Note: Descriptions are shown in the official language in which they were submitted.
7~i
It is described (see, for example, Bach and G. Fiehn,
Zellstoff und Papier 21, 3 (1972); H.H. Holton, Pulp and
Paper Canada 78, 19 (1977); U.S. Patent Specification
L~,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 112,903/7j,
Japanese Laid-Open Specification 43,4~3/76, Japanese Laid-
Open Specification 109, 303/76 and Cerman Democratic Republic
Patent Specification 98,549) that anthraquinone, certain
anthraquinone derivatives and certain diketohydroanthracenes
exert a favourable effect in certain processes for the
production and bleaching of pulp from lignocellulose
materials, such as wood, straw and bagasse, when from 0.001
to 10~ by weight thereof, relative to the lignocellulose
ma-terial, are employed. In addition to anthraquinone,
anthrahydroquinone and Diels-Alder adducts of butadiene and
its derivatives with p-benzoquinone or 1,4-naphthoquinone,
the mono- and poly-alkyl, -alkoxy, -amino~ -hydroxyl and/or
-sulpho derivatives of these compounds are recommended for
this. In the following text, these substances are
collectively designated additives.
In general, the additives are accessible in the form
of powders. However, the incorporation of pulverulent
additives of this type into processes for the production of
25 pulps from lignocellulose materials and for the bleaching
thereof presents problems. If the pulverulent additives
are added to the lignocellulose material to be employed, it
must be expected, in this case, that the finer constituents
of the additives pass into the environment in the form of a
30 dust and are thus partly withdrawn from the intended use,
are troublesome to people working near the place of addition
and can give rise to the danger of dust explosions. In
addition~ uniform distribution is difficult with the rela-
tively small amount of additives required. However,
35 uniform distribution of the additives is desirable in order
to achieve uniform ~uality of the pulp.
Le_A lS 8~5
~,$~
~4(~7~6
Uniform distribution of the additives is also made
difficult by the fact that the additives are generally only
very slightly soluble in wa-ter and in the aqueous electro-
ly-te solutions used in pulp production (for example, only
6.10 4 g of 9,10-anthraquinone dissolves in 1 litre o~
water at 50Cj.
Furthermore, the additives are so poorly wetted by
water and aqueous electrolyte solutions, such as are
used in pulp production, that the finer constituents of
the pulverulent additives cannot be stirred in, or can
only be stirred in to a poor extent, but float non-wetted
on the surface, air sometimes being occluded. Moreover,
the additives have a relatively high specific gravity (for
example anthraquinone has a specific gravity of 1.438 g/cm3
at 20C), so that the coarser constituents of the pul~eru-
lent additives, which can be stirred into water or an
electrolyte solution, rapidly settle again and, after stand-
ing for a short time, form on the floor of the vessel a
compact layer which can be stirred up again only with
difficulty. The addition of the additives directly to
the cooking liquor, to the mixture of lignocellulose
material and cooking liquor or in the form of a paste in
water or dilute electrolyte solutions is thus also no way
of achieving with certainty a uniform distribution of the
additives.
An agent has now been found for use in pulp
production, which is characterised in that it contains
organic, cyclic compounds containing keto groups and/or
hydroxyl groups, in a finely divided form, and surface-
active agents.
Here and in the following text, the expressionpulp production is understood as all processes and process
stages in which the lignin in materials containing lignin
and cellulose is acted upon in a chemical manner. Examples
of these processes are alkaline, neutral and acid pulping
processes with lignocellulose materials~ such as wood, straw,
bagasse and grasses, and bleaching processes with partially
or substantially pulped lignocellulose materials.
Le A 18 87~
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The o~ganic, cyclic compounds containing keto groups and/or hydroxyl
groups which can be used in accordance with the invention are p-benzoquinone,
1,4-naphthoquinone, 9,10-anthraquinone and/or Diels-Alder adducts of 1,3-dienes,
for example of unsubsti~uted or substituted butadiene, with p-ben~oquinone and/or
1,4-naphthoquinone, and/or mono- and poly-alkyl, -hydroxyl, -amino, -alkoxy,
-alkylamino and/or sulpho derivatives thereof, and the reduced forms thereof.
The alkyl, alkoxy and alkylamino moieties can each contain, for example~ 1 to
12 C, preferably 1 to 4, carbon atoms. For example, the dispersions according
to the invention can contain 9,10-anthraquinone, 2-methylanthraquinone,
2-ethylanthraquinone, 2,3-dimethyl-9,10-anthraquinone, 2,6-dimethylanthraquinone,
2,7-dimethylanthraquinone, 2-aminoanthraquinone, l-methoxyanthraquinone,
1,4,4a,9a-tetrahydro-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,5,8J8a,9a,10a-octahydro-9,10-diketoanthracene, 1,3-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. Compounds which can also be used are the
above named compounds in reduced form containing hydroxyl groups instead of
keto groups, for example hydroquinone and anthrahydroquinone. The dispersion
according ~o the invention can contain ~wo or more of these substances, in
particular two or more of these substances which have specific gravities which
are close to one another. It is also possible to employ compounds which carry
two or more of the substituents mentioned, for example hydroxyl groups and
amino groups. However, the dispersion according to the invention
preferably contains
Oq~6
only one of these substances, very particularly preferably
9,10-anthraquinone. In the followin~ text, the organic,
cyclic compounds containing keto groups and/or hydroxyl
groups are designated as pulping auxiliaries.
It is a particular feature of the agent according
to the invention tha~ the pulping auxiliaries, in particular
9,10-anthraquinone, are present in a finely divided form.
For example, the pulping auxiliaries, in particular 9,10-
anthraquinone, can consist to the extent of at least 80 %
10 by weight of particles with particle sizes of less than
10 ~m. The pulping auxiliaries, 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.
Possible surface~ac-tive agents contained in the
agent according to the invention can be virtually any
cationic, non-ionic and anionic surface-active agents.
Examples of possible cationic surface-active agents
are quarternary long-chain and/or oxethylated amines,
20 quarternary pyridinium compounds or long-chain phosphonium
compounds. Long-chain means here a carbon chain of at
least 4 C atoms, preferably of at least 6 C atoms.
Examples of cationic surface-active agents are in
particular: trimethyl-hexadexyl-ammonium bromide, cetyl-
25 pyridinium bromide, lauryl-dimethylbenzy~-ammonium chloride,
monoesters of triethanolamine with stearic acid as formic
acid salts or acetic acid salts, N-lauryl-methylbenzimida-
zole hydrochloride and dodecyl-trimethyl-phosphonium bromide.
A large part of these compounds and further cationic
30 surface-active agents which can be used are described, for
example, in K. Lindner, Tenside - Textilhilfsmittel -
Waschrohstoffe [Surface-active Agents - Textile Auxiliaries -
Detergent Raw Materials], volume 1, pages 963-1041 (1964).
Examples of non-ionic surface-active agents which
35 can be used are adducts of alkylene oxides, in particular
ethylene oxide, with higher fatty acids, alcohols, phenols,
acid amides, mercaptans, amines or alkylphenols. The
adducts can be obtained, for example~ from 5 to 50 mols of
Le A 18 875
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alkylene oxide and 1 mol of fatty acid, alcohol, phenol,
acid amide, mercaptan, amine or alkylphenol, these compounds
containing at least 4, preferably at least 6, C atoms.
Non-ionic surface-active agents which can be used are also
5 adducts of alkylene oxides, in particular ethylene oxide,
with polypropylene oxide or with sugars, as well as oxethy-
lated and non-oxethylated sugar derivatives, such as fatty
acid asters of pentaerythritol or of sucrose.
Particular examples of non-ionic surface-active
10 agents are: adducts of 5 to 20 mols of ethylene oxide ~ith
stearic acid, oleyl a~cohol, polypropylene glycol, nonyl-
phenol, oleic acid amide and dodecylamine.
A large part of these compounds and further non-
ionic surface-active agents which can be used are described,
15 for example, in N. Sch~rfeldt, Grenzfl~chenaktive Athylen-
oxid-Addukte ~Surface-active Ethylene Oxide Adducts], pages
42 to 95 (1976), and in K. Lindner, Tenside-~extilhilfs-
mittel - Waschrohstoffe [Surface-active Agents - Textile
Auxiliariès - Detergent Raw Materials~, volume 1, pages 837
20 to 917 (1964).
Preferably, the agent according to the invention
contains anionic surface-active agents. Examples of
anionic surface-active agents which can be used are alkyl-
sulphonates, sulphated unsaturated higher fatty acids,
25 sulphonates of polycarboxylic acid esters, alkylbenzenesul-
phonates, sulphated aliphatic alcohols, adducts of ethylene
oxide with higher amines, acids, phenols or alcohols, which
adducts have been converted into acid esters with an
inorganic polybasic acid, such as phosphoric acid or parti-
30 cularly sulphuric acid, and also ligninsulphonates orderivatives of ligninsulphonates, condensation products of
aromatic sulphonic acids with formaldehyde,and polyphos-
phates.
Particular examples of anionic surface-active agents
are: sodium dodecylsulphonate, sodium laurylsulphate, sodium
dodecylbenzenesulphonate, dibutylnaphthalenesulphonate,
acid sulphuric acid esters of the adduct of 2 mols of ethy-
lene oxide with 1 mol of nonylphenol, sodium dioctyl-sul-
Le A 18 _ 15
~14~q~;
phosuccinate, condensation products of cresol, 2-naphthol-
6-sulphonic acid and formaldehyde, and also sulphonic acids
of naphthalene, terphenyl or ditolyl ether in each case
condensed with formaldehyde. All the anionic surface-
active agents are preferably employed in the form of theiralkali metal salts and/or ammonium salts.
A large part of these compounds and further anionic
surface-active agents which can be used are described in
K. Lindner, Tenside-Textilhilfsmittel - Waschrohstoffe
[Surface-active Agents - Textile Auxiliaries - Detergent
Raw Materials], volume 1, pages 571 to 83$ (1964).
Particularly preferably, the agent according to the
invention contains ligninsulphonates and/or condensation
products of aromatic sulphonic acids and formaldehyde as the
surface-active agents.
m e agent according to the invention can also con-
tain any desired mixtures of anionic and non-ionic surface-
active agents.
m e agent according to the invention can be made
available in two forms, either in the form of a pulverulent
mixture which contains organic cyclic compounds, containing
keto groups and/or hydroxyl groups, and surface-active
agents in a finely divided form, or in the form of a dis-
persion which contains the above constituents dispersed in
water and/or an organic, water-miscible solvent having a
boiling point above 80C. Preferably, the organic sol-
vent has a boiling point above 100C. Examples of
organic solvents which can be used are alcohols, in parti-
cular polyhydric alcohols, and acid amides and substituted
acid amides. Examples of these are: dimethylformamide,
propylene glycol, glycol monoethyl ether, diethylene glycol
monoe-thyl ether, formamide, glycol, glyercol, diols, triols
and polyols. In conjunction with water, these solvents
having 40iling points ov~r 100C also act as agents which
prevent drying out. If the dispersion according to
the invention contains water and organic solvents, -these
two components can be present in an~ desired mixing ratio.
Prefe~ably, a dispersion of this type contains 5 to 20 %
by weight of solvent (relative to the -total dispersion).
The pulverulent mixture according to the invention
can, for example, contain 30 to 98 % by ueight of one or
more pulping auxiliaries, in particular 9,10-anthraquinone,
in a finelydivided form and 2 -to 70 % by weight of one or
more surface-active agents. Preferably, the pulveru-
lent mixture according to the invention contains 50 to 95 %
by weight of one or more pulping auxiliaries, in particular
9!10-anthraquinone, in a finely divided form and 5 to 50 %
by weight of one or more surface-active agen-ts.
Pulverulent mixtures according to the invention can
be prepared, for example, by dry grinding of the components
individually and subsequent mixing or by first preparing
the mixture of the components and grinding the mixture.
Grinding is preferably carried out in such a way that, after
the grinding procedure, at least 80 % by weight of the
pulping auxiliaries have a particle size of less than 10 ~m,
preferably less than 5 ~m. To carry out a grinding
procedure of this type, conventional dry comminution appara-
tuses can beused9for example ball mills, rotor/stator mills,pinned disc mills, hammer mills and jet mills. Jet
mills can be operated, for example, with air or steam.
The surface-active agents do not have to be present
in a finely divided form, that is to say they do not neces-
sarily have to be ground, since they generally dissolvereadily when the pulverulent mixture is used in processes
for the production of pulp. It is preferred, however,
to add the surface-active agents before the grinding pro-
cedure. In this way, an agglomeration, which may occur,
3 of the ground particles can be prevented.
If the pulverulent mixtures according to the inven-
tion are to be employed in processes for the production of
pulp, carried out in an alkaline medium9 it can be advan-
tageous to add small quantities of a material, having an
alkaline reaction, to the mixture. Substances of this
type, ~or example NaOH, KOH, Na2C03, K2C03 or LiOHt can be
added, for example, in quantities of 0.2 to 5 % by weight
(relative to the total mixture).
Le,18 8?~
~L~4~q~6~
The pulverulent mixture according to the invention
can be employed direct in processes for the production of
pulp. It is also possible, however, first to convert
the pulverulent mixture according to the invention into a
dispersion by stirring it into water, for example into 30
to 300 % by weight of water (relative bo the pulverulent
mixture) and to employ this dispersion in the process for
the production of pulp.
If the pulverulent mixture according to the inven-
tion is converted into an aqueous dispersion, before it isemployed in a process for the production of pulp, it can be
advantageous to add substances, which effect a stabilisation
of dispersions, to the pulverulent mixture. Examples
of substances of this type can be: highly disperse silica,
magnesium silicates and aluminium silicates, montmorillonites
which can also contain organic bases, chalk and/or thickeners,
such as methylcellulose, hydroxymethylcellulose, hydroxy-
ethylcellulose, carboxymethylcellulose as well as polyacry-
lates and/or polymethacrylates and/or copolymers thereof,
and also combinations of the substances mentioned. Sub-
stances of this type can be added to the pulverulent mix-ture
according to the invention, for example, in quanti-ties of
0 to 5 % by weight. Preferably, substances of this type
are added to the pulverulent mixture according to the inven-
tion in quantities of 0.1 to 1 % by weight.
~ he agent according to the invention in the form ofa dispersion can, for example, contain 30 to 70 % by weight
of one or more pulping auxiliaries in a Pinely divided form,
in particular 9,10-anthraquinone, 0.5 to 30 % by weight of
3o one or more surface-active agents and at least 30 % by
weight of water and/or organic, water-miscible solvents
having a boiling point above 80C. Preferably, the
agent according to the invention in the form of a dispersion
contains 45 to 65 % by weight of pulping auxiliary in a
finely divided form, in par-ticular 9,10-anthraquinone, 1 to
10 % by weight of surface-active agents and at least 35 %
by weight of water and/or organic solvent~
The agent according to the invention in the form of
Le A 18 875
~ ~LQ~6
a dispersion can additionally contain further substances,
for example preserving agents, agents which prevent drying
out, if one of the organic solvents mentioned has no-t
already been added, and/or agents for stabilising dispersions.
Preserving agents which can be used are those sub-
stances which prevent, for example, the ~ormation of mould
and/or an attack by bacteria. Customary preserving
agents, such as sodium pentachlorophenolate, adducts of para-
formaldehyde with aromatic alcohols, in particular benzyl
alcohol, and/or formaldehyde solutions are suitable for this
purpose. Preserving agents can be added to the agent
according to the invention in the form of a dispersion, for
example, in quantities of 0 to 3 % by weight, preferably
in quantities of 0.05 to 0.5 % by weight.
Examples of agents which prevent drying out, which
can be used, are customary soluble agents which prevent
drying out and which can be identical to the water-miscible
solvents having a boiling point above 80C, described above
in more detail. For example, formamide, glycol, glycol
derivatives, glycerol, diols, triols and polyols are par-ti-
cularly suitable. Agents which prevent drying out can
be added to the agent according to the inven-tion, if it is
present in the form of a dispersion, for example in quan-ti-
ties of 2 to 20 % by weight, preferably in quantities of 5
to 10 % by weight ( in each case relative to the total
dispersion).
As the agents which effect a stabilisation of dis-
persions, the same agents which are indicated above for the
pulverulent agents according to the invention can be employed.
3 Stabilisers can be added to the agent according to the inven-
tion in the form of a dispersion, for example, in quantities
of 0 to 2 % by weight, preferably in quantities of 0.1 to
1 % by weight
Agen-ts according to -the invention in the form of a
dispersion can, for example, be prepared by introducing
water or mixtures of water and the solvents described above,
or only one of the solvents described above, surface-active
agents~ one or more pulping auxiliaries, in particular 9,10-
Le A 18 875
()7~9~
-- 10 --
anthraquinone, and, if appropriate, stabilisers,mixed in thedesired ratio to a customary wet comminution apparatus.
Suitable wet comminution apparatuses are, for example,
kneaders, kneading screws, ball mills, rotor/stator mills,
dissolvers, corundum disc mills and vibration mills.
Preferably, high-speed stirred ball mills are used, the
grinding bodies preferably having a diameter in the range
from 0.1 ~o 10 mm. Grinding is preferably continued
until the solid particles have, at least to the extent of
10 80 % by weight, a particle size of less -than 10 ~m, prefer-
ably less than 5 ~m. If appropriate, the preserving
agents and/or agents which prevent drying out can be added
to the dispersion before or after grinding.
In addition to the possibilities, described above,
15 for preparing the agent according to the invention in the
form of a pulverulent mixture, pulverulent mixtures accord-
ing to the invention can also be prepared by drying from
agents according to -the invention in the form of a disper-
sion. Such drying can be carried out for example, in
20 a circulating air cabinet, in continuous or discontinuous
paddle driers, in drum driers, in thin-layer contact driers
and in freeze-driers. Advantageously, a spray-drier
with atomiser discs, two-material nozzles or single-
material nozzles is used for drying. In this way, free-
25 flowing granules can be obtained.
If the agent according to the invention in the formof a dispersion is to be introduced into pulp production
processes which are carried out in an alkaline medium, it
can be advantageous to add small amounts of a substance
30 having an alkaline reaction to the dispersion. Substances
of this type, for example aqueous sodium hydroxide solution
or aqueous potassium hydroxide solution, can be added, for
example, in quantities of 0 to 2 ~ by weight.
m e agent according to the invention, in particular
35 an agent containing 9,10-anthraquinone, is used in processes
for pulp production. In pulp production, the agent
according to the invention can be fed in before the cooking,
but advantageously already before the impregnation, in which
Le A 18 875
~LJ.g~07q~i
-- 11
the lignocellulose material is impregnated with an aqueous
solution of the pulping chemicals at a temperature of 80 to
100C. The aqueous solution of the pulping chemicals
also serves as a conveying medium for charging the impreg-
5 nator and/or cooker with lignocellulose material. m eagent according to the invention, in particular an agent
containing 9,10-anthraquinone, can be metered into the
refluxing solution or into the solution charged with chips,
or optionally also directly into the impregnator or cooker~
~he amount of agent according to the invention
used in pulp production can be chosen so that, for example,
0.001 to 10 % by weight, relative to the lignocellulose
material, of the agent according to the invention are added.
When using the agent according to the invention, the
15 pulping auxiliary is finely distributed in the pulping
liquid liquid.
m e agent according to the invention, in-the form ofa
dispersion, in particularin the form of a dispersion containing
9,10-anthraquinone,has additional advantages. Thus,the prepa-
20 ration ofthis d~e~onissi~.The agent according to the inven-
tion in the form of a dispersion can be pumped, that is to
say it can be metered, and conveyed through pipelines, with
the aid of a pu~p suitable for pumping dispersions, for
example a peristaltic pump, an eccentric screw pump or a
25 piston pump. The agent according to the invention in
the form of a dispersion is stable for a relatively long
time as a dispersion. A dispersion of this type can be
stored for at least several days, in general for one or more
weeks, during which the dispersed subs-tances do not settle
30 or float to the surface, or settle or float to the surface
only to such a slight extent that they can be brought into
the dispersed state again by simple means, for example a
slow~speed stirrer. m is has the advantage that a
relatively large amount of the dispersion can be prepared
35 all at once, the metering of which can then be effected,
for example, by a simple measurement of volume or amoun-t.
Depending on which possibility appears to be more
advantageous, the agent according to the invention can also
Le A 18 875
~4~7~
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be made available as a pulverulent mixture from which a
dispersion can be prepared, if desired, only shortly before
use in pulp production.
By employing the agent according to the invention
5 in processes for pulp production, including the bleaching
of pulp, the favourable effects of the presence of organic,
cyclic substances con-taining keto groups and/or hydroxyl
groups can be~tilised in an optimum manner, since a uniform
distribution thereof is obtained.
It is to be described as distinctly surprising that
the agents according to the invention completely fulfil the
requirements for use in pulp production, including -the
bleaching of pulp, since a recrystallisation with an enlarge-
ment of the particles was to be expected due to the slight,
-though significant solubility in water of the organic, cyclic
compounds containing keto groups and/or hydroxyl groups, in
particular 9,10-anthraquinone, and it was thus not possible
to anticipate that the finely divided state and hence the
stable dispersions could be maintained for prolonged periods.
20- Moreover, a process has been found for pulp produc-
tion from lignocellulose materials in the presence of
organic, cyclic compounds containing keto groups and/or
hydroxyl groups, which is characterised in that the organic,
cyclic compounds containing keto groups and/or hydroxyl
25 groups are employed in the form of the agent accord-
ing to the invention. With the exception of the use of
the agent according to the invention, this process can be
carried out in a manner which is in itself known. For
example, this process can be carried o~t by digesting ligno-
30 cellulose materials in a sulphite solution~ which can beacid, neutral or alkaline, and feeding the agent according
to the invention to the digestion solution, before or after
adding the lignocellulose material It is also possible
to employ the agent according to the invention in the
35 known processes for pulp production, which are called the
Kraft process and polysulphide process. Furthermore, the
agent according to the invention can be employed in the
known oxygen/alkali process for pulp production and/or in the
Le A 18 87~
7~6
bleaching processes known for pulp production.
The agent according to the invention can be employed
in the process according to the inven-tion for pulp production
and the bleaching of pulp in an amount of, for example,
5 3.001 to 10 % by weight (relative to the lignocellulose
material).
Preferably, 9,10-anthraquinone is employed in the
process according to the invention in the form of the agent
according to the invention. In -this case, it is parti-
10 cularly preferable to use the agents designated as particu-
larly preferred within the scope of the agent according to
the invention.
The process according to -the invention has a number
of advan-tages. Thus, for example~ it is possible to
15 meter and uniformly distribute the organic, cyclic compounds
containing keto groups and/or hydroxyl groups without diffi-
culties, and as a result thereof, pulps of uniform quality
are obtained. Furthermore, it is possible to realise
the advantageous effects, determined on a laboratory scale
20 under ideal conditions, of the addition of organic, cyclic
compounds containing keto groups and/or hydroxyl groups, in
industrial installations for pulp production.
In the laboratory experiments, for example, the
lignocellulose material were agitated in the pulping liquid
25 or bleaching liquid, which facilitates distribution of the
additives. In industrial installations for pulp produc-
tion, this is the case only to a minor extent, and the dis-
tribution of the additives is thus made more difficult if
they are not employed in the form of the agent according
30 to the invention.
Examples
Example 1
A paste of 500 g of 9,10-anthraquinone in a mixture
of 248 ml of water, 2 g of sodium pentachlorophenolate,
100 g of ethylene glycol and 150 g of 50 % strength sodium
ligninsulphonate as obtained in pulp production, is ground
for 15 minutes with glass beads of 0.3 to o.L~ mm diameter
in a high-speed stirred ball mill as described in the
Le A 18 875
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o~
- 14 -
journal "Farbe und Lack" 71 (1965), page 377. After
the end of grinding, the particle size of the anthraquinone
in the pumpable dispersion obtained is less than 10 ~m.
About 95 % of the particles are smaller than 5 ~m. Even
after standing for several weeks at room temperature, the
anthraquinone does not sediment.
Example 2
A paste of 600 g of 9,10-anthraquinone in 316 ml
of water and 60 g of ethylene glycol is ground~ with the
addition of 20 g of sodium dinaph-thylmethanesulphonate, in
a high-speed stirred ball mill corresponding to Example 1.
After the end of grinding, the particle size of the anthra-
quinone is as indicated in Example 1. Subsequently, 4 g
of a swellable aluminium silicate or magnesium silicate
are stirred as a thickener into the dispersion. The
free-flowing dispersion of the anthraquinone does not sedi-
ment and, when stirred into the wood-pulping liquor of -the
Kraft process and soda process, gives a stable dispersion
in the wood-pulping liquor.
Example 3
A paste of 600 g of 9,10-anthraquinone in a mixture
of 312 g of water, 60 g of ethylene glycol, 20 g of a con-
densation product of naphthalenesulphonate and formaldehyde,
4g of swellable aluminium silicate, 3 g of 45 % strength
sodium hydroxide solution and 2 g of a formaldehyde depot
compound is premixed in a dissolver and ground in a mill
corresponding to Example 1. After the end of grinding,
the particle size of the anthraquinone is as indicated in
Example 1. A pumpable dispersion is obtained which
does not separate even after prolonged standing and can be
readily dispersed in the so-called white liquor (-a~ueous
solution of the pulping chemicals) in the Kraft process and
soda process.
Example 4
Analogously to Example 2, 600 g of 9,10-anthraqui-
none are ground inlOO g of ethylene gl~col, 250 g of water
and 30 g of sodium ligninsulphonate and are thickened with
20 g of chalk or 5 g of methylcellulose and preserved by
~ .
- ~4(~16
- 15 -
means of formaldehyde addition products. As in
Example 1, a pumpable, stable dispersion is obtained.
Example 5
Analogously to Example 2, 600 g of 9,10-anthraqui-
none in 90 g of ethylene glycol monoethyl ether9 250 g ofwater and 20 g of a condensation product of naphthalene-
sulphonate and formaldehyde are ground, thickened with 20 g
of chalk and rendered alkaline with 3 g of 45 % s~rength
sodium hydroxide solution. As in Example 4, a pumpable,
stable dispersion is obtained which can readily be stirred
into wood-pulping liquors of the Kraft process and socla
process.
Example 6
500 g of 9,10-anthraquinone are ground, as in E~y~e
1, in 490 gof an aqueous pulping solution (= black liquor)
obtained in a pulp production process and containing lignin-
sulphonates, and are thickened with 1 /0 by weight of
swellable aluminium silicate, a stable, pumpable anthra-
quinone dispersion being obtained which can readily be
stirred into wood-pulping liquor.
Example 7
A paste of 500 g of 9,10-anthraquinone in a mixture
of 323 ml of water, 2 g of sodium pentachlorophenolate,
100 g of ethylene glycol and 75 g of a condensation product
of cresol, 2-naphthol-6-sulphonic acid and formaldehyde is
comminuted corresponding to Example 1. The anthraqui-
none does not sediment out of the dispersion obtained.
Example 8
516 g of 50 % strength aqueous sodium ligninsul-
phonate are added to a dispersion, obtained according toExample 1, without sodium pentachlorophenolate and with the
corresponding additional am~unt of water in place of ethylene
glycol. Subsequently, this dispersion is dried in a
spray drier (inlet temperature 180C, outlet temperature
90C)~ The granules obtained, which consist of 60 ~
by weight of anthraquinone and 40 % by weight of sodium
ligninsulphonate, can readily be divided by stirring into
water or wood-pulping liquor of the Kraft process or soda
Le A 18 8~5
13L407
process.
Example 9
Corresponding to Example 8, granules which can readily be divided in
water or woDd-pulping liquor of the Kraft process or soda process and which con-tain 50 % by weight of anthraquinone and 50 % by weight of sodium ligninsulphon-ate, are obtained by adding 850 g of 50 % strength aqueous sodium ligninsulphon-ate.
Example 10
Corresponding to Example 8, granules which can very readily be divided
in water or wood-pulping liquor of the Kraft process or soda process and which
consist of 30 ~ by weight of anthraquinone and 70 % by weight of sodium lignin-
sulphonate, are obtained by adding 2,084 g of 50 % strength a~1eous sodium
ligninsulphonate.
Example 11
Anthraquinone formulations which were prepared analogously to Examples
8 to 10 but in which a condensation product of naphthalenesulphonate and formr
aldehyde was employed in plaoe of sodium ligninsulphonate, can readily be
divided in water or wood-pulping liquor of the Kraft pro oess or soda process bysimply stirring in.
Anthraqlinone form~lations which were prepared in a corresponding
manner, but with a condensation product of sulphonated ditolyl ether and form-
aldehyde, or a oondensation product of sulphonated diphenyl ether and formal-
deyde, or a condensation product of sulphonated terphenyl and formaldehyde, can
likewise be readily divided in water or wood-pulping liquor of the Kraft processor soda process by simply stirring in.
Example 12
500 g of 9,10-anthraquinone which was comminuted by jet grinding with
- 16 -
0~6
alr to particle sizes of less than lO ~m, are intensively mlxed with 333 g of
sodium ligninsulphonate. A dispersion of good fine division is obtained by
stirring this preparation illtO water or wood-pulping liquor of the Kraft process
or soda process.
Example 13
A preparation which, when stirred into water or ~cod-pulping liquor of
the Kraft process or soda process, gives a good fine division, is obtained by
mixing 500 g of 9,10-anthraquinone which was com~inuted according to Example 12,
and 500 g of sodium ligninsulphonate.
Example 14
A preparation which contains 30 ~ by weight of anthraquinone and 70 %
by weight of sodium ligninsulphonate is obtained by mixing 500 g of 9,10-anthra-
q~inone which was ccmminuted corresponding to Example 12, with 1,117 g of sodium
ligninsulphonate. When stirred into water or wo~d-pulping liquor of the Kraft
pro oe ss or soda process, this preparation leads to a dispersion of good -fine
division.
Example 15
500 g of 9,10-anthraquinone and 50 g of a condensation product of
naphthalenesulphonate, diphenyl ether-sulphonate, or ditolyl ether-sulphonate
and formaldehyde, were ground dc~n to a pa~ticle size of less than 10 ~m in a
jet mill which was operated with air. When stirred into 290 g of water or
corresponding am~unts of Kraft pulping liquor or soda pulping liquor, this pre-
paration leads to a pumpable dispersion which is stable for a prolonged time and
which is readily distributed in further Kraft pulping liquor or soda pulping
liquor.
Example 16
500 g of 9,10-anthraq~Linone and 10 g of a condensation product of
- 17 -
06
naphthalenesulphonate and formaldehyde were ground together. me -finely
divided pulverulent mixture obtained gives, when stirred into 330 g of a water/
glycol mixture in the ratio of 2 : l to lO : 1 or corresponding amoun-ts of Kraft
pulping liquor or soda pulping liquor, stable pumpable dispersions which are
very readily distributed in Rraft pulping liquors or soda pulping liquors. The
same results were obtained when 10 g of a condensation product of diphenyl-
sulphonate and formaldehyde or 10 g of a condensation product of ditolylsulphon-
ate and formaldehyde are employed.
- 17a
~14(~7~
- 18 -
Example 1/
600 g of 9,10-anthraquinone, 100 g of a condensation
product of naphtalenesulphonate and formaldehyde, 2 g of
aluminium silicateand 2 of sodium hydroxide are Jet-
milled together to give a particle size o~ 5 to 20 ~m.
A preparation is obtained which gives a stable dispersion,
when stirred wi-th 600 g of water or wood-pulping liquor of
the Kraft process or soda process.
Example 18
When Examples 1 to 17 are employed, using anthra-
quinone derivatives 9 such as mcnoalkyl-, dialkyl-, hydroxy-,
dihydroxy-, amino-, alkoxy- and alkylamino-anthraquinone,
or correspondingly substituted Diels-Alder adducts of 1,3-
dienes with 1,4-naphthoquinones or 1,4-benzoquinone in place
of anthraquinone, this gives s-table pumpable dispersions or
pulverulent mixtures which can be converted into stable
pumpable dispersions, using the indicated amounts of liquid.
The dispersions obtained are distinguished in -that they can
be dispersed without any problems in Kraft pulping liquors
or soda pulping liquors.
Example 19
400 g of 9,10-anthraquinone were ground in 580 g of
ethylene glycol and 20 g of sodium dinaphthylmethanesul-
phonate in a bead mill analogously to Example 1. As in
Examples 3 and 4, a pumpable dispersion is obtained which
is stable and can readily be stirred into wood-pulping
liquors of the Kraft process and soda process.
Le A 18 875
