KR830002040B1 - Pulp manufacturing agent - Google Patents

Abstract

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Description

Pulp manufacturing agent

The present invention relates to a medicament for the manufacture of pulp comprising an organic cyclic compound in a finely divided form containing a keto group and / or a hydroxyl group and a surfactant.

Several publications have been published on anthraquinones, anthraquinone derivatives and diketo hydroanthracenes which have desirable effects in the process for the preparation and bleaching of pulp from lignocellulosic materials such as wood, straw and sugar cane husks (see for example Bach). And G. Fiehn, Zellstoff and Papier 21, 3 (1972); HH Holton, Pulp and Paper Canada 78, 19 (1977); US Patent Specification No. 4,012,280: US Patent Specification No. 4,036,680: US Patent Specification No. 4,036,681 It is described in Canadian Patent Specification No. 986.662, Japanese Patent Publication No. 112,903 / 75, Japanese Patent Publication No. 43,403 / 76, Japanese Patent Publication No. 109,303 / 76, and German Federal Republic Specification No. 98,549. 0.001 to 10% by weight relative to the lig noceulorose material. Diels-Alder adducts of derivatives of P-benzoquinone or 1,4-naphthoquinone, mono- and poly-alkyl, alkoxy, -amino, -hydroxyl and / or-of these compounds Sulfoder derivatives are used for this purpose, hereinafter these materials are collectively referred to as additives.

Generally these additives are obtained in dry form. However, there is a problem in the use of this type of powdery additive in the process for the preparation and bleaching of pulp from lignocellulosic material. If a powdered additive is used in addition to the lignocellulosic material, the fine components of the additive are scattered into the environment in the form of dust, causing harm to workers near the place of addition and the risk of dust explosion. Moreover, the uniform amount is difficult because the amount of additive required is small. However, a uniform distribution of additives is desirable to obtain pulp of uniform quality.

The homogeneous distribution of the additives also results in very low solubility in the aqueous electrolyte solution in which the additive is generally used for water and pulp production (eg, 6.10 ^-4 of 9,10-anthraquinone in 1 liter of water at 50 ° C). Difficult by the fact that

Moreover, the additives used in the manufacture of pulp are very weakly moistened in water and aqueous electrolyte solutions and the microcomponents of the powdered additives are either agitated or only slightly agitated so that the unwetted microcomponents that float on the surface are dispersed in the air. In addition, since the additive has a fairly high specific gravity (eg, anthraquinone has a specific gravity of 1.438 g / cm ³ at 20 ° C.), it is a coarse of powdery additive that can be stirred in water or electrolyte solution. The components settle rapidly again, and after a short time, they form a dense layer at the bottom of the vessel and are difficult to stir again. The additives cannot be reliably achieved by adding the additives directly to cooking liquor, a mixture of lignocellulosic material and cooking liquor or onto a paste in water or diluted electrolyte solution.

The liquid preparation is a pulp preparation agent comprising an organic cyclic compound in a finely divided form containing a keto group and / or a hydroxyl group and a surfactant.

The expression pulp is understood here as all processes and process steps that apply chemical methods to lignin in lignin and cellulose-containing materials. Examples of such processes include alkaline, neutral and acidic pulp removal processes using lignocellulosic materials such as wood, straw, sugarcane husks and grasses, and bleaching processes of lignocellulosic materials partially or almost entirely pulped. .

Possible organic, cyclic compounds containing keto groups and / or lysoxyl groups are, for example, monocyclic, dicyclic and / or polycyclic compounds, in particular monocyclic, dicyclic and / or tricyclic Carbocyclic compounds, such as ric compounds, are preferred, particularly preferred are tricyclic compounds, in particular fused tricyclic compounds containing in each case two keto groups and / or two hydroxyl groups, Hydrocarbons other than hydroxyl group stars and / or other substituents are preferred. Compounds that may be used herein include P-benzoquinone, 1,4-naphthoquinone, 9,10-anthraquinone, and / or 1,3-diene (eg, unsubstituted or substituted buradiene) And Diels-Alder adducts with P-benzoquinone and / or 1,4-naphthoquinone, and / or mono- and poly-alkyl, -hydroxyl, -amino, -alkoxy, alkylamino and / or Sulfo derivatives are preferred. The alkyl, alkoxy and alkylamino moieties each contain, for example, 1 to 12 carbon atoms, preferably 1 to 4 carbon atoms. For example, the dispersions according to the invention are 9,10-anthraquinone, 2-methylanthraquinone, 2-ethylandhraquinone, 2,3-dimethyl-9,10-anthraquinone, 2,6-dimethyl-anthraquinone, 2,7-dimethylanthraquin is 2-aminoanthraquinone, 1-methoxy-anthraquinone 1,4,4a, 9a-tetrahydro-9,10-diketoanthracene, 2-ethyl-1,4,4a , 9a-tetrahydro-9,10-dikeroanthracene, 2,3-dimethyl-1,4,4a, 9a-tetra-hydro-9,10-diketoanthracene, 1,4,4a, 5,8, 8a, 9a, 10a-octahydro-9,10-diketoanthracene, 1,3-dimethyl-1,4,4a, 9a-tetrahydro-9,10-dikeroanthracene and 2,3,6,7- Tetramethyl-1,4,4a, 5,8,8a, 9a, 10a-octa-hydro-9,10-dikeroanthracene. Compounds which may also be used include reduced forms of the compounds of the above name which contain hydroxyl groups instead of keto groups, for example hydroquinone and anthrahydroquinone. Dispersants according to the invention may contain two or more components, in particular two or more of these components having similar specific gravity to one another. It is also possible to use compounds which carry two or more of the mentioned substituents, for example hydroxyl groups and amino groups. However, the dispersant according to the invention preferably contains only one of these components, with 9,10-anthraquinone being particularly preferred. Hereinafter, in the present specification, an organic, cyclic compound containing a keto group and / or a hydroxyl group is represented as an auxiliary for preparing pulp.

It is a feature of the medicaments according to the invention that the auxiliary pulp preparation, particularly 9,10-anthraquinone, is present in finely divided form. For example, pulp preparation aids, in particular 9,10-anthraquinone, may contain at least 80% by weight of particles having a particle size of 10 μm or less. Auxiliaries for preparing pulp, in particular 9,10-anthraquinone, preferably contain at least 80% of particles having a particle size of 5 μm or less.

Possible surfactants included in the medicaments according to the invention may be substantially cationic, nonionic and anionic surfactants.

Examples of possible cationic surfactants are quaternary long chain and / or oxylyl and amines, quaternary pyridinium compounds or long chain phosphonium compounds. Long chain means here carbon chain of 4 or more carbon atoms, preferably 6 or more carbon atoms.

Examples of cationic surfactants are in particular monoesters of stearic acid and triethanol amines such as trimethyl-hexadecyl-amnonnium bromide, cetyl-pyridinium bromide, lauryl-dimethylbenzyl-amnonnium chloride, formate or acetate, N -Lauryl-methylbenzimidazole hydrochloride and dodecyl-trimethyl-fogfonium bromide and the like.

Most of these compounds that can be used and also cationic surfactants are described in K. Linder, Tendise-Textihilfsmittel-Waschrohstoffe [Surface-active Agents-Tuxiliaries Auxiliaries-Detergent Raw Materials], Vol. 1, pp. 963-1041. 1964).

Examples of nonionic surfactants that can be used include adducts of alkylene oxides, in particular ethylene oxide with higher fatty acids, alcoholphenols, acidamides, mercaptans, amines or alkylphenols. Such adducts can be obtained, for example, from 5 to 50 moles of alkylene oxide and 1 mole of fatty acids, alcohols, phenols, acidamides, mercaptans, amines or alkylphenols and these compounds are preferably at least 4 carbon atoms. It has 6 or more carbon atoms. Nonionic surfactants that can be used also include additions of alkylene oxides, in particular ethylene oxide and polypropyl-based oxides or sugars such as oxethylated and non-oxethylated sugar derivatives (e.g. pentaerythritol or fatty acid esters of sucrose). There is water.

Specific examples of nonionic surfactants include adducts of 5 to 20 moles of ethyl oxoxide with stearic acid, oleyl alcohol, polypropyl glycol, nonylphenol, oleic acid amide and dodecylamine.

For most of these compounds and for the use of nonionic surfactants, see, for example, N. Schonfeldt, Grenzflachenaktive Athylenoxid-Addukte [Surface-active Ethylene Oxide ADDUCTS], pages 42-95 (1976), and K. Lindner, Tenside -Texilhi; fs-mittel-Waschrohstoffe (Surface-active Agents-Textile Auxililaries-Detergent Raw Materials), volume 1, pages 837-917 (1964).

Preferably, the medicament according to the invention comprises an anionic surfactant. Examples of anionic surfactants that can be used include alkylsulfonates, sulfated unsaturated fatty acids, sulfonates of polycarboxylic acid esters, alkylbenzenesulfonates, sulfated aliphatic alcohols, addition of ethylene oxide and higher amines, acids, phenols or alcohols. Water (these adducts are converted to acid esters with inorganic polybasic acids such as phosphoric acid or lateral sulfuric acid) and also ligninsulfonates or derivatives of ligninsulfonates, condensation products of formaldehyde with aromatic sulfonic acids and poly Phosphate and the like.

Specific examples of anionic surfactants include sodium dodecyl-sulfonate, sodium laurylsulfate, sodium dodecyl benzene sulfonate, dibutylnaphthalenesulfonate, adducts of two moles of ethylene oxide and one mole of nonylphenol, Sodium dioctyl-sulfosuccinate, cresol, a condensation product of 2-naphthol-6-sulfonic acid and formaldehyde, or in each case a sulfonic acid of naphthalene, terphenyl or ditolylether condensed with formaldehyde. All anionic surfactants are preferably used in the form of their alkali metal salts and / or ammonium salts.

For most of these compounds available and anionic surfactants, see K. Lindner, Tenside-Texilhi; fs-mittel-Waschrohstoffe [Surface-active Agents-Textile Auxililaries-Detergent Raw Materials], volume 1, pages 571 to 835 ( 1964).

Particularly preferred medicaments according to the invention comprise ligninsulfonates and / or condensation products of aromatic sulfonic acids and formaldehyde as surfactants.

The medicaments according to the invention may also comprise a mixture of the desired anionic and nonionic surfactants.

The medicaments of the invention can be prepared in two forms, i.e. in finely divided form, in the form of a powdered mixture containing a surfactant and an organic cyclic compound containing a keto group and / or a hydroxyl group, or water And / or a dispersion state in which the above-mentioned components are dispersed and contained in an organic water miscible medium having a boiling point of 100 ° C. or higher. The organic solvent preferably has a boiling point of 100 ° C. or higher. Examples of organic solvents that can be used include alcohols, in particular polyhydric alcohols, and acid amides and substituted acid amides. Examples of these are dimethylform amide protylene glycol, glycol monoethyl ether, diethylene glycol monoethyl ether, form amide, glycols, glycol, diols, triols and polyols. In combination with water, these solvents having a boiling point of 100 ° C. or higher act as a medicament to prevent drying. If the dispersion according to the invention contains water and an organic solvent, these two components may be present in any desired mixing ratio. Preferably, this type of dispersion contains 5 to 20% by weight of solvent (relative to starch).

The powdery mixtures according to the invention contain only one or more pulp preparation aids, in particular 30 to 98% by weight 9,10-anthraquinone and 2 to 70% of one or more surfactants in finely divided form. Preferably, the powdery mixtures according to the invention comprise from 50 to 95% by weight and from 5 to 50% by weight of one or more auxiliaries for preparing one or more pulp, in particular 9,10-anthraquin, and one or more surfactants in finely divided form. Contains%

Powdery mixtures according to the invention can be prepared, for example, by dry grinding of the individual components and then mixing, or by first preparing a mixture of the components and grinding the mixture. The pulverization is preferably carried out by a method such that after the pulverization process, at least 80% of the centering agent of the pulp-making aid has a particle size of 10 m or less, preferably 5 m or less. This type of milling process can be carried out using conventional dry mills, for example ball mills, rotor / stator mills, pinned disk mills, hammer mills and jet mills. The jet mill can be operated using, for example, air or steam.

Surfactants do not need to be present in finely divided form, i.e., do not need to be pulverized, since they generally dissolve easily when powdered mixtures are used in the pulp making process. However, it is preferable to add a surfactant before the grinding process. In this way, agglomeration of the pulverized particles can be prevented.

If the powdery complexes according to the invention are used in the pulp making process carried out in an alkaline medium, it may be advantageous to add a small amount of material with an alkaline reaction to the mixture. Components of this type are, for example, NaOH, KOH, Na ₂ CO ₃ , K ₂ CO ₃ and LiOH, which can be added in an amount of 0.2 to 5% by weight based on the total mixture.

The powdery mixtures according to the invention can be used directly in pulp making processes. However, the powdery mixture according to the invention may first be converted into a dispersion by stirring in water, for example 30 to 300% by weight (relative to the pulverized mixture), which may be used in the pulp making process.

If the powdered mixture according to the invention is converted to an aqueous dispersion prior to use in the pulp manufacturing process, it may be advantageous to add the powdered mixture to a substance which stabilizes the dispersion. Materials of this type are, for example, highly dispersed silica, magnesium silicate and aluminum silicate, montmorillonite, which may contain organic bases, chalk and / or methylcellulose, hydroxymethylcellulose, hydroxyethyl cellulose, carboxymethylcellulose and polyacrylates. And / or thickeners such as polymethacrylates and / or copolymers thereof, or combinations of the aforementioned components. Materials of this type can be added to the powdered mixtures according to the invention, for example in amounts of 0 to 5% neutral. This type of material is preferably added to the powdered mixture according to the invention in an amount of (.1 to 1% by weight).

Pharmaceuticals according to the invention in the form of dispersions may comprise, for example, 30 to 70% by weight of one or more auxiliary pulp preparation aids, 30% by weight of one or more surfactants, in a finely divided form, in particular 9,10-anthraquinone, and It may contain at least 30% by weight of water and / or organic water miscible solvent having a boiling point of 80 ° C or higher. Preferably the medicaments according to the invention in the form of dispersions are in particular in the form of finely divided pulp preparation aids of from 9,10-anthraquinone, 45-65% by weight, 1-10% surfactant and water and / or organic It contains 35% by weight solvent.

Agents according to the invention in the form of dispersions may be added with additional ingredients such as preservatives, anti-drying agents (if one of the aforementioned organic solvents has not been added in advance), and / or dispersion stabilizers.

Preservatives may be used to prevent the formation of mold and the invasion of bacteria. Conventional preservatives such as sodium pentachlorophenolate, adducts of paraformaldehyde and aromatic alcohols, in particular benzyl alcohol, and / or formaldehyde solutions are suitable for this purpose. The preservative may be added to the medicament according to the invention in the form of a dispersion, for example from 0 to 3% by weight, preferably from 0.05 to 0.5% by weight.

Examples of drying inhibitors that can be used are conventional solubilizing agents which prevent drying and may be the same as the water miscible solvents having a boiling point of 80 ° C. or higher. Examples are formamide, glycol, glycol derivatives, glycerol, diols, triols and polyols. The desiccant may be added in an amount of 2 to 20% by weight, preferably 5 to 10% by weight (for each starch dispersion), if the agent according to the invention is present in the form of a dispersion.

As formulations effective for stabilizing dispersions, formulations as described above for the powdered medicaments according to the invention can be used. Stabilizers may be added to the medicaments according to the invention in the form of dispersions, for example in an amount of 0 to 2% by weight, preferably 0.1 to 1% by weight.

Pharmaceuticals according to the invention in the form of dispersions are, for example, water or mixtures of water with the solvents described above or with only one, surfactant, one or more of the above-mentioned pulp preparation aids, in particular 9,10-anthraqui And, if appropriate, may be prepared by mixing the stabilizers in desired ratios and introducing them into conventional wet grinding apparatus. Suitable wet grinding devices are, for example, kneaders, kneading screws, ball mills, rotor / stator mills, dissolvers, corundum disc mills and vibration mills. Preferably a high speed stirring ball mill is used in which the diameter of the grinding bodies is in the range of 0.1 to 10 μm.

Grinding is continued until at least 80% by weight of the solid particles have a particle size of 10 μm, preferably 5 μm or less. If appropriate, preservatives or anti-drying agents can be added to the dispersion before and after grinding.

In addition to the above-described method of preparing a medicament according to the invention in the form of a powdery mixture, the powdery mixture according to the invention can be prepared by drying the compound of the invention in the form of a dispersion. Such drying can be carried out, for example, in rotary air cabinets, continuous or discontinuous paddle dryers, drum dryers, thin layer contact dryers and freeze dryers. It is advantageous to use a spray dryer with an atomizer disc, two material nozzles or a single material nozzle for drying. According to this method, particles free of flow can be obtained.

If the medicament according to the invention in the form of a dispersion is introduced into a pulp making process carried out in an alkaline medium, it may be advantageous to add a small amount of the component having an alkaline reaction to the dispersion. This type of component may be added, for example, in an aqueous sodium hydroxide solution or aqueous potassium hydroxide solution, for example in an amount of 0 to 2% by weight.

The medicaments according to the invention, in particular medicaments containing 9,10-anthraquinone, are used in the pulp making process. In the manufacture of pulp, the agent according to the invention can be supplied before the cooking process, but it is advantageously supplied in advance before the impregnation, and the lignocellose material is impregnated in the aqueous solution of the pulp medicine at a temperature of 80 to 100 ° C. The aqueous solution of the pulp-making agent also serves as a carrier medium for filling the impregnator and cooker with lignocellulosic material. The medicaments of the invention, in particular medicaments containing 9,10-anthraquinone, are metered into the solution together with the reflux solution or chips or optionally directly into the impregnator or cooker.

The medicament according to the invention used in the manufacture of pulp may be added in an amount of 0.001 to 10% by weight relative to the lignocellulosic material.

When using the agent of the present invention, the auxiliary agent for pulp production is finely distributed in the pulp preparation liquid.

펌프, 엑센트릭 스크류펌프 또는 피스톤 펌프와 같은 분산물의 펌핑에 적합한 펌프를 사용하여 파이프 라인을 통하여 운반된다. 분산물 형태의 본 발명에 따르는 약제는 꽤장기간동안 분산물로 안정하다. 이러한 형태의 분산물은 적어도 며칠간 일반적으로 1주일 이상 저장할 수 있고 분산된 성분이 침전되지 않으며 표면에 떠오르지 않으나 약간 침전되거나 표면에 떠오르더라도 간단한 방법 예를들면 저속교반기에 의하여 다시 분산상태로 된다. 이는 분산물의 뙈 많은 양을 한꺼번에 제조할 수 있는 이점을 가지며, 다량은 예를들어 간단한 용량 또는 중량측정에 의하여 효과적으로 계량된다.Pharmaceuticals of the invention in the form of dispersions Pharmaceuticals in the form of dispersions containing 9,10-anthraquinone have additional advantages. In other words, the preparation of this dispersion is simple. The agent according to the invention in the form of a dispersion is pumped, ie metered and peristaltic

It is conveyed through the pipeline using a pump suitable for pumping dispersions such as pumps, axial screw pumps or piston pumps. The agents according to the invention in the form of dispersions are stable as dispersions for quite a long time. This type of dispersion can be stored for at least a few days, usually for a week or more, and the dispersed components do not precipitate and do not float on the surface, but are slightly precipitated or float on the surface and are dispersed again by a simple method such as a slow stirrer. This has the advantage of producing large amounts of dispersion at one time, with large quantities being effectively metered, for example by simple dose or weighing.

According to the production process, which shows more advantageous advantages, the medicaments according to the invention can also be prepared in a powdery mixture from dispersions which can be prepared immediately before being used for making pulp if desired.

By using the medicament according to the invention in a pulp manufacturing process including pulp bleaching, since the desired effect due to the presence of organic cyclic components containing keto groups and / or hydroxyl groups can be used in an optimal manner, These uniform distributions are obtained.

As mentioned above, the medicaments according to the invention are particularly surprisingly satisfactory for the manufacture of pulp, including the bleaching of pulp, in particular organic cyclic compounds containing 9,10-anthraquinones, keto groups and / or hydroxyl groups. In spite of sufficient solubility, recrystallization occurs slightly as the particles grow, so that the finely divided state cannot be prepared in advance for a long time.

In addition, in the presence of an organic, cyclic compound containing a keto group and / or a hydroxyl group, characterized in that an organic, cyclic compound containing a keto group and a / hydroxyl group is used in the form of a medicament according to the invention. Processes for making pulp from lignocellulosic materials have been found. As an example of the use of a medicament according to the invention, this process can be carried out by methods known per se. For example, this process is carried out by cooking the lignocellulosic material in an acidic, neutral or alkaline sulfite solution and feeding the agent according to the invention to the cooking liquor before and after the lignocellulosic material is added. The pharmaceutical agent according to the present invention can also be used in known pulp manufacturing processes called so-called kraft processes and polysulfide processes. Furthermore, the medicaments according to the invention are applicable in known oxygen / alkaline processes and / or known bleaching processes for pulp production.

The agent according to the invention can be used in pulp making and bleaching processes, for example in amounts of 0.001 to 10% by weight (relative to lignocellulosic material).

Preferably, 9,10-anthraquinone is used in the process according to the invention in the form of a medicament according to the invention. In this case it is particularly preferred to use medicaments which are illustrated as being particularly preferred within the scope of medicaments according to the invention.

The process according to the invention has many advantages.

That is, for example, metering and uniform distribution of organic cyclic compounds containing keto groups and / or hydroxyl groups are possible without difficulty, resulting in pulp of uniform quality. Furthermore, the addition of organic cyclic compounds containing keto groups and / or hydroxyl groups in industrial facilities for pulp production has been found to have a beneficial effect on a laboratory scale under ideal conditions.

In laboratory tests, for example, the lignocellulosic material is stirred in a pulp preparation or bleach solution which promotes the distribution of the additive. In industrial installations for pulp production this case falls within the minimum range and the distribution of additives is more difficult if the pharmaceutical form according to the invention is not applied to them.

Example 1

In a mixture of 248 ml of water, 2 g of sodium pentachlorophenolate, 100 g of ethylene glycol and 150 g of 50% sodium titanate ligninsulfonate obtained from pulp preparation, 500 g of 9,10-anthraquinone was added to a high speed stirring ball mill. Pulverize for 15 minutes with 0.3 to 0.4 mm diameter glass beads in Farbe und Lack "71 (1965) described on page 377). The particle size of the anthraquinone in the pumpable dispersion obtained after milling was less than 10 μm. About 95% of the particles were less than 5 μm. Anthraquinone did not precipitate even after standing at room temperature for several weeks.

Example 2

A paste in which 600 g of 9,10-anthraquinone was added to 316 ml of water and 60 g of ethylene glycol was added to 20 g of sodium dinaphthylmethinesulfonate, and ground in a high-stirring ball mill designated in Example 1. After grinding, the particle size of the anthraquinone was the same as in Example 1. 4 g of swellable aluminum silicate or magnesium silicate are then added to the dispersion as a thickener and stirred. The free-flowing dispersion of anthraquinone does not precipitate and upon stirring in the wood pulp liquors of the craft and soda processes, it becomes a stable dispersion in the wood pulp liquor.

Example 3

9,10-anthraquinone in a mixture of 312 g of water, 60 g of ethylene glycol, 20 g of a condensation product of naphthalene sulfonate and formaldehyde, 4 swellable aluminum silicates, 3 g of 45% titer sodium hydroxide solution and 2 g of formaldehyde depot comound. The paste to which 600 g is added is premixed in a dissolver and ground in a mill corresponding to Example 1. After grinding, the size of the anthraquinone was as in Example 1. A pumpable dispersion is obtained which does not separate even after long periods of storage and which is easily dispersed in the so-called whote liquor (aqueous solution of pulp chemical) in the craft and soda processes.

Example 4

Similar to Example 2, 600 g of 9,10-anthraquinone was pulverized in 100 g of ethylene glycol, 250 g of water, and 30 g of sodium ligninsulfonate, and the viscosity was increased to 5 g with 20 g of chalk or methyl cellulose, thereby forming a formaldehyde adduct. Preserve using As in Example 1, a pumpable and stable dispersion is obtained.

Example 5

Similarly to Example 2, 90 g of ethylene glycol monoethyl ether, 250 g of water, and 20 g of a condensation product of naphthalene sulfonate and formaldehyde were pulverized by adding 600 g of 9,10-anthraquinone and concentrated to 20 g of chalk to 45%. Titer Alkaline is eluted with 3 g sodium hydroxide solution. As in Example 4, pumps that can be easily stirred in woodpulp liquors of the craft and soda processes are possible and stable dispersions are obtained.

Example 6

As in Example 1, 500 g of 9,10-anthraquinone was pulverized in 490 g of an aqueous pulp solution (= black liquor) containing ligninsulfonate and thickened to 1% by weight of swellable aluminum silicate. A stable, pumpable anthraquinone dispersion is obtained that can be easily stirred in the liquid.

Example 7

A paste obtained by adding 500 g of 9,10-anthraquinone to a mixture of 323 ml of water, 2 g of sodium pentachlorophenolate, 100 g of ethylene glycol and 75 g of cresol, 2-naphthol-6-sulfonic acid and formaldehyde condensation product was prepared as in Example 1. Crush. Anthraquinone does not precipitate from the dispersion obtained.

Example 8

For sodium pentachlorophenolate, 516 g of an aqueous 50% titer sodium ligninsulfonate solution is added to the dispersion obtained according to Example 1 by adding an equal amount of water instead of ethylene glycol. This dispersion is then dried in a spray dryer (inlet temperature 180 ° C. outlet temperature 90 ° C.). The obtained granules, consisting of 60% by weight of ankraquinone and 40% by weight of sodium lignin sulfonate, are easily dispersed by stirring in water or in a craft pulp or soda wood pulp solution.

Example 9

As in Example 8, it is easily dispersed in water or in the wood pulp preparation during the craft or soda process, and granules containing 50% by weight of anthraquin and 50% by weight of sodium ligninsulfonate are 50% titer of water-soluble sodium liginine. 850 g of sulfonate are obtained.

Example 10

As in Example 8, the granules can be easily dispersed in water or in the wood pulp solution during the craft or soda process, and the granules containing 30% by weight of anthraquinone and 70% by weight of sodium lignin sulfonate are 50% aqueous sodium lignin sulfonate aqueous solution. Obtained by adding 2,084 g.

Example 11

Prepared in a similar manner to Examples 8 to 10, except that instead of sodium lignin sulfonate, a condensation product of naphthalene sulfonate and formaldehyde is used to prepare the anthraquinone composition in water or in the craft of creep or soda, with a simple stirring in woodpulp liquor. Can be easily dispersed.

In a corresponding manner, however, anthraquines prepared using condensation products of sulfonated ditolylether and formaldehyde, or condensation products of sulfonated diphenylether and formaldehyde, or condensation products of sulfonated terphenyl and formaldehyde, The composition can be easily dispersed by simple agitation in wood or pulp liquor during the water or craft process or soda process.

Example 12

9,10-anthraquin, which is pulverized by air and pulverized to a particle size of 10 μm or less, is strongly mixed with 500 g of 333 mg of sodium lignin sulfonate.

This formulation is stirred in water or woodpulp liquor during the craft or soda process to obtain a very finely dispersed dispersion.

Example 13

The preparation which is very finely dispersed when stirred in the wood pulp liquor during water or in the craft or soda process is prepared by mixing 9,10-anthraquin ground in accordance with Example 12 with 500 g of sodium ligninsulfonate and 500 g of sodium ligninsulfonate. Obtained.

Example 14

9,10-anthraquin ground in accordance with Example 12 was mixed with 1,117 g of sodium ligninsulfonate to obtain a formulation containing 30% by weight of anthraquinone and 70% by weight of sodium lignin sulfonate. The preparation is stirred in water or woodpulp liquor during the craft or soda process to obtain a very finely dispersed dispersion.

Example 15

500 g of 9,10-anthraquinone and 50 g of a condensation product of naphthylenesulfonate, diphenylether sulfonate, or ditolylether sulfonate and formaldehyde are ground to a particle size of 10 μm or less in a gel mill operated by air. do. Stirring the formulation in 290 g of water or the corresponding amount of kraft pulp liquor or soda pulp liquor results in a pulpable dispersion which is stable for a long time and readily dispersed in either kraft pulp liquor or soda pulp liquor.

Example 16

500 g of 9,10-anthraquinone and 10 g of the condensation product of naphthalenesulfonate and formaldehyde are ground together. Very easily distributed in kraft pulp or soda pulp when stirred at 330 g of a mixture of finely divided powdery water / glycol in a ratio of 2: 1 to 10: 1 or a corresponding amount of kraft pulp or soda pulp A stable pumpable dispersion is obtained. The same results are obtained when 10 g of condensation product of diphenylsulfonate and formaldehyde or 10 g of condensation product of ditolylsulfonate and formaldehyde are used.

Example 17

600 g of 9,10-anthraquinone, 100 g of a condensation product of niphthalenesulfonate and formaldehyde, 2 g of aluminum silicate and 2 g of sodium hydroxide are ground together with a gel mill to obtain a 5-20 μm particle size formulation. The formulation is stirred with 600 g of water or wood pulp liquor during the craft or soda process to obtain a stable dispersion.

Example 18

Anthraquis such as monoalkyl-, dialkyl-, hydroxy-, amino-, alkoxy- and alkylamino-anthraquinones are derivatives or anthraquines instead of 1,3 dienes and 1,4-naphthoquinones or 1, Using Examples 1-17 using the correspondingly ringed Diels-Alder adduct of 4-benzoquinone, a powdered mixture or stable pump that can be converted into a stable and pumpable dispersion using a predetermined amount of liquid Possible dispersions are obtained. The dispersion obtained is characterized by crab dispersing without problems in either crep pulp or soda pulp liquor.

Example 19

400 g of 9,10-anthraquinone are ground in a bead mill similarly to Example 1 in 580 g of ethylene glycol and 20 g of sodium dinaphthylmethanesulfonate. A pumpable dispersion is obtained which is stable as in Examples 3 and 4 and which can be easily stirred in woodpulp liquor during the craft and soda processes.

Claims (1)

At least 80% by weight of the particles have a size of less than 5 μm, and are used as surfactants in the form of finely divided organic, cyclic compounds, and lignin sulfonates or aromatic sulfonic acids and formaldehyde condensation products containing keto groups or hydroxyl groups. A pulp manufacturing agent, characterized in that it contains as.