Filter Rods and Cellulose Acetate

- Life-Cycle from the Tre e

to the Consumer

RHODI A

Chodia

Ace tow

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 Filter Rods and Cellulose Acetate
- Life-Cycle from the Tre e
to the Consume r

AUTHOR
PAUL RUSTEMEYE R

ENGLISH TRANSLATION
DUNCAN CUMMIN S

EDITOR
RHODIA ACETOW AG
FREIBURG MAY 199 8

®Podia Rhodia Acetow AG

Postfach 10 04 44
D-79123 Freiburg
Tel. 0761/.511-0
Acetow Fax . 0761/511-3222

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 18. Decomposition C O 2
17 . Action -.00,111a k.
of cigarette filters

16 . The burning cigarett e

15 . Manufacture
of cigarettes

14 . Filter ro d

13. From Filter Tow

to filter rods

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 Photosynthesis of cellulos e

2 . Cellulose in woo d

3 . Structure
of cellulose

6. Activation
of cellulose

7 . Acetylation
of cellulose

8. Technological way to
cellulose-2 .5-acetate

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 IF

Contents

page
1. Cellulose in plants -
the most abundant biologically replaceable raw material on earth 6

2. Cellulose fibres -
as supporting components hidden in the fascinating structure of wood 10

3. Cellulose fibres and their extremely fine crystalline structure 12

4. Manufacture of cellulose - Example : magnefite process 16

5. Cellulose 20

6. Activating cellulose 21

7. Acetylation of cellulose - Anatomy of a chemical reaction 22

8. The technological process to produce cellulose-2 .5-acetate 24

9. Overview of the acetate spinning process of Filter Tow 28

10 . The spinning solution 32

11 . The birth of a filament 34

12 . The crimping process 36

13 . Processing filter tow to filter rods 40

14. The filter rod 46

15 . The manufacture of cigarettes 50

16 . The burning cigarette 54

17. The action of the acetate filter 57

18. The fate of used filters 60

19 . The history of cellulose acetate 63

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 Foreword

The manufacture and spinning of cellulose acetate in Freiburg celebrated its 70th birthday in
1997. On the occasion of this anniversary and the associated family event day, where our raw
materials come from, what processes are carried out in our factory and what our customers do
with the filter tow was to be presented in the form of an exhibition .
This resulted in a collection of impressive pictures and interesting aspects, giving an overall
insight into the process chain of cellulose acetate from the forest to the smoked and biodegra-
ded filter. The manufacture and consumption of cellulose and cellulose acetate in this chain can
be considered as a part of the global carbon dioxide cycle .

This information is now to be made available in the form of this brochure to interested employ-
ees at Rhodia, our customers in the cigarette industry and our suppliers in the cellulose indu-
stry.
Perhaps this comprehensive survey can contribute toward a better mutual understanding of the
activities of all involved to overcome interface problems in order to make advances in the over-
all cellulose acetate and filter tow process .

I would like to express my warm thanks to the companies Weyerhaeuser and Reemisma for
their active assistance in procuring picture material .

An especial thank you also goes to all those who contributed their expert advice to ensure the
success of the exhibition and this brochure : Mr. Greiner. Mr. Kramis, Mr. Kuner, Mr. Rahm.
Dr. Stark, Dr. Stein, Dr. Steinmeier. Dr. Thomas, Mr. Teufel, as well as Ms. Teuber, Mr. Meier and
Mr. Zahringen for creating the computer graphics and Ms . Rahm-Mahler for the type matter.

Paul Rustemeyer
May 1998

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 1 . Cellulose in plants - the most abundant
Photosynthesis : With the aid of sunlight plants synthesise ou r
carbon dioxid e
1 .1 . How do trees grow ?
The most amazing thing about the growth of plants
takes place in the leaves :
From the root region they take up water and from the air
carbon dioxide (CO2) and, under the influence of sun-
light, transform these into sugar and oxygen . Dissolved
in water the sugar is transported back into the
branches, twigs and roots and there converted into the
typical components of wood, such as
- cellulose (in conifers approx . 50%)
- hemicelluloses (approx . 10%) and
- lignin (approx . 30% )
In this way, growing optimally, a pine tree can generate
approx . 50 g biomass per day, at the same time re-
leasing approx . 20 I oxygen . Thus, this process is the
most important known for maintaining our oxygen
atmosphere, essential to life .
Only 2% of the sunlight energy is stored chemically in
woody fibres ; 15% of the light is reflected, 40% con-
verted to thermal energy and 43% of sunlight is used in
the evaporation of water.
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1 .2 . Tree growth in height
In the majority of plants the annual gain in height is lost
again when the section above ground dies in autumn .
Only trees continue their increase in height each year
over that from the previous year.
How big a tree becomes depends not only on the
species of the tree concerned but also on the following
growth site factors :
- water supply ,
- nutrient-rich soil, allowing good root penetration,
- spacing to neighbouring trees .
With a great deal of experience a forest can be ma-
naged in such a way that the wood yield per unit is opti-
mised by the selection of trees, use of fertilisers and
regulation of tree spacing, e .g ., by thinning the forest .
Due to the constant world-wide increase in the demand
for wood, it is becoming more and more important, on
the one hand, to implement a sustained forest manage-
ment with optimal yields of wood, on the other hand, to
leave untouched the large, coherent jungle areas as a
genetic and ecological "pool" .
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 biologically renewable raw material on earth
raw material, cellulose, from water and carbon dioxid e
height
Iml

45 .L
very good
site
4046

354.

30 .L good site

25 ..

2046
bad site
15 i

10

A
0
10 20 30 40 50 60 70 80 90 100 110 120 year s

Wood yield depending on the site Use of wood world-wid e

1 .3 . Forests as sources of raw materia l
About 1/3 of the land surface area of the earth is still
covered by forest . This contains approx . 600 billion tons
of wood - approx . 5 .6 billion tons of wood grow in
replacement annually. Of this man harvests the tremen-
dous amount of 2 .6 billion tons - this is equivalent to a
cube of sides 1 .3 km !
As long as the forest areas are sustained and continue
to be used, wood represents the largest amount of
replaceable raw material in existence . Sustained mana-
gement means not taking more from the forest than can
be replaced .
In underdeveloped countries wood is used primarily as
a source of energy, in the developed countries already
predominately as a raw material (see Fig .) .
In countries like the Federal Republic of Germany at the
current time there is an excess of wood in supply, or, an
inadequate capacity for processing wood, resulting,
despite the abundance of the raw material available, in
wood pulp having to be imported .
1 .4. Where our suppliers culture their wood and
how they implement sustained managemen t
Due to the high demands on quality, when processing
wood to chemical pulps ever greater quantities of fresh
wood of the same kind must be available . These
demands are fulfilled most ideally by the South East
(southern pine) and North West (hemlock fir) of North
America.
Our cellulose suppliers in the USA manage their
immense forests using a sustained system : small
parcels of approx . 18-year-old southern pines and
50-year-old hemlock firs are harvested and within one
year reforested with young trees . To grow these trees
fertilization of especially strong plants is carried out and
their seeds grown in the suppliers' own tree nurseries,
producing up to 500,000 young trees a year. These are
then planted in the harvested areas and growth pro-
moted in the first few years by applying fertilisers and
implementing plant protection measures .

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 1 .5 Forest with systematically harvested and replanted tree s

At the age of 50 years

hemlock trees are
mature for harvestin g

.6 Harvest inof the large forests

our supplier i4 he North-West of the
Inited States .j ; •, .

The forest is periodically

thinned to improve the
growth of the remainin g
trees : :'

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 The forest-cycl e
In sustainable forest
management trees grow
on 98% of the land

1 .7 Nursery to grow more than 500,000 trees per yea r

The forest is
replanted within one
year of harvesting
with 3-4 year
old seedlings

1 .8 Nutrients are applied to improve

tree growth and to maintain soil
productivity.

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 2. Cellulose fibres - as supporting components
an expedition into the microcosm of wood from cell bundles t o
Structure of a tree trun k
Size of picture : ca . 200 mm
Magnification : 0 .25 times
2 .1 . What is the structure of the trunk of a tree ?
On taking a close look every tree stump reveals the
following structure of the wood :
- Surrounding the pith in the middle there are alter-
nating layers comprising smaller and larger wood
cells . The difference in size of the wood cells is a
result of the seasonal changes in the climate (warm
and cold, or dry and wet) . The larger early wood cells
serve, above all . for the transport of liquids from the
roots to the leaves, the small, thick-walled late wood
cells give the trunk its mechanical stability.
- Onto the inner layers of the predominately dead
heartwood follows the outer layer of the actively
growing sapwood .
- The actual growth layer in wood is the so-called
cambium, from this wood cells grow in one direction
and phloem (inner bark) in the other direction .
- On the exterior the trunk is protected by the bark, i .e .,
flaked off phloem .
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Arrangement of wood cells
Size of picture: ca. 0,2 mm
Magnification : 450 times
2 .2 . Wood - a composite of many wood cell s
Wood owes its strength and elasticity to its microscopic
structure of different types of cell, the structure of
conifers being simpler than that of deciduous trees : in
conifers the elongated, dead wood cells (tracheids)
make up the greater part of the wood . On average, they
are 3 - 5 mm long and have a mean diameter of 40 - 60
pm (0 .04 - 0.06 mm) .
In conifers, apart from in the sapwood, living primary
tissue is only to be found in the lining of the resin
channels and in the medullary rays in the trunk running
from out-to in and which serve for the lateral transport of
water and nutrients.
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BATCU US DOl V Philip Mono
 hidden in the fascinating structure of woo d
fibre bundles
Layer structure of the cell wells
of wood calls (tracheids)
Size of picture : ca. 0,02 mm
Magnification : 4 500 times
PR'9 7
2.3 The cell walls - the supporting components
of wood
Over the last few decades, with the application of
sophisticated methods, e .g ., electronmicroscopy, the
fascinating structure of the cell walls of wood have been
elucidated .
On a so-called middle lamella, the connecting layer
between each of two adjacent cells, follow the very thin
primary wall and thin secondary wall S1, in which the
cellulose fibres are embedded in a spiral form .
The most important load-bearing cell wall is the secon-
dary wall S2, in which the cellulose fibres are arranged
parallel to the longitudinal direction of the cell .
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Compoelte structure of cellulose fibres ligni n
and polyoses (hemlcelluloses)
Size of picture: ca. 0,0002 mm (200 nm)
Magnification : 45 000 times
PR'9 7
2 .4 Cellulose fibres (microfibrils) -
suppliers of strength to the cell walls
Recent findings permit the model concept comprising a
fine structure within a cell wall layer comparable to rein-
forced concrete :
Bundles of cellulose fibres (comparable to the steel) are
embedded in a mass of lignin (comparable to the con-
crete) . Between the cellulose fibres and the lignin there
is a layer comprising polyoses (hemicelluloses) as an
adhesive .
11
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 3. Cellulose fibres and their extremely fine
from fibril bundle through polymeric molecular bundle dow n
cellulose fibre hemi-
Cellulose
Structure of cellulose fibre s
Size of picture : 0,00006 mm (60 nm)
Magnification : 150 000 times
3.1 . The fine structure of cellulose fibre s
With a greater magnification of a cellulose fibre this
reveals areas which are far beyond the range of human
perceptive experience : the world of atoms and mole-
cules can then be presented in the form diagrammatic
model concepts . The figure above shows a two-
dimensional section from the outer boundary of a
cellulose fibre .
Only by using X-rays was it possible to reveal the
molecular structure of cellulose fibres . Today there is a
great deal of evidence that within the cellulose fibres
approx . 50 - 100 giant cellulose molecules are
combined together parallel to one another to form a pre-
dominately crystalline bundle . Between the crystalline
areas there appear to be less organised amorphous
areas which, in contrast to the crystalline, rigid part,
impart flexibility.
In an amazing way, during the course of evolution, a
strong yet flexible structure was developed within wood,
which, in different orders of magnitude, are based on
the principle of bundling : molecular bundles, fibre
bundles, cell bundles .
In cellulose, i .e ., in cellulose fibres isolated from wood,
the crystalline fraction makes up approx . 68% .
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I_
I
Crystalline and amorphous cellulose
Size of picture : 0,00001 mm (10 nm)
Magnification : 1 000 000 times
PR
3 .2. Crystalline and non-crystalline areas
With an increasing magnification of the outer boundary
of a cellulose fibre this enables the gradual identifi-
cation of the molecular fine structure of the cellulose
molecules : they comprise a chain of constantly re-
peated units composed of six-rings . Chemists call such
a chain unit a monomer. In the case of the cellulose
molecule the monomer is glucose . In fact, in the wood
cell there are up to 8000 glucose molecules combined
together to form cellulose chain molecules, i .e ., the
degree of polymerisation (DP) is 8000 . Such a molecule
is approx . 5/1000 mm long . In the two-dimensional
diagrammatic representation of the outer boundary of a
cellulose fibre it is possible to see very distinctly the
regular arrangement of the molecular chains in the
crystalline fraction . The crystals fray out at the sides
and the ends into the non-crystalline (= amorphous)
areas . These amorphous cellulose chains react elasti-
cally under a weak mechanical load ; under large loads
the cellulose chains shift against each other and lead to
a permanent deformation . Water promotes this shifting
as a "plasticiser'", explaining why wet wood is more
flexible than dry.
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 crystalline structure
into the atomic level of cellulose

OH
H2 C" O
HO~CH~CH~
CH ,OH
HO-` H~ 'C H
OH
Molecular structure of cellulose fibres A monomeric unit of glucose
Size of picture : 0,000003 mm (3 nm) Size of picture: 0,0000001 mm
Magnification : 3 000 000 times Magnification : 10 000 000 time s

3 .3 What holds the cellulose fibres together internall y 3 .4 . A bit of chemistr y

Only at a magnification of 3 million times could one
detect the molecular structure of cellulose and the
arrangement of its atoms .
Chemists prefer to show such structures so that the
position of the atoms are identified by their centre and
the chemical bonds to the adjacent atoms by a connec-
ting line . The matrix diagram only serves as a general
overview. As is shown in the figure, the molecule almost
completely fills the entire space of the matrix .
As will be described in more detail in 3 .4, at some
points the cellulose molecules are electrically charged .
Points bearing opposite charges attract each other
accordingly. Such forces of attraction are shown as
broken connecting lines .
These forces of attraction, together with the regular
arrangement of the molecular chains, are the main
reason for the crystallinity and hence the strength of the
cellulose fibres.
The structure of a glucose monomer unit contains 6
carbon atoms, 12 hydrogen atoms and 6 oxygen atoms,
so that chemists abbreviate this as the formula
C6H1206-
The chemical bonds between the atoms are very stable .
only after heating do these bonds break . Thus, in the
absence of air, cellulose breaks down at 250°C into car-
bon dioxide and water, the name carbohydrate being
derived from this .
The OH groups visible in the structure are polar, i .e ., the
oxygen atom (0) is slightly negative, the hydrogen atom
(H) slightly positive . This charge pattern effects the
cohesion of the cellulose chains and the affinity to
water .
With oxygen from`the air cellulose burns to carbon
dioxide and water vapour, i .e ., the substances which the
tree used to produce the molecule . The sunlight energy
originally stored is released again during combustion in
the form of heat and light .

13

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 .6 Scanning electron micrograph of a cross-section of
3 .5 (above) Wood chips from hemlocks - the raw material 3
for wood pulp manufacturing hemlock wood with nice annual rings .

1 .00mm

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 1. (

3 .7 and 3 .8 Scanning electron micrograph of a cross leaves, the small, thick walled late wood cells give the
section of hemlock wood . The larger early wood cells strength its mechanical stability.
serve for the transport of liquids from the roots to the (photos Weyerhaeuser)

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 4. Manufacture of cellulos e
How hemicelluloses and lignin are separated from the cellulos e
recovery of the
sulphuric acid and
magnesiu m
f
wood chips
forest
4 .1 Preparation of the wood and the sulphite
cooking liquo r
During the cellulose process, on the one hand, the
complex structure of wood should be broken down
sufficiently, so that the components lignin and hemi-
celluloses are as completely separated as possible . On
the other hand, the process should be very gentle to
ensure that the cellulose fibrils remain as undamaged
as is possible and the cellulose molecules remain as a
uniform end product comprising long chains .
Preparing the wood :
In the first stage of the process the tree trunks are cut
into approx . 1 .5 x 1 .5 cm wood chips in a rotor chip
cutter. These are then sieved to obtain chips of the
same size as the sulphite cooking liquor should soak
into the wood evenly.
Preparing the sulphite lye :
A greater part of the wood hydrolysing cooking liquor is
obtained from subsequent phases by concentrating the
spent liquor by vaporisation (the vapour also serves as
the process vapour) and the concentrate is then burned
(the heat is used for pulp mill processing) . New sulphite
lye for the cellulose process is then obtained by dissol-
ving the residue of combustion with water .
16
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sulphonation disintegration
of lignin of the wood
4 .2 Rough separation of wood components
in the pulping process
The wood chips and the magnesium sulphite lye are
heated in a reactor (digester) with a capacity of 200 t,
for example, at approx . 140 °C for about 6 hours . Under
these conditions the following is achieved :
0 Lignin, a strongly cross-linked, insoluble polymeric
molecule, is broken down into smaller units and with
the integration of the sulphite groups converted into
watersoluble lignin suiphonic acid salts .
0 Similarly, the hemicelluloses and the cellulose are
also split into shorter chains .
Carrying out this reaction is very tricky as heating de-
stroys too much of the desired cellulose ; on the other
hand, all the lignin must be removed .
At the end of the reaction the content of the digester is
under pressure ; this is reduced by transferring its con-
tent into a large blow-tank . During this process the
wood structure of the chips is completely disintegrated,
yielding a brown slurry of cellulose fibres and separated
lignin . This slurry is taken up by a washing drum (a
sieve drum with a negative internal pressure) and
rinsed with water. The main separation of the wood
components is achieved with these steps .
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 Example : magnefite process
fibres in the complex composite structure of woo d
hydrogen peroxide
screening of the extraction of th e
i cellulose fibres hemicelluloses bleaching
4.3 Further purification steps for the
cellulose fibres
After the first step the fibre slurry still contains about 4%
lignin and 5% hemicelluloses as well as a number of
knots and other non-homogenous components . To
remove the latter the fibre slurry passes through a
knotters and unbleached screens, which permits the
cellulose fibres to pass through small slits .
Since the later spinning process for cellulose acetate
requires cellulose in a very pure form, further chemical
reaction stages follow in the manufacture of chemical
pulp which are designed to make the lignin and the
hemicelluloses soluble in order to optimize the quality
and the yield of the cellulose . There are many different
methods : the most important include :
0 chlorine-free bleaching including hydrogen peroxide
to dissolve any remaining lignin ,
0 treatment with lyes to separate off the hemicellu-
loses .
After each phase of treatment intensive washing
follows . The concentration of the washing solution and
the waste water is a considerable cost factor.
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fourdrinier presses
sheet formation
4 .4 From cellulose fibre slurry to cellulose
The purified cellulose fibre slurry is run onto a screen
belt . On this belt the slurry is drained and the cellulose
fibres interlock to form a cardboard-like layer . Further
water is squeezed out in roll presses, the cellulose
becomes more and more compact . In a large hot-air
dryer it is then dried, leaving a residual water content of
about 5% .
For our purposes this sheet formation and drying
process must proceed very evenly since
0 the sheets must not be too stiff, so that they dissolve
evenly in our reactors ,
0 we cannot adequately activate areas that are too dry
(see 6 .) .
Cutting to form the sheets takes place directly or via so-
called jumbo rolls (these are rolls weighing up to 10
tons), which in a second step are cut into sheets and
packed into small bales .
17
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 4 .6 View into a washer, where the bleaching liquor
and side-products of the wood are separated
from the cellulose pulp .

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 4 .7 The slurry of cellulose pulp is drained and
condensed on the sieve of the fourdrinier .

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 5. Wood pul p
a pulp out of wood cellulose fibre s
5.1 Chemical pulps
Chemical pulps differ from normal cellulose due to the
very high purity of the cellulose . This high purity is
necessary since the components of wood, such as
lignin and hemicelluloses, lead to disruptive side
products in the further processing .
Chemical pulps are considerably more expensive due
to the costs involved achiving cellulose purity.
The main areas of application for chemical pulp are :
- Viscose fibres
- Cellulose esters, such as our cellulose acetat e
- Cellulose ethers, e .g ., wallpaper paste, thickeners in
the foodstuff industry, etc .
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5 .2 Demands on the cellulose for the
acetate proces s
The acetate manufacturing process puts very high
demands on the quality of the cellulose used :
To ensure a consistent reaction process the cellulose
should always be of a consistent quality.
The sheet structure of the cellulose should be loose
and consistent enough that the cellulose disinte-
grates easily when activated .
- The fraction of side products should not exceed 4% .
- The molecular chains of the cellulose fibres shoul d
not be too greatly broken down .
The cellulose should have an evenly distributed water
content and have no areas that are too dry to ensure
equal reactivity of each fibre .
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 6 . Activating cellulos e
Cellulose is prepared for the reaction to cellulose acetat e

Key to symbols in figures in Chapters 6 . and 7 6.2 Preparing the cellulose for acetylatio n

* Glucose unit of cellulos e An important prerequisite for successful acetylation

comprises the cellulose fibres all being made equally
• Water well accessible for the reaction . The cellulose sheets
must thus first of all be made into a homogenous slurry
♦ Acetic aci d again, and the reagents must be distributed evenly. To
achieve this the catalyst required later, sulphuric acid
H Acetic anhydrid e with acetic acid, are premixed and added to the cellu-
lose sheets under heavy mechanical mixing . The cellu-
Bound acetate lose sheets become saturated with the reagents and
disintegrate into individual fibres .
OC Sulphuric aci d
Some sulphuric acid molecules already become bound
as cellulose sulphate .
6 .1 Initial state

The following diagrams attempt to make the processes

occurring during the actylation of cellulose to cellulose
acetate comprehensible to the non-chemist as well .
To achieve this once again the border of a cellulose fibril
with its crystalline and amorphous parts is looked at (cf .
3 .2 .) . In contrast to the crystalline areas, the amorphous
regions are accessible for other molecules . Still remai-
ning from the cellulose manufacturing process, water
molecules are here loosely bound to the polar surfaces
of the cellulose molecules .

21

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 7. Acetylation of cellulos e
First of all, the cellulose fibrils are dissolved to form triacetat e
7.1 Onset of acetylatio n
After the addition of acetic acid anhydride to dissolve
(activate) cellulose the following reactions begin :
O Reaction of wate r
In the presence of water and sulphuric acid acetic
acid anhydride is rapidly converted into acetic acid :
anhydride + water => 2 acetic aci d
0 Acetylation of cellulose
The acetic acid anhydride reacts in the presence of
sulphuric acid with cellulose to form cellulose acetate :
H As the cellulosetriacetate has a poor solulility in Ace-
+ * ---~ *
H
0 The cellulose crystals gradually open up during this
reaction like a zipper.
22
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7.2 End of the reaction forming triacetate
At the end of the acetylation reaction practically all the
cellulose crystals have dissolved to form cellulose tria-
cetate .
Heat is released during reactions 0 and 0, so that the
temperature in the reactor rises . The higher the
temperature becomes the more frequently a cellulose
chain will be split under the action of sulphuric acid . To
obtain the desired chain length for the spinning process
of approx . 200 - 250 glucose acetate units, the reaction
must be conducted with adequate cooling . The best
moment to terminate the reaction is a question of
optimisation : On the one hand, the chains should
remain long enough, on the other, all cellulose crystals
should already be dissolved to later obtain an optimal
spinning solution .
tone it has to be transformed into cellulose-2 .5-acetate
with excellent solulility in acetone.
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 Anatomy of a chemical reaction
and then saponified to yield cellulose-2 .5-acetat e
7.3 . Terminating acetylatio n
When all the fibres have been dissolved and the
degradative reaction has sufficiently progressed,
acetylation is terminated by destroying any remaining
acetic acid anhydride with the addition of water .
anhydride + water => 2 acetic aci d
The triacetate is now pumped out of the reactor into the
saponification vessel .
Here the water activated with sulphuric acid splits off
the acetate groups from triacetate on a purely statistical
basis .
H2SO4
0 +
This reaction is terminated in such a way that on a
statistical average the cellulose acetate chains still bear
2 .5 acetate groups per glucose unit .
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7 .4 Cellulose-2 .5-acetate
After neutralisation the sulphuric acid and the recovery
of concentrated acetic acid the viscous cellulose-2 .5-
acetate solution is mixed with sufficient water to make
the acetate insoluble and so that it precipitates in the
form of flakes. All the remaining secondary ingredients
of these flakes are washed out with a copious amount
of water. To stabilise the acetate a certain amount of
calcium salt (which can bind later immediately to any
acetic acid that may split off) is added to the last
washing phase .
The flakes are then dried and stored temporarily in
silos . Similar to the hemicellulose, the free, non-
acetylated groups of the glucose units attract water
molecules, explaining why cellulose-2 .5-acetate usually
contains some water .
The structural diagram very nicely illustrates that the
cellulose-2 .5-acetate surfaces are generated with
randomly distributed polarity patterns . These patterns
are very important for the ability to absorb smoke
constituents mentioned later.
23
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BATCo US DUI V Philip Morrie
 8. The technological process to produc e
How cellulose bales and acetic acid anhydride are converte d
cetene
sulphuric
wood pulp reaction to
cellulose acetate
8 .1 Acetylation to triacetate
In Freiburg the acetylation reaction is performed in bat-
ches in drum reactors ; this permits an environmentally
friendly method, requiring especially little sulphuric acid
as a catalyst .
First of all, several tons of the raw material cellulose are
mixed in the reactor with the solvent, acetic acid, and
the catalyst, sulphuric acid . During this so-called
activation the cellulose sheets break down into flakes,
the cellulose fibres become saturated evenly with the
solvent and the catalyst.
For the actual acetylation acetic acid anhydride is
added . This initially reacts very rapidly with the water
out of the cellulose to form acetic acid . With the genera-
tion of large amounts of thermal energy the acetylation
reaction of the cellulose to cellulose acetate proceeds
on the surface of the cellulose fibres . The cellulose
fibres gradually become fully dissolved until finally a cle-
ar solution of cellulose acetate is obtained .
At the end of the reaction the excess acetic acid an-
hydride is destroyed with water and the reaction mass
cooled down to prevent the breakdown of acetate
chains .
24
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acid
hydrolysis to precipitation of
cellulose-2 .5-acetate the acetate flakes
8 .2 Hydrolysis (saponification) to 2 .5-acetate
After the reaction is complete the contents of the drum
reactor (the solution of cellulose triacetate in acetic
acid) are emptied into a hydrolysis tank, and at the
same time mixed with water and sulphuric acid .
During the hydrolysis reaction, which proceeds slowly,
part of what was achieved during acetylation is re-
versed : statistically, isolated acetyl groups of the
cellulose triacetate are split. The reaction is allowed to
continue until the 2 .5-acetate phase has been reached,
i .e . every 6th acetyl group has been split .
To terminate the hydrolysis at a certain defined point
the catalyst, sulphuric acid, is neutralised . This leaves a
solution of cellulose-2 .5-acetate . Some of the acetic
acid is recovered in the next step, involving vaporisation
and condensation (distillation), and the cellulose-2 .5-
acetate solution concentrated .
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 cellulose-2 .5-acetate
into "acetate flakes" .
acetic acid
recovery
maturing and washing
of the acetate flakes
8.3 Precipitation and washing of cellulose acetat e
Since cellulose-2 .5-acetate is insoluble in dilute acetic
acid, a copious amount of water is added to the
concentrated acetic acid :
During this process cellulose-2 .5-acetate precipitates
rapidly in the form of flakes . The flakes are porous and
fully saturated with acetic acid . It is hence necessary to
remove all acidic constituents by intensive washing . To
achieve this the flakes are first of all given sufficient time
in a ripening tank to give up a large part of their secon-
dary constituents into the surrounding liquid . The flakes
then undergo an intensive washing process, where all
acidic constituents in the pores are replaced by fresh
water. Finally, the flakes are stabilised in the last was-
hing phase with water rich in calcium .
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
hot air dryer silo
8 .4 Drying the flake s
After the washing process the flakes are freed of water
absorbed to the surface in a roll press . Subsequently,
they are transported in a hot air dryer and dried in a
counterflow of hot air.
The residual moisture of the flakes is approx . 3% .
The flakes are stored temporarily in large silos for
further internal or external processing .
Recycling the acetic aci d
The profitability of the acetate flake manufacturing
process depends largely on succeeding in using as little
acetic acid as possible and recovering as much of the
dilute acetic acid from the washing process as possible .
In our case the acetic acid is practically recycled
quantitatively, the water fraction enters the waste water
after being largely freed of sulphates by precipitation of
gypsum .
25
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 IF

8 .5 Wood pulp -just debaled and rea-

dy for the reaction to cellulose
acetate . Only high purity wood
pulp with a well defined sheet
structure can be used .

8.7 Hydrolysis tank in which the reaction from cellulose triacetate 8 .8 Sampling valve with viscous dope of cellulose-2 .5-acetate
to cellulose-2 .5-acetate Is carried out . Only the latter is readily
soluble in acetone and spinnable.

http://legacy.library.ucsf.edu/tid/iun71a99/pdf
 from the
productio n

8.9 Just precipitated flakes of cellu-

lose-2 .5-acetate in the matu-
ring tank, where soluble side
products are washed out

8 .10 Flakes coming out of the roll

press where water is squee-
zed out of the flake's surface .

8.11 View into a hot air dryer

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 9 . Overview of the acetate spinning process o f

9 .2 The spinning machine

The spinning machine for filter tow comprises three

acetate
acetone parts :
flakes
- the spinning head, in which the spinning solution is
maintained at the exact temperature and which is fed
to the spinning jets by spinning pumps ,
- a series of spinning cells, in which the actual thread
formation takes place below the spinning jet and the
almost complete evaporation of acetone with the help
of air.
- tow band guide, in which the elementary threads
from the individual cells are united to form a cable .

metering pump
I

dissolving of the filtration of the

cellulose-2.5-acetate spin dope

Flow sheet of a filter tow

spinning plant

9 .1 Making the spinning solution (= spin dope)

To make the spinning solution acetate flakes, acetone

and some water are mixed together intensively in a
mixer . spinnin g
0 .6 % titaniumdioxide is added as a white pigment . To
ensure a stable spinning process it is important that the
initial substances are of the same consistent quality and
the composition of the spinning solution does not
fluctuate . Furthermore, the spinning solution should be 9 .3 The spinning process
freed of as many particles, e .g ., pieces of bark from the
cellulose manufacturing process, cellulose fibre After the spinning solution has come out of the spinning
remnants and larger titaniumdioxide agglomerates, as jets, the newly born filament solidifies and becomes
possible . To achieve this the spinning solution is filtered thinner as the solvent evaporates and the filament is
in filter presses with a very large surface area . stretched.
This ensures that the fine spinning jets do not get
blocked . Acetone is an ideal solvent for cellulose For a typical filter tow more than 10 .000 filaments are
acetate ; moreover, it is safe from a health point of view . spun from many jets at the same time and united to
form a cable .

28

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 filter tow

9 .4 Recovery of acetone 9 .6 Drying, storage, pressing, packagin g

Since more than 70% of the spinning solution com-
prises acetone, the acetate spinning process can only
be profitable and environmentally friendly when
practically all the acetone is recovered . To achieve this
the suction-extracted air/acetone mixture is washed
with water and then separated in a distillation column .
The fresh crimp structure is fixed as it passes through a
drier and the filter tow is brought to a constant final
humidity. The filter tow is then laid into filling boxes
several metres tall in regular patterns . This loosely
packed tow layer is then compressed in bale presses to
filter tow bales and packed for dispatch .

wate r

absorbtion of
the aceton e

pressing of
the bales baling

crimpin g drying

9.5 Crimping LE 4-

The crimping process serves to emboss a crimping

structure onto each filament in the filter tow (Chap . 13) .
In the crimper the uncrimped tow band is pressed via
two feed rolls into a stuffer box . This is constructed so
that over a prolonged period a very consistent, fine and
regular crimping along the entire tow width is achieved -
laying into the
as is required by the customer for a constant-quality filling boxes
filter rod production .

29

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 Views into a
filter tow
spinning plan t

9.7 Spin dope flowing into a tan k

9 .8 Spinnerette in operation

9 .9 The filament bundles coming out of the spinning cabinets and

being unified to form the Filter Tow

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 i

9 .10 A freshly pressed Filler Tow bal e

RHODIA ®
FILTER TO W

Chodia

9 .11 Just packed and ready for transportation into the warehouse

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 r

10 . The spinning solutio n

The polymer molecules of cellulose-2 .5-acetate are dispersed i n

When cellulose acetate is dissolved in acetone the polymer clusters are surrounded by aceton e

10 .1 Why is cellulose-2 .5-acetate dissolved 10 .2 The viscosity of acetate solution s

in acetone of all solvents?

When one substance dissolves in another like sugar in
water, for example, a total mixing of the molecules of
the solvent and the dissolved substance takes place .
Important prerequisites for good solubility are :
• The molecules of the solvent must be highly motile,
as is normally the case for liquids .
• Solvent and dissolved substance must be of a similar
nature, i .e ., the type of electrical charge distribution
on the surface of the molecules (their polarity) should
be similar.
• The internal cohesion of the substance to be
dissolved must be lower than that of the new
cohesion between the solvent and the dissolved
substance.
For cellulose acetate the internal cohesion between the
acetate molecules is weak, and the surface of the
acetate molecule is only slightly polar . Thus, there is
i only a small interaction with strongly polarised water, in
which the cellulose-2 .5-acetate is insoluble . With
respect to its polarity pattern acetone, on the other
hand, is an ideal partner for the cellulose acetate ; it can
be mixed with acetate in any ratio.
If flakes of cellulose acetate are added to a large
quantity of acetone, the acetone molecules very rapidly
penetrate the flakes, "surround" the individual acetate
molecules, separate the polymeric clusters from one
another, penetrate into the polymeric clusters, swell
them up and after a while create the state of an ideal
solution, in which acetate molecules can move against
and inside one another freely.
If more acetate flakes are added to this solution, the
acetate molecules will have "less space", they hook
onto and coil around each other, manifesting this in the
form of a drastic increase in viscosity .
If cellulose acetate receives a little acetone spread
evenly, when subjected to a load it becomes plastic, i .e .,
acetone acts here like a "plasticiser" .

32

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 acetone to form an elastic solution .
How the viscosity of a cellulose acetate solution
increases with increasing concentratio n
How the viscosity decreases with increasing shearing
velocity
10 .3 Elastic behaviour of acetate solution s
When polymeric molecules are dissolved in solvents,
these solutions not only show the behaviour of a liquid,
but also that of an elastic body. Such elastic behaviour
manifests itself when the polymeric solution is exposed
to greatly differing speeds, when stirring or transporting
in pipes, for example . The greater the differences in
speed are the greater the drop in the viscosity of the
solution since the molecules in such a flow field are ali-
gned parallel to one another.
Under these conditions the solution behaves similarly to
an elongated piece of chewing gum : if the external
traction lets up, it jumps back into its original form . In the
case of acetate solution coming out of the spinning jets
this means that the freshly extruded solution thread
widens laterally to the direction of spinning (bulb
formation, see Chap . 11) .
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
How the acetate solubility depends on the quantity
of bound acetyl groups and the water content of the
acetate
10 .4 How the solubility of cellulose acetates
depends on their degree of substitutio n
As already mentioned in 10 .1, the polarity of the surface
of solvents and dissolved substance have a strong influ-
ence on solubility.
In this respect the system cellulose/cellulose acetate
shows itself to be highly variable : the more acetyl
groups bound by the original cellulose chains the less
polar the molecule becomes .
This explains why there is an optimal solvent for
differing acetyl group contents and why the acetyl group
content must remain constant to yield a stable spinning
solution . In the case of the 2 .5-acetate in acetone, if the
acetyl group content is too high or too low, the solution
gels as either the free OH groups or the cellulose-
triacetate groups interlink, thus creating a matrix
structure within the solution .
33
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BATCU US PO7 r Pluli4 Moms
 11 . The birth of a filamen t
How a triangle becomes a "Mercedes star" .
In the spinning solution the cellulose acetate molecules
are in the form of clusters and are "completely soaked"
with acetone .
Above a concentration of about 24% they are strongly
hooked into and coiled around each other, so that they
can practically no longer shift against adjacent mole-
cules . If the highly viscous acetate spinning solution is
now pressed through the holes in the spinning jets, the
polymeric clusters undergo elastic deformation and are
oriented in the direction of spinning . In doing this they
absorb a large part of the energy brought into the
system by the spinning pumps.

When coming out of the spinning jet the polymeric

clusters relax again and the solution stream expands up
to a diameter of aprox . twice that of the diameter of the
jet bore . The elastic energy is converted into heat .

From the moment the solution is extruded the solvent,

acetone, evaporates and the polymeric solution
concentrates and cools down . Both effects cause a
rapid solidifying of the filament surface.
Since the draw down speed is usually higher than the
extrusion speed from the spinnerette holes, the plastic
filament is stretched, orienting the polymeric molecule
clusters in the direction of the fibre .

To increase the surface area of the thread in the case of

filter tow, star-shaped cross-sections are normally
required. Interestingly, these are generated from spin-
nerette holes with originally triangular cross-sections, in
which during the evaporation of the acetone the skin of
the filament solidifies, followed by further acetone
diffusing from the inside of the filament through this skin
to the outside . The edges of this triangle solidify first
and then the surfaces shrink during the drying process
toward the centre of the triangle . The figure below
shows the cross-sections of acetate filaments within the
corresponding geometric shapes of the nozzle :

The thickness of the filament, the "titre", is then given in "den"

(denier), which represents the weight of 9000 m filaments .
1 den = 1 g / 9000 m

The product description 3 Y 35000 means : 3 denier per filament

with a Y-shaped cross-section and 35000 total denier. This cable
thus contains 11666 filaments . for example .

34

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 A4
11 .1 Cross section of acetate filaments
(view under a microscope)
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
0<
11 .2 Y-shaped cross section of an acetate filament
under a scanning electron microscope
32502368 4
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 12 . The crimping process
How the filter tow filaments get their quality-determining three-
staffer box
12 .1 Why are acetate filaments crimped in
filter tow?
By crimping is meant zig-zag-shaped deformation of
the originally straight filaments . In the case of filter tows
crimping is one of the most important criteria deter-
mining quality as the crimping determines, on the one
hand, the elastic behaviour of the tow in the processing
in the filter rod machine and, on the other hand, the
appropriate matrix structure on the finished cigarette
filter.
The following criteria are those which determine a
continuous improvement in the filter tow :
Number of crimps per c m
The higher the number of small crimps present in the
filament the higher is its elasticity and spring-back
resilience, the higher the number of points of inter-
section and the higher the air resistance the diversions
generate later in the filter.
Consistency of the crimpin g
The consistency of the crimping is decisive for the
consistency of the cigarette filters later produced .
36
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12 .2 How does the stuffier box crimping
process work ?
A so-called stuffer box crimping process is used to
crimp acetate filter tow.
A crimping machine basically comprises a stuffier box,
in which the tow band of over 10,000 filaments (= cable)
is continually introduced via two feed rollers . At its rear
end the compression chamber has a flap which is pres-
sed under constant pressure against the acetate cable
as it fills the chamber. The feed rolls thus press the
cable against a plug, the cable first of all being
compressed like an accordion into a finely crimped
form . These primary crimped packets are then
compressed like an accordion into secondary crimped
layers and, finally, into tertiary crimped layers . It goes
without saying that at equilibrium exactly the same
amount of crimped acetate cable leaves the chamber
as uncrimped cable is fed in .
The fineness of the crimping in this process is mainly
determined by the elasticity of the filaments, the applied
compression and the overall geometry of the crimping
machine .
325023685
BATCo US 003 V Philip Mom,
 dimensional crimped structure
12 .3 How does the crimping process begin ?
The crimping process was simulated with a strip of
paper in order to clearly document optically how
crimping begins : in the top picture above the strip of
paper is still running unhindered into the compression
chamber (on the right), meets resistance from the walls,
compresses and finally crimps, clearly exhibiting
primary and secondary crimping .
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
12A What is the crimping index ?
The crimping index I indicates how much (in %) the filter
tow stretches when subjected to a load of 2 .5 kg instead
of 0 .25 kg (tertiary crimping pulled out) .
stretched length under 2 .5 kg load
initial length (0 .25 kg preload)
37
325023686
BATCO US DOJ V Plubp M .-
 .,+1~-+r '~~yf'iii~ ~. .~`~ ~~ yam.
ago f ~•~jj- .y
.+w~~~~~~

y7 loop,
12 .5 Filter Tow seen under a
scanning electron microscope vwppoF

12 .6 The Filter Tow bale has O W

to debale without an y
problems at our custo-
mers .

This photo makes clear

that for good debaling the
filaments must have
excellent cohesion .

http://legacy.library.ucsf.edu/tid/iun71a99/pdf
 12 .7 The secondary crimp of
the Filter Tow is clearly
visible .

12 .8 The tow webbiness shows

how regular the filaments
interfere with each other .

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 f'
13 . Processing filter to w
1st
spreading jet

I
feed and ratio
rollers wit h
screw thread- 3rd
C-=P like surface spreading
2nd
spreading
jet

pretensioning
rollers
(400 m/min)

(490 m/min) (690 m/min )

0
d

3
Functional principle of a filter rod machine (KDF 2)

13 .1 The function of the filter rod machin e 13 .2 Blooming the filter tow

Filter tow is processed in two stages in a filter rod
machine :
1 . The filter tow is bloomed as much as possible so that
it develops its maximum filling capacity .
2 . The bloomed filter tow is compacted into the shape of
the future cigarette filter and surrounded by paper.
For the purposes of problem-free production and
consistent quality the filter rod manufacturers would
naturally like the filler tow bales to run without jamming,
tugging or producing dust . The filter tow manufacturer
achieves this in giving the filter tow a web structure and
laying the tow in a carefully worked out pattern into the
filling boxes .
The cohesion of the filaments must not be too strong,
however, since optimal blooming of the filter tow
requires that all individual filaments are disentangled
and can shift against one another in order to achieve
maximum filling capacity, optimal pressure drop within
1 the filter and optimal hardness of the filter rod .
During the stuffer box crimping process large groups of
filaments were given a parallel crimping structure at the
same point . This also supports the cohesion of the filter
tow. To achieve an optimal blooming of the filter tow the
filaments must now be shifted individually and in the
crimping ripples against one another . This is accomplis-
hed in the filter rod machine under the application of two
principles :
- Depending on the filter tow's webbiness, spreading
jets driven by compressed air draw the filter tow apart,
as much as possible .
- A system of paired feed and ratio rollers, running at
different speeds and partly due to their screw thread-
like surface only grasp parts of the spread out filter tow,
stretch and shift the individual groups of filaments
against each other .
These steps are illustrated in sections 13 .5 to 13 .11 .

40

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 to fliter rods

delivery rollers

garniture
spray booth
(400 m/min )
rotating
blade

(415 mlmin) glue

finished
filter rods

wrapping pape r
Speeds exemplary for 3Y35000

13 .3 From bloomed filter tow to filter ro d 13.4 Hardening the filter rods

The spread out filter tow with predominately individual
filaments is now fed into the spray booth, in which
rotating brushes create a fine spray of glyceryl-
triacetate, which is applied onto the acetate filaments .
The glyceryltriacetate etches the surface of the acetate
filament and sticks together the acetate filaments to
form a three-dimensional matrix structure in the finished
filter rod with the necessary filter hardness for further
processing and to meet the demands of the consumer.
In the next step the filter tow is fed by delivery rollers
into the transport jet driven by compressed air. The
transport jet compacts the processed tow and feeds it to
the tongue, which, due to its funnel-like geometry, com-
presses the filter tow to desired diameter of the future
filter rod . The filter tow bundle, together with the plug
wrap paper strip, is then transported on a small
garniture into a tube that sticks the paper with hot-melt
adhesive and at the end of the tube the finished filter
rods are cut off by means of a rotating blade .
In the spray booth the finely dispersed glyceryltriacetate
droplets are applied onto the acetate filaments . Each
droplet etches the acetate surface immediately and
makes it sticky.
In the freshly compacted filter rod, when two such sticky
filaments collide, they spontaneously remain stuck to
one another . As a result of many such adhesive zones,
a three-dimensional matrix structure of acetate fibres
comes into being .
In the hours succeeding the manufacture of the filter
rods the glyceryltriacetate diffuses evenly throughout
the entire cellulose acetate ; the adhesive zones
become firm again - the filter hardens .
This hardening can also be measured macroscopically
by observing the increasing hardness of the entire filter
rod .

41

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 13 .5 Structure of the filter tow before 13 .6 The filter tow after the pretensioning rollers
the 2nd spreading jet
Compared with the previous figure it can be seen that
These figures clearly document the web structure of the the tow band is already clearly more stretched, but still
filter tow, i .e ., the internal cohesion of the tow as a resul t has its collective "in-phase" crimped structure .
of the crimped structure running c
the random orientation of indiv i
In the subsequent processin g
to be separated from one
shifted against one another.

42

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 I

ratio rollers and the delivery roller s

the opportunity to relax, the individua l
shifting to differing degrees, henc e
he collective structure - the tow band ha s
isintegrated .

.9 The 3rd spreading jet spreads the filaments t o

13.7 In between the feed and ratio rollers the filament the entire width of the spray booth .
bundles are now shifted considerably against one another The crimped structure of the now completely separated
and stretched by means of the screw thread-like surface filaments can be seen clearly in the figure below .
of the upper driving roller .

http://legacy.library.ucsf.edu/tid/iun71a99/pdf
 I

Inside the spray boot h Transport jet with funnel and RHODIA tongu e

5p! iy DOO1 ?

t F. Ir,; r v rr :,l ie, r ir .:trtsport let

tunrw :

13 .10 In the spray booth the glyceryltriacetate is finely

dispersed by a rotating brush and applied to the spread
out filter tow.
The droplets serve to stick the filter tow in the next step .

13 .11 The transport jet compacts the tow band and

compresses it via a funnel into the tongue and then into
the garniture with the desired cigarette filter diameter . In
many factories the RHODIA tongue is used to improve
the yield .
At the same time the plug wrap paper is fed in from
below . This is then stuck together at the seam with hot-
melt adhesive .

44

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 A filter rod machine (right) The rotating blade cuts the endless filter rod .
with a tray filler (left) .

.i ., -, . ;u•,

13 .12 To make the crimping of the filter tow visible a 13 .13 Tray fille r
little dye was added to the filter tow for the photo below . The filter rods have ample time to harden in the trays .

45

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 I
14. The filter rod
A simple system with a series of customer demand s
pressure dro p
tow weight
The capability line of a filter tow shows the working
range of one filter tow type with respect to filter weight
and pressure drop.
14 .1 The capability line of a filter tow -
orientation for the desired filter properties
When making a cigarette filter an optimum is striven for
betwee n
- the pressure drop (approx . 50 mm water-column
pressure )
- the desired tar retention (approx . 40 - 50%)
- the hardnes s
- the materials require d
- the pressure drop variations of the filter.
An important consideration for the construction of a
cigarette filter is the so-called capability line of the tow,
which describes what quantity of a filter tow (denier per
filament, total denier) leads to a particular pressure
drop.
Due to technological considerations the capability line
is limited at the top and the bottom :
- At weight minimum the filter tow shrinks in the filter
rod (recessed ends) . The hardness becomes low and
the retention small .
- At weight maximum, due to the inadequate filter tow
tension, the danger of roll wraps at the delivery
rollers of the filter rod machine increases . Moreover,
the pressure drop values show great variation .
46
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
1 .5 de n
5 6 7 6
tow weight (mg/mm rod length )
Such families of capability lines are the basis of the
CABLE software for selecting the optimum type of fil-
ter tow for a particular filter functio n
14 .2 How the pressure drop is influence d
by the denier per filament and the total denie r
The diagram above shows the capability lines of
different filter tows (denier per filament, total denier) .
This indicates clearly that :
- The higher the total denier is the higher the pressure
drop .
- For filter tows each with the same denier per filament,
there is an almost continuous family of curves.
- The finer the denier per filament is the higher the
pressure drop with the same weight of acetate .
A saving in material related to a finer denier per filament
unfortunately leads to a lower retention, less hardness
and problems at hot collapse (=> 14 .4 .) .
A large number of experimentally determined capability
lines of tows form-the basis of the software CABLE,
which is made available by Rhodia Acetow AG to the
cigarette industry for the efficient development of ciga-
rette filters .
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7t
- - - - nicotin e
- tar retention
5,0 don
[%1
20 30 40 50 070~►
retentio n
These families of curves show the retention values of
the filter tow types so important for taste and effect of
nicotine
14 .3 How the retention of nicotine and condensate
Is influenced by the denier per filament and
total denier of the filter to w
The retention value of a filler indicates what percentage
of a substance is retained by the filter.
Experimental investigations on the filters described in
14 .2 . yielded the nicotine and tar retention values
summarised in the graph above .
This can be interpreted as follows :
There is a tendency for the retention values to increa-
se with increasing pressure drop .
This also reflects the expectation that more filter
material leads to a higher retention capacity .
The finer the denier per filament the higher the re-
tention values are at the same pressure drop .
The higher specific surface area of the fine filaments
and the greater number of the fine filaments per
weight unit are the reason for this effect .
These relationships - useful for the development of light
cigarettes, for example - are also integrated in the
software CABLE .
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
hardness (Flitrona)
96 T
82 t +
0 2 8 6 8 10 12 1 4
% triacetine
Dependency of filament hardness on triacetine con-
tent .
14 .4 . Hardness and hot collaps e
The hardness of a filter rod made of cellulose acetate
mainly depends on the following parameters :
- Amount of filter tow in the filte r
The more filter tow there is the denser the matrix and
the harder the filter .
- Amount of triacetate
The more triacetine the harder the filter :
above 20% saturation effect - above 7% problems
with hot collapse !
- How glyceryltriacetate is applie d
Larger droplets provide fewer adhesive sites .
- Moisture content of the filter to w
Too much water acts as a plasticiser.
- State the filter rod machine is i n
Badly processed tow reduces the hardness.
- Denier per Filamdht .
The finer the filaments are the smaller the bending
resilience and the softer the filter.
Many smokers want the filter to remain hard until the
last draw - and not to collapse under the influence of the
ever-hotter and more moist smoke gases (hot collapse) .
The danger of hot collapse increases when the filter is
soft as a whole and when it contains too much glyceryl-
triacetate .
47
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 I

14 .5 Longitudinal section of filter rods from 3 Y 35000, above in "mini", below in "maxi"- setting of the rod maker (cf . 14 .1 .) .
Magnification approx . 20 times . Clearly visible in the bottom picture is the higher filament density and the greater lateral
orientation of the filaments . These crimps at right angles to the flow cause the considerably higher pressure drop .

48

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 14 .6 Cross-section through a filter rod 3Y 35000 (magnification approx . 300 x )

14 .7 Typical adhesive sites on filaments that have

been "welded" together with triacetine (cf. 13 .4 .)

49

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 I
15. The manufacture of cigarettes
In an unbelievably fast process tobacco, filter rods and pape r
Schematic diagram of the manufacture of filter-tipped cigarette s
15 .1 Processing tobacco
What determines the taste of a cigarette is the selection
and treatment of the various sorts of tobacco . Thus, in
an American blend cigarette, for example, tobaccos
with very different characteristics are mixed together :
- Burley (high in nicotine and protein, slightly acidic)
- Virginia (low in nicotine and protein, slightly acidic )
- Maryland (low in nicotine, high in protein and sugar,
alkaline )
The tobacco leaves are freed mechanically of the leaf
veins and, depending on the taste to be achieved, sub-
jected to the following refining steps :
Casing = Application of humectants, sugars, and high-
boiling flavour additives to optimise the taste and to pre-
vent dehydration .
Toasting = Caramelisation of the sugar applied during
casing .
Flavouring = Addition of the volatile flavourings .
Expansion = Swelling up of the tobacco cells by steam
explosion to increase the filling capacity of the tobacco .
The different tobacco fractions are intimately mixed and
fed, finely cut, to the cigarette-making machine .
50
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
cutting of the
tobacco colum n
15 .2 The manufacture of filter-tipped cigarette s
The manufacture of filter-tipped cigarettes comprises
many steps :
1 . The completely processed tobacco is continually
dosed onto a sheathing paper strip, which passes by .
Seam adhesive is applied to the edge of the
sheathing paper, similar to the process in manu-
facturing filter rods, and the paper containing the
tobacco compressed to form an endless cigarette .
2. This endless cigarette is then cut with a rotating
blade to the final length of the tobacco columns, each
separated by a gap allowing the insertion of a twin
filter.
3 . A twin filter is now inserted into the gap between two
raw cigarettes and the twin filter sheathed and with
coating paper stuck so that it overlaps onto the raw
cigarettes . -
4 . The twin filter is then cut through on the continuous
string, every second cigarette turned and fed into the
continuous stream of cigarettes via the cigarette
hopper of the cigarette-making machine . A modern
cigarette-making machine can manufacture up to
14,000 cigarettes per minute .
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 are transformed into cigarettes
Elements of a cigarette :
adhesive seam

1
tipping pape r

assembling of a cutting
double cigarette

15 .3 Types of cigarette 15 .4 . Cigarette components

The cigarettes currently available on the market can be It is amazing how a relatively simple product like the
classified according to the following criteria : cigarette has been developed and optimised over th e
last few decades in several developmental steps both
from the viewpoint of the smoker's enjoyment and the
1 . Condensate values technology of cigarette manufacture . This relates to
practically all components of the cigarette :
Name Tar (mg) Type of Filter
Full flavour 10 - 15 Monoacetate the tobacco with its taste, filling capacity and burning
Medium 8-10 Monoacetate behaviour,
Light 4- 8 Monoacetate
Ultra-light <4 Special filter the cigarette paper, whose porosity has a conside-
rable influence on the combustion rate of the cigarette ,

2 . Cigarette forma t the cigarette filter, which should selectively hold back
the substances which have an adverse effect on the
Name Format (mm x mm) taste and which are harmful ,
King-size 7,8 x 8 5
100-R 7,8 x 10 0 the plug wrap, whose porosity is adapted to the
Slimline 5,4 - 6,4 x 12 0 required ventilation ,

the tipping paper, which is perforated for ventilation

3 . Types of tobacc o purposes, using laser technology, for example .

E .g ., American blend, German blend, Virginia,

Maryland, Orient

51

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 Interesting details of a cigarette machin e

15 .5 View into the garniture, where

I the tobacco column is wrapped
by cigarette paper.

15 .6 The cut tobacco columns are

taken pairwise by vacuum grabs
and passed onto the cigarette
machine.

15 .7 The transport rollers bring the

tobacco columns (right) and
double filters together .

15.8 A double cigarette is formed by

sticking the plug wrap around .

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 15 .9 A rotating blade cuts the double
cigarette (the ventilation holes
in the plug wrap can be clearly
seen) .

15.1OAfter cutting the cigarette is

finished .
i

15.11 Every second cigarette is tur-

ned round by 180" and orien-
ted for packaging

15.12 In the last step the pressure

drop of every cigarette is
checked . cigarettes out of
range are sorted out .

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 16 . The burning cigarette
How the aromas are set free and how smoke is generate d
combustion zone decomposition zone
carbonisation zone
Schematic diagram of a burning cigarett e
16 .1 . How should the burning process of a
cigarette proceed ?
A detailed look at how a cigarette burns reveals a highly
complex process.When smoking a cigarette the burning
process is subject to highly sensitive control as not only
it is organic material simply to be combusted, but furt-
her tasks should be fulfilled in addition :
- release of the desired aroma and active substances
to the smoker by means of correct burning condition s
- reduction of the tar and nicotine content by an
appropriate filter design (cf . Chap. 14 .) and by dilution
(ventilation, porous paper )
- sufficiently slow burning time by using appropriate
cigarette paper (porosity, fillers) and suitable tobacco
- holding together of the white ash by means of
suitable paper fillers, e .g . chal k
- continuous glow, even when not draw n
- pH of the smoke (slightly acidic, pH 5.5 - 6.5 desired) .
54
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condensation zone
evaporation zon e
16 .2 . What happens in the burning cigarett e
When a smoker draws on a cigarette the following
zones are created from the side of the inflowing air, i .e .,
from the incandescent cone to the filter :
1 . The combustion zone, in which the charred tobacco
is burned into CO2 and CO at a temperature of over
800°C .
2. The carbonisation zone, in which the hot air from
the burning zone breaks tobacco down into charcoal .
Escaping steam and carbon dioxide catapult smoke
particles into the air (> 100'C) .
3 . Decomposition zone, in which at approx . 200 -
400°C the substances contained in tobacco, such as
proteins and celluloses, are broken down into volatile
and semi-volatile substances, involving a high con-
sumption of thermal energy .
4. The evaporation zone, in which the highly volatile
substances which contribute to the aroma of the
cigarette and water vapour escape from the tobacco
(< 100°C) .
5 . The condensation zone, in which the greater part of
the volatile substances from the hotter zones con-
dense again onto the cold tobacco. As the incandes-
cent front advances the condensed substances are
continually vaporised .
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 close to the approaching combustion lin e
cigarette wrapper tipping paper ventilation
filter rod ai r
16 .3 . Cigarette smoke, a dynamic syste m
The particles in cigarette smoke comprise thousands of
different substances, which form small solid or liquid
particles in the carbonisation zone . The size of these
particles varies between 0 .1 and 1 pm (thousandth of a
mm) .
In 1 cm3 of such an aerosol 100 million to 10 billion
particles can be determined . These many tiny particles
have an extremely high surface, permitting a constant
evaporation and condensation of volatile substances .
Thus, a very dynamic exchange of substances takes
place both between the particles themselves as well as
with the surrounding material of the tobacco column
and the filter.
The substance exchange is very rapid - the smoke only
has 0 .2 sec from its coming into existence to its leaving
the cigarette .
Important for the taste is the slightly acidic character of
the cigarette smoke . The acidity binds a large fraction of
the volatile nicotine vapour as a salt to the smoke
particles .
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
mainstream smoke
16 .4 . Ventilatio n
Since the seventies the tipping paper of most cigarettes
has been equipped with a fine perforated crown to
permit fresh air to enter the filter from the outside .
This so-called ventilation has positive effects on the
smoke :
- All substances contained in the cigarette smoke are
diluted with the ambient air (depending on the degree
of ventilation, approx . 20 - 40%) . Thus, ventilation is
an important principle for the manufacture of light
cigarettes .
- The carbon monoxide and prussic acid content is
reduced beyond that due to the normal dilution effect,
since, based on the slower flow within the tobacco
column, more time remains for these gases to diffuse
through the porous cigarette paper.
55
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 A

.
p

17.1 Laminar flow of smoke gases in the filter . The 17 .2 A volume element of smoke gas, which passes
flow curves always run around the acetate filaments . through the filter with a mean flow velocity of 0 .5 m/s . It
contains gas molecules, which fly erratically with a
mean velocity of 0 .7 m/s .

17 .3 As a result of mutual "jostling" (here indicated

with arrows) the molecules can diffuse at right angles to
the direction of flow and collide into an acetate surface

17 .4 Larger particles in the smoke gas too can be

easily knocked permanently out of its flight path by
collisions with molecules . As a result of this so-called
Brownian movement more particles make contact with
the filter surface the more filter tow filaments are
aligned at right angles to the direction of flow in the
filter.

---------------------

17.5 In the case of heavy smoke particles and

condensate droplets the mass inertia of the particles
becomes so great that they cannot follow the changes
in direction of the filaments of flow around acetate fibres
so that they strike the acetate filament .

56

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 17 . The action of the acetate filte r
There are different mechanisms for the deposition process,
depending on the size of the smoke particle s
17 .6 . Flow behaviour within the cigarette filte r
The loosely packed matrix of acetate fibres in the
cigarette filter only fills a volume fraction of about 10%
(cf. Fig . 14 .5) .
As a result of the filter manufacturing process the fibres
are mainly parallel to the direction of flow ; with their
crimps, however, they are at many points at an angle to
the direction of flow . This latter fraction has a great
influence on the filter's pressure drop (cf . 14 .2 . : the
more material there is in the filter the higher the fraction
of fibres standing at right angles to the flow and the
higher the pressure drop) .
In order to enable a better appreciation of the flow
behaviour the flow curves in the graphs on the left were
drawn in one plane . These flow curves are parallel in the
working range of the filter (pressure drop of approx . 50
mm water-column pressure), only surrounding the fila-
ments they are closer .
Such a flow behaviour is called laminar - in contrast to
the turbulent flow, the volume flow through the filter is
strictly proportional to the pressure drop between the
two ends of the filter .
17 .7 . Filtration mechanism 1 :
Escape of volatile substances by diffusio n
Gases comprise freely moving molecules . Their mean
velocity is higher the higher the ambient temperature .
Thus, a nitrogen molecule (80% of the air) at 25°C has
a mean velocity of 0 .5 m/s, for example . The distance
between these nitrogen molecules is approx . 200 times
higher than their own diameter . Hence, the nitrogen
molecules collide with their neighbours about 7 billion
times per second, continuously changing their direction
of movement .
The flow velocity of the cigarette smoke through the
filter of approx. 0 .7 m/min is about the same as the velo-
city of the molecules themselves . Thus, it is simple for
the molecules to also move at right angles to the direc-
tion of flow (to diffuse) .
This means that vaporised molecules of substances
contributing to the aroma from the cigarette smoke can
collide with the adjacent acetate surfaces and adhere to
them .
The higher the acetate surface area and the more fibres
per unit volume in the filter the higher is the adsorption
of volatile substances onto the filter .
http://legacy.library.ucsf.edu/tid/iun71a99/pdf
17 .8 . Filtration mechanism 2 :
Removal of small smoke particles
and droplets through Brownian movemen t
As a result of the collisions of numerous gas molecules,
smaller smoke particles and droplets in the smoke are
permanently diverted from the main direction of flow by
the filter. The lighter the particles are the more erratic
their course . This erratic movement can be observed
under the microscope and is called "Brownian move-
ment" .
The Brownian movement contributes towards the
droplets and smoke particles breaking away from the
flow curves, which run around the acetate fibres, and
colliding with and adhering to the acetate surface . In
this way the acetate is gradually covered by a sticky lay-
er of condensate. Volatile substances contributing to the
aroma can evaporate again from this layer and less
volatile substances can be deposited from the smoke .
The higher the fraction of fibres at right angles in the
filter the higher is the precipitation of condensate as a
result of the Brownian movement mechanism .
17 .9 . Filtration mechanism 3 :
Collision of larger particles as a result of
mass inertia and effects of gravit y
In the case of heavy smoke particles and condensate
droplets the mass inertia of the particles becomes so
high that they cannot follow the changes in direction of
the flow curves around the acetate fibres, and thus
collide with the acetate filament . This type of filtration
can also be improved by a larger fraction of filaments at
right angles to the direction of flow.
Very heavy smoke particles can already "precipitate"
onto the, tobacco of the filament material due to the
effect of gravity.
Selective filtration means that a filter holds back one
type of substance better . This special affinity of acetate
is quite high for phenols and tobacco-specific nitro-
samines, for example . These matters are first of all
adsorbed to the acetate surface and then pass into the
acetate fibres .
Plasticisers in the cellulose acetate, such as triacetate,
increase the specific retention of phenol considerably .
Celluloseacetate is particularly appreciated as cigarette
filter due to this selective filtration .
57
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 17 .10 Longitudinal section of cigarettes after 0, 1, . . . 8 puffs . The 17.11 View into an open smoking machine .
brown colour of the filter indicates the retention . To be clearly Tare is collected in a central filter device .
seen : the ventilation through the lateral orifices .

58

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 Die EG-Gesundheitsminister : Rauchen gelahrdet die Gesundheit . Der Rauch einer Cigarette
diesel, Marke enthalt : 0,9 mg Nikotin and 13 mg Kondensat (Teem . (Durchschnittswerte Hach ISO )

3 .1
17.12 This example of an advert with its mandatory comment
36 .0
2.9 demonstrates the emotional and rational aspects of smoking .
34 .0
2 .7
32 .0 -I
2 .5

30 .0
2 .3

28 .0
17 .13 The reduction of the cigarette smoke's tar and nicotine
26 .0 1 content was the result of the right selection of tobacco as well as
the improvement of the cigarette filter and ventilaton .
a 24 .0
E

22 .0

20.0 1
1 .3
18.0
1.1

16. 0
0.9
14.0
0.7

12. 0
0.5

10.0
; 0.3
l r r r ,
1950 1955 1960 1965 1970 1975 1980 1990 2000

59

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 18 . The fate of used filter s
The natural cycle closes with the degradation into CO2 and wate r
Irregular 112 %
otMn 3 .0 %
waste water
toilettes - 0 .1 %
roads - 0,3 %
Incineration
22%
lake,
beach - 0,1 %
roads,
grass - 0,6 %
a
landfill
75%
0.3% disposed by
street cleaning service
18 .1 . Where used filters end u p
Depending on the disposal possibilities for the smoker.
the cigarette filter either lands up after enjoying a
cigarette in an orderly fashion in the domestic waste or
in a disorderly fashion on the street . in the grass . etc . . .
According to Wiethaup . approx . 98 .8°0 of the filters in
Germany end up directly on the waste dump or in
refuse incineration plants .
Of the remaining 1 .200 of the cigarette-ends . which
have been thrown by the smoker onto the street . onto
the beach, into a river . onto the grass or down the toilet,
about 0 .3°o are disposed of in an orderly fashion by the
street-cleaning services and 0 .4°6 disintegrate in the
digestion towers of the sewage plants .
Approx . 0 .406 remains over a longer period in the
environment and is, above all, an aesthetic problem .
this being the reason for the repeatedly expressed wish
that cellulose acetate filters should be biodegradable -
and they are . although this does require its own due
time .
Incidentally, the motivation for more discipline in the atti-
tude towards waste is achieved in some Asian
countries, not only by fines, but also by the introduction
of a "pocket ashtray" .
60
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0 10 20 30 40
days
Biodegradation of filter tow In the Sturm test
according to DIN 54600 (draft)
Inoculum: Sewage sludge from the Breisach sewage
plant
Carbon source : cellulose acetate
as filter tow 1 .5 Y 38000
Degradation test: Determination of C02
Result : 76% of the theoretical amount of carbon
dioxide. After a delay at the beginning (split-
ting off of the acetyl groups) the rate at which
the final degradation products are formed is
approximately the same as for cellulose .
18 .2 . The biodegradation of cellulose acetate
Biodegradation proceeds in three phases :
During the first phase the acetic acid is split off from
cellulose acetate by enzymes (esterases), then the
ether bonds to the cellulose chain are broken down by
further enzymes (cellulases) to sugars, which are finally
"digested as nutrients to carbon dioxide and water" by
micro-organisms . In this way the cycle is closed :
cellulose can be built up again from these components
by photosynthesis .
This biodegradation is always possible where there is
an adequate supply of water and micro-organisms .
In sewage plants an acetate filter disappears in the
digestion tower without any problems within 3 weeks .
In compost nothing remains of the filter after 3 months .
On the grass the filter disintegrates within about 2
years .
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 18 .4 Cellulose acetate filament - partially biologically decomposed (magnification : 2000 times )

18 .5 Holes in a filament of cellulose acetate - caused by light (photooxidation around the T102 pigment)

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 I

18 .3 Decomposition of a filter in gras s months in grass

18 .4 Test field after 3 months . Many of the test filters Following the decomposition in nature is difficult since
have simply disappeared . Some of them were found different modes of decomposition are active, depending
under the surface, others were presumably removed by on the intensity of the sun, wind, humidity, fauna and
mice and birds . mechanical stress .

For the above test series (see 19 .3) the filters were atta-
ched to a Nylon thread .

62

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 19 . The history of cellulose acetat e

800
Annual world production of acetate (in 1000 t)
700 + (estimate based on different sources )

6004-

5004-

400 +

300 +

200+
aircraft
paint
100

0
1900 1910 1920 1930 1940 1950 1960 1970 1980 1990 200 0

1865 Schutzenberger describes the acetylation of factory at Spondon . Later C . Dreyfus also set up a
cotton with acetic acid anhydride . production plant in the USA .

1879 Franchimont observes that sulphuric acid strongly
accelerates the acetylation of cellulose .
1903 Miles works on the hydrolysis of cellulose acetate
and notices that acetone-soluble products are formed
during this process .
1905 Bayer develops the technological process for the
acetone-soluble cellulose-2 .5-acetate and in 1907
starts production (Artificial silk Ji lich) .
1921 Expanding on the demand for acetate the Dreyfus
brothers begin with the production of acetate fibres
(British Celanese) .
1921 First production of acetate flakes in Roussillon .
1923 Starting up of the spinning in Roussillon .
1927 Founding of the German Rhodiaceta, todays
Rhodia Acetow AG, for the manufacture of acetate silk .

1910 Acetate is used successfully in the form of paint to
stiffen the fabric covering of aircraft wings, replacing the
inflammable nitro-cellulose paint .
1912 Production of cellulose acetate for paint in St .
Fons .
1914 Acetate production capacity increased in
Germany as acetate was a strategic raw material for the
construction of war aircraft .
Following an invitation by the British Government, the
Swiss chemists H . and C . Dreyfus founded an acetate
1952 Growing trend towards filter-tipped cigarettes .
1956 Starting up of the production of filter tow in
Freiburg .
1968 Starting up of the production of filter tow in Santo
Andre (Brazil) .
from 1970 on drop in the consumption of acetate fibres
for textiles as a result of the greater use of nylon, acrylic
fibres, polyester , . .

63

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 References
(the numbers refer to the chapers )

1 .1 Lewis, T. A . : Walder . Amsterdam, 199 3

1 .2 Stern, H . : Rettet den Wald, Munchen, 199 7

2 .1 Sell, J . and T. Zimmermann : Spektrum der Wissenschaft 4/1997, S . 86

Drawings reprinted by permission of Patricia J . Wynne

2 .2 Fengel, D . and G . Wegener : Wood, Berlin, New York 198 9

3 .1 Krassig, H . A . : Cellulose : Structure Accessibility, and Reactivity, Paris, Berlin, Amsterdam 1993

10. Kroschwitz, J . : Cellulose Esters, Organic Fibers in Polymers : Fibers and Textile s
New York, Chichester, Brisbane, Toronto 1990
1
10 .4 Malm, C . J . : et al . ind . Eng . Chem . 49, 79 (1957 )

14 . Wendeborn, R . and L . Zink : Zigarettenfilter aus Rhiakabel, Anwendungstechn Mitt . Rhodia 1982

14.4 Teufel, E . : Rhodia hardness-tester HDS 4, Anwendungstechn . Mitt . Rhodia 1983

15.4 Imbery, D . and E . Teufel : Behaviour of Pressure Drop and Ventillation Degree of Vented Cigarettes
During Smoking, R&D Information, Rhodia 198 6

16 . Samfield, M . : R&D in the US Cigarette Industry, New York 1980

16 . Browne . C. L . : The Design of Cigarettes, Charlotte 199 0

16 .4 D . Hoffmann and I . Hoffmann : The Changing Cigarette, 1950 - 1995,

J .Toxicol Environ . Health, 50 307 (1997)

17. Wynder E . L . and D. Hoffmann : Tobacco and Tobacco Smoke, New York and London 1967

17. Barrow, G . M . : Physikalische Chemie, Braunschweig 196 4

17.12 Tabakwerbung der Fa . Reemtsma

17.13 AFFCO : Filtration and Separation 3/1998 P . 11 8

18.1 Wiethaupt, W. : The Fate of Cigarette Filters in the Environment, TJI 3/1996 P 34

19. Harris : Handbook of Textile Fibers, Washington 1954

19 . Kroschwitz, J . : Cellulose Esters, Organic Fibers in Polymers : Fibers and Textiles

New York . Chichester, Brisbane, Toronto 199 0

19. Reveley, A . : A Review of Cellulose Derivates and their Industrial Apllications in „Cellulose
and its Derivates" ect . Kennedy et al, 198 5

64

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