Please take notice of: (c)Beneke/Lagaly. Don't quote without permission.

Published in:
ECGA (European Clay Group Association) Newsletter No.5, July 2002, page 57-78

Klaus Beneke and Gerhard Lagaly

Institute of Inorganic Chemistry
Christiana Albertina University
D-24098 Kiel

From Fuller´s Earth to Bleaching Earth:

A Historical Note.

Page

Washing in ancient times 1

The use of fuller´s earth 2
The use of urine and salpetre 4
Lanolin 6
Dying 7
Kimolian and other earths 8
Plant dyestaff in ancient times 9
Fulling millers in the medival age 12
The English fuller´s earths 13
Bleaching earths 13
Bleaching earth industry in Bavaria 14
Organic activated bentonites 18
Application of bleaching earth 19
Bibliography 21
 57
Klaus Beneke and Gerhard Lagaly
Institute of Inorganic Chemistry
Christiana Albertina University
D-24098 Kiel

From Fuller´s Earth to Bleaching Earth:

A Historical Note.

Washing in ancient times

The washing of cloth and clothes is traced from Ancient Egypt, the Middle East,
Homeric and Classical Greece, Rome and ownwards to the 20th century (ROBERTSON,
1986a; NOVELLI, 2000)

One of the most ancient historical quotation about the washing the raw clothes in
fresh water is find in the Odyssey of Homer (about 800 BC):
“...(Athena talks to Nausica in her sleep) Oh, Nausica, why did your mother
give your birth so slowly? You let your clothes neglected, altough your wedding day
is coming soon, when you will have to dress your limbs with airy clothes, to offer
them to those who will see you under your husband´s roof...Thus, your beautiful
clothes, as white as heaven, shall be rinsed into the waves...(Afterwards, when
Nausica addresses her father to ask for a chariot to take her to wash her clothes)
She told him: will you let me have the light-wheeled airy chariot ready; so that I can
take those neglected and darkened clothes to the river and let it turn them white
again? You deserve too much, you who own a seat among the sovereign councils,
you must have neat clothes around you. Five beloved sons you can see in your
house, two sons to be married and three whose youth still laughs in their unmarried
faces. These ones will go to dance with fresly cleaned clothes. And those things are
all in my care... Once they got to the silvery river flowing purely, and to the washing
stones wet by eternal water that sheds any stains, they untied the mules... Then from
the chariot, they let the clothes fall down from their arms into the river, among the
waves, which all got darkened; and in large grooves they threw them, treading with
58
fast feet to get them cleaned. Purged and neat from any dirt, one by one they hanged
them to dry on the shore, where the sea lapped the little stones..“ (NOVELLI, 2000).

The use of fuller´s earth

The English word “fuller”, as “foulon” in French or “fullone” in Italian, derives from the
Latin term “fullo”, indicating a person whose job was that of degreasing and
thickening clothes.
Before Homer´s description, two detergents were occasionally found out, river
mud and old urine. The first must be found by washing (sheep´s) fleece in the river.
The other detergent, old urine, was perhaps found by a woman who observed that
the baby´s bed which got wet was whiter if washed after a few days, especially in the
part which got wet with the urine.
The washing of woollen cloth with fuller´s earth was certainly practised in
Cyprus about 5000 BC. Sheeps were fully domesticated nearly thousand years
before. There were found in houses lumps of fuller´s earth, in 1969 carbon-dated
about 5000 BC. The greenish gray clay was rich in montmorillonite.

In Mesopotamia along the Tigris and the Euphrates the fuller´s earth were not
of high quality. It will be possible that fleeces and cloth were fulled in the river mud in
the earliest times. Later, other detergent materials were be used. Detergent materials
as wood ashes or soda were used when washing in a large tub in which the fuller
stirred the contents with a staff of pole because the alkali damaged the skin of the
feet. Finally, a special bath (mazûru) was used to beat the cloth. In the Akkadian
language fulling was called either “mazarū” or “kabāsu”. The former is named from
the fulling-billet “mazûru” and its primary mining is to tramble. Respectively these
words may represent fulling by hand and feet.
Ancient centres of the woollen industry were Mesopotamia and northern Syria,
there was no religious ban on the wearing of woollens, in difference to Egypt which
produced linen of exellent quality (ROBERTSON, 1986).
Sumerian clay tablets and a clay cylinder, found in Lagash (about 2500 B C),
describe the production of cloth, fulling and washing, and also the preparation of
soaps by mixing oil and potash in a volume ratio 1 : 5.5 and boiling the mixture. This
soap was used for washing and cleaning cloths and clothes. The Sumerians were
also aware of the preparation of medical and cosmetic scented soaps.
 59
The Stockholm papyrus
manuscript, found 1828 in a tomb in
Thebes and dated to 3000 BC,
describes a washing powder expec-
ially for wool. This powder was
composed of aqueous soda solu-
tion, Cimolian earth (clay from
Kimolos, an Aegean island north-
east of Melos), dispersed in vine-
gar, slaked lime, fine clay, and cau-
stic potash solution.
Also vegetable compounds
were added. Soap wort (Seifen-
kraut; Saponaria officinalis) and
Asphodill (Liliaceae). Soap wort
(but also Gypsophyllum (Gipskraut)
and Lychnis species1 (Lichtnelke)
cause faoming and cleaning due to
the presence of saponine, a vege-
Sumerian clay tablet (about 2 500) BC
table glycoside which can be pre-
sent in the plants up to 18 percent
(LAGERCRANTZ, 1913; VOLKE, 1989;
BENEKE, 1995a).
Medical prescribings and
treatments with oil and water are
known from Hammurabi´s time
(king of Babylonia, 1728 - 1686
BC). Remedies and cosmetics were
prepared from vegetable, animal
and mineralic substances (fuller´s
earth). Preparation of ointments
and emulsions was diversified and
up to 30 compounds were used.
The basic compounds were animal
Hammurabi code fats (wool fat, lanoline) and vege-
table oils; emulsifying agents were
gumarabic, slimes, proteins, casein etc. The papyrus manuscript Ebers (dated about
1600 BC, but representing a copy of a papyrus from 2500 BC) shows more than 700
remedies and therapies and also reports the use of urine for cures (BENEKE,
1995b). In Roman times, pieces of cloth were first steeped into old urine (very rich in

1
Lychnis is derived from the greek word meaning “lamp“ because the leaves of Lychnis
coronaria were used as wicks.
60
ammonia) or other alkaline solutions. Then they were heavily tread upon in a large
bowl or a basin containing mud, the so called “fuller´s earth”, or “creta fullonia“ in
Latin. Several rinses were needed with fresh water in order to remove the fuller´s
earth, which took away with it the main part of grease and dirt present into the fleece
(ROBERTSON, 1986; NOVELLI, 2000).

A fuller treading the cloth, and others rinsing

Indications of the use of the fuller´s earth, old urine as detergent and the cloth
washing can be detected in the Bible, particulary in the Old Testament. In the 20th
century, 19 km east of Jerico a mix of earth and ashes was found and dated back to
3000 BC. In this settlement was a local washerman of the time, the name of the
place has an arabian verb for “to wash”. Moreover, within the same area, a clay
source was not apparentely found. Still today, Israel does not have any clay reserves
of its own, as it still imports clays from Cyprus (ROBERTSON, 1986; NOVELLI, 2000).

The use of urine and salpetre

As seen before urea was an important additive in washing processes. In Rome urine
was collected. Large earthenware vessels “dolia curta” or “testae” were placed at
street corners or in the narrow streets between the houses, and collected by the
fullers when they had been filled by the passers-by. The urine of the toper had no
good quality and the fullers did not like them because the nitrogen content was too
low. It was just the most inveterate drinkers who had most often occasion to use the
urinals. Macrobius (about 430 AD) gives a double social condemnation of the wine-
bibbing dignitaries of his days:
“They sit at the gaming tables perfumed in a manner to which they have given
much forethought, and surrounded by courtesans. When it is the tenth hour, they
summon a slave to take them to the “comitium”, to find out what happening in the
forum: what the tribunes have decreed, what they have prohibited. Then they make
for the “comitium”, for fear of involment in personal responsibility for matters they
have not thought about. On the way, there is not an alleyway at which they do not
 61
stop to add to the contents of the urine vessels: their bladders beeing ever full
because of quantity of wine they drink. They come with abored air into the
“comitium”. They order the trial to begin, the parties concerned state their case, the
judge requires witness and goes out to urinate” (ROBERTSON, 1986).
Vespasian (9 - 79 AD; emporer of Rome 69 - 79 AD) collected a tax on the
products of public urinals, which was used in the fullers trade at the time. When his
son Titus (39 - 81 AD) complained about this method of raising money, Vespasian
handed him a silver denarius. “Does this smell?” he asked. Titus answered “Pecunia
non olet - money don´t stink”. From this very day public urinals in French are called
“Collones Vespasiennes” or short “Vespasiennes”.
Flavius Josephus (37 - 100 AC) recoun-
ted in the “War of Jews” that asphaltene
from the Dead Sea was solidified by
urine. Urine was spread on the aspha-
tene, after a certain time the liquid phase
was squeezed out.
Primitive people used urine to
transform the skin (animal fibers) in
leather. Another application of urine was
for dying. The Inuits (Eskimo) used an
extract of pine tree bark in urine for red-
dying of leather. In 1669, Hennig Brand
(died around 1710) was looking for the
philosopher´s stone but recovered the
element phosphorus. During concentra-
ting urine by evaporation in the absence
of air he observed a radiation, the typical
chemoluminescence of phosphorus. Guil-
laume François Rouelle (1703 - 1770)
dedected the urea in the urine.
Vespasian, emporer of Rome
During the medival age urine and
other nitrogen containing waste were used for formation of salpetre (nitre, KNO3)
which was required as a component in black blasting powder, a mixture of sulphur,
salpetre, and charcoal.
In the 18th century the army in Bavaria used salpetre formed from liquid
manure and found in the farmhouses. In the early hours representatives of the
“Salpeterkommission“ accompanied by soldiers, attacked the farms, removed the
floor boards and scraped off the salpetre. The farmers were not much enjoyed about
this procedure but found help by the catholic priests. The catholic church did not
allow to demage all parts and areas in the house which were used for religious
meditation. A lot of family altars were built (“Herrgottswinkel“), religious statues and
pictures of saints were distributed all over the house, the “Salpeterkommission“ was
62
often forced to restrict its activity to small areas. Is this the reason of the
religiousness of the Bavarian people in the country side? (KRÄTZ, 2001).

“Hergottswinkel“ in a bavarian house

Lanolin

Wool fat (Adeps lanae anhydricus; lanolin, from latin: lana = wool, oleum = oil) is
produced by the sebceous glands of sheeps and covers the skin and wool fibres to
protected the sheeps against weather factors and rain. It makes the coat hydrophobic
so that water trickles down. Before dying, this fat must be removed, e. g. by fulling
with fuller´s earth. Raw lanolin is a greasy, foul smelling mixture of different esters. It
contains more than 130 fatty acids, about 70 aliphatic alcohols (C14-C36) and 6
sterols. Oxidation removes the smelling and dying components so that lanolin smells
more agreably. It does not easily become rancid, takes up large amounts of water
and forms stable emulsions. Lanolin easily penetrates into the pores of the skin and
is, therefore, used as a basic component in ointments and creams. Furtheron, lanolin
is used for greasing cloths and leather and is an anti-rust agent (RÖMPP, 1990).
The Egyptian people also knew how to extract and use lanolin, because it was
used in the Egypt pharmacy and cosmetics. Dioscorides (first century AD) gave in
Greek a good description of how lanolin was prepared (LANGBECK, 1890):
“Wool-fat is called the grease out of filth of new shorn wool. You will prepare it
in this manner: Having taken sweet, newly shorn wool, not treated with soap wort
(Saponaria officinalis), wash it in hot water, at the same time squeezing out all the
filth; having put this in wide-mouthed vessel, pour water over it, and agitating it
violentely until froth is formed, pour it out again of the vessel; or agtiate it vigorously
with a stick until much scum and filth collects; therupon sprinkle sea water over it,
 63
and when the fat swimming on the top has set, put it into another earthenware
vessel; pour more water into the tub, stir it up again, sprinkle the froth with sea water
and take it out again, and do so until after the fat has been exhausted, [when] no
more froth gathers. Smooth the collected wool fat with the hand, and if there is any
filth remove it forthwith, squeezing out the first water and pouring on fresh and
agitating it with the hand until, applied to the tongue, it does not bite but has an
astringent taste and looks brilliant and pure and white. In this condition store it away
in an earthenware vessel. But all must be made in hot sunshine. Some treat the fat
by washing it in cold water, rubbing it with hands as woman [do with] wax, thus
rendering it whiter. Others, after washing the wool and squeezing out the grease, boil
it together with water in a cauldron over a slow fire, and having gathered the fat
which swims on the top they wash it with water, as has been said, and straining it into
an earthenware dish containing hot water, and concerning it with a linen cloth they
place it into the sun until it becomes sufficiently thick and white. Some pour off the
first water after a lapse of two days, and pour on fresh. Better is that which has not
been treated with soap wort and is smooth, smelling of the oily wool, washed with
cold water in a shallow dish, and having been bleached and containing in itself no
hard or solid [particles], as for instance that which is adulterated with wax or tallow. It
possesses a power to close up wounds; to soften, especially with melilot and butter“
(ROBERTSON, 1986).
Langbeck wrote that Nicolas Culpeper had published in 1653 “The manner of
preparing Oesypus”, which was based on Dioscorides (first century AD). In 1882
Braun and Liebrich took out a patent for the purificication of wool fat, which, mixed
with water, they called “lanolin“. The product was dirty yellow and still contained free
fatty acids from the soap. Langbeck and Ritsert took out a German patent in 1886 to
purify wool fat. At this time, LANGBECK (1890) published the story of purifying wool fat
from Dioscorides (HUSEMANN, 2002).

Dying

Cleaning and decreasing of wool and cloths was an important condition for dying. In
ancient Egypt the job of washer had a special importance, these people were not
found in lower social classes. A few hieroglyphic texts report washing operations.
More than 4000 years ago the Egyptians not only used vegetable dyes, animal
dyes (purple) and a few mineral pigments for dying wool and cloths but also knew the
complicated procedure of dye vatting with indigo.
Wool was often first dyed blue with indigo and then dyed again with some
other dye like madder (Krapp); the result yielded a purplish colour. A recipe for this
re-dying with madder can be found int the earliest alchemical papyrus. Ash is
scattered over the indigo-dyed wool, and then trodden with the feet. Then the wool
was rinsed in water and clay (fuller´s earth) and pickled in alaun. The madder was
dissolved, together with some flour of beans to make the water softer. The treated
64
wool was dyed for the second time. In the last century fuller´s earth has been used
for preventing indigo-dyed uniforms from bleeding (ROBERTSON, 1986).
Saffron-dyed bandages were found on Egyptian mummies of the 12th dynasty
(about 2500 BC) (BENEKE, 1995c).
The ancient method of preparing woad was by fermentation in urine. Dyers did
not always escape the odium experienced by fullers. In an Egyptian papyrus (about
2000 BC) it was said of a dyer: “His hands stink, they have the odour of rotten fish,
and he abhorreth the sight of all cloth”.

Kimolian and other earths

In Greek theatre Aristophanes (c. 445-385 BC) was the first to mention Cimolian
earth. In the “Frogs“ (c. 405 BC) is written:

“That Cleigenes shifty and small,

the wickedest bathmann of all
Who are lords of the earth, which is brought
from the isle of Kimolos, and wrought
with nitre and lye into soap
not long shall be next us, I hope“.

Dioscorides confirms the value of this mixture that the best soap is made with nitre
and kimolian earth. The product was a body detergent and not a fulling agent. The
mixture, to be more precise, consisted of sodium montmorillonite, an impure form of
sodium carbonate, and plant ash. The products of the reaction being sodium and
potassium montmorillonite and calcium carbonate. Kurd Endell (1887 - 1945) and
Ulrich Hofmann´s (1903 - 1986) process for transforming calcium montmorillonite into
sodium montmorillonite was a German patent by S. Erbslöh, 1934 (British patent 447
710; 1935):
The calcium bentonite was dispersed with water and 2-2.5 % (w/w) sodium
carbonate. The diluted slurry was allowed to stand for a certain time before the
product was filtered, washed and dried. The dried material consisting of sodium
montmorillonite and calcium carbonate become thixotropic when 15-20 % (w/w)
water were added. As drying was expensive, Ulrich Hofmann and Kurd Endell
changed the process 1936. The sodium carbonate was added to the calcium
bentonite containing 20-30 % moisture. By intense mixing (grinding) a product very
similar to the product of the wet process was obtained. Hofmann and Endell took out
a German and British patent (458 240) in addition 447 240. Aristophanes was cited to
legal counsel (ROBERTSON, 1986a; NOVELLI, 2000).
 65
Plant dyestaff in ancient times
(VOLKE, 1988; BENEKE, 1995c)

Color Name Latin Family Organ Dyestaff

English (German) Term
Red Madder Rubia tinctoria Rubiaceae Roots Alizarin,
(Färberröte, Dihydroxy-
-wurzel, Krapp) anthraquinone,
Purpurin
Red Safflower Carthamus Compositae Blossom Safflor red,
False Saffron tinctorius Carthamin
(Saflor, Falscher
Safran,
Färberdistel)
Blood red Alkanet Alkanna tincoria Boraginaceae Roots Alkannin,
(Alkannastaude)
Dark red Garnet, Inkberry, Phytolacca Phytolaccaceae Sape of berry Phytolacca red
Pigeonberry, americana (Kermes red)
Pokeweed,
Scoke
(Kermesbeere)

Orange red Henna, Lawsonia Lythraceae Leaves 2-Hydroxy-1,4-

Mignonette-Tree inermis naphtoquinone
(Henna)

Gold yellow Greater Chelidonium Papaveraceae Roots Chelidonine

celandine, Majus
Swallow-wort,
(Schöllkraut,
Schöllwurz)

Yellow Saffron Crocus sativus Iridaceae Stigma Crocin,

(Safran) Polychroit

Yellow Wild Mignonette Reseda luteola Resedaceae Green plant Luteolin

(Färberkraut, sections
Wau)

Yellow Dyer´s Genista tinctoria Papilionaceae Blossom Glucosido-

Greenweed genistein
(Färberginster,
Gilbkraut)
Blue Litmus lichen Rocella tinctoria Rocellaceae Total lichen Phenoxazon-
(Lackmus- and further (fermentation) derivative
flechte) species

Dark blue Dyer´s Woad Isatis tinctoria Cruciferae Leaves Indigo,

(Färber-Waid) (fermentation) Indigoblue

Dard blue Indigo Indigofera Papilionaceae Branches Indigotin,

(Indigostrauch) tinctoria (Leguminosae) Indigoblue
Indigofera
suffruticosa (=
Indigofera anil)

Purple Orchella Weed Rocella tinctoria Rocellaceae Total lichen Phenolorcinol,

(Orseilleflechte) (fermentation) Orcein
66
Theophrastus (372 - 287 BC), born at
Eresos on the island of Lesbos, was the son of
Melantas, a fuller. He wrote one of the earliest
known scientific works “On Stones” (about 314
BC) dealing with stones, industrial minerals
and artificial products derived therefrom.
Theophrastus wrote in Greek:
„...there are, roughly speaking, three or
four natural earths which are useful as well as
unusual, namely the Melian, the Cimolian, the
Samian, and finally besides these the
Tymphaic, otherwise known as gypsum...”
Theophrastus says nothing more about
the Kimolian earth. It must be well known.
Melian earth, used in painting pictures, was
Theophrastus
rough, not greasy and of loose texture, and
probably the naturally-occurring fine silica, known now as “Milowite”. Dioscorides
adds that it makes a sound when rubbed between the fingers. Samian earth,
probably a kaolin, was extracted from a narrow sloping vein. The lower quality
material was nearest the headwall and footwall; and the best quality, selectively
mined, bore the trade name “The Star”, either because it was stamped with this
figure or because it was highly reflecting. According to Dioscorides it clings closely to
the tongue; this and its use in plasters and salves also suggest that the clay was
kaolin. Deposits of kaolin, no doubt from a more accessible site, were worked in
ancient times in the island for making ceramic ware. The “Star” grade of earth,
according to Theophrastus, was used mainly, if not entirely, for treating cloaks,
presumably because its white crystallites gave the cloth a clean and white
appearance as in pipe-clayed webbing or china clay-coated art paper (ROBERTSON,
1958, 1986).
Pliny the Elder (23/24 - 79 AD) explicitly quotes the so-called “Terra Cimolia”
in his “Naturalis historia” (77 AD). For this work he has used over 2000 works from
elder authors. He refers to a quotation of a Greek physician from Anazarba, Dioscuri
Pedanio, who lived in the first century AD near Tasso, Cilicia. Pliny describes
deposits of Kimolos clay, distinguishing them in two types, a white one and a reddish
one. He cites other varieties in Thessaly, Lycia and near Bubo. He wrote also about a
Sardinian quality, used exclusively for white garments, not for coloured ones. It must
be known that until now an exellent bentonite quality is found on the island of
Kimolos.
Pliny the Elder wrote in his “Naturalis historia”: “Cimolean creta has another
use, too - the whitening of clothes. The kind which comes from Sardinia, and is called
Sarda, being employed only for white garments and useless for coloured ones, is the
least valuable of all kinds in Cimolia. The Umbrian sort and the one they call Saxum
 67
are more highly prized. Saxum has the property of increasing in bulk when soaked in
water and is purchased by weight, whereas Umbrian is sold measure. The only use
of Umbrian creta is for imparting lustre to garments.
This routine, therefore, must be
observed: the garment is first washed
with Sarda, them fumigated with sulphur,
and finally scoured with Cimolian creta,
provided that the dye is fast, for bad dye
is detected by this procedure and
blackens, and its colour is destroyed by
sulphur. On the other hand, the valuable
fast colours are softened by Cimolian
creta, with freshens and brightens hues
which have been dulled by sulphur. If
thegarments are white, it is better to
follow the sulphur by saxum, but this
cannot be used with colours. Instead of
Cimolian earth, the Greeks use the
gypsum of Tymphaea“. The fumigation
with sulphur was to bleach the cloth and
was a standard method early last century
in Italy (ROBERTSON, 1986, NOVELLI,
2000).
Gaius Plinius Secundus, Pliny the
Elder, died on sulphur dioxide poisoning
when Pompeii was buried in the ash of
Mount Vesuvius in 79 AD. He went to
investigate the type of violent volcanic
eruption which bear his name (Plinian
eruptions), and to see if he could help in
any way.
Excavations at Pompeii have revealed
better than any literary accounts the art
of the fuller. Pompaii was at the time of
its overwhelming one of many cloth
manufacturing towns in Italy, and
prominent as a center of production of
finer quality materials. In 1929 four large
Gaius Plinius Secundus “fullonicae” were excavated in Pompeii.
One belongs to the freedman Stephanus,
whose installations are the best preserved.
68

Fullonicae Stephani in Pompaii

Fulling millers in the medival age

The mills (for milling grain) and paper

mills (to chop up rags, the basis material
of paper before the introduction of
cellulose) were invented in the medival
age. The first paper mill was built in
Nuremberg in 1391. The mills were
water-driven. A few years later, in 1408,
a windmill was constructed in the area
which is now Netherland. This windmill
was used to pump water from inland
areas into the sea. Mills were also built
for washing and combing wool and
cloths. The profession of “fulling miller”
came into being, a profession which
disappeared in the time of
industrialisation. This miller produced
Paper mill in Nuremberg (1391) loden wollen fabric in the following way:
After shearing the sheeps, cleaning and
removing the fat, the wool was combed and weaved in wooden vats. The slack fabric
was soaked in a dispersion of soap and fuller´s earth. The textile was fulled with
water-driven wooden mallets to felt and condense the fabric. Finally the cloths were
lifted and lowered by a water-driven shaft.
 69

The English fuller´s earths

In Great Britain the fuller´s earth was

not only used for fulling cloths but also
in pharmaceutical and cosmetic appli-
cations in form of powders and oint-
ments, in particular in the 17th century
after detecting deposits of fuller´s earth.
These deposits were located in a
circular around London, in Surrey
around Reigate, in Kent at Madstone,
and in Bedfordshire near Woburn. The
English fuller´s earth was particularly
effective. At the continent, deposits
Fuller´s Earth Cream existed in 1929 in Bohemia, Rhône area
(France), Italy (western side of the
Apennine Mountains) and Transsilvania (Romania). Large deposits were found in the
Caucasus near Kutais in Georgia.
The process of fulling was described 1847 in a Handbook of Technology:
“The important component for fulling is rotted urine containing ammonium
carbonate. Further impartent additives are soap and fuller´s earth, a special sand-
free clay. Clay and urine are mixed, and the soap is dissolved in the mixture. Other
fullers start with fulling in urine and in a subsequent step with aqueous soap solution“
(KNAPP, 1847).
Because of the need of urine, textile factories were often placed near
barracks. Today fulling is no longer in use; the wool is now cleaned with special
washing powders.

Bleaching earths

An American traveller in the Middle East observed that people used clay to lighten
olive oil. Fairnanks & Co. in Chicago tested the clays to bleach cotton seed oil. The
best results was obtained with the English fuller´s earth. This earth was then used for
bleaching vegetable oils in USA since 1878, and became the most important fuller´s
earth on the European and American market. However, about ten years later, John
Olson found clays in Arkansas (in 1891) which were similar to the English fuller´s
earths. When, a few years later, large deposits were found near Quincy in Florida,
the monopoly of the English fuller´s earths was broken.
The Florida earth (about 33 000 tons in 1912) was mainly used for oil refinery.
Vegetable and animal oils were purified with English fuller´s earth (about 20 000 tons
in 1912) up to the First Word War.
70
Production of Fuller´s Earth by decades (1854-1970) in United Kingdom
(ROBERTSON, 1986)

Period Thousand tons Average tons

Per annum

(1854-1860) 85 12140
1861-1870 81 8100
1871-1880 Not known not known
1881-1890 154 15400
1891-1900 178 17800
1901-1010 242 24200
1911-1920 303 30300
1921-1930 239 23900
1931-1940 203 20300
1941-1950 446 44600
1951-1960 790 79000
1961-1970 1347 134700
Total:
1854-1970 4068

Before bleaching with fuller´s earths, all types of oil, fats, and waxes were
bleached with very different materials, in particular residues from melts for production
of prussiate of potash and animal charcoal. These expensive materials adsorbed the
dying components in oil but also bound large amounts of the oil it self (up to 2.5 g oil
per g adsorbent !).
Production and use of bleaching earths increased in USA, and 1924 allmost all
material was mined and produced in the South-States of USA. The fuller´s earths
were dried, milled, and divided into several fractions, but unfractionated material was
also used.
As only a few deposits of fuller´s earths were found in Germany (Saxonia,
Westerwald, Silesia), several thousand tons of American and English fuller´s earths
were imported.
Since 1924 modified clays from Death Valley, bentonite from California,
Nevada (Utah), Wyoming (Montana) etc. began to threaten the market of the fuller´s
earths. Following an American patent these bentonites were treated with sulfuric acid
and became superior to natural fuller´s earths (ECKART AND WIRZMÜLLER, 1929).

Bleaching earth industry in Bavaria

The bleaching earth industry in Bavaria goes back to 1904. During ground
excavation one of the future founders of the Pfirschinger Mineralwerke in
 71
Kitzingen/Main discovered a bentonite deposit. The white and lightly bentonites were
used as white pigments (Pfirschinger Weißerde). The more yellow types were
marked in 1906 as bleaching earths.
The Pfirschinger Mineralwerke Gebr. Wildhagen und Falk in Kitzingen/Main
developed in 1906/07 the acid treatment of the bentonites to increase the bleaching
ability, and a production facility was built in 1908. An amount of 1000 tons of this
bleaching earth was selled in 1909 under the trade name “Frankonit“.
An other bentonite deposit was discoverd by von Delling in Kronwinkl near
Moosburg during ground exacavation for a villa. This white material could not be
used for ceramics, neither for production of cement and in the chemical industry. It
was only used as binder (“Fixiererde“) in paints. The Erdwerke Kronwinkl Franz
Schmid & Co. were founded in 1906. Shortly later the name was changed in
Tonwerke Moosburg A. und M. Osterrieder, today Süd-Chemie AG.
Dr. E. Theobald (partner of this company) invented in 1909 the acid-activation
of bentonite by hydrochloric acid without knowing the procedure of the Pfirschinger
Mineralwerke. Since 1909 this bleaching earth was and is marked as “Tonsil“
(ECKART AND WIRZMÜLLER, 1929).
The production of bleaching earth from bentonites comprizes the reaction with
acids at boiling temperature, washing with water, drying and milling. During the acid
attack the interlayer cations are replaced by protons and the octahedral cations (Al3+,
Mg2+, Fe2,+, Fe3+) are dissolved. The products are X-ray amorphous, of high SiO2
content, and show a high specific surface area and micro- and mesopores (FAHN,
1973). The bleaching power depends on the activation procedure (acid
concentration, temperature, pressure, time) (FAHN, 1973).
As a patent for bleaching earth preparation was not submitted, the procedure
was kept secret, neverless, it became generally known within a short time. The
bleaching earth preparation was promoted by the First World War. Because of
insufficient washing, the earths were often of low quality. The materials retained
some amounts of acid which reduced the bleaching power.
The Pfirschinger Mineralwerke in Kitzingen/Main tried in 1919 to receive
supplementary protection for their procedure by a patent which was granted by D. R.
P. 339 919. Compared with a few patents before (Ludwig Kern D. R. P. 304 076;
Josef Kohlndorfer D. R. P. 305 452; Westfählische Mineralölwerke Schmitz und von
der Heide D. R. P. 315 467), D. R. P. 339 919 was of much more practical
importance. In the patent the procedure is described in the following way:
“It is known that filter and clearing materials such as bone char, resides of the
preparation of prussian of potash and clarifying earths are washed with diluted
inorganic and organic acids before using. Washing removes impurities and by
dissolving certain compounds increases the effectiveness. Experiments of the
inventor have shown that the clarifying and bleaching power of bleaching earths for
oils, fats, waxes, paraffins, mineral oils etc. mainly depends on the amounts of
hydrated silica in the bleaching earth. Reacting natural silicates with sufficiently
72
strong acids leads to formation of this silica which strongly enhances the clarifying
and bleaching effect. Further experiments have shown that hydrochloric acid can be
fully or partially replaced by other acids. Silicates have to be reacted with the acid
until they are decomposed to silica to a large extend. There is also the possibility to
dissolve the silicates with aqueous or melted alkaline compounds (for instance soda)
and in a following step to precipitate the silica with acids. The temperature at which
the silicates are decomposed depends on the agents used and the intented degree
of decomposition. It also depends on the reacting component and the degree of
decomposition if the reaction is carried out in air, at pressure or in vacuum. The
obtained bleaching earth may be washed with water and dried. A special procedure
is the use of alumosilicates like clay, kaolin etc. Their content of natural silica can
strongly enhanced by the described method. One finds in the journal “Der
Seifenfabrikant“ (1908, page 942) the „bleaching earths are treated with concentrated
acids like concentrated hydrochloric and sulfuric acid“. However, the main process of
this procedure is the removal admixtures. Even if a certain decomposition of the
material is observed, the experiments reported in the journal reveal that the
bleaching effect is not influenced in a way as described in the present procedure. As
reported in the journal the bleaching power of the earth treated in concentrated acids
can even be reduced in comparison with the untreated earth.“

(a) silicate layers of montmorillonite

(b) disorientation of acid-treated montmorillonite layers with amorphous
silica in edge regions of crystallites (FAHN, FENDERL, 1983)

The patent claim of D. R. P. 339 919 is: „Verfahren zur Erhöhung der Ent-
färbekraft von Silikaten für Fette, Öle, Wachse, Paraffin, Mineralöle und dergl., da-
durch gekennzeichnet, daß die Kieselsäure natürlicher Silikate durch aufschließende
Behandlung, insbesondere mit genügend starker Salzsäure, ganz oder größtenteils
in Kieselsäurehydrat übergeführt wird.“
 73
(Procedure for increasing the decolourising power of silicates for fat, oils,
waxes, paraffin, mineral oils and others, where the silicic acid (“Kieselsäure“) of
natural silicates fully or partially is transformed by decomposition, especially with
sufficiently concentrated hydrochloric acid, into hydrated silica (“Kieselsäurehydrat“)).

World productions (in thousands tons) of bentonite in

the decade 1984-1993
(NOVELLI, 2000)

1984 1985 1986 1987 1988 1989 1990 1991 1992 19931
Main
Regions
EU 1159 1289 1921 1892 1358 2063 1559 1728 1697 1708
Other Europe - - 148 154 125 129 103 85 56 51
Africa 143 83 161 204 213 215 209 206 170 166
Asia 552 621 663 708 678 727 804 847 822 814
America 3733 3554 3101 3042 3408 3563 3977 3911 3331 3468
Oceania 46 35 43 30 37 36 36 35 35 35
Total MEC 5633 5582 6037 6030 5819 6733 6688 6812 6111 6242
Other NMEC 3194 3205 3241 3253 3226 3229 2957 2604 2181 1785
World Total 8827 8787 9278 9283 9045 9962 9645 9416 8292 8027

Main
Countries
Argentinia 126 147 146 109 174 119 123 136 82 90
2 1 1
Brazil 201 236 229 217 147 118 180 130 130 1301
Germany3 - - 179 167 197 515 577 583 581 575
Greece 314 506 346 404 444 601 554 559 552 544
Italy 304 297 300 313 319 234 228 385 360 300
Japan 410 462 478 469 455 526 549 554 534 519
Mexico 268 268 137 130 164 124 145 145 136 127
1
Romania 180 180 185 180 180 175 150 150 120 120
1 1
Spain 73 90 115 103 104 143 151 150 150 1501
USA 3119 2898 2552 2546 2871 3112 3474 3432 2954 3093
1
USSR/CIS 2880 2890 2900 2900 2900 2900 2700 2400 2000 1600
1 2 3
Units: : estimate values; : beneficiated; : includes the former East Germany

D. R. P 339 919 provided the Pfirschinger Mineralwerke the monopoly for

preparation of an effective bleaching earth. Nevertheless, more and more companies
developed which tried to keep secret their procedure but it was evident that their
procedures were similar to the patented procedure or even identical. A long patent
74
controversy developed, and at June 23, 1924 the “Reichspatentgericht“ decided that
D. R. P. 339 919 has to be considered not granted (ECKART AND WIRZMÜLLER, 1929).
Bleaching earths are world-wide produced and used for refining,
decolourisation, clarifying and stabilisation of vegetable and animal oils and fats, of
mineral oils, fining of wine, must, juices, stabilisation of beer, clarifying of saccharose
syrup, catalysator for oil cracking, filters, adsorbents of radioactive compounds,
binding of oil on water.

Organic activated bentonites

John W. Jordan Jr. (1912 - 2001) was the first fellow who developed a research
group on organophilic bentonites (1949), today known as bentones (JORDAN, 1949;
JORDAN, HOOK, FINLAYSON, 1950; JORDAN AND WILLIAMS, 1954). Besides alkali
activated and acid activated (bleaching earths) organophilic bentonites are used in
many applications.
 75
Application of acid-activated (a), soda-activated (s),
organic-activated (o) and raw (r) Bentonites

Areas of applications Uses Type of

activation
Agriculture, Soil improvement; r, s
Horticultere Composting r, s
Supporting dispersions for r, s
cut-off diaphragma wall
Constructions,
Shield tunneling r, s
Building industry Subsoil sealing; r, s
Antifricton agents for r, s
pipejacking and shaft
sinking
Plasticizing of organic r, a
Ceramics masses, improvement of
strength;
Fluxing agents r, a
Sulphur production: r, a
refining, decolourising,
bitumen extraction;
Catalysts r, a, s
Chemical industry Catalyst supports; r, a, s
Supports for insecticides, r, a, s, o
fungicides; r, a, s, o
Fillers; r, a, s
Dehydrating agents; r, a, s
Adsorbents for radioactive
materials
Regeneration of organic a
fluids for dry cleaning;
Polish and dressings; r, s
Cleaning industry Additives for washing and r, s
cleaning agents and soap
production
Forest and water r, a
conservation: Fire
extinguishing powders;
Binding agents for oil on r, a
water;
Environment Animal husbandry: r, s
manure treatment, r, s
cat litter; r, s
Water and waste water r, a, s
purification;
Sewage sludge pellettising; r, a
Barriers r, s
76
Refining, decolourising, r, a
purification and
stabilisation of vegetable
and animal oils and fats;
Foodstaff industry Fining of wine, must, and r, a, s
juices;
Beer stabilisation; r, a, s
Purification of saccharine r, a, s
juice and syrup
Binding agents for special r
moulding sands;
Binding agents for s
synthetic moulding sands,
Foundries
core sands;
Binding agents for o
anhydrous casting sands,
for thickening blackwashes
Refining, decolourising, r, a
purification and
stabilisation of mineral oils,
Mineral oil industry
fats, waxes, and paraffines;
Drilling fluids; r, a, o
Thickening of greases; o
Catalysts for oil cracking r, a
Thickening, thixotroping, s, o
stabilising, and antisettling
Paints and varnish
agents for paints and
industry varnishes;
Coating materials; s, o
Sealing cements, waxes, s, o
adhesives
Pigment and colour r, a, s
developer for carbonless
Paper making copying paper; r, a, s
Adsorption of impurities in
circulation water; r, a, s
De-inking in waste-paper
recycling
Bases of creams, oitments r, a
Pharmaceutical and cosmetics;
Drug carriers, powders, r, a, s
industry, cosmetics
ointments, tablets;
Stabilisator of emulsions; r, o
Odour control, liquid r, a, s, o
adsorption
Emulsification and a, o
Tar exploitation thixotroping of tar-water
emulsions;
Tar and asphalt coatings a, o
 77
Acknowledgement
We thank Dr. Helmut Uhlarz, Institute of Botany and Botanical Garden, Section
Systematical Botany, University of Kiel, for translations and corrections in Table
“Plant dyestaff in ancient times“.

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