Note: Descriptions are shown in the official language in which they were submitted.
11'127i.~`
It has been reported (see, for example, Bach,
G. Fiehn, Zellstoff und Papier 21, 3 (1972); H.H.Holton,
Pulp and Paper Canada 78, 19 (1977); U.S. Patent
Specification 4,012,280; U.S. Patent Specification
4,036,680; U.S. Patent Specification 4,036,681;
Canadian Patent Specification 986,662; Japanese Laid-
Open Specification 112,903/75; Japanese Laid-Open
Specification 43,403/76; Japanese Laid-Open Specifica-
tion 109,303/76 and East German Patent Specification
98,549) that anthraquinone derivatives and certain di-
ketohydroanthracenes have a favourable action in certain
processes for the production and bleaching of pulp from
lignocellulose materials, such as wood, straw and
bagasses, when they are employed in amounts of 0 001 to
10% by weight, relative to the lignocellulose material.
Besides anthraquinone, anthrahydroquinone and Diels-
Alder adducts of butadiene and its derivatives and p-
benzoquinone or 1,4-naphthoquinone, the mono- and poly-
alkyl, -alkoxy, -amino, -hydroxy and/or -sulpho deriva-
tives of these compounds are also recommended for this.In the following text, these substances are collectively
termed additives.
The additives are in general accessible in the
form of powders. However, introduction of such
pulverulent additives into processes for the production
of pulps from lignocellulose materials and for bleach-
ing of the pulps presents problems. When the pul-
verulent additives are added to the lignocellulose
material to be employed, it should be taken into con-
sideration that the finer constituents of the additivespass into the environment in the form of a dust and are
thus partly withdrawn from the intended use, are a
nuisance to persons working in the vicinity of the point
of addition and can give rise to the danger of dust
explosions. Furthermore, uniform distribution of the
relatively small amounts of the required additive is
Le A 19 408
. .
:; ~
114~714
difficult. However, uniform distribution of the additive is
desirable in order to achieve a uniform pulp quality.
Uniform distribution of the additives is moreover made
more difficult by the fact that the additives are in general only
very slightly soluble in water and in the aqueous electrolyte
solutions used for the production of pulp (for example only
6 . 10 4 g of 9,10-anthraquinone dissolve in 1 1 of water at 50).
Furthermore, the additives are so poorly wetted by water
and aqueous electrolyte solutions such as are used in the
production of pulp that the finer constituents of the pulverulent
additives cannot be stirred in or can be stirred in only with
difficulty and float on the surface in the unwetted state, air being
included in some cases. The additives moreover have a relatively
high specific density (for example anthraquinone has a specific
density of 1.438 g/cm3 at 20C), so that the coarser constituents
of the pulverulent additives which can be stirred into water or
the electrolyte solution rapidly settle again, and after the
mixture has stood for a short time, a compact layer which can only
be stirred up again with difficulty is formed on the bottom of the
vessel. Introduction of the additives directly into the digesting
liquor, into the mixture of lignocellulose material and digesting
liquor or in the form of a slurry in water or dilute electrolyte
solutions is thus likewise no reliable way of achieving uniform
distribution of the additives.
The present invention now provides granules of an
organic cyclic compound containing keto and/or hydroxyl groups,
suitable for use in the production and bleaching of pulp from
2~
lignoceliulose materials, said compound being selected from the
group consisting of (a) p-benzoquinone, (b) l,4-naphthoquinone,
(c) 9,10-anthraquinone, (d) Diels~Alder adducts of a 1,3-diene
and p-benzoquinone or l,4-naphthoquinone, (e) monoalkyl, dialkyl,
hydroxyl, amino, alkoxy or alkylamino derivatives of such
compounds, and tf) the reduced forms of (a) to (e), said granules
comprising 60 to 99 % by weight of said organic cyclic compound,
and 40 to 1 % by weight of surface active agent.
Organic cyclic compounds containing keto and/or hydroxyl
groups which can be employed in the granules according to the
invention are, for example, 9,10-anthraqu-none, 2-methyl-
anthraquinone, 2-ethylanthraquinone, 2,3-dimethyl-9,10-
anthraquinone, 2,6-dimethylanthraquinone r 2,7-dimethylanthraquinone,
2-aminoanthraquinone, l-methoxyanthraquinone, 1,4,4a,9a-tetra-
hydro-9,10-diketoanthracene, 2-ethyl-1,4,4a,9a-tetrahydro-9,10-
diketoanthracene, 2,3-dimethyl-1,4,4a,9a-tetrahydro-9,10-
diketoanthracene, 1,4,4a,5,8,8a,9a,10a-octahydro-9,10-diketo-
anthracene, l,3-dimethyl-1,4,4a,9a-tetrahydro-9,10-diketoanthracene
and 2,3,6,7-tetramethyl-1,4,4a,5,8,8a,9a,10a-octahydro-9,10-
diketoanthracene. 2 or more of these substances can also beemployed. It is also possible to use compounds which carry 2 or
more of the substituents mentioned, for example hydroxyl groups
and amino groups. Preferably, however, only one of the substances
is employed, and 9,10-anthraquinone is very particularly preferred.
The organic, cyclic substances containing keto and/or
hydroxyl groups, in particular 9,10-anthraquinone, are employed in
preparing the granules according to the invention in a finely
r ~ 3
7:14
divided form. For example, the organic, cyclic compounds
containing keto and/or hydroxyl groups, in particular 9,10-
anthraquinone, can consist to the extent of at least 80% by
weight of
~ 3a-
1~27~14
particles with particle sizes of less than 10 ~m.
The organic, cyclic substances containing keto and/or
hydroxyl groups, in particular 9,10-anthraquinone,
preferably consist to the extent of at least 80% by
weight of particles with a particle size of less than
5 ~m.
The organic, cyclic compounds containing keto
and/or hydroxyl groups can be converted into such a
finely divided form by grinding. Such a grinding
operation can be carried out, for example, using the
customary apparatuses for dry comminution, such as ball
mills, rotor-stator mills, pinned disc mills, hammer
mills and jet mills, if appropriate with suitable down-
stream sifters. The jet mills can be operated, for
example, with air or steam.
Virtually all the cationic, non-ionic and
anionic surface-active agents can be employed as the
surface-active agents in the process according to the
invention.
Examples of possible cationic surface-active
agents are quaternary long-chain and/or oxyethylated
amines, quaternary pyridinium compounds or long-chain
phosphonium compounds. Long-chain in this context
means a carbon chain with at least 4 C atoms, preferably
with at least 6 C atoms.
Particular examples of cationic surface-active
agents are: trimethyl-hexadecyl-ammonium bromide, cetyl-
pyridinium bromide, lauryl-dimethylbenzyl-ammonium
chloride, monoesters of triethanolamine with stearic
acid in the form of formic acid salts or acetic acid
salts, N-lauryl-methylbenzimidazole hydrochloride and
dodecyl-trimethyl-phosphonium bromide.
Most of these compounds and other cationic
surface-active agents which can be used are described,
for example, in K. Lindner, Tenside - Textilhilfsmittel -
Waschrohstoffe (~urface-active Agents - Textile
Auxiliaries - Detergent Bases), Volume 1, pages 963 to
1041 (1964).
Le A 19 408
~14~71~
Examples of possible non-ionic surface-active agents are
addition products of alkylene oxides, in particular ethylene oxide,
and higher fatty acids, alcohols, phenols, acid amides, mercaptans,
amines or alkylphenols. The addition products can be obtained, for
example, from 5 to 50 mols of alkylene oxide and 1 mol of fatty
acid, alcohol, phenol, acid amide, mercaptan, amine or alkylphenol
containing at least 4, preferably at least 6, C atoms. Other
possible non-ionic surface-active agents are addition products of
alkylene oxides, in particular ethylene oxide, and polypropylene
oxide or sugars, as well as oxyethylated and non-oxyethylated
sugar derivatives, such as fatty acid esters of pentaerythritol
or of sucrose.
Particular examples of non-ionic surface-active agents
are addition products of 5 to 20 mols of ethylene oxide and stearic
acid, oleyl alcohol, polypropylene glycol, nonylphenol, oleic acid
amide or dodecylamine.
Most of these compounds and other non-ionic surface-active
agents which can be used are described, for example, in
N. Schonfeldt, Grenzflachenaktive Ethylenoxid-Addukte (Surface-
Active Ethylene Oxide Adducts), pages 42 to 95 (1976) and in
K. Lindner, Tenside - Textilhilfsmittel - Waschrohstoffe
(Surface-Active Agents - Textile Auxiliaries - Detergent bases),
Volume 1, pages 837 to 917 (1964).
Anionic surface-active agents are preferably employed in
the granules according to the invention. Examples of possible
anionic surface-active agents are alkylsulphonates, sulphated
unsaturated higher fatty acids, sulphonates of polycarboxylic acid
esters, alkylbenzenesulphonates, sulphated aliphatic alcohols,
~ -5-
,.. .
ll~Z7~4
adducts of ethylene oxide and higher amines, acids, phenols or
alcohols, which adducts have been converted to acid esters with
an inGrganic polybasic acid, such as phosphoric acid or especially
sulphuric acid, as well as ligninsulphonates or derivatives of
ligninsulphonates, condensation products of aromatic sulphonic
acids and formaldehyde, and polyphosphates.
Particular examples of anionic surface-active agents are:
sodium dodecylsulphonate, sodium laurylsulphate, sodium
dodecylbenzenesulphonate, diisobutylnaphthalenesulphonate, acid
sulphuric acid esters of the addition product of 2 mols of
ethylene oxide and 1 mol of nonylphenol, sodium dioctyl-
sulphosuccinate, condensation products of cresol, 2-naphthol-6-
sulphonic acid and formaldehyde, and sulphonic acids of naphthalene,
terphenyl or ditolyl ether, in each case as condensation products
with formaldehyde. All the anionic surface-active agents are
preferably employed in the form of their alkali metal salts and/or
ammonium salts.
Most of these compounds are other anionic surface-active
agents which can be used are described in K. Lindner, Tenside -
Textilhilfsmittel - Waschrohstoffe (Surface-Active Agents -
Textile Auxiliaries - Detergent Bases), Volume 1, pages 571 to
835 (1964).
Lignin-sulphonates and/or condensation products of
aromatic sulphonic acids and formaldehyde, for example the
lithium, sodium, potassium, magnesium, calcium and/or ammonium
salts of lignin-sulphonic acid, are particularly preferably
employed as surface-active agents in the granules according to the
-6-
714
invention. Any desired mixtures of anionic and non-ionic
surface-active agents can also be employed.
The surface-active agents can be employed, for example,
in an amount such that the dried granules contain 60 to 99% by
weight of organic, cyclic compounds with keto and/or hydroxyl
groups and 40 to 1% by weight of surface-active agents. The
surface-active agents are preferably employed in an amount such
that the dried granules contain 80 to 90% by weight of organic,
cyclic compounds with keto and/or hydroxyl groups and 20 to 10%
by weight of surface-active agents.
The preparation of the granules according to the
invention can be carried out by a procedure in which the organic,
cyclic compounds containing keto and/or hydroxyl groups are mixed
with the surface-active agents, this mixture is ground, the ground
mixture is then sprayed with water or an aqueous liquid and the
granules thus formed are dried. It is also possible to grind the
surface-active agents separately in a manner corresponding to
that for the organic, cyclic compounds containing keto and/or
hydroxyl groups, and to mix them, in the ground form, with the
ground organic, cyclic compounds containing keto and/or hydroxyl
groups. It is furthermore also possible to dissolve the
surface-active agents in water and to use an aqueous solution of
this type to spray the ground organic, cyclic compounds containing
keto and/or hydroxyl groups. Moreover, some of the surface-active
agents can be ground together with or separately from the
organic, cyclic compounds containing keto and/or hydroxyl groups,
the ground surface-active agents and the ground organic, cyclic
compounds containing keto and/or hydroxyl groups can be mixed
-` 114Z714
and the remainder of the surface-active agents can be added to the
water or the aqueous liquid used for spraying. The preparation of
the granules according to the invention is preferably carried out
by a procedure in which the surface-active agents are ground
together with the organic, cyclic compounds containing keto and/or
hydroxyl groups.
If agents prepared according to the invention are to be
used in pulp production processes which are carried out in an
alkaline medium, it can be advantageous to add small amounts of
an alkaline substance to the organic, cyclic compounds containing
keto and/or hydroxyl groups before the grinding or to the water
or the aqueous liquid before the spraying. Such alkaline
substances, in particular alkaline salts, can furthermore first be
ground in a manner corresponding to that for the organic, cyclic
compounds containing keto and/or hydroxyl groups and then mixed,
in the ground form, with the ground organic, cyclic compounds
containing keto and/or hydroxyl groups, before the spraying.
Examples of suitable-
-7a-
11427:14
alkaline substances to be added are NaOH, KOH, Na2C03,
K2C03 and/or LiOH Alkaline substances can be added
in amounts of, for example, 0.2 to 5% by weight (rela-
tive to the finished granules) Such substances are
preferably added to the water or to the aqueous liquid
used for spraying.
If the agents prepared according to the inven-
tion are to be converted into an aqueous dispersion
before being used in a process for the production of
pulp, it can be advantageous, before grinding, to add to
the organic, cyclic compounds containing keto and/or
hydroxyl groups substances which have a stabilising
effect on dispersions. Such substances can also first
be ground in a manner corresponding to that for the
organic, cyclic compounds containing keto and/or hydroxyl
groups and can then be mixed, in the ground form, with
the ground organic, cyclic compounds containing keto
and/or hydroxyl groups. Substances which have a
stabilising effect on dispersions can be, for example:
highly disperse silicic acid, magnesium silicates and
aluminium silicates, montmorillonites, which can also
contain organic base, chalk and/or thickeners, such as
methylcellulose, hydroxymethylcellulose, hydroxyethyl-
cellulose or carboxymethylcellulose, as well as poly-
~5 acrylates and/or polymethacrylates and/or copolymers
thereof, and combinations of the substances mentioned.
Such substances can be added in amounts of, for example,
O to 5% by weight, preferably 0.1 to 1% by weight (in
each case relative to the finished granules).
Furthermore, preservatives can be added to the
organic, cyclic compounds containing keto and/or
hydroxyl groups and/or to the water or to the aqueous
liquid used for spraying. Possible preservatives are,
for example, substances which prevent the formation of
mould and/or bacterial attack. Substances which aresuitable are the customary preservatives, for example
sodium pentachlorophenate and addition products of
Le A 19 408
~l~Z7~
g
paraformaldehyde and aromatic alcohols, in particular
benzyl alcohol. Preservatives can be added in amounts
of, for example, 0 to 3% by weight, preferably in amounts
of 0.05 to 0.5% by weight (in each case relative to the
finished granules). If the preservatives are
insoluble or poorly soluble in water, they are prefer-
ably added to the organic, cyclic compounds containing
keto and/or hydroxyl groups before grinding, or are
ground separately in a manner corresponding to that for
the organic, cyclic compounds containing keto and/or
hydroxyl groups and mixed, in the ground form, with the
ground organic, cyclic compounds containing keto and/or
hydroxyl groups. Wate~ soluble preservatives are
preferably added to the water or to the aqueous liquid
used for spraying.
It can be advantageous to introduce other con-
stituents, if appropriate in addition to alkaline sub-
stances and/or preservatives, in the preparation of the
agent according to the invention. Such other con-
stituents can be, for example, inorganic salts, carbo-
hydrates, urea, urea derivatives and/or water-soluble
polymers.
The abovementioned inorganic salts, urea and
urea derivatives, carbohydrates and/or water-soluble
polymers can in general be added to the water or to the
aqueous liquid used for spraying and/or to the organic,
cyclic compounds containing keto and/or hydroxyl groups
before or after these are ground. If they are added
after the grinding of the organic, cyclic compounds con-
taining keto and/or hydroxyl groups, they are approp-
riately ground separately in the same manner as the
organic, cyclic compounds containing keto and/or hydroxyl
groups.
Examples of inorganic salts are chlorides and
sulphates of alkali metals, magnesium or ammonium, in
particular magnesium sulphate, potassium sulphate,
sodium sulphate, potassium chloride, ammonium sulphate,
Le A 19 408
11427~4
-- 10 --
lithium sulphate and ammonium chloride. Such com-
pounds can be added, for example, in amounts of 0 to 80%
by weight, preferably 0 to 20% by weight (relative to
the finished granules). Inorganic salts are prefer-
ably added to the organic, cyclic compounds containingketo and/or hydroxyl groups before these are ground.
Urea and urea derivatives can be added, ~or
example, in amounts of 0 to 20% by weight, preferably 0
to 10% by weight (relative to the finished granules)
Urea or urea derivatives are preferably added to the
organic, cyclic compounds containing keto and/or
hydroxyl groups before these are ground.
Examples of carbohydrates are starch, sugars,
methylcellulose and hydroxypropylmethylcellulose
These compounds can be added, for example, in amounts of
0 to 20% by weight, preferably 0 to 10% by weight (rela-
tive to the finished granules). Carbohydrates can be
added to the organic, cyclic compounds containing keto
and/or hydroxyl groups before these are ground and/or to
the water used for spraying.
Examples of water-soluble polymers are polyvinyl
alcohol, polyvinylpyrrolidone and mixtures of cane sugar
and sodium salts of polymeric carboxylic acids and
polyoxyethylene ethers. These compounds can be added,
for example, in amounts of 0 to 15% by weight, prefer-
ably 0 to 8% by weight (relative to the finished gran-
ules). Water-soluble polymers are preferably added
to the water used for spraying.
All these additives have the advantage that they
promote the formation of bridges between the individual
particles of the organic~ cyclic compounds containing
keto and/or hydroxyl groups, and the build-up of the
granules is thus facilitated
If alkaline substances, preservatives, inorganic
salts, urea or urea derivatives, carbohydrates and/or
water-soluble polymers are also used, in addition to the
surface-active agents, in preparing the agents according
Le A 19 408
114Z7~l4
-- 11 --
to the invention, the total sum of these additions
(including the surface-active agents) is advantageously
not more than 30% by weight (relative to the finished
granules).
The water or the aqueous liquid used for spraying
can also contain organic water-miscible solvents.
Such solvents can be, for example, alcohols, in particu-
lar those with 1 to 8 C atoms, for example methanol,
ethanol, isopropanol and butanol. Such solvents can
be added to the water or to the aqueous liquid in amounts
of, for example, 0 to 40% by weight (relative to the
water), and have the advantage that they can effect
better surface-wetting of the organic, cyclic compounds
containing keto and/or hydroxyl groups.
It is furthermore possible to use liquids which
contain water, if appropriate surface-active agents, and
one or more of the abovementioned additives, in any
desired combination, for the spray~ng.
The finely divided organic, cyclic compounds
with keto and/or hydroxyl groups which can optionally
contain the additives described can be sprayed with water
or an aqueous liquid in customary apparatuses for form-
ing granules by layering. For example, mixing
granulators, screen granulators, disc granulators,
extruders and fluidised bed or moving bed granulators
can be used for this purpose. The granulation can be
carried out either discontinuously or continuously.
The spraying is carried out with water or an aqueous
liquid, which can contain the constituents described
above, in an amount of 5 to 30% by weight of water or
aqueous liquid (relative to the finely divided constitu-
ents). This amount is preferably 5 to 15% by weight.
Customary nozzles can be used for the spraying. Two-
material nozzles are preferably used, in order to produce
as fine as possible a spray mist.
The spraying can be carried out, for example, at
10 to 60C and under pressures in the range from 0.5 to
Le A 19 408
~14271~
- 12 -
2.5 bar~ Spraying is preferably carried out at room
temperature up to 40C, and under pressures in the range
from l to 2 bar.
After the spraying, moist granules are present.
According to the invention, these are subsequently dried.
The customary drying apparatus can be used for the dry-
ing~ for example tubular dryers, circulating air drying
cabinets, drying belts or freeze-dryers. Fluidised
bed or moving bed dryers are preferably employed.
Suitable drying conditions are, for example, tempera-
tures in the range from 40 to 90C and pressures in the
range from 0.5 to 2.5 bar. Drying is preferably
carried out at temperatures in the range from 60 to 80C
and under pressures in the range from 1 to 2 bar.
It can be advantageous to remove dust-like and
coarser agglomerates from the resulting dry granules by
sieving. The customary sieving machines can be used
for this purpose. The granules prepared according to
the invention preferably have, if appropriate after
sieving, a particle diameter in the range from 0 1 to
5 mm, preferably in the range from 0.2 to 2 mm. The
finer constituents can optionally be recycled again to
the spraying, and the coarser constituents can option-
ally be recycled to the grinding.
The agents prepared according to the invention
can have a very high content of the actual active sub-
stance from the group of organic, cyclic compounds con-
taining keto and/or hydroxyl groups, and this content
can be, for example, 80 to 90% by weight (relative to
the finished granules) ~hen introduced into water
or into digestion solutions customary in the production
of pulp (for example by the kraft process or soda pro-
cess), the agents prepared according to the invention
spontaneously form dispersions in which the organic,
cyclic compounds containing keto andlor hydroxyl groups
are present predominantly with particle sizes of less
than lO ~m. Optimum use of the favourable effects of
Le A l9 408
114Z714
-- 13 _
the presence of these compounds in processes for the
production of pulp can thus be made, since uniform dis-
tribution of these compounds is achieved in a simple
manner. The agents prepared according to the inven-
tion do not change under customary storage conditions,even on prolonged storage. Because of their granu-
lar nature, they are readily free-flowing, can easily
be metered and can be handled with a high degree of
safety.
Customary layered granules which are used in
industry, for example in the field of dyestuffs, plant
protection agents and pharmaceuticals, and which have
been produced in a manner similar to the granules pro-
duced according to the invention in general contain 5
to at most 70% by weight of the substance essential for
the use. Surprisingly, granules which contain up -to
90% by weight and more of organic, cyclic compounds with
keto and/or hydroxyl groups can be prepared by the pro-
cess according to the invention. Such highly concen-
trated granules have the advantage that, on the one
hand, small amounts of additives are used, and the
transport costs and the risks during use are thus kept
at a low level, but on the other hand, however, a sub-
stance form which disperses readily is obtained.
The present invention relates to a process for
the production of pulp from lignocellulose materials in
the presence of organic, cyclic compounds containing
keto and/or hydroxyl groups, which is characterised in
that the organic, cyclic compounds containing keto and/
30 or hydroxyl groups are employed in the form of the
agent prepared according to the invention.
By the term "process for the production of pulp",
there are to be understood all processes and process
stages in which lignin in materials containing lignin
35 and cellulose is subjected to chemical treatment.
Examples in this context are alkaline, neutral and acid
digestion processes on lignocellulose materials, such as
Le A 19 408
1142~14
- 14 _
wood, straw, bagasses and grass, and bleaching processes
on lignocellulose materials which have been partially or
largely digested.
Apart from the use of the agents prepared accord-
ing to the invention, the production of pulp by theprocess according to the invention can be carried out in
a manner which is in itself known. For example, this
process can be carried out by digesting lignocellulose
materials in a sulphite solution, which can be acid,
neutral or alkaline, and the agent prepared according to
the invention can be added to the digestion solution
before or after addition of the lignocellulose material.
The agent prepared according to the invention can also
be employed in the known pulp production processes,
which are known as the kraft process 9 soda process and
polysulphide process. The agent prepared according
to the invention can furthermore be employed in the
known oxygen/alkali process for the production of pulp
and/or in the bleaching processes known for the produc-
tion of pulp.
The agent prepared according to the inventioncan be employed in the process, according to the inven-
tion, for the production of pulp and for bleaching pulp
in an amount of, for example, 0.001 to 10% by weight
(relative to the lignocellulose material). 9,10-
Anthraquinone in the form of the agent prepared accord-
ing to the invention is preferably employed in the pro-
cess, according to the invention, for the production of
pulp. The use of the agent mentioned as preferred in
the context of the agents prepared according to the
invention is particularly preferred.
The process 9 according to the invention, for the
production of pulp has a number of advantages. Thus,
for example, metering and uniform distribution of
organic, cyclic compounds containing keto and/or hydroxyl
groups can be effected without difficulties, and as a
result pulps of uniform quality are obtained. It is
Le A 19 408
~42~14
- 15 -
furthermore possible to realise the positive effects,
established under ideal conditions on a laboratory scale,
of the addition of organic, cyclic compounds containing
keto and/or hydroxyl groups to large-scale industrial
plant for the production of pulp.
In the laboratory experiments, for example, the
lignocellulose material was agitated in the digestion
liquid or bleaching liquid, and this facilitated dis-
tribution of the additives. In large-scale indus-
trial plants for the production of cellulose, suchagitation is carried out only to a minor extent and
distribution of the additives is thus made more diffi-
cult if they are not used in the form of the agents
prepared according to the invention.
Examples
In the following text, the abbreviation PW means
parts by weight
Example 1
80 PW of 9,10-anthraquinone were mixed with 18
PW of spray-dried sulphite waste liquor, containing
lignin-sulphonates, and 2 PW of sodium diisobutyl-
naphthalene sulphonate, and the mixture was jet-milled.
Thereafter, the particle size of the pulverulent mixture
was less than lO ~m. This pulverulent mixture was
granulated in a mixing granulator with grinding ele-
ments, whilst spraying with 8% by weight of water
(relative to the pulverulent mixture). After drying
the granules, the particles with a particle size in the
range from 0.2 to 2.0 mm were sieved off The pro-
duct was free from dust and could be dispersed spon-
taneously in water The product can be metered by
volume and could easily be stirred into a digestion
liquor for wood.
Example 2
The process followed was as in Example 1, but
85 PW of 9,10-anthraquinone, 13 PW of spray-dried
sulphite waste liquor, containing lignin-sulphonates,
Le A l9 408
71
-- 16
and 2 PW of sodium diisobutylnaphthalene sulphonate were
employed and the pulverulent mixture was granulated in
a screen granulator. The product thus obtained had
the same properties as the product from Example 1.
Example 3
The procedure followed was as in Example 1, but
75 PW of 9,10-anthraquinone, 23 PW of spray-dried
sulphite waste liquor, containing lignin-sulphonates,
and 2 PW of sodium diisobutylnaphthalene sulphonate were
employed and the pulverulent mixture was granulated in
a disc granulator The product thus obtained had
the same properties as the product from Example 1.
Example 4
The procedure followed was as in Example 1, but
90 PW of 9,10-anthraquinone, 2 PW of sodium diisobutyl-
naphthalenesulphonatè and 8 PW ofspray-dried sulphite waste
liquor were granulatedin a fluidised bed granulator (manu-
facturer: Aeromatik, Muttenz, Switzerland). The
product thus obtained had the same properties as the
product from Example 1. The product could easily be
stirred into the digestion liquors for wood which are
used in the kraft process and soda process.
Example 5
80 PW of 1,4-benzoquinone were mixed with 18 PW
of spray-dried sulphite was-te liquor, containing lignin-
sulphonates, and 2 PW of sodium diisobutylnaphthalene
sulphonate, and the mixture was jet-milled There-
after, the particle size of the pulverulent mixture was
less than 10 ~m. This pulverulent mixture was
granulated in a fluidised bed granulator (manufacturer:
Aeromatik, Muttenz, Switzerland), whilst spraying with
9% by weight of water (relative to the pulverulent mix-
ture). After drying the granules, the particles with
a particle size in the range from 0.2 to 2.0 mm were
sieved off. The product was freé from dust and free-
flowing and could be dispersed spontaneously in water.
Le A 19 408
1~4~7~
- 17 -
Example 6
The procedure followed was as in Example 5, but
90 PW of 2-aminoanthraquinone, 8 PW of spray-dried
sulphite waste liquor, containing lignin-sulphonates,
and 2 PW of sodium diisobutylnaphthalene sulphonate
were employed and the mixture was granulated whilst
spraying with 8% by weight of water. The constitu-
ents with particle sizes of less than 0.2 mm and more
than 2.0 mm sieved out after drying were recycled into
the process. The product could readily be stirred
into so-called white liquor (= aqueous solution of the
digestion chemicals) in the kraft process and soda pro-
cess and spontaneously formed a dispersion in this
liquor.
Example Z
The procedure followed was as in Example 4, but
a continuously operating moving bed granulator (moving
bed unit 38, manufacturer: Anhydro, Copenhagen, Denmark)
was used instead of the discontinuously operating
fluidised bed granulator.
When stirred ir.to water or a digestion liquor,
for wood, of the kraft process or soda process, the
product spontaneously gave very fine dispersions.
Example 8
The procedure followed was as in Example 6, but
a moving bed granulator according to Example 7 was used.
When stirred into water or a digestion liquor,
for wood, of the kraft process or soda process, the
product spontaneously gave very fine dispersions.
Example 9
The procedure followed was as in Example 4, but
the following substances were employed:
Le A 19 408
18
Organic, cyclic compoundSpray-dried Sodium
containing keto and/orsulphite diisobutyl
hydroxyl groups waste liquor naphthalene
(PW) (PW) sulphonate
(PW)
1-Methyl-anthraquinone (70)28 2
1,5-Dimethyl-anthraquinone (80) 17 3
l-Hydroxyanthraquinone (75)22 3
1,5-Dihydroxyanthraquinone (80) 18 2
1-Methyl_8-amino- 23 2
anthraquinone (75)
Granules which disperse spontaneously in kraft
digestion liquors and soda digestion liquors, are free
from dust and free-flowing and can be metered by volume
were obtained.
Example 10
80 PW of 9,10-anthraquinone, 8 PW of spray-dried
sulphite waste liquor, containing lignin-sulphonates,
2 PW of sodium diisobutylnaphthalene sulphonate and 10
PW of urea were mixed, and the mixture was jet-milled.
Thereafter, the particle size of the pulverulent mixture
was less than 10 um. This mixture was granulated in
the same manner as described in Example 1. The pro-
duct was free from dust and could be dispersed spon-
taneously in water. The product can be metered byvolume and could readily be stirred into a digestion
liquor for wood
ExamPle 11
The procedure followed was as in Example 10, but
10 PW of polyvinyl alcohol were employed instead of urea.
The properties of the product were as indicated in
Example 10.
Example 12
The procedure followed was as in Example 10, but
10 PW of sugar were employed instead of urea. The
properties of the product were as indicated in Example 10.
Le A l9 408
