WO2004048680A2 - Method of removing printing ink from waste paper by flotation deinking - Google Patents

Method of removing printing ink from waste paper by flotation deinking Download PDF

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Publication number
WO2004048680A2
WO2004048680A2 PCT/EP2003/012281 EP0312281W WO2004048680A2 WO 2004048680 A2 WO2004048680 A2 WO 2004048680A2 EP 0312281 W EP0312281 W EP 0312281W WO 2004048680 A2 WO2004048680 A2 WO 2004048680A2
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WIPO (PCT)
Prior art keywords
flotation
value
range
pulp
waste paper
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PCT/EP2003/012281
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French (fr)
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WO2004048680A3 (en
WO2004048680A8 (en
Inventor
Hans Ulrich SÜSS
Ralf Grimmer
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Degussa Ag
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Application filed by Degussa Ag filed Critical Degussa Ag
Priority to DE2003618480 priority Critical patent/DE60318480T2/en
Priority to EP03811749A priority patent/EP1565611B1/en
Priority to AU2003302433A priority patent/AU2003302433A1/en
Publication of WO2004048680A2 publication Critical patent/WO2004048680A2/en
Publication of WO2004048680A3 publication Critical patent/WO2004048680A3/en
Publication of WO2004048680A8 publication Critical patent/WO2004048680A8/en

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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/02—Working-up waste paper
    • D21C5/025—De-inking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the invention is directed towards a method of removing printing ink from waste paper by flotation deinking.
  • the method comprises two flotation steps and is suitable especially for deinking waste paper which, in addition to conventionally printed paper, also contains paper printed with water-soluble inks, such as ink et inks.
  • Water-soluble printing inks on the other hand, such as flexographic printing inks and inkjet printing inks, which may also contain very small colouring ' pigments which have been rendered hydrophilic by sulfonation, cannot be separated off by conventional flotation deinking or cannot be separated off very satisfactorily.
  • Office waste paper which in itself is a high quality raw material, therefore becomes a problem material because it is too dark even for printing paper of the lowest brightness, newsprint.
  • the dissolved printing inks contaminate the water circuit.
  • the fillers are also removed at the same time, so that the yield of such a deinking process falls to values of about/below 70 %.
  • waste paper printed with conventional intaglio printing and with aqueous inks can be deinked as follows: the waste paper is broken up in the presence of alkali, hydrogen peroxide and sodium silicate, the pulp is diluted and deflaked, the pulp is washed, followed by thickening and alkaline flotation and flocculation of the slurry formed in the washing step.
  • the process as a whole is technically very complex and results in a poor yield.
  • waste paper of which at .least some is printed with flexographic printing inks can be deinked at least partly by a combination of conventional alkaline flotation with subsequent acid flotation in the presence of a quaternary ammonium salt having a hydrophobic side chain.
  • the pulp from the alkaline flotation step is adjusted to pH 5 using sulfuric acid.
  • the brightness (% ISO) obtainable by that method is still very low at about 54, so that the inclusion of a subsequent washing step is proposed.
  • the above- mentioned document proposes maintaining the pH value in the 10 . acid range by the continuous addition of an acid: Using aluminium sulfate as the acid, the pH value should be maintained in the range of from 6.5 to 6.8.
  • the deinking methods according to US Patents 5,225,046 and 5,227,019 comprise five and six method steps, respectively, and accordingly are technically very complex.
  • a pulp is washed at a pH value of equal to/less than 7, in the presence of a surface- active deinking agent, the washed pulp is then bleached, and the bleached pulp is treated in a further washing or flotation operation at a pH value ' of equal to/less than 7 in the presence of an alcohol ethoxylate or propoxylate.
  • the pulp is washed after a first alkaline flotation step, then bleached with hydrogen peroxide under alkaline conditions and subsequently treated in one or more flotation steps at a pH value of equal to/less than 7 in the presence of an alcohol ethoxylate or propoxylate.
  • the yield is drastically reduced owing to the ' necessarily prescribed washing step.
  • the object of the present invention is directed towards the provision of an improved method of removing printing inks.
  • the method which comprises an alkaline flotation step and a neutral to weakly acid flotation step, it is to be possible to obtain a deinked material with as high a brightness as possible in a satisfactory yield.
  • a method of removing printing inks comprises breaking up the waste paper in the presence of alkali to obtain a pulp, a first flotation step at a pH value in the range of from greater than 8 to 11 in the presence of sodium silicate and an anionic or non-ionic surfactant, and a second flotation step, wherein an acid is added to the pulp at the beginning of that step, characterised in that the pH value of the pulp from the first flotation step is lowered at the beginning of the second flotation step to a pH value in the range of from 5 to 7.5 using carbonic acid as the acid.
  • first and second flotation step are not to be understood as meaning that these two steps are strictly separate from one another, but rather that the flotation conditions relating to the -pH value and/or the added flotation auxiliary substances, especially therefore the surfactants having flotation activity, have changed.
  • the measure according to the invention that is to say the lowering of the pH value during the flotation using carbon dioxide, the additional loss of fibres and fillers is at a low level. Under optimised conditions, the loss in the second flotation step can be reduced to value ' s below 5 % .
  • the fact that only a small amount of chalk goes into solution in the method according to the invention is also demonstrated by the small increase in the water hardness to values of about 4 to 5 mmol . Ca/1.
  • the waste paper is broken up in a known manner in the presence of alkali and sodium silicate and sorted.
  • the subsequent alkaline flotation step is likewise carrie , out in a known manner, an anionic- or non-ionic surfactant preferably being present as collecting agent.
  • the surfactant which may also be added during the breaking up of the waste paper, is used in an effective amount.
  • anionic surfactants such as especially alkali salts of fatty acids having more than 12 carbon atoms, especially from 16 to 20 carbon atoms.
  • the pulp is diluted in one or two steps to give a consistency capable of flotation - usually from 0.3 to 3 wt.%.
  • the consistency for the flotation is preferably in the range of from 0.5 to 1.5 wt . % .
  • the alkalinity for the first flotation step results from the added sodium silicate and also from added alkali hydroxide solution, especially sodium hydroxide solution, and/or added alkali carbonate solution.
  • the pH value during the first flotation step is preferably in the range of approximately from 8 to 10.5, especially from 8.5 to 10 and particularly preferably about 9 (9 ⁇ 0.3) .
  • Air is usually used as the flotation gas; the amount of gas is- governed by conditions relating to the apparatus and by the operating conditions, especially the effectiveness of the added collecting agent (s) , and can be determined by simple optimisation.
  • the pH value is lowered at the beginning to a value in the range of from 5 to 7.5 using carbonic acid.
  • the pH value is lowered to from 5.5 to approximately 7.
  • the pH value is in the range of approximately from 8.5 to 10 ' during the first flotation step and in the range of from approximately 5.5 to. approximately 7 at the beginning of the second flotation step.
  • the pH adjustment for the second flotation step can be achieved using carbon dioxide or air enriched with carbon dioxide, for example flue gas.
  • the flotation can be carried out without further supply of further carbon dioxide, whereby the pH value slowly rises owing to the buffer action of the salts contained in the waste paper and the hardness of the water and may reach values of around or slightly above 8.
  • the decolouring action is substantially maintained in the second flotation step, even though the pH value may slowly migrate from the approximately neutral or weakly acid region to the weakly alkaline region.
  • carbon dioxide or a gas enriched with carbon dioxide it is also possible for carbon dioxide or a gas enriched with carbon dioxide to be introduced continuously or periodically into the pulp to be floated throughout the duration of the second flotation step, . in order to maintain the pH value below 8 and preferably in the range from 6.0 to approximately 7. in a flotation line comprising a plurality of flotation cells, carbon dioxide can be introduced into one or more of the last flotation cells to lower the pH.
  • the amounts of carbon dioxide or of a gas enriched with carbon dioxide that are used are advantageously such that, although the desired pH regulation is possible, carbon dioxide substantially does not act as a flotation gas . It is desirable for safety- related considerations to limit the amount of carbon dioxide used in a deinking installation.
  • the second flotation step is advantageously carried out in the presence of an effective amount of a non-ionic and/or cationic surfactant.
  • a non-ionic and/or cationic surfactant especially a quaternary ammonium salt or an ammonium salt of a tertiary a ine.
  • the flotation auxiliary substances to be used act as a foaming agent and/or a collecting agent.
  • the effective amount of such flotation auxiliary substances that is used in the second flotation step is usually in the range of from 0.01 to 1.0 wt.%, based on the waste paper used in the pulp.
  • the amount of the one or more flotation-active auxiliary substances that is used is preferably in the range of from 0.05 to 0.5. The person skilled in the art will determine the optimum amount of the mentioned auxiliary substance (s) by orientating experiments .
  • the flotation time of the two flotation steps can vary within wide limits, but preference is given to a total flotation time which can be implemented in existing flotation lines in practice.
  • the total time for the two flotation steps is preferably in the range of from 4 to 20 minutes, especially from -4 to 10 minutes, the time for the second step being so chosen that an effective increase in the brightness can be obtained.
  • the time for the second step is usually in the range of from 10 to 90 %, especially in the range from 20 to 50 %, of the flotation time for the two steps.
  • the flotation time of each of the two steps is in the range of from 2 to 5 minutes .
  • the method according to the invention is suitable for separating from waste paper conventional, that is to say hydrophobic, printing inks as well as water-soluble printing inks and hydrophilic colouring pigments
  • the waste paper used in the method according to the invention preferably contains correspondingly printed papers .
  • the non-ionic surfactants used in the second flotation step are surface-active substances which have a hydrophobic grouping and a hydrophilic non-ionic grouping. Particular preference is given to alkoxylated alcohols and alkoxylated fatty amides, which can readily be prepared from the corresponding fatty alcohols or fatty amides by alkoxylation with ethylene oxide or propylene oxide.
  • the preferred cationic surfactants are quaternary ammonium salts which have at least one medium- to long-chained hydrocarbon radical (especially C1 2 -C24) •
  • QUATS medium- to long-chained hydrocarbon radical
  • Tri (C 1 -C 3 ) alkyl- (C 12 -C 18 ) alkylammonium salts with hexadecyl-trimethylammonium salts, such as the chloride, being particularly preferred;
  • Ester quats which are to be understood as meaning, for example, reaction products of an alkanolamine with a medium- to long-chained fatty acid and subsequent quaternisation with an alkylating agent, such as dimethyl sulfate.
  • an alkylating agent such as dimethyl sulfate.
  • quaternisation products of reaction products of a natural fatty acid or a fatty acid mixture such as tall oil fatty acid, with monoethanolamine, diethanolamine or triethanolamine;
  • Fatty acylamidoamine ethoxylate QUATS Such substances are obtainable, for example, by reaction of a fatty acid
  • a triglyceride with a polyvalent amine such as dialkylenetriamine
  • a polyvalent amine such as dialkylenetriamine
  • an alkylating agent such as, for example, dimethyl sulfate
  • Particularly suitable substances from the last- 10 mentioned class can be obtained, for example, by - - amidation of diethylenetriamine with, oleic acid or tall oil fatty acid (molar ratio 1:2) with subsequent ethoxylation with ethylene oxide and quaternisation with dimethyl sulfate.
  • -quaternary ammonium salts which are readily obtainable from a fatty amine by ethoxylation and subsequent quaternisation with an ' alkylating agent, such as dimethyl sulfate.
  • coconut fatty amine can- first be ethoxylated and then converted into
  • a further class of effective cationic surfactants are fatty acylamidoalkylimidazolium salts, which are obtainable, for example, from reaction products of dialkylenetriamines with a fatty acid or a triglyceride,
  • the method according to the invention can be varied in many ways in respect of the individual features , but a particularly preferred method is characterised in that waste paper is broken up in the presence of sodium hydroxide, sodium silicate and hydrogen peroxide, the pulp is diluted to a consistency suitable for flotation, a first flotation step is carried out for from 2 to 10 minutes in the presence of from 0.3 to 1.5 wt.%, based on the waste paper used (absolutely dry) , of an anionic surfactant, especially an alkali salt of a fatty acid having from 16 to 18 carbon atoms, at a pH value of approximately from 8.5 to 10.0, and the pH value of the pulp so contained is lowered to a value in the range of from 5.5 to 7.5, especially from 6 to 7, by introduction of a C0 2 -rich gas, and the flotation is continued for a period of from 2 to 10 minutes in the presence of from" 0.05 to 0.5 wt.%, based on the waste paper used (absolutely dry) , of a
  • the method according to the invention is also suitable for improving the brightness of deinked material.
  • the pulp fed to the two-step method is produced by suspending a deinked material .
  • Waste paper was broken up for 30 minutes in a Hobart kneader with 0.75 wt.% H 2 0 2 , 0.8 wt.% Na oleate, 2 wt.% sodium silicate and 0.8 wt.% NaOH at 40°C and a consistency of 15 %. Dilution to a consistency of 5 % was then carried out and, after a further 15 minutes' treatment, to the consistency of 1 % used for the flotation (percentages based in each case on the dry waste paper) .
  • flotation was carried out in a 10 1 flotation cell with 2 1 of air/minute at approximately 40°C for a total time of 10 minutes (standard) . After the flotation, which was carried out in the presence of the indicated surfactants, thickening on a suction filter was carried out and the sheet was formed.
  • the brightness was determined in accordance with ISO2470.
  • the yield was determined by the dry determination of acceptor and flotation foam. Where washing- was carried out,- this took place in a conventional washing cell using 2 1 of . washing water per minute.
  • Example El of the invention show that it is possible, according to Example El of the invention, to carry out the acidification during the normal flotation time of 10 minutes and thereby remove the inkjet inks directly from the approximately neutralised pulp .
  • the intermediate thickening between the alkaline and the neutral flotation according to CE5 accordingly proved to be unnecessary.
  • Mixtures of paper can also be decoloured acceptably by means of washing (CE4) , but the yield is very low.
  • Example E2 to E4 the waste paper mixture (NP + BP (1:1)) was deinked in two steps at 40°C, wherein in the second step the pH value was lowered to ⁇ pH 7 using C0 2 (this takes place in a few seconds) and maintained substantially constant.
  • the surfactant used was Na oleate (0.8 %) in the first step and HDTMA (0.3) in the second step.
  • the flotation time was varied.
  • CE6 shows washing again, it being clear that, despite higher losses in yield, no ' better brightness is obtained than in the two-step flotation according to the invention. Table 2 shows - the parameters and results .
  • Office paper printed with inkjet ink (OP) was deinked; according to the invention, the amount of the surfactant HDTMA used being varied.
  • the first flotation step was carried out in the standard manner, i.e. 10 minutes at 40°C in the presence of 0.8 % Na oleate.
  • the pH value was then lowered using C0 2 and flotation was then carried out without the supply of further C0 2 .
  • an increase in the amount of HDTMA used led to a further increase in the brightness, the yield was reduced at the same time.
  • a waste paper mixture of office paper and newsprint was decoloured.
  • the two-step flotation was studied, the first step being carried out in the conventional manner at pH 9.6 in the presence of 0.8 % Na oleate as collecting agent.
  • CE7 shows the result of the first step after 10 minutes ' flotation.
  • E7 to E12 the flotation of the first step was carried out under the same conditions for only 5 minutes.
  • the second flotation step was carried out after lowering the pH value to approximately 6.4 using C0 2 and maintaining that pH value during a 5-minute flotation. Table 4 shows individual parameters and the results .
  • a deinked material from an operating installation was subjected to secondary flotation in two steps in accordance with the invention.
  • the first flotation step was carried out after addition of 2 % sodium silicate and 0.8 % Na oleate to the pulp at a pH value of 9.2 and a consistency of 1 % at 40°C.
  • the pH was lowered to 6.8 using C0 2 . Once that pH value had been reached, the C0 2 supply was discontinued and flotation was carried out with air.
  • alkaline flotation was carried out for 10 minutes, in Examples E13 and E14 flotation was carried out for 5 minutes in each step. The surfactant and the amount used were varied.
  • Table 5 shows the fundamental parameters and the results . Even a very small amount of a cationic surfactant produced a marked increase in the brightness .
  • imidazolium salt cationic surfactant
  • CE9 Alkaline flotation, 10 minutes at 40°C, at pH 9.2 in the presence of 0.3 % Na oleate and 2 % sodium silicate

Abstract

Continuous flotation deinking of waste paper under alkaline conditions may not satisfactorily remove hydrophilic and water-soluble printing inks. The invention solves that problem by a two-stage flotation method. An alkaline flotation step is immediately followed by a flotation step in the neutral to weakly acid pH range, the pH value being lowered at the beginning of the second flotation step to a pH value in the range of from 5 to 7.5 using carbon dioxide.

Description

Method of removing printing ink from waste paper by flotation deinking
Description:
The invention is directed towards a method of removing printing ink from waste paper by flotation deinking. The method comprises two flotation steps and is suitable especially for deinking waste paper which, in addition to conventionally printed paper, also contains paper printed with water-soluble inks, such as ink et inks.
An important step in the recycling of waste paper is the removal of the printing inks as far as possible. In conventional flotation deinking, the fibres of the waste paper are made to swell by the use of alkali, as a result of which the printing ink can be separated off. Hydrophobic printing ink particles can be collected and floated from the suspension of fibres, fillers and printing inks by a fatty acid salt precipitated in si tu . By means of this conventional method,.-which .comprises. breaking up .the.paper,, sorting, flotation under alkaline conditions and, optionally, a secondary flotation operation, hydrophobic printing ink can in most cases be removed satisfactorily.
Water-soluble printing inks, on the other hand, such as flexographic printing inks and inkjet printing inks, which may also contain very small colouring 'pigments which have been rendered hydrophilic by sulfonation, cannot be separated off by conventional flotation deinking or cannot be separated off very satisfactorily. Office waste paper, which in itself is a high quality raw material, therefore becomes a problem material because it is too dark even for printing paper of the lowest brightness, newsprint. In addition, the dissolved printing inks contaminate the water circuit. Although it is possible to separate off such water-soluble inks and hydrophilic colouring pigments by washing the waste paper, the fillers are also removed at the same time, so that the yield of such a deinking process falls to values of about/below 70 %.
The currently known prior art for deinking is described in detail in the article "Zweistufige, alkalisch-saure Flotation zur Eliminierung schwerentfernbarer Druckfarben aus Altpapier" by H. U. Suss et al . in "Das Papier" 45, No. 3 (1991), pages 89 - 96. According to that article, waste paper printed with conventional intaglio printing and with aqueous inks can be deinked as follows: the waste paper is broken up in the presence of alkali, hydrogen peroxide and sodium silicate, the pulp is diluted and deflaked, the pulp is washed, followed by thickening and alkaline flotation and flocculation of the slurry formed in the washing step. The process as a whole is technically very complex and results in a poor yield.
According to the above-mentioned document, waste paper of which at .least some is printed with flexographic printing inks can be deinked at least partly by a combination of conventional alkaline flotation with subsequent acid flotation in the presence of a quaternary ammonium salt having a hydrophobic side chain. In that process, the pulp from the alkaline flotation step is adjusted to pH 5 using sulfuric acid. The brightness (% ISO) obtainable by that method is still very low at about 54, so that the inclusion of a subsequent washing step is proposed. For the deinking of waste paper printed with offset inks and flexographic printing inks, H.U. Suss et al . ( loc. ci t . ) proposed carrying out high-consistency thickening after the alkaline flotation, with acidification and flotation in the presence of a cationic surfactant not taking place until dilution to flotation consistency has been carried out again. Although that method yields good brightnesses, it is technically very complex. In addition, the yield is low on account of the dissolution of the filler chalk during the 5 acidification.
For the secondary flotation of waste paper that has already been deinked in the conventional manner, the above- mentioned document proposes maintaining the pH value in the 10 .acid range by the continuous addition of an acid: Using aluminium sulfate as the acid, the pH value should be maintained in the range of from 6.5 to 6.8.
The article "Papierrecycling: Flotation von Fύllstoffen und 15 Fasern" by H.U. Suss et al . in "Wochenblatt fur
Papierfabrikation" 8 (1992), pages 303 to 307 also describes a two-step flotation - first under alkaline conditions and then under approximately neutral conditions - for the removal of printing inks from waste paper. Sodium 20 oleate is used as the collecting agent in the alkaline flotation step, with hexadecyltrimethylammonium chloride (HDTMA) being used in the neutral flotation step. There is no reference in that document as to how the pH value is to be adjusted in the virtually neutral flotation step.
25
Within the scope of considerations relating to the economy ' ' of flotation deinking under alkaline as well as under neutral conditions - see "Wochenblatt fur
Papierfabrikation", 123 (20), pages 916 - 919 (1995) - it 0 has been found that fatty acids have a good collecting action in the alkaline flotation, while neutral surfactants, such as ethoxylated alcohols, are effective as foaming agents and lower the surface tension but do not generate any actual collector effect. Accordingly, neutral foaming agents are recommended only for use in secondary flotation.
The deinking methods according to US Patents 5,225,046 and 5,227,019 comprise five and six method steps, respectively, and accordingly are technically very complex. In the method according to US 5,225,046, a pulp is washed at a pH value of equal to/less than 7, in the presence of a surface- active deinking agent, the washed pulp is then bleached, and the bleached pulp is treated in a further washing or flotation operation at a pH value' of equal to/less than 7 in the presence of an alcohol ethoxylate or propoxylate. In the method according to US 5,227,019, the pulp is washed after a first alkaline flotation step, then bleached with hydrogen peroxide under alkaline conditions and subsequently treated in one or more flotation steps at a pH value of equal to/less than 7 in the presence of an alcohol ethoxylate or propoxylate. In addition to the fact that the process is very complex from a technical point of view, the yield is drastically reduced owing to the 'necessarily prescribed washing step.
From EP 0 737 774 Al it is known that aqueous waste products from deinking installations can be freed of inorganic particles and fibres contained therein by precipitating the mentioned solids particles together with calcium carbonate formed in si tu from calcium hydroxide and introduced carbon dioxide. That method is, therefore, not a flotation method but a means of allowing the aqueous waste products to be returned to the deinking process again. While carbon dioxide has not been used in the above- mentioned documents either as a flotation gas or as an agent for lowering the pH value, EP 0 927 789 Al teaches that paper fibres can be separated by flotation from an aqueous suspension containing them, as is obtained in paper technology, for example flotation foams, by the use of carbon dioxide or a gas enriched with carbon dioxide. That flotation is not, however, so-called flotation deinking. In the article "Evaluation of carbon dioxide as a carriergas in flotation deinking" by Lorenzo Marchildon et al . in Tappi Journal, Vol. 76, No. 3, pages 155 - 159, it is stated that, in the case of acid flotation, beginning at a pH value of approximately 5, the optical properties when carbon dioxide is used as the flotation gas are better than those when air or nitrogen is used, but the mechanical properties are adversely affected. Although that disadvantage can be eliminated by a subsequent alkaline washing operation, the yield of deinked material is considerably reduced by such a process step. That document gives no indication as to how alkaline flotation is carried out first of all, immediately followed by flotation under neutral or weakly acid conditions.
As has been explained above, printing inks can be removed from waste paper in different ways, but those methods have deficiencies in one respect or another. Accordingly, the object of the present invention is directed towards the provision of an improved method of removing printing inks. By means of the method, which comprises an alkaline flotation step and a neutral to weakly acid flotation step, it is to be possible to obtain a deinked material with as high a brightness as possible in a satisfactory yield. According to a further object of the invention, it is to be possible to carry out the method in such a manner that no undesirable substances, such as sulfate, are introduced into the system and treatment of the waste water from the deinking process does not give rise to any new problems .
It has been found that, by using carbon dioxide immediately following a flotation step carried out under alkaline conditions, and by continuing the flotation under the pH conditions that become established in the weakly acid to neutral or weakly alkaline range, waste paper can be deinked to obtain high brightness in a good yield.
Accordingly, a method of removing printing inks has been found, which method comprises breaking up the waste paper in the presence of alkali to obtain a pulp, a first flotation step at a pH value in the range of from greater than 8 to 11 in the presence of sodium silicate and an anionic or non-ionic surfactant, and a second flotation step, wherein an acid is added to the pulp at the beginning of that step, characterised in that the pH value of the pulp from the first flotation step is lowered at the beginning of the second flotation step to a pH value in the range of from 5 to 7.5 using carbonic acid as the acid.
The further claims are directed towards preferred embodiments of the method according to the invention.
Accordingly, it has been found, surprisingly, that it is possible to combine the conventional alkaline flotation process and a weakly acid to neutral flotation directly, that is to say without the interposition of a washing step or a concentration step, if, during the conventional flotation, the pH value is shifted to the approximately neutral or weakly acid range by means of carbonic acid. By the use of carbonic acid to lower the pH value to the approximately neutral or weakly acid range during the conventional flotation, a marked improvement in the removal of water-soluble inks, such as inkjet printing inks, is obtained.
By means of the method according to the invention it is possible to dispense not only with a washing step between the two flotation steps, which reduces the yield, but also with an additional thickening operation between an alkaline and an acid flotation step, as was considered to be necessary in the document mentioned at the beginning (Das Papier, 45/3 (1991), pages 89 - 96). By the use of carbon dioxide to lower 'the pH value instead of a strong acid, such as sulfuric acid, there is also no loss of chalk, which has recently become increasingly important as a filler in paper. In addition, concentration of salts in the circulating water does not occur, and no new problems arise during the water treatment when carbonic acid is used instead of a strong acid to lower the pH value. A further advantage of the method according to the invention is that the flotation foams from the alkaline flotation step and from the neutral to weakly acid flotation step can be collected and processed together.
It is a particular advantage of the method according to the invention that it can be carried out in existing flotation devices in the paper industry, that is to say in a flotation line comprising a plurality of flotation cells.
In order to carry out the method according to the invention it is simply necessary to provide in one or more of the rear cells a device for introducing carbon dioxide into the pulp or/and for enriching the flotation air with carbon dioxide. Because of the absence of foreign substances in the method according to the invention, it is preferred to combine the flotation foams of all the cells and feed them to a secondary flotation operation in a manner known per se for the purposes of separating off fibres .
The terms "first" and "second" flotation step are not to be understood as meaning that these two steps are strictly separate from one another, but rather that the flotation conditions relating to the -pH value and/or the added flotation auxiliary substances, especially therefore the surfactants having flotation activity, have changed.
By the measure according to the invention, that is to say the lowering of the pH value during the flotation using carbon dioxide, the additional loss of fibres and fillers is at a low level. Under optimised conditions, the loss in the second flotation step can be reduced to value's below 5 % . The fact that only a small amount of chalk goes into solution in the method according to the invention is also demonstrated by the small increase in the water hardness to values of about 4 to 5 mmol . Ca/1.
In order to carry out the method according to the invention, the waste paper is broken up in a known manner in the presence of alkali and sodium silicate and sorted.
The subsequent alkaline flotation step is likewise carrie , out in a known manner, an anionic- or non-ionic surfactant preferably being present as collecting agent. The surfactant, which may also be added during the breaking up of the waste paper, is used in an effective amount.
Particular preference is given to anionic surfactants, such as especially alkali salts of fatty acids having more than 12 carbon atoms, especially from 16 to 20 carbon atoms. After the waste paper has been broken up, which takes place at a consistency in the range of about 15 % ± 5 %, the pulp is diluted in one or two steps to give a consistency capable of flotation - usually from 0.3 to 3 wt.%. The consistency for the flotation is preferably in the range of from 0.5 to 1.5 wt . % .
The alkalinity for the first flotation step results from the added sodium silicate and also from added alkali hydroxide solution, especially sodium hydroxide solution, and/or added alkali carbonate solution. The pH value during the first flotation step is preferably in the range of approximately from 8 to 10.5, especially from 8.5 to 10 and particularly preferably about 9 (9 ± 0.3) . Air is usually used as the flotation gas; the amount of gas is- governed by conditions relating to the apparatus and by the operating conditions, especially the effectiveness of the added collecting agent (s) , and can be determined by simple optimisation.
In the second flotation step, which directly follows the first flotation step, the pH value is lowered at the beginning to a value in the range of from 5 to 7.5 using carbonic acid. According to a preferred' embodiment, the pH value is lowered to from 5.5 to approximately 7. According to a preferred embodiment, the pH value is in the range of approximately from 8.5 to 10' during the first flotation step and in the range of from approximately 5.5 to. approximately 7 at the beginning of the second flotation step. The pH adjustment for the second flotation step can be achieved using carbon dioxide or air enriched with carbon dioxide, for example flue gas. After the pH value has been lowered in the second flotation step, the flotation can be carried out without further supply of further carbon dioxide, whereby the pH value slowly rises owing to the buffer action of the salts contained in the waste paper and the hardness of the water and may reach values of around or slightly above 8. Surprisingly, the decolouring action is substantially maintained in the second flotation step, even though the pH value may slowly migrate from the approximately neutral or weakly acid region to the weakly alkaline region.
According to an alternative embodiment, it is also possible for carbon dioxide or a gas enriched with carbon dioxide to be introduced continuously or periodically into the pulp to be floated throughout the duration of the second flotation step, . in order to maintain the pH value below 8 and preferably in the range from 6.0 to approximately 7. in a flotation line comprising a plurality of flotation cells, carbon dioxide can be introduced into one or more of the last flotation cells to lower the pH. The amounts of carbon dioxide or of a gas enriched with carbon dioxide that are used are advantageously such that, although the desired pH regulation is possible, carbon dioxide substantially does not act as a flotation gas . It is desirable for safety- related considerations to limit the amount of carbon dioxide used in a deinking installation.
The second flotation step is advantageously carried out in the presence of an effective amount of a non-ionic and/or cationic surfactant. Particular preference is given to the use of a cationic surfactant, especially a quaternary ammonium salt or an ammonium salt of a tertiary a ine. The flotation auxiliary substances to be used act as a foaming agent and/or a collecting agent. The effective amount of such flotation auxiliary substances that is used in the second flotation step is usually in the range of from 0.01 to 1.0 wt.%, based on the waste paper used in the pulp. The amount of the one or more flotation-active auxiliary substances that is used is preferably in the range of from 0.05 to 0.5. The person skilled in the art will determine the optimum amount of the mentioned auxiliary substance (s) by orientating experiments .
It has been found that, by optimising the choice of surfactant for the 2nd step, an amount in the range of only approximately from 0.02 to 0.1 wt.% is sufficient to achieve high activity, and a further increase in the amount used does not lead to a further increase in the brightness. A small amount is suitable especially in the case of a two- step secondary flotation, in order to increase the brightness of a moderately bright deinked material.
The flotation time of the two flotation steps can vary within wide limits, but preference is given to a total flotation time which can be implemented in existing flotation lines in practice. The total time for the two flotation steps is preferably in the range of from 4 to 20 minutes, especially from -4 to 10 minutes, the time for the second step being so chosen that an effective increase in the brightness can be obtained. The time for the second step is usually in the range of from 10 to 90 %, especially in the range from 20 to 50 %, of the flotation time for the two steps. According to a particularly preferred embodiment, the flotation time of each of the two steps is in the range of from 2 to 5 minutes . Because the method according to the invention is suitable for separating from waste paper conventional, that is to say hydrophobic, printing inks as well as water-soluble printing inks and hydrophilic colouring pigments, the waste paper used in the method according to the invention preferably contains correspondingly printed papers .
The non-ionic surfactants used in the second flotation step are surface-active substances which have a hydrophobic grouping and a hydrophilic non-ionic grouping. Particular preference is given to alkoxylated alcohols and alkoxylated fatty amides, which can readily be prepared from the corresponding fatty alcohols or fatty amides by alkoxylation with ethylene oxide or propylene oxide.
The preferred cationic surfactants are quaternary ammonium salts which have at least one medium- to long-chained hydrocarbon radical (especially C12-C24) • Of the quaternary ammonium salts having surfactant activity, which are frequently referred to as QUATS for short, the following classes of substances may be mentioned by way of example:
❖ Tri (C1-C3) alkyl- (C12-C18) alkylammonium salts, with hexadecyl-trimethylammonium salts, such as the chloride, being particularly preferred;
❖ Ester quats, which are to be understood as meaning, for example, reaction products of an alkanolamine with a medium- to long-chained fatty acid and subsequent quaternisation with an alkylating agent, such as dimethyl sulfate. There are suitable, for example, quaternisation products of reaction products of a natural fatty acid or a fatty acid mixture, such as tall oil fatty acid, with monoethanolamine, diethanolamine or triethanolamine;
❖ Fatty acylamidoamine ethoxylate QUATS: Such substances are obtainable, for example, by reaction of a fatty acid
5 or a triglyceride with a polyvalent amine, such as dialkylenetriamine, with subsequent alkoxylation with, for example, ethylene oxide and subsequent alkylation with an alkylating agent, such as, for example, dimethyl sulfate. Particularly suitable substances from the last- 10 mentioned class can be obtained, for example, by - - amidation of diethylenetriamine with, oleic acid or tall oil fatty acid (molar ratio 1:2) with subsequent ethoxylation with ethylene oxide and quaternisation with dimethyl sulfate.
15 ❖ Fatty acylamidoamine carboxylic acid salts, the above- mentioned reaction sequence taking place, instead of with alkylation, with salt formation with an acid, such as a lower carboxylic acid or hydroxycarboxylic acid, for example lactic acid.
20 ❖ Also effective are -quaternary ammonium salts, which are readily obtainable from a fatty amine by ethoxylation and subsequent quaternisation with an' alkylating agent, such as dimethyl sulfate. For example, coconut fatty amine can- first be ethoxylated and then converted into
25 QUAT using dimethyl sulfate.
❖ A further class of effective cationic surfactants are fatty acylamidoalkylimidazolium salts, which are obtainable, for example, from reaction products of dialkylenetriamines with a fatty acid or a triglyceride,
30 by imidazole ring formation.
The method according to the invention can be varied in many ways in respect of the individual features , but a particularly preferred method is characterised in that waste paper is broken up in the presence of sodium hydroxide, sodium silicate and hydrogen peroxide, the pulp is diluted to a consistency suitable for flotation, a first flotation step is carried out for from 2 to 10 minutes in the presence of from 0.3 to 1.5 wt.%, based on the waste paper used (absolutely dry) , of an anionic surfactant, especially an alkali salt of a fatty acid having from 16 to 18 carbon atoms, at a pH value of approximately from 8.5 to 10.0, and the pH value of the pulp so contained is lowered to a value in the range of from 5.5 to 7.5, especially from 6 to 7, by introduction of a C02-rich gas, and the flotation is continued for a period of from 2 to 10 minutes in the presence of from" 0.05 to 0.5 wt.%, based on the waste paper used (absolutely dry) , of a cationic or non- ionic surfactant, especially a cationic surfactant, wherein the pH value of the pulp in the second step, which is initially lowered, may rise owing to the buffer action of the pulp and/or the hardness of the water used in the production of the pulp or is maintained in the range of from 6 to approximately 7 for an effective period by the periodic or continuous introduction of a C02-rich gas.
The method according to the invention is also suitable for improving the brightness of deinked material. The pulp fed to the two-step method is produced by suspending a deinked material .
The method according to the invention is illustrated further by means of the following Examples . Examples
General procedure for pulp production and flotation :
Waste paper was broken up for 30 minutes in a Hobart kneader with 0.75 wt.% H202, 0.8 wt.% Na oleate, 2 wt.% sodium silicate and 0.8 wt.% NaOH at 40°C and a consistency of 15 %. Dilution to a consistency of 5 % was then carried out and, after a further 15 minutes' treatment, to the consistency of 1 % used for the flotation (percentages based in each case on the dry waste paper) .
'
Unless indicated otherwise, flotation was carried out in a 10 1 flotation cell with 2 1 of air/minute at approximately 40°C for a total time of 10 minutes (standard) . After the flotation, which was carried out in the presence of the indicated surfactants, thickening on a suction filter was carried out and the sheet was formed.
The brightness was determined in accordance with ISO2470. The yield was determined by the dry determination of acceptor and flotation foam. Where washing- was carried out,- this took place in a conventional washing cell using 2 1 of . washing water per minute.
Comparison Examples CEl to CE5 and Example El .
The results of a standard alkaline flotation (CEl and CE3 ) and of the washing (CE2 and CE4) of office paper printed with inkjet inks (=0P) (CEl and CE2 ) and of a 1:1 mixture of offset newspapers and inkjet-printed office paper (OP + NP) (CE2 and CE4) are shown in Table 1. This table also contains the results of a two-step flotation deinking wherein, in accordance with the prior art, intermediate thickening was carried out between the "alkaline" and the "neutral" flotation (CE5) and, according to Example El according to the invention, no intermediate thickening took place and, in addition, the total flotation time of 10 minutes was divided over the two steps equally. In the second flotation step of Example El and step (3) of Comparison Example CE5, hexadecyl-trimethylammonium chloride (= HDTMA) was used as the surfactant.
The tests show that it is possible, according to Example El of the invention, to carry out the acidification during the normal flotation time of 10 minutes and thereby remove the inkjet inks directly from the approximately neutralised pulp . The intermediate thickening between the alkaline and the neutral flotation according to CE5 accordingly proved to be unnecessary. Mixtures of paper can also be decoloured acceptably by means of washing (CE4) , but the yield is very low.
Table 1
Figure imgf000018_0001
Figure imgf000018_0002
Examples 2 to 4
In Examples E2 to E4, the waste paper mixture (NP + BP (1:1)) was deinked in two steps at 40°C, wherein in the second step the pH value was lowered to < pH 7 using C02 (this takes place in a few seconds) and maintained substantially constant. The surfactant used was Na oleate (0.8 %) in the first step and HDTMA (0.3) in the second step. The flotation time was varied. CE6 shows washing again, it being clear that, despite higher losses in yield, no' better brightness is obtained than in the two-step flotation according to the invention. Table 2 shows - the parameters and results .
Table 2
Figure imgf000020_0001
Figure imgf000020_0002
Examples E5 and E6
Office paper printed with inkjet ink (OP) was deinked; according to the invention, the amount of the surfactant HDTMA used being varied. The first flotation step was carried out in the standard manner, i.e. 10 minutes at 40°C in the presence of 0.8 % Na oleate. The pH value was then lowered using C02 and flotation was then carried out without the supply of further C02. Although an increase in the amount of HDTMA used led to a further increase in the brightness, the yield was reduced at the same time.
Table 3
Figure imgf000022_0001
Figure imgf000022_0002
Examples E7 to E12 and CEl
A waste paper mixture of office paper and newsprint was decoloured. The two-step flotation was studied, the first step being carried out in the conventional manner at pH 9.6 in the presence of 0.8 % Na oleate as collecting agent. CE7 shows the result of the first step after 10 minutes ' flotation. For Examples E7 to E12 the flotation of the first step was carried out under the same conditions for only 5 minutes. The second flotation step was carried out after lowering the pH value to approximately 6.4 using C02 and maintaining that pH value during a 5-minute flotation. Table 4 shows individual parameters and the results .
Using the indicated cationic surfactants, a brightness that was one to 2 points higher was obtained with the same total flotation time, although the yield was somewhat reduced.
Notes to Table 4:
11 to 51 are products of ' Degussa AG
" is an ester quat based on quaternised ethoxylated tall amine
21 and 4) are imidazolinium salts
) is an ester quat based on an amidoamine of triethanolamine and a fatty acid
5) Pseudo-QUAT = amidoamine ethoxylate salt Table 4: 1st flotation step alkaline (pH 9.6) (conventional conditions] 2nd flotation step with different cationic surfactants
Figure imgf000024_0001
Figure imgf000024_0002
Examples El 2 and El 4 and CE8
A deinked material from an operating installation was subjected to secondary flotation in two steps in accordance with the invention.
The first flotation step was carried out after addition of 2 % sodium silicate and 0.8 % Na oleate to the pulp at a pH value of 9.2 and a consistency of 1 % at 40°C. In the second step, the pH was lowered to 6.8 using C02. Once that pH value had been reached, the C02 supply was discontinued and flotation was carried out with air. In Comparison Example CE8, alkaline flotation was carried out for 10 minutes, in Examples E13 and E14 flotation was carried out for 5 minutes in each step. The surfactant and the amount used were varied.
Table 5 shows the fundamental parameters and the results . Even a very small amount of a cationic surfactant produced a marked increase in the brightness .
Table 5
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000026_0003
*) imidazolium salt = cationic surfactant
**) ethoxylated fatty alcohol = non-ionic surfactant
Examples El 5 and CE9 : Secondary flotation of a deinked material of industrial origin
CE9 : Alkaline flotation, 10 minutes at 40°C, at pH 9.2 in the presence of 0.3 % Na oleate and 2 % sodium silicate
Brightness 67.4 % (ISO) Yield 90.9 %
E15: Two-step flotation, in each case 5 minutes/step; 40°C. Conditions in the first step as above, but flotation time only 5, minutes. In the second step, the pH was lowered to 6.8 using C02 and flotation was then carried out at that pH value in the presence of 0.05 % Rewoquat W3690 PG.
Brightness (after 1st step) 68.1 Brightness (after 2nd step) 70.8

Claims

Patent claims :
1. Method of removing printing ink from waste paper by flotation deinking, comprising breaking up the waste paper in the presence of alkali to obtain a pulp, a first flotation step at a pH value in the range of from greater than 8 to 11 in the presence of sodium silicate and an anionic or non-ionic surfactant, and a second flotation step, wherein an acid is added to the pulp at the beginning of that step, characterised in that
" the pH value of the pulp from the first flotation step - is lowered at the beginning of the second flotation step to a pH value in the range of from 5 to 7.5 using carbonic acid as the acid.
2. Method according to claim 1, characterised in that the first flotation step is carried out in the presence of from 0.2 to 2 wt.%, based on the waste. paper used (absolutely dry) , of an anionic surfactant at a pH value in the range of from greater than 8 to 10.5, especially from 8.5 to 10, and the pH value is lowered at the beginning of the second flotation step to a value in the range of from 5.5 to approximately 7.
3. Method according to' claim 1 or 2 , characterised in that the second flotation step is carried out in the presence of an amount in the range of from 0.01 to 1.0 wt . %, especially from 0.05 to 0.5, in each case based on the waste paper used (absolutely dry) , of a non-ionic or cationic surfactant.
4. Method according to any one of claims 1 to 3 , characterised in that the flotation is carried out at a consistency in the range of from 0.3 to 3 wt.%, especially from 0.5 to 1.5 wt.%.
5. Method according to any one of claims 1 to 4, characterised in that the pH value is lowered at the beginning of the second flotation step by the introduction of C02 or of air enriched with C02 and, if required, the pH value is maintained below 8 , especially in the range of from 6.0 to 7.5, during the flotation by the continuous or periodic introduction of such a gas.
6. Method according to any one of claims 1 to 5 , characterised in that the flotation of the two flotation steps is carried out for a total time of from 4 to 20 minutes, the second step accounting for from 10 to 90 %, especially from 20 to 50 %, of the total time.
7. Method according to any one of claims 1 to 6, characterised in that a waste paper mixture containing conventionally printed ' paper and paper printed with inkjet inks or/and other water-soluble inks is deinked.
8. Method according to claim 1, characterised in that waste paper is broken up in the presence of sodium hydroxide, sodium silicate and hydrogen peroxide, the pulp is diluted to a consistency suitable for flotation, the first flotation step is carried out for from 2 to 10 minutes in the presence of from 0.3 to 1.5 wt.%, based on the waste paper used (absolutely dry) , of an anionic surfactant, especially an alkali salt of a fatty acid having from 16 to 18 carbon atoms, at a pH value of approximately from 8.5 to 10.0, the pH value of the pulp so contained is lowered to a value in the range of from 5.5 to 7.5, especially from 6 to 7, by introduction of a C02-rich gas, and the flotation is continued for a period of from 2 to 10 minutes in the presence of from 0.05 to 0.5 wt.%, based on the waste paper used (absolutely dry) , of a cationic or non-ionic surfactant, especially a cationic surfactant, wherein the pH value of the pulp in the second step, which is initially lowered, may rise owing to the buffer action of the pulp and/or the hardness of the water used in the production of the pulp or is maintained at a value in the range of from 6 to 7 over an effective period by the periodic or continuous introduction of a C02-rich gas .
9. Method according to any one of claims 1 to 8 , characterised in that there is used in the second flotation step a cationic surfactant from the group of the tri(Cι- to C3-)alkyl- (Ci2- to Cis- ) alkylammonium salts, N-fatty acylamido- alkylimidazolinium salts, ester quats, quaternary fatty acylamidoamine ethoxylate quats and fatty acylamido- amine-carboxylic acid salts .
10. Method of increasing the brightness of a deinked material obtained by deinking, comprising the secondary flotation of a pulp produced from the deinked material, characterised in that immediately after an alkaline flotation step, the pH value is lowered to a pH value in the range of from 5 to 7.5, especially from 5.5 to 7, using carbonic acid, and flotation is continued for an effective period in the presence of a cationic or non-ionic surfactant.
PCT/EP2003/012281 2002-11-25 2003-11-04 Method of removing printing ink from waste paper by flotation deinking WO2004048680A2 (en)

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EP03811749A EP1565611B1 (en) 2002-11-25 2003-11-04 Method of removing printing ink from waste paper by flotation deinking
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WO2006123996A1 (en) * 2005-05-18 2006-11-23 Linde Aktiengesellschaft Process for deinking recycled fibers and use of an acid in deinking
WO2009034056A1 (en) * 2007-09-13 2009-03-19 Linde Aktiengesellschaft Removal of stickies from a pulp suspension, reduction of calcium compounds in reject and use of carbon dioxide in papermaking
WO2010043882A1 (en) 2008-10-17 2010-04-22 Stephenson Group Limited Recycling of fibre products
WO2011020982A1 (en) * 2009-08-03 2011-02-24 Stephenson Group Limited Recycling of fibre products
US8524036B2 (en) 2009-11-11 2013-09-03 Kemira Chemicals, Inc. Polyester surfactants for deinking
JP2016125153A (en) * 2014-12-26 2016-07-11 王子ホールディングス株式会社 Method of producing deinked pulp
JP2016125154A (en) * 2014-12-26 2016-07-11 王子ホールディングス株式会社 Method of producing deinked pulp
CN113060910A (en) * 2021-04-06 2021-07-02 武汉汇森创新科技有限公司 Method for comprehensively treating emulsion oil-containing filter paper in combination with steel rolling enterprises
WO2021219776A1 (en) * 2020-04-29 2021-11-04 Kübler & Niethammer, Papierfabrik Kriebstein Ag Method for producing label paper from detached wet labels

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Cited By (12)

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Publication number Priority date Publication date Assignee Title
WO2006123996A1 (en) * 2005-05-18 2006-11-23 Linde Aktiengesellschaft Process for deinking recycled fibers and use of an acid in deinking
EP1885941A1 (en) * 2005-05-18 2008-02-13 Linde Aktiengesellschaft Process for deinking recycled fibers and use of an acid in deinking
EP1885941A4 (en) * 2005-05-18 2012-01-25 Linde Ag Process for deinking recycled fibers and use of an acid in deinking
WO2009034056A1 (en) * 2007-09-13 2009-03-19 Linde Aktiengesellschaft Removal of stickies from a pulp suspension, reduction of calcium compounds in reject and use of carbon dioxide in papermaking
WO2010043882A1 (en) 2008-10-17 2010-04-22 Stephenson Group Limited Recycling of fibre products
EP2362015A1 (en) * 2008-10-17 2011-08-31 Stephenson Group Limited Recycling of fibre products
WO2011020982A1 (en) * 2009-08-03 2011-02-24 Stephenson Group Limited Recycling of fibre products
US8524036B2 (en) 2009-11-11 2013-09-03 Kemira Chemicals, Inc. Polyester surfactants for deinking
JP2016125153A (en) * 2014-12-26 2016-07-11 王子ホールディングス株式会社 Method of producing deinked pulp
JP2016125154A (en) * 2014-12-26 2016-07-11 王子ホールディングス株式会社 Method of producing deinked pulp
WO2021219776A1 (en) * 2020-04-29 2021-11-04 Kübler & Niethammer, Papierfabrik Kriebstein Ag Method for producing label paper from detached wet labels
CN113060910A (en) * 2021-04-06 2021-07-02 武汉汇森创新科技有限公司 Method for comprehensively treating emulsion oil-containing filter paper in combination with steel rolling enterprises

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ATE382734T1 (en) 2008-01-15
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