EP1417375A2

EP1417375A2 - Use of emulsions during de-inking

Info

Publication number: EP1417375A2
Application number: EP02760308A
Authority: EP
Inventors: Ingo Von Medvey; Thomas Rajcsanyi; Johann Schulte; Joachim Werres
Original assignee: Stockhausen GmbH; Stockhausen GmbH and Co KG; Chemische Fabrik Stockhausen GmbH
Current assignee: Ineos Composites IP LLC
Priority date: 2001-08-08
Filing date: 2002-08-03
Publication date: 2004-05-12
Also published as: WO2003014468A3; DE10138029A1; WO2003014468A2

Abstract

The invention relates to the use of oil in water emulsions in order to reduce points of dirt during the de-inking of waste paper materials.

Description

Use of emulsions for deinking

The present invention relates to the use of oil-in-water emulsions to reduce the dirt points when deinking waste paper materials.

In the course of material recycling, printed paper is often used in the manufacture of paper. This printed paper must be freed from color pigments as completely as possible before reuse so that the whiteness of the paper produced is not reduced and dirt spots are avoided. There has been no shortage of attempts to improve deinking in the past.

For example, EP 0 027 922 A1 teaches a flotation agent for removing pigments from waste paper, consisting of a carboxylic acid ester and 0 to 10% by weight, based on the ester, of a surface-active compound.

DE 42 04 915 C2 discloses a method in which the reprocessing of waste paper in the presence of peroxides and flotation aids is taught. Multifunctional carboxylic acids, which in addition to the acid group also contain at least one carboxyl, carboxylate, hydroxyl and / or vinyl group, are used as flotation aids together with polymeric compounds.

EP 0 906 465 B1 teaches a deinking process, preferably flotation deinking, in which an alkaline earth metal dispersion is added to the pulp slurry in an amount sufficient to remove the printing ink from the slurry and to increase the brightness of the pulp.

EP 0 823 949 B1 teaches a process for deinking waste paper materials which have dye pigments. The waste paper is processed into a slurry, which is mixed with an aqueous medium that contains a surface-active substance.

EP 0 738 341 discloses a collector for decolorizing waste paper using the flotation process, which contains a polyester. DE-OS 27 56 711 B1 claims a process in which the waste paper is impregnated with surface-active agents and, if appropriate, alkalis and treated with terpenic hydrocarbons and alcohols or their mixture with the addition of carrier substances which contain calcium soaps, and the suspension formed is treated in the usual way.

However, all of the above methods have the disadvantage that the reduction of so-called dirt points, i.e. Dye particles with an area-like circle diameter of> 100 μm, only insufficiently done.

It was therefore the task of avoiding the above-mentioned disadvantages of the prior art and in particular of identifying means with which the dirt points can be reduced during deinking.

This object is achieved according to the invention by the use of oil-in-water emulsions to reduce the dirt points when deinking waste paper materials which, as part of the oil phase, contain at least one of the following substances, alone or as a mixture with one another:

1. a saturated or unsaturated, open-chain or cyclic, normal or isomeric hydrocarbon with 8 to 30 carbon atoms

2. a saturated or unsaturated fatty alcohol, a saturated or unsaturated fatty acid, a fatty acid monoalkyl ester, a fatty acid amide or a fatty acid monoalkylamide of a saturated or unsaturated fatty acid, the fatty alcohol, the fatty acids and fatty acid residues of the listed compounds having 8 to 30 carbon atoms.

3. a mono- or polyester of a saturated or unsaturated mono- or polyvalent carboxylic acid with 2 to 30 carbon atoms and a monoalcohol and / or a polyol, with the exception of polyethylene glycols, preferably diesters of aliphatic and / or aromatic di- and / or tricarboxylic acids. 4. a polyamide of saturated or unsaturated fatty acids with 8 to 3 t) carbon atoms and aliphatic polyamines with two to six nitrogen atoms

5. an acyclic, preferably monocyclic and / or bicyclic terpene, in particular a terpene hydrocarbon and / or a terpene alcohol and / or

6. a polyoxyalkylene compound based on alkylene oxides.

Mono- or polyester of a saturated or unsaturated carboxylic acid or dicarboxylic acid having 4 to 30 carbon atoms and a monoalcohol and / or a polyol, with the exception of polyethylene glycols, are preferably used as the oil phase, alone or in a mixture. The oil phase very particularly preferably has di-n-butyl adipate.

The use of these oil-in-water emulsions is known from various fields. However, it was surprising to find that these emulsions succeed in reducing dirt spots on waste paper significantly better than is possible with methods according to the prior art.

The preparation of the emulsions to be used according to the invention, in particular stable oil-in-water emulsions, is known. For this purpose, the oil component is preferably emulsified in water by means of a suitable, known emulsifier, preferably at least one oil-in-water emulsifier and / or at least one emulsifying aid. Such emulsifiers and emulsifying aids are in Ulimann's Encycl. of ind. Chem Vol. 9, pages 312-325 (19). This text passage is hereby introduced as a reference and is therefore considered part of the disclosure. The hydrophobic phase mainly represents the active ingredient.

The following are examples of hydrophobic oil components: saturated hydrocarbons such as octane, tetradecane, octadecane, icodecane, decene, hexadecene and technical alpha-olefins,

Fatty alcohols such as octanol, dodecanol, tridecanol, hexadecanol, octadecanol, behenyl alcohol, Fatty acids such as capric acid, stearic acid, melissic acid, oleic acid and linolenic acid,

Fatty acid esters such as stearyl acid methyl ester, palmitic acid octadecyl ester, oleic acid octyl ester, glycerol mono- and trioleate, ethylene glycol dilaurate, sorbitan stearates and oleates as well as esters, especially diesters of aliphatic and / or aromatic di- and / or tricarboxylic acids such as Ci and C- _I3 alkyl esters ₂ - Cι ₂ dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, l suberic acid, sebacic acid, malic acid, tartaric acid, citeronic acid, phthalic acid, dodecanoic acid, C9-dicarboxylic acid (trimethyladipic acid) and maleic acid and fumaric acid. Further examples of such esters are: di-n-butyl oxalate, di-n-butylmalonate, di-n-butyl succinate, di-n-butyl glutarate, di-n-butyl adipate, di-n-butyl suberate, di-n-butyl sebacate, dimethyl adipate, Diethyl adipate, di-n-propyl adipate, diisopropyl adipate, diisobutyl adipate, di-tert-butyl adipate, di-isoamyl adipate, di-n-hexyl adipate, di- (2-ethylbutyl) adipate, di- (2-ethylhexyl) adipate, diisodecyl adipate, diisodecyl adipate, diisodecyl adipate Diethyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, di (2-ethylhexyl) phthalate and diisodecyl phthalate.

Fatty acid amides such as stearylamide, coconut fatty acid butylamide, acetic acid oleylamide and ethylene bisstearylamide.

Terpenes, such as menthol or orange terpene (company Weißmer Baltische HG, Hamburg).

Other suitable commercially available hydrocarbons or hydrocarbon mixtures are paraffin oil or mineral oil.

Fats and oils on a native basis are also suitable, in particular vegetable oils and preferably rapeseed oil.

The saturated or unsaturated fatty alcohols, which according to the invention as Emulsion components can be used by known methods, for. B. the oxo synthesis as oxo alcohols or after the Guerbet reaction available as Guerbet alcohols.

Polyoxyalkylene compounds based on alkylene oxides and / or fatty acid glycerides of C ₂ -C 8 fatty acids are those which are described, inter alia, in DE-AS-1 270 542 and EP 0 247 509 B1.

When terpenes are used, they are preferably used in a mixture with a saturated or unsaturated fatty alcohol.

The proportion of the oil phase in the oil-in-water emulsion is 1-90% by weight, preferably 1-50% by weight and particularly preferably 5-30% by weight, based on the total oil-in-water Emulsion.

The oil-in-water emulsions to be used according to the invention are used as such or in dilution with water or water- and / or solvent-containing mixtures.

The oil-in-water emulsion to be used according to the invention can be added to the waste paper at any location before the first flotation. However, the addition is preferably already made in the pulper, in which the waste paper is crushed and mixed with water.

In a preferred embodiment of the present invention, the pulper is operated in such a way that the pulp slurry is preferably at least 3.5, particularly preferably 4-24, very particularly preferably 6-16 and most preferably 8-12 hours in the presence of the oil-in-water Emulsion swells.

In the use according to the invention, 0.5-20.0 g, preferably 3.0-10.0 g and particularly preferably 5.0-8.0 g of the oil-in-water emulsion are preferably used per kilogram of waste paper stock. The oil-in-water emulsions described can be used in any deinking process. However, they are preferably used for neutral inking, which is described, for example, in the weekly paper paper paper 11/12, pages 754-764. This publication is hereby introduced as a reference and is therefore part of the disclosure.

The invention is explained below with reference to Comparative Example 1 and Examples 2-4. These explanations are only examples and do not limit the general idea of the invention.

The experimental plant had a pulper, a first flotation, a dispersion and a second flotation. All tests were carried out with this system using aged German telephone books of editions 97/98 and 98/99. In all experiments, 0.75% by weight of H ₂ O ₂ , 0.8% by weight of NaOH, 2.0% by weight of water glass and 0.8% by weight of Olinor were added to the waste paper in the pulper. The percentages by weight relate in each case to the pulp content of the dispersion. Olinor is a product of NOPCO Paper Technology GmbH, Düsseldorf, Federal Republic of Germany.

The dirt spots [mm ² / m ² ] were determined in each test after the 1st or 2nd flotation using an image analyzer (DOT Counter 2.0). The determination was made according to the Voith-Sulzer method: Determination of dirt spots in the visible range:

Rapid-Köthen laboratory sheets with 80 g / m ² (lutro) area-related mass are produced from the sample to be tested.

The number of sheets per measuring point is matched to the respective quality requirement and is for

Newspaper printing: 2 sheets

LWC / SC: 2 sheets before dispersion I

5 sheets after dispersion • DIP quality for increased requirements: 2 sheets before dispersion I 5 sheets after dispersion I 10 sheets after dispersion II

with loading <10 ppm (mm ² / m ² ) increase to 20 sheets (+ investigation report 6/6/95)

The dirt spot is measured on both sides of the sheets with a measuring area of 100 cm ² each on the DOT Counter 2.0.

The DOT Counter 2.0 is a scanner for determining the size, number and area of particles. Ten size classes are freely programmable, with the smallest resolution being 50 μm. The average of the individual measurements is given.

Alternatively, the dirt points can be determined using the T213 or T563 method (T = Tappi).

The whiteness is measured with an Elrepho 2000, filter 0 110 mm. The measurement is carried out in accordance with DIN 53145 / Part 1 + 2, ISO 2469 and ISO 2470.

The examples according to the invention were carried out either with Tallofin ^® DB or with Tallofin ^® S1449. Tallofin ^® is a trademark of Stockhausen GmbH & Co. KG., Bäkerpfad 25, D-47805 Krefeld.

Comparative Example 1

In this experiment the waste paper was mixed with the above chemicals in the pulper. The resulting pulp slurry had a swelling time in the pulper of 16 hours. Example 2

The test conditions correspond to those of the comparative test. However, in addition to the chemicals mentioned above, the waste paper was also mixed with 1 g Talofin ^® DB per kilogram of waste paper.

Example 3

The test conditions correspond to those of the comparative test. However, in addition to the chemicals mentioned above, 0.2 g Talofin ^® S 1449 per kilogram of waste paper was added to the waste paper in the pulper.

Example 4

The test conditions correspond to those of the comparative test. However, in addition to the chemicals mentioned above, the waste paper was additionally mixed with 0.4 g Talofin ^® S 1449 per kilogram of waste paper.

The results of the tests are shown in the following table:

Table 1

Another series of tests (comparative example 5 and example 6) was carried out on a test installation which is shown in FIGS. 1 and 2.

Figure 1 shows the first section of the test facility.

Figure 2 shows the second section of the test facility.

Both flotation units in the pilot plant each consisted of six flotation cells connected in series. All experiments were carried out using household collectibles. In all experiments, the waste paper in the pulper was treated with 1.2% by weight H ₂ O ₂ , 0.5% by weight NaOH, 1.8% by weight water glass and 0.7% by weight Serfax MT 90 , an alkali soap (Na) of d ₆ - C-ι ₈ fatty acids. Serfax MT 90 is a product of Stephenson Recycling Chemicals, PO Box 305, Listerhills Road, Bradford, West Yorkshire, BD 7 1 HY, England. The percentages by weight are based in each case on the pulp content of the dispersion. The swelling time in these experiments was only 10 minutes.

A further 0.4% by weight of Serfax MT 90 is added before the second flotation.

The areas covered with dirt spots [mm ² / m ² ] were determined in each experiment after the 1st or 2nd flotation in accordance with an image analyzer (DOT Counter 2.0). The determination was carried out in accordance with the Voith-Sulzer method described. Alternatively, the determination can be carried out according to methods T213 or T563 (T = Tappi).

The brightness is measured according to DIN 5033. The inventive examples were carried out either with TALLOFIN ^® DB. Tallofin ^® is a trademark of Stockhausen GmbH & Co. KG., Bäkerpfad 25, D-47805 Krefeld.

Comparative Example 5

In this experiment the waste paper was mixed with the above chemicals in the pulper. The results are summarized in Table 2.

Example 6

The test conditions correspond to those of the comparative test. However, in addition to the chemicals mentioned above, the waste paper was mixed with 0.8 g Talofin ^® DB per kilogram of waste paper. The results are summarized in Table 3.

Table 2

Table 3

Claims

claims:

1. Use of oil-in-water emulsions to reduce the dirt points when deinking waste paper materials, characterized in that they contain at least one of the following substances as a component of the oil phase, alone or as a mixture with one another:

3. a mono- or polyester of a saturated or unsaturated mono- or polyvalent carboxylic acid with 2 to 30 carbon atoms and a monoalcohol and / or a polyol, with the exception of polyethylene glycols

4. a polyamide of saturated or unsaturated fatty acids with 8 to 30 carbon atoms and aliphatic polyamines with two to six nitrogen atoms

6. a polyoxyalkylene compound based on alkylene oxides.

2. Use according to claim 1, characterized in that the oil phase has at least one diester of aliphatic and / or aromatic di- and / or tricarboxylic acids, preferably di-n-butyl adipate.

3. Use according to claim 1 or 2, characterized in that the oil-in-water emulsion contains at least one emulsifier and / or at least one emulsifying aid for the oil phase.

4. Use according to one of claims 1 to 3, characterized in that the oil-in-water emulsions are added to the waste paper materials when the pulp is slurried.

5. Use according to claim 4, characterized in that the pulp slurry swells at least 3.5, preferably 4-24, particularly preferably 6-16, very particularly preferably 8-12 hours.

6. Use according to any one of claims 1-5, characterized in that 0.5 - 20.0, preferably 3.0 - 10.0 and particularly preferably 5.0 - 8.0 g of the oil-in-per-kilogram of waste paper stock Water emulsion can be added.