form of sheared nylon carpet
face fibers, using aliphatic carboxylic acids, has been
invented by Moran for DuPont (17). Unlike the previ-
ous depolymerization processes, the acid used in this
case is also one of the reactants. Suitable carboxylic
acids include acetic and propionic acid. In the depoly-
merization of nylon 6, one mole of acid is required for
every two moles of repeat polymer units, and the re-
sulting monomer is caprolactam. In the depolymeriza-
tion of nylon 6.6, two moles of acid are required for
every mole of repeat polymer units, and the monomer
produced is adipic acid. A particular advantage of this
process, as claimed by the patent, is that mixtures of
nylon 6 and nylon 6,6 can be simultaneously depoly-
merized to caprolactam and adipic acid, respectively,
without requiring any prior separation. Generally, the
carboxyk acid is added in excess, and the by-prod-
ucts of the reaction are 6-alkylamidohexanoic acid
(from nylon 6) and N,N-hexamethylenebisalkylamide
(from nylon 6.6). The reaction is carried out in an au-
toclave at temperatures preferably above 250"C, and
autogenous pressure. Once substantial conversion
has been achieved, the reactor is cooled down, and
the monomers are separated by steam distillation or
other methods. In the examples given in the patent,
sigruficant amounts of the by-products were formed,
with approximately 3% caprolactam produced, and
10%-20% adipic acid.
An improvement of the aliphatic carboxylic de-
polymerization method was proposed by Moran and
McKinney also for DuPont (18). In this case, the
6-alkylamidohexanoic acid and N,N'-hexamethylene
bisalkylamide byproducts are further oxidized to
adipic acid. The oxidation (by air, oxygen or hydrogen
peroxide) can take place either simultaneously with
the depolymerization or in a separate step. Altema-
tively, electrochemical oxidation techniques can also
be applied. According to the patent, this method also
applies to carpet materials. In this case, waste carpets
can be entirely dissolved in the aliphatic acids used,
at temperatures of about 110°C and atmospheric
pressures. Carpet components, such as the primary
and secondary backings and adhesive binder, which
are insoluble in the acid solution, can be separated by
hot filtration. The acidic filtrate, containing the nylon
fibers, can then be subjected to the depolymerization
process.
3.2.3Base-Catalyzed Deplgmerization
A process based on the thermal depolymerization of
nylon 6 to caprolactam in the presence of potassium
1462 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
carbonate was invented by Nielinger et aL for Bayer
AG (19). In the context of this patent, polyamide 6 is
understood to be pure polyamide 6 as well as mix-
tures of polyamides with over 50% (and preferably
over 80%) polyamide 6 content. The polyamides and
the potassium carbonate catalyst (0.5 to 2.5 wt%) are
heated in an inert nitrogen atmosphere to tempera-
tures up to 270"C-3OO0C. The caprolactam formed is
distilled off under reduced pressures (below 100
mbar). The distilled caprolactam can then be fraction-
ated to obtain a pure monomeric product. Unlike
other processes, the Bayer process does not utilize liq-
uid water or steam. As a result, there is no need to re-
move the water from the caprolactam before or during
fractionation. Additionally, the caprolactam can be re-
covered from this process in very high yields (greater
than 90%)and with high purity.
Mixtures of nylon 6 and/or nylon 6,6 can also be
depolymerized by alkali or alkaline earth hydroxide
catalysts. In a process developed by M o m for DuPont
(201, such catalysts are used for the depolymerization
of polyamide mixtures, and efficiently produce capro-
lactam from nylon 6 and hexamethylene diamine from
nylon 6,6. This process claims to accommodate vari-
ous feeds, which is expected when mixed post-con-
sumer and industrial waste are being processed. Also,
this invention can be used to process either pure
nylon 6, and nylon 6,6 as well as any combination of
the two,The same group has also been involved in the
development of acid depolymerization routes (see pre-
vious section) and notes that acid catalysts are very
effective in converting nylon 6 to caprolactam, but
also form a variety of undesirable by-products in the
case of nylon 6,6, such as pentyl amine, pentyl nitrile,
aminmapronitrile and butyl amine. On the contrary,
basic catalysts produce negligible amounts of the
undesirable by-products. In the DuPont process, a
mixture of nylon 6 and nylon 6,6 is added to the reac-
tor along with a sufficient amount of a basic catalyst,
such as sodium hydroxide. The reactor is maintained
at a temperature of at least 275"C, and high-temp-
erature steam is continuously added to carry the
monomer products out of the non-volatile polymer
melt. In the examples shown in the patent, analysis of
the steam distillate from the reactor revealed only the
presence of caprolactam and hexamethylene diamine.
A similar process for the depolymerization of
polyamides in the presence of water and a basic cata-
lyst was developed by Thomissen for DSM (21). This
process operates at pressures between 0.5 and 1.8
MPa and suitable basic catalysts include alkaline-
earth oxides, hydroxides, and carbonates, sodium and
potassium amino caproates. the sodium and potas-
sium salts of the linear dimer or trimer of amino
caproic acid or mixtures thereof. Preferably, sodium
hydroxide and/or sodium amino caproate are used.
The reaction is carried out in the absence of oxygen
at a temperature between 250°C and 300°C with
the feed being in its molten form. The amount of the
basic catalyst required is 0.2% of the weight of the
 Review: Recycling of Nylon From Carpet Waste
polyamide. Superheated steam is passed through the
polymer melt, and the products are withdrawn
through the gas phase, which is then condensed in
order to recover the monomer. The patent states that
this process can be used for a mixture of different
polyamides: however, only examples using nylon 6
and its cyclic oligomers were presented. A very high
conversion (over 98%) to caprolactam was obtained in
these examples. According to its inventor, the advan-
tages of this process over commonly used acid-cat-
alyzed depolymerization processes are the shorter
reaction times required, and the elimination of phos-
phate wastes (from the phosphoric acid catalyst used
in acid catalyzed processes).
3.2.4Depolymerizdion With Water
In addition to acid-catalyzed or base-catalyzed de-
polymerization processes described in the previous
sections, the patent literature also reveals the devel-
opment of processes for the depolymerization of nylon
6 to caprolactam that require only the presence of su-
perheated steam. One such process was invented by
Sifniades et aL (22)and Braun et aL (23)for AlliedSig-
nal. The use of carpet made from nylon 6 is empha-
sized in this case, since the desired monomer to be re-
covered is caprolactam. Nevertheless, the feed to the
reactor may contain up to a total of 10'70of non-nylon
6 carpet fibers, such as nylon 6,6or PET, since these
low levels of "contamination"do not interfere with this
depolymerization process. Unlike most other depoly-
merization processes that require separation of the
nylon fibers from the other carpet components, this
process works efficiently even when the feed consists
of the entire carpet waste material, not subjected to
any prior separation. It is preferred, however, that the
feed be in the form of a melt. This is achieved by the
use of an extruder, gear pump, or other similar de-
vices. It is also recommended that the melt be briefly
contacted with water in the extruder, in order to initi-
ate the depolymerization reaction at this early stage
and facilitate the overall process (24). The unsepa-
rated polymer melt is then sent to a continuous reac-
tor where it is heated to a temperature between 290°C
and 340°C and pressurized to a pressure between 3
and 15 atm. The melt is then contacted with a stream
of superheated steam, which acts as the primary heat
source. owing to contact between the polymer and
steam at elevated temperatures and pressures, the
caprolactam formed is collected via the overheads as a
vapor stream, and the nylon Mepleted melt is col-
lected at the bottoms. The overhead can then be con-
densed in order to recover caprolactam, which can be
further purifled as desired. The role of the steam, in
addition to heating the reactor, is to promote the cleav-
age of the amide bonds of the polymer, which initiates
the depolymerization process. Pressure is also found
to have an effect on the reaction. At low pressures
(e.g. 1 atm), relatively large amounts of caprolactam
cyclic dimer are formed, (approximately 4% of the
caprolactam in the overheads).Increasing the pressure
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
while maintaining the temperature and amount of
steam constant also results in a n increase in the
amount of water dissolved into the nylon 6 melt, and
hence accelerates the depolymerization reaction. The
examples used in the patent show conversions of
nylon 6 to caprolactam of approximately 90 mol%,
with side products such as the dimer and ammonia
being less than 1% and 3'70,respectively. The patent,
however, does not incorporate any recovery, recycling
or further processing of the nylon Mepleted polymer
melt that exits from the reactor bottoms.
In a second AlliedSignal patent, Jenczewski et aL
(25) describe a process in which the carpet is first
shredded and then introduced into the reactor via a
pump so that a high pressure can be maintained.
Water is then introduced into the reactor, and the
mixture is heated to a temperature between 250°C
and 350°C at pressures between 465 and 2700 psi.
Significantly higher pressures are required in this
process, since it is desirable to maintain water in its
liquid state. Consequently, the operating pressure has
to be higher than the vapor pressure of water at the
elevated temperatures used. Under these conditions,
the nylon 6 fiber is dissolved in the water, and the de-
polymerization is initiated. At the completion of the
depolymerization process, a two-phase mixture re-
mains in the reactor, consisting of the nylon 6 depoly-
merization products dissolved in the aqueous phase,
and an insoluble component consisting of the non-
nylon 6 components of the initial unseparated carpet
material. At that point, the reactor is cooled down in
order to facilitate the separation of the soluble
monomers from the insoluble components. The cool-
ing tends to solidify the insolubles, thus making their
separation much easier. These materials, which con-
sist of polypropylene, fiuers and rubber adhesives, can
be sent off for heat recovery. The aqueous portion of
the reaction is distilled and condensed in order to re-
cover the dissolved caprolactam monomer, which can
then be purified as necessary. High purity caprolac-
tam yields in the order of 80% are reported in the
patent. Although the inventor claims that this process
is also suitable for the depolymerization of nylon 6,6
carpet, yielding adipic acid and hexamethylene di-
amine as the monomers, only examples using nylon
kontaining carpet were presented.
3.2.5 Pyrolysis
The depolymerization of nylon 6 in the absence of
oxygen at high temperatures (pyrolysis) has been in-
vestigated as another possible route of nylon recy-
cling. A study involving the heterogeneous catalytic
pyrolysis of nylon 6 has been recently published by
Czernik et aL (26). Using a fluidized bed reactor, with
nitrogen as the fluidizing gas, this group investigated
the depolymerization of nylon 6 to caprolactam in the
presence of an alumina-supported KOH catalyst at
temperatures between 300 and 700°C. The product
contained caprolactam, a dimer of caprolactam, and
a series of low-molecular-weight fragments. In the
1463
 Corina Mihut, Dinyar K. Captain,Francis Gadala-Maria, and Michael D. A M i s

absence of a catalyst, high caprolactam yields were ob- data. These models are based on the mechanism of
tained at temperatures above 450°C. However, such the hydrolytic polymerization of caprolactam and on
high process temperatures can be detrimental when the assumption of reversibility. The three main reac-
applied to polymeric mixtures, when the decomposition tion steps are as follows (28):
of other plastic materials present in the carpet mixture
can contaminate the caprolactam. The use of a catalyst Ring Opening: C +W kdKi
S1
allows for higher reaction rates at lower o p e r a w tem-
peratures, and thus improved selectivity and caprolac-
tam yield. Czernik et aL reported that a 5 wt!??KOH/
&03 catalyst best satisfies the optimization criteria at
temperatures between 330°C and 360°C yielding 85Yo kS
Polyaddittorx C + Sn sn+, (3)
of the possible caprolactam with a purity of 86%89%. WK3
Although this study focused on the pyrolysis of pure where C stands for caprolactam, W for water, and S,
nylon 6, it can be potentially applied for the recovery of for a polymer molecule containing n monomer units.
caprolactam from carpet waste material. Rate expressions were written for the reverse reac-
Using TG/MS and closed-loop reactor analysis, tions (depolymerization),and can be used in the de-
Bockhorn et aL (27) have investigated the kinetics of velopment of reactor models (e.g. batch or semi-
the catalyzed and non-catalyzed pyrolysis of nylon 6 batch). Good agreement between model predictions
under isothermal as well as transient conditions. Ki- and experimental data was obtained. Simulation re-
netic parameters (apparent activation energies and re- sults were compared to experimental data reported in
action orders) were calculated in all cases. At 450°C the literature. The acid-catalyzed depolymerization
the non-catalyzed thermal degradation was found to can also be simulated by this method, since acid end-
generate primarily caprolactam (92% yield). Among groups are present in the reaction scheme. In this
the by-products the cyclic dimer was the main one case, however, a good fit between the model predic-
(approximately 4% yield), and its yield increased at tions and the experimental data was obtained only at
temperatures above 420°C. The use of a 10 wt% high acid catalyst concentrations.
ortho-phosphoric acid catalyst increases the caprolac- A kinetic model of the depolymerization of nylon 6
tam yield to 97%. while the degradation temperature and nylon 6.6 mixtures via DuPont's ammonolysis
is decreased by approximately 100°C.Once again, the route was more recently proposed by Kalfas (29).In
main by-product was the cyclic dimer (2%) and its this case, the polyamide mixture reacts with excess
yield increased above 320°C.A lower apparent activa- ammonia at elevated temperatures and pressures,
tion energy and a higher apparent kinetic order (163.9 and yields hexamethylene diamine (nylon 6,6mono-
kJ/mol vs. 211 W/mol, and 1.9vs. 1.3,respectively) mer) and caprolactam (nylon 6 monomer). The reac-
were observed as compared to the non-catalyzed case. tions involved in this process are shown below (29):
When a base catalyst was used (60:40 molar ratio
eutectic mixture of NaOH and KOH) the apparent acti-
vation energy was further reduced and the caprolac-
tam yield was increased to 98% at 260°C,with all the
by-products being below 1%.
-f
NH-(cH,), -NH-CO
Nylon 6,b
-(cH,), -CO +
3.2.6 Mathematical M o d e m of the
&polymerization Process n H,N-(CH,)6 -NH, +
r 2n NH3
n HZN--CO-(CHz), -CO-NH,
Hexamethylene Diamine Adipamide
Although a significant number of patents focus on
depolymerization of carpet fibers, a very limited
amount of fundamental work has been published in nNC
tl
--(cH,),-cT + nH,(
this area. Most of these fundamental studies have fo- Adiponitrile
cused on the kinetics of the depolymerization process.
Kinetic models that capture the basic chemistry tak-
ing place during depolymerization are critical for the
design of process equipment and the selection of opti-
mal operating conditions. In this section, we review
ICO-(CH,), -NH H C O -(CH,), -NH

Nylon 6
some of the modeling efforts for the depolymerization
of nylon 6 to caprolactam (28) as well as the a m -
n Fl2NCO-(CH?),--NH, CO-(pH,),-NH
monolysis of nylon 6.6 and nylon 6 mixtures (29). + 111

The first attempt to describe the kinetics of the A m in o c a p r o a m i d e C n p r o ln c t a m

nylon 6-to-caprolactam reaction was made by Ogale
in 1984 (28).Kinetic models were developed in this
case for batch and semi-batch reactors, and the II
ti
NC--(ClI,),-NH, + n HI 0
model predictions were compared with experimental A m in o c a p r o n it r ile

1464 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Yo/,41, No. 9

 Review: Recycling of Nylon From Carpet Waste
This mechanism involves amide link breakage and
amide end dehydration (nitrilation) reactions, as well
as ring addition and ring opening reactions for the
conversion of the cyclic lactams present in nylon 6.
The model proposed by Kalfas is based upon this
mechanism, and was developed for an isothermal
batch reactor. Simulation studies conducted with this
model examined the effect of different parameters
such as the ammonia concentration and the values of
the equilibrium constant for the amide end dehydra-
tion reaction. Simulations were conducted for homo-
geneous polyamide systems (nylon 6 or nylon 6,6),as
well as mixtures of the two components. However, no
comparison was shown between the model predic-
tions and any experimental results, presumably be-
cause of the proprietary nature of such data. Never-
theless, this study is valuable, since it demonstrates
the effect of the different parameters on critical
process characteristics such as polymer conversion
and monomer selectivity.
3.3 Extraction of Polyamidem
Extraction methods attempt to separate and recover
the polyamides from the other carpet components
without converting them back to the original mono-
mers. Usually, the separated nylon obtained from
such processes is injection molded into other prod-
ucts. Several extraction processes have been proposed
in the patent literature. Most of them utilize organic
solvents, which, at elevated temperatures, can sepa-
rate different carpet components in sequential steps.
The main challenge in choosing a solvent for such ex-
traction processes is the required selectivity in dis-
solving only the nylon fibers. The more selective such
a solvent is, the better the purity of the separated
nylon obtained from the process. Furthermore, the
potential chemical interaction of the solvent with
other carpet components, and especially the inorganic
fillers and adhesives, is an issue that needs to be con-
sidered. If the solvent indeed interacts with these
components, the separated nylon obtained contains
impurities that alter its properties and reduce its
value.
A DuPont process developed by Subramanian (30)
recovers polyamides from mixtures containing "for-
eign" materials (such as carpet backing, glass fiber,
other polymers, etc.) with minimal loss of molecular
weight (i.e. reclamation without depolymerization).
The procedure consists of dissolving the material con-
taining the polyamides at elevated temperatures in a
polar solvent such as a polyol or an aliphatic car-
boxylic acid. Ethylene glycol and propylene glycol are
typical examples of the polyols used. Aliphatic car-
boxylic acids having 2 to 6 carbon atoms (such as
acetic acid or propionic acid) are also effective sol-
vents. The solvents used must be anhydrous, since
water reduces the solubility of the polyamide. Cooling
the solution causes the dissolved polyamide compo-
nents to precipitate out, and these can be further iso-
lated by filtration.
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
The main problem associated with this method is
the reactivity of the solvent with the polymeric mater-
ial, which causes degradation of the polyamide chain.
Examples used in the DuPont patent show that pro-
longed exposure of nylon to a glycol solution at the
boiling point of the glycol signikmtly reduces its mol-
ecular weight. In fact, the decrease in molecular
weight, and thus the degradation of the polyamide
chain, is proportional to the exposure time. To prevent
this reaction, the process includes a quenching step
following the dissolution of the polyamide compo-
nents. During quenching, a low enough temperature
is reached so that any potential reaction between
the polyamide and the solvent is inhibited. The two
main advantages of the quenching technique, as de-
scribed in the DuPont patent, are the recovery of the
polyamides with minimal degradation (since the expo-
sure time at high temperatures is minimized),and po-
tential reuse of the solvent. Since the solubilities of
different polyamides vary with temperature, control-
ling the quenching temperature enables one to precip-
itate the polyamides sequentially, thus separating
them from mixtures. However, in the examples shown
in the patent, the only results presented are from the
recovery of nylon 6,6from carpet and automotive ra-
diators.
A process based on extraction with pure and mix-
tures of aliphatic alcohols, as well as mixtures of
water and aliphatic alcohols, has been developed by
Booij et al. for DSM (31). As in the DuPont process,
the face fibers are separated from the rest of the car-
pet components by selectively dissolving the fibers
in an appropriate solvent at high temperatures. The
solvent containing the polyamides is then physically
separated from the insolubles, and the nylon is pre-
cipitated out of the solution by lowering the tempera-
ture. Once again, separation of different types of nylon
fibers can be achieved by controlled decrease of the
temperature. Different solvents, such as Cl-C12
aliphatic alcohols, and monohydric and dihydric alco-
hols can be used, with methanol and ethanol being
designated as the preferred extraction agents. The ad-
vantage of this process over the previous DuPont
process is that there is minimum interaction between
the polyamides and the solvent and it also allows sep-
aration of the dyes from the fibers. The DSM process
applies to carpets containing a variety of components
(such as polypropylene, jute, fillers, rubbers, and ad-
hesives) and it generates a directly reusable nylon,
since the polyamide chains are not decomposed dur-
ing the process.
Along the same lines, extraction of polyamides with
a glycolic compound was also proposed by Stefandl
(32).The Stefandl process applies well to mixed nylon
carpet scrap, which can be separated based on the
relative solubility of the nylon fractions as a function
of temperature. Nylon 6,for example, is soluble in
glycerol at 155"C,whereas nylon 6,6is soluble at
195°C.Carpet scrap containing both nylon 6 and nylon
6.6 is first dissolved in glycerol at 165°C to solubilize
1465
 Corina Mihut, Dinyar K. Captain, Francis Gadala-Maria, and Michael D. Amiridis
the nylon 6 component. The solution obtained is with-
drawn in a separate vessel, where, by rapid cooling to
40°C. nylon 6 precipitates. The residue containing
nylon 6,6 along with the rest of the carpet compo-
nents is dissolved in a second vessel at 200°C. The
precipitation of nylon 6,6 from the hot solution is also
achieved by rapid cooling to 40°C. Both polymeric pre-
cipitates are washed with water to remove traces of
glycerol, and then dried under vacuum. Since, at high
temperatures, nylon can undergo oxidation with oxy-
gen and/or hydrolysis with water present in the sol-
vent, an inert atmosphere is required. Relative viscos-
ity and differential scanning calorimetry were used to
determine the purity of the obtained polyamides in
the patent examples. According to the results, both
recovered nylon samples exhibited single melting
points corresponding to those of the pure polymers.
An extraction method that uses supercritical CO, as
the extraction agent to separate individual polymeric
materials from carpet scraps has been developed by
Sikorski for the Georgia Tech Research Corp. (33).Al-
though other extraction agents such as ethane and n-
butane are also capable of performing the supercriti-
cal stage-wise separation, CO, is preferred because of
its low cost, low chemical reactivity, and low toxicity.
The carpet components in this case are gradually dis-
solved in supercritical COz in the increasing order of
their melthg points. Carpet scrap is introduced in an
extraction vessel along with supercritical CO,. Tem-
perature and pressure are adjusted so that the carpet
component with the lowest melting point is dissolved
first in the extraction fluid. The solution obtained
is withdrawn in a separation vessel, where, by de-
creasing the temperature and pressure, the carpet
component is separated from the extraction fluid. In
subsequent steps, the temperature and pressure are
systematically increased so that each individual com-
ponent of the carpet scrap mixture can be eventually
recovered. The recovered extraction fluid can then be
recirculated. The carpet components are separated in
the following order: grease and lubricants, latex
(styrene-butadiene rubber), backing (polypropylene),
and, finally, face yams (nylon 6 or 6.6).
Finally, a method that combines the use of a solvent
and a supercritical fluid antisolvent (non-solvent) to
separate nylon 6,6 from other carpet materials has
been recently reported by Griffith et aZ. (34).This
process takes place in three steps. First, the carpet ma-
terial is treated with a solvent (e.g. formic acid solution)
to separate the nylon 6.6 from the other carpet compo-
nents. In the second step, nylon is precipitated out of
this solution by the use of supercritical CO,. The oper-
ating conditions are chosen such that nylon 6,6 is solu-
ble only in formic acid and CO, and formic acid are
miscible. Contact of the two solvents causes precipita-
tion of nylon 6.6, due to the lowering of the solution's
solvent strength. In the third and final step, the pres-
sure is lowered, formic acid and CO, separate and are
recycled back into the process, and nylon is recovered
in powder form (particles smaller that 20 pm). The
1466 POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
operating conditions, such a s solvent and nylon con-
centration, and upstream and downstream pressures
have been found to have little to no effect on the mean
nylon particle size and particle size distribution.
3.4 Melt Blending
Tertiary recycling of carpet materials consists of
reusing the carpet as a whole, by melting or extruding
it to form a blended mixture that is subsequently
used in the production of injection molded polymers
and thermoplastics. An advantage of this process is
low cost, since no expensive separation and depoly-
merization procedures are required. However, depend-
ing on the chemical compatibility of the waste carpet
components melt blending usually results to low qual-
ity melt-blended plastics with limited uses. Kotlair
and Fountain (6)developed a relatively simple process
that converts carpet waste (industrial and post con-
sumer) to fibrous composites that can be used as
*syntheticwood." The carpet waste is first converted
to individual "shreds" approximately one-half inch in
length. These shreds (still containing the polypropy-
lene backing and latex adhesive) are then coated with
low viscosity prepolymers used as structural adhe-
sives. Examples of such prepolymers include phenol-
formaldehyde and epoxy resins. The resin-coated
shreds are then cured at approximately 15O"C-19O0C
and pressed into the fibrous composites. Methods of
curing include high temperature pressing, or the use
of a vented extruder. A large variety of composite ma-
terials can be produced following this approach. Their
properties and quality depend on the composition of
the original carpet (carpet fiber to backing ratio) and
the type and amount of resin used. These parameters
also affect the process conditions and the potential
uses of the final recycled product.
Another method of carpet scrap recycling, which
converts the heterogeneous carpet into a homoge-
neous thermoplastic blend has been developed by
Young et al for Lear Corporation (3).This process fo-
cuses primarily on automotive carpet scrap. The typi-
cal automotive carpet consists of nylon 6 or nylon 6,6
face fibers, a polypropylene or polyester primary back-
ing, a polflethylene-co-vinyl acetate) (or EVA) precoat,
and a CaCO, or BaSO, filled poly(EVA) back coat.
This composition differs from the composition of typi-
cal residential carpet in the type of backing and the
amount of inorganic particulate fillers (i.e. CaCO, and
BaSOJ used. Increased amounts of fillers &e added
in this case as sound insulators. In the Lear Corpora-
tion process the carpet scraps are first shredded and
granulated before being fed to a twin-screw extruder.
The extruder is operated a t a temperature between
210°C and 230°C.The melt produced is then pel-
letized and used in injection molding applications.
Such applications include the production of other au-
tomotive parts, such as flexible floor mats to replace
the currently used vinyl or rubber mats, or automo-
tive carpet backing with superior sound-insulating
properties. Additionally, rigid materials such as door
 Review: Recycling oflvybn From Carpet Waste
panels and truckliners can be manufactured from the
recycled material. Although the melt-blended material
already behaves as a thermoplastic, the addition of a
compatibilizing agent greatly improves its quality.
Generally, thermoplastics resulting from a mixture of
polymers produce melts with poor mechanical proper-
ties because of incomplete mixing of the different
components. Compatibilizing agents promote such
mixing, and hence, improve the overall characteristics
of the blend and of the resulting injection molded
products. EVA, which is already present in automo-
bile carpets. is an example of such a compatibilizer.
The compatibilization between nylon 6 and poly-
propylene was investigated by Datta et al. (35). This
group studied the effect of the addition of a compatibi-
lizer (maleic anhydride gr&ed polypropylene, MA-g-PP)
on the final properties of a blend of nylon 6 and
polypropylene. They used two samples of shredded car-
pet waste containing nylon 6 and polypropylene face
fibers, with and without calcium CarbonateiYled SBR
The properties of the final blend were optimized by
varying the extrusion and compression molding para-
meters, and the percentage of the compatibilkr added.
The results show that this approach can be used to
produce resins with good mechanical properties.
The compatibilization of nylon 6 and polypropylene
was also investigated by Dagli et aL (36).A n acrylic
acid grafted modified polypropylene (PP-g-M) was
used as the compatibilizer in this study. The results
indicate the formation of a grafted copolymer, which
suggests that PP-g-AA is another effective compatibi-
lizer that can be used for this type of application.
An alternative method for the melt blending of waste
carpet has been developed by David et aL (37,381 for
Monsanto. This process also uses unseparated, post-
consumer and post-manufacture waste carpet and
melts it at high temperatures and pressures to pro-
duce a thermoplastic material. The carpet waste is first
cleaned to remove excess dirt, which can have a nega-
tive effect on the quality of the final product, and is
then introduced into a conventional twin-screw ex-
truder at a shear rate of 200 to 400 sec-', a tempera-
ture between 250°C and 350°C and a pressure of 350
to 450 psi. The intense mixing taking place at these
temperatures and pressures converts the carpet into a
flowing homogeneous mixture containing all of its
components (face fiber, backing and SBR adhesive).
The process conditions result in effective blending of
all the carpet materials, and thus, a compatibilizer is
not required (although it may be optionally used). The
blend is then cooled, and cut into easily transportable
pellets or chips. According to the inventors of this
process, the resulting material exhibits thermoplastic
characteristics. Consequently, it can be used to pro-
duce high quality injection-molded products, either di-
rectly or mixed with other thermoplastics.
3.5 Separation of Carpet Waste Components
As was pointed out in = d o n 3.2,one of the most
attractive methods for the recycling of carpet waste is
POLYMER ENG/NEEi?lNG AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
the depolymerizationof the tufted nylon fibers to their
constituent monomers. Depolymerization processes
usually require the nylon fibers to be free of any other
carpet material, and hence, a sepcvation step is nec-
essary prior to the depolymerization. Such a separa-
tion step can increase the cost of depolymerization-
based recycling processes slgniflcantly, making most
of them prohibitively expensive. The different available
separation methods are reviewed in this section. It
should also be noted that current development efforts
in the carpet recycllng field focus on recycling routes
that utilize the carpet scrap as a whole, or require
minimum separation.
In 1993 Hagguist and Hume (39)invented the "Car-
pet Reclaimer," an apparatus that disintegrates and
separates post-consumer carpet into its principal
components. The carpet is first moved along a con-
veyor belt to a rotating cutter, which shears the loops
of the continuous carpet yam (tuft fiber]. The carpet is
then sent to another station where it is treated with
air, water, steam and several chemical solutions
under conditions of high temperature and pressure
(the choice of which depends on the type of the carpet
processed). The purpose of this step is to "debond the
latex binder from the secondary backing of the carpet.
The debonded secondary backing is then removed
using a series of mechanical impingement devices
that strip the backing off the rest of the carpet matrix.
Subsequently, the carpet is treated with cup brushes
and rotating high-pressure nozzle heaters that loosen
and remove the SBR adhesive from the rest of the car-
pet, leaving the cut tufted fibers and primary backing
intact. The final step of this process is the removal of
the pile fibers from the primary backing. This is
achieved with the help of a number of rotating me-
chanical combs suspended below the primary back-
ing, which separate the nylon fibers and deposit them
into a collection chamber for further processing.
A significantly different and much simpler carpet
separation process has been developed by Sharer for
JPS Automotive Products (40). During the first step
the carpet is cut into even-sized square pieces be-
tween two and four inches in length. These pieces are
then fed to a granulating apparatus that further
grinds them with the help of high-speed cutting rolls.
This granulating process also initiates the separation
of the fibers from the backing materials. The fine
pieces exiting the granulating apparatus are then
transferred to an elutriator that separates the backing
from the fibers by employing an air stream, which
carries off the fibrous material vertically through a
separate conduit. At the same time the heavier back-
ing material gravitates onto a conveyor located below.
The fibers and the backing material are then trans-
ported to storage containers. We should point out that
this process does not separate the latm binder from the
backing material. However, this is not significant if the
recycled backmg is remelted with a virgin feed stream
of backing material and remolded onto new carpets as
secondary backing. Unfortunately, no experimental
1467
 Corina Mihut, Dinyar K. Captain, Francis Gadala-Maria, and Michael D. Arniridis
results regarding the effectiveness of the separation
were presented in the patent, which makes evaluation
and comparison with other available methods very dif-
ficult.
A similar method of carpet separation has been also
developed by Sferrazza et al. for BASF Corporation
and Shred-Tech Limited (41).Once again, the different
carpet components are separated by initially shred-
ding and hammering the waste carpet in order to
loosen the nylon fibers from the backing materials of
polypropylene and SBR adhesive. The shredded car-
pet is then sent to a primary reduction unit. In this
unit, the carpet fibers are removed from the backing
materials. This is achieved by subjecting the carpet to
a hammer mill-like process, where the more brittle
backing materials get dismantled from the fibers. The
heterogeneous mixture is then sent to an air elutriator
where the lighter nylon fibers (overhead stream) are
separated from the heavier backing components (bot-
tom stream). The nylon fibers are then screened to
separate any impurities of backing materials present
in the overhead stream, and transferred to a metal
particulate removal unit, which magnetically removes
any ferrous metal particles present in the fibers. The
primary bottom stream (backing materials) is re-sent
to a grinding/reduction unit, where a second attempt
i s made to separate any remaining fibers. The
BASF/Shred-Tech process represents an extensive yet
effective way of separating the nylon fibers from the
backing materials. However, no separation of the poly-
ethylene backing material from the SBR adhesive is
achieved in this process.
A process that has been developed by Dilly-Louis et
al. for Zimmer AG also starts with the pre-shredding
of the waste carpet material (42). In this case, how-
ever, an aqueous suspension is prepared by grinding
the shredded carpet in a commercial cutting mill.
During grinding, the carpet components separate, and
the particles in suspension are uniform (i.e. each par-
ticle consists mainly of either the nylon fibers, the pri-
mary backing, or the secondary backing, but not com-
binations of them). The presence of water controls
heat generation during the grinding process and
cleans the carpet materials of any impurities. The
density of the suspension is adjusted to a level be-
tween the densities of the two main carpet compo-
nents by adding an aqueous salt solution. Separation
of the main components of the carpet material is
achieved during this step. The concentration of solids
(i.e. carpet materials) is approximately 10-30 wt%.
The suspension is passed through a 5 to 8 mm filter
and fed to a receiving tank where the concentration of
the solids is lowered to between 3 and 10 wtYo. A salt
solution of calcium chloride or potassium carbonate is
added to the receiving tank in order to adjust the den-
sity of the suspension to a level between the highest
and second highest density of the main carpet compo-
nents. The suspension is then sent to a double-cone
full-jacketed screw centrifuge, which can separate
phases with different densities. As a result, the heaviest
1468 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
of the three carpet components (usually the fillers) are
separated from the suspension. The suspension con-
taining the other two solid components (i.e. tufted
fibers and polypropylene primary backing) is then,
once again, passed through a receiving tank,where
its density is adjusted for a second time, and re-sent
to the centrifuge for separation. Carpet components
recovered in this process u s u d y have a purity of over
90%.
A method similar to the one described above has
been developed by Costello and Keller for AlliedSignal
and DSM (43). This process also utilizes pre-shred-
ding and/or impact size reduction of the waste carpet
materials. The shredding process reduces the size of
the carpet and initiates the separation of the latex ad-
hesive from the rest of the carpet materials. The
shredded particles are then subjected to screen sepa-
ration to remove the adhesive and post-consumer dirt
from the nylon fibers and primary backing. Next, the
separated material is washed to remove additional
amounts of the adhesive. Finally, the residual carpet
components are mixed with an aqueous solution and
introduced into a hydrocyclone, where they are sepa-
rated. The components that are heavier than water
(nylon 6 and nylon 6,61flow out through the bottom of
the hydrocyclone, whereas the lighter components
(such as the polypropylene backingl flow through the
overflow of the hydrocyclone along with the water.
An outline of a proprietary carpet separation
process used by DuPont was presented by Smith and
Gracon at Recycle '95 (11). In this case, the post-con-
sumer carpet is first put through a dry separation
process where it is cut, shredded, hammer milled,
separated by size and further ground to 1.5 mm
pieces. The carpet component mixture formed is then
mixed with water, washed and wet screened prior to
introduction into a density separation process. This
process produces a stream of 98% pure polypropy-
lene. The separated nylon stream is further dried, ex-
truded and melt filtered to produce a 98.5% pure
nylon resin that can be sent to depolymerkation units
or other recycling processes.
The Zimmer, AlliedSignal and DuPont separation
processes are similar in that they all use an initial dry
separation process (which involves shredding and
grinding the carpet) followed by a specific gravity
based wet separation. High purity nylon fibers and
polypropylene backing are the separated components.
It should be pointed out that in addition to the nylon
fibers, the high purity polypropylene co-produced dur-
ing the separation could also be easily recycled or
reused.
4.CARPET RECYCLING TODAY
In this final section we examine some of the recy-
cling processes that have been put into practice at ei-
ther the pilot or commercial scale, and attempt to
offer a synopsis of the current state of the carpet recy-
cling industry and the challenges that lie ahead. Infor-
mation in this section has been obtained from special
 Review: Recycling of Nylon From Carpet Waste
reports in recent issues of High P m f o m e Plastics
(44) and the International Fiber Journal (5, 451, and
Carpet and Rug Industry (46).
Reconditioning of carpets is a procedure in which
an old discarded carpet is cleaned, trimmed and re-
colored. The "reconditioned" carpet is then sold for
reuse, making the reconditioning process one of the
most cost-effective approaches for recycling. Indepen-
dent operators and carpet manufacturers (such as
Milliken) are involved in these efforts. The extent of
such operations is currently limited.
Several companies such as Monsanto, United Recy-
cling Inc., and Collins & Aikman are involved in the
melt blending of carpet waste. United Recycling Inc.
produces two grades of thermoplastic material from
nylon 6 carpets with added polypropylene. A similar
process is carried out by Monsanto, which produces
molding compounds from nylon 6,6. Collins & Aik-
man is limited to recycling only its own carpet tiles. In
its carpet construction process, Collins & Aikman has
replaced the primary and secondary backing, and the
fdler with vinyl, while the face yam is made of nylon.
During the extrusion process, post-consumer low-
density polyethylene (LDPE)is added for improved fin-
ish of the recycled product. The resulting material has
properties similar to wood, and can be used as indus-
trial block flooring, parking blocks and plastic wood.
The depolymerization of waste carpet nylon fibers is
currently the most active route of carpet recycling.
The processes described in section 5.2 involve the
separation of the nylon face fibers from the other car-
pet components and the depolymerization of these
fibers to the corresponding monomer. AlliedSignal,
DSM, BASF and DuPont (allfiber producing compa-
nies) are actively involved in carpet recycling via de-
polymerization routes.
BASF recycles nylon 6 fibers that are depolymerized
to caprolactam in the presence of steam and an acid
catalyst. The other carpet materials (i.e. backing and
latex adhesive) are incinerated. The ash produced is
used as filler for other plastic products. EMSF accepts
for recyclmg all carpets made under its "Six Again" pro-
gram, and has established for this purpose four used
carpet collection centers in the U.S.and two in Canada.
DuPont also recycles used carpets from seventy-six col-
lection centers, which are first sent to a separation unit
in Chattanooga,Tennessee. The nylon is then sent to a
pilot ammonolysis plant in Kingston, Ontario, for de-
polymerization. Some of this W o n t recycled nylon is
incorporated in mineral-reinforced nylon 6.6, reused by
Ford Motor Co. in engine &-cleaning housings for ap-
proximately three million vehicles each year (47).
AUiedSignal and DSM are currently operating the
largest carpet recycling program as a 50/50 joint ven-
ture. A new $80 million plant called "Evergreen Nylon
Recycling" was built for this purpose in Augusta,
Georgia, and began operation in November 1999. The
plant has an annual depolymerization capacity of 200
million lbs of nylon 6-containing post-consumer car-
pet waste, and generates 1 0 0 million lbs of caprolactam
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
(48). The Evergreen project also recycles the non-
nylon carpet materials that are separated during the
process. Evergreen claims that the quality of its recy-
cled caprolactam is equivalent to that of the virgin
material, with the possibility of repeated recycling of
the same material without any detrimental effects on
its properties (48).The AUiedSignal share of the recov-
ered caprolactam is included in polymeric materials
and fibers trademarked under the name Infiity Re-
newable Nylon, whereas DSM sells its share of capro-
lactam into caprolactam markets.
Major carpet recycling efforts are also under way in
Europe. A three-year joint European project called
RECAM (recycling of carpet materials) was funded by
the European Commission to explore the economical
feasibility of developing a closed-loop system for recy-
cling of post-consumer and industrial carpet waste.
The whole process consists of collection, identifica-
tion, size reduction, mechanical recycling, chemical
recycling, and energy recovery steps. The collection
step was studied in Germany at a pilot plant facility.
The identification and sorting step was done using a
portable apparatus developed by DSM and AlliedSig-
nal that uses near-infrared technology to identify,
within seconds, the fiber type.The size reduction and
pelletizing step was performed by Recotex at a pilot
plant also located in Germany. The mechanical recy-
cling step utilized equipment developed by LaRoche
and included the recovery of wool for reuse in non-wo-
vens. Finally, the chemical recycling step used the
processes developed by DSM and Enichem to produce
caprolactam from nylon 6 face fibers. It is expected
that on a long-term basis, the RECAM project will
prove the cost effectiveness of such an approach.
5. ACKNOWLEDGMENTS
The authors acknowledge useful discussions on the
carpet recycling topic with Dr. George W a s , and ex-
press their gratitude to the South Carolina Hazardous
Waste Management Research Fund for financial sup-
port of the preparation of this review.
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