WO1991014821A1 - Recyclage de produits fibreux - Google Patents

Recyclage de produits fibreux Download PDF

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Publication number
WO1991014821A1
WO1991014821A1 PCT/GB1991/000434 GB9100434W WO9114821A1 WO 1991014821 A1 WO1991014821 A1 WO 1991014821A1 GB 9100434 W GB9100434 W GB 9100434W WO 9114821 A1 WO9114821 A1 WO 9114821A1
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WO
WIPO (PCT)
Prior art keywords
general formula
integer
inclusive
group
dispersant
Prior art date
Application number
PCT/GB1991/000434
Other languages
English (en)
Inventor
Seppo Jakola
Desmond Clive Weed
Original Assignee
Stephenson Group Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Stephenson Group Limited filed Critical Stephenson Group Limited
Publication of WO1991014821A1 publication Critical patent/WO1991014821A1/fr

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Classifications

    • 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
    • D21C5/027—Chemicals therefor
    • 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

  • This invention relates to a method of recycling fibre products, namely printed paper products.
  • the invention relates in particular to a method of recycling fibre products involving subjecting them to a mechanical treatment to separate fibres, removing the ink therefrom (commonly known as "deinking") , and recovering the fibres.
  • a common method of paper recycling is to subject waste paper to a mechanical pulping treatment to break the paper down into fibres in an aqueous medium, and then to use a flotation technique to remove ink, followed by a washing treatment.
  • a chemical commonly referred to as a collector chemical
  • air is introduced at the bottom of the flotation chamber. The air, in the presence of the collector chemical, transports ink to the surface of the aqueous medium. At the surface, the ink-rich foam is removed by mechanical means.
  • the collector chemical is an essential component, in assisting the transport of ink to the surface and trapping the ink in a stable foam at the surface.
  • the collector chemical must, of course, cause the ink particles to be taken up efficiently and form a sufficiently stable foam but there are other requirements to be borne in mind. For example, if solid, it should dissolve readily; if liquid, it should be easy to handle; it must be safe; it should be inexpensive to use; it should be easy to transport; and so forth.
  • the fatty acid soaps of alkali metals for example sodium or potassium, are widely used as collector chemicals.
  • the fatty acids are available in a liquid form, either as hot molten fatty acids or in aqueous emulsion.
  • a disadvantage of the former is in their transportation and disadvantages of the latter are that aqueous emulsions at most contain only 30% active material, and there can be problems of emulsifier build up. So, in both cases there is a penalty in terms of transportation costs.
  • a very small part of the market for collector chemicals is taken by synthetic detergents, for example ethoxylates, which are not derived from fatty acids.
  • a third approach which is more common than the approach of using synthetic detergents, but less common than the approach of using fatty acids saponified in situ or ju ⁇ t before introduction into the deinking chamber, is to use alkali metal soaps of long-chain fatty acids, transported as soaps to the paper recycling plant.
  • soaps are naturally solid materials and have to be dissolved in situ or before introduction into the deinking chamber.
  • the soaps are available in pelletized form, there can be a problem since dissolution can still be slow.
  • the soaps can be supplied in aqueous solution, but only to a maximum 30 wt% of the soap in the solution. So, again there is a penalty in terms of transportation cost.
  • wash deinking process Another method of paper recycling is the wash deinking process in which the substantially broken-down paper products are washed, without gas being employed to carry ink particles to the surface. Instead, ink removed from the paper products is extracted on removal of the aqueous medium, for example by a draining step. A collector chemical is present to aid the removal of the ink from the paper products.
  • a wash deinking process employs several cycles of dilution, washing and water removal and/or rinsing.
  • a method of removing ink from paper products comprising providing an aqueous medium which contains paper fibres derived from the paper products, in substantially broken-down form, and which also contains a collector chemical, characterised in that the collector chemical comprises a salt formed by reaction of a long-chain fatty acid, and an amine of general formula R ** R 2 R 3 N, wherein R l represents a group of general formula -C n H 2n+1 or -C ⁇ OHJH ⁇ , where n represents an integer from 1 to 6 inclusive, R 2 represents a hydrogen atom or a group of general formula -C m H 2m+1 or -C m (OH)H 2m , where m represents an integer from 1 to 6 inclusive, and R 3 represents a hydrogen atom or a group of general formula -C p H 2p+1 or -C p (
  • salts formed by reaction of an amine and a long-chain fatty acid may ameliorate many of the problems encountered with prior art methods.
  • salts formed by reaction of certain amines and certain long-chain fatty acids may be solid materials at room temperature (and it should be noted that the use of such materials is within the scope of the present invention in its broadest aspect)
  • certain such reaction products are liquids, or else have a melting point sufficiently close to normal ambient temperatures that they may be made liquid by addition of appropriate fluidising agents.
  • Preferred salts formed by reaction of amines and long-chain fatty acids used in the present invention are liquid at normal temperatures of use and transportation, for example in the range 5-25°C, or are components of compositions which are liquid within that temperature range (for example being liquifiable by addition of relatively minor amounts of fluidising agent(s) .
  • Such salt reaction products of amines and long-chain fatty acids are preferred for use in the method of the present invention because they are readily transportable in high concentration, up to 100% for certain examples which are liquid without the requirement of a fluidising component, or at least 50%, preferably at least 75%, and most preferably at least 90% by weight of total composition for other examples.
  • collector materials have the advantage of being pre-manufactured saponaceous materials, which do not have to be dissolved to form a liquid composition on site.
  • Preliminary experimental tests have shown that the efficiency of such saponaceous products in the removal of ink from fibre products is high.
  • a fluidising agent when present, may suitably be selected from a polyhydric alcohol or a polyoxyalkylene glycol.
  • suitable polyhydric alcohols are alkylene glycols, for example C ⁇ alkylene glycols, for example ethylene glycol and hexylene glycol, glycerol, polyal ylene glycols, for example polyethylene glycol, and the series of polyhydric alcohols available from Shell under the Trade Mark DOBA OL.
  • suitable polyoxyalkylene glycols are polyethylene oxide glycol, polypropylene oxide glycol and the copolymers thereof.
  • the fluidiser component when present, is a polyhydric alcohol, especially a C i alkylene glycol, most preferably hexylene glycol.
  • the amine may comprise a primary and/or a secondary and/or, most preferably, a tertiary amine.
  • the amine is of general formula R ** R 2 R 3 N wherein R 1 represents a group of general formula -C n (OH)H 2n , where n represents an integer from 1 to 6 inclusive, R 2 represents a hydrogen atom or a C w alkyl group or a group of general formula -C m (OH)H 2m , where m represents an integer from 1 to 6 inclusive, and R 3 represents a hydrogen atom or a C w alkyl group or a group of general formula -C p (OH)H 2p , where p represents an integer from 1 to 6 inclusive.
  • hydroxyalkyl or alkyl groups R 1 and/or R 2 and/or R 3 is/are straight chain, and a hydroxy group is terminal in the respective chain.
  • R 1 represents a straight chain group of general formula -C n H 2n -OH where n represents an integer of from 1 to 4 inclusive
  • R 2 represents a hydrogen atom or, more preferably, a straight chain group of general formula ⁇ c ⁇ - r - 2+ ⁇ or -C m H-j m -OH where m represents an integer of from 1 to 4 inclusive
  • R 3 represents a hydrogen atom or, more preferably, a straight chain group of general formula -C p H 2p+1 or -C p H 2p -OH where p represents an integer of from 1 to 4 inclusive.
  • each of symbols n, m and p represents the integer 1 or, more preferably 2.
  • the amine may suitably be a monoalkanolamine, dialkanolamine or trialkanolamine, for example monoethanolamine, diethanolamine or triethanolamine.
  • the amine comprises a trialkanolamine, preferably triethanolamine, preferably substantially solely or in major proportion.
  • a commercially available composition comprising 85 wt% of triethanolamine and 15 wt% of a mixture of amines, predominantly diethanolamine and monoethanolamine, may suitably be employed.
  • Suitable long-chain fatty acids may readily be selected, forming soaps with the amines which are useful in the method.
  • such long-chain fatty acids may be C J2 . 22 fatty acids, or fatty acids having equivalent properties, for example C 24 _ 44 dicarboxy fatty acids, effectively dimers of C 222 monocarboxy fatty acids.
  • fatty acids which would lend themselves to use in the method of the present invention.
  • a fatty acid is selected, which provides a salt reaction product with the amine selected which is liquid at normal temperatures of use, or which can be made liquid by addition of an appropriate fluidiser component, as referred to more fully above.
  • suitably fatty acids may include saturated fatty acids, mono-unsaturated fatty acids, di-unsaturated fatty acids and tri- unsaturated fatty acids, fatty acids with hydroxy groups in the molecule, and cyclic fatty acids.
  • the commercially available fatty acids of this type will typically comprise a mixture of different fatty acids most of which are within the definition C ⁇ . ⁇ fatty acid.
  • individual fatty acids of this type include lauric acid, myristic acid, palmitic acid, stearic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, arachidic acid and erucic acid.
  • the preferred commercially available fatty acids are characterised by a high degree of unsaturation.
  • the amine and the long-chain fatty acids are desirably present in approximately stoichiometric proportion.
  • the fluidiser component when present, is desirably present in small quantity relative to the other two components.
  • the fluidiser component may be present as 0-10% by weight based on the total weight of the composition.
  • a saponaceous reaction product which is liquid at normal ambient temperatures which is a preferred composition for use in the method of the present invention, may simply be prepared, in many cases, by mixing the amine and the fatty acid, suitably at ambient temperature, and adding, at any convenient stage, a fluidiser component, if required.
  • the conditions may be selected by the skilled man, using trial and error and analysis of the reaction products if necessary, to provide that a salt is the primary product formed, rather than an ester (from a tertiary amine) or an amide or ester (from a primary or secondary amine) .
  • a salt should be the major product, if it is not the only product. Thus, minor quantities of covalent reaction products can be tolerated.
  • the method in accordance with the invention may for example be a flotation deinking method, or a wash deinking method, or a dual method.
  • the method may be of particular benefit in relation to flotation deinking.
  • the collector chemical may advantageously be used in association with a dispersant. This may be of particular benefit in permitting the said collector chemical to be used with advantage in a wash deinking method of removing ink from paper products. It may also enhance the effect of the collector chemical in a flotation deinking method, to a substantial and surprising degree.
  • the said collector chemical and the said dispersant when present, may be components of a single composition, preferably liquid, added together, preferably at the deinking stage, otherwise at the pulping stage. However, preliminary tests have indicated that there may be advantages in adding the dispersant at the pulping stage, and adding the collector chemical subsequently, at the deinking stage.
  • Any dispersant effective to aid the dispersion and/or dissolution of ink removed from the paper products by the collector chemical, to the extent that on removal of aqueous medium effective co-removal of ink from the washing bath in a wash deinking process is achieved, may be employed.
  • examples may include alkoxylates, for example alkylphenol ethoxylates, alcohol ethoxylates, amine ethoxylates, ester ethoxylates, acid ethoxylates; sulphonates, for example alkylaryl sulphonates, alkane sulphonates; and esters of alkylene oxide polymers.
  • a preferred dispersant is an ester derived from an ethylene oxide/propylene oxide co-polymer (preferably of molecular weight in the range about 600 to 3000), and a C, 2 . 22 fatty acid, for example stearic or tallow fatty acid.
  • an alkyl aryl sulphonate may desirably be present to modify the dispersant properties, and if so it is desirable for reasons of stability of the dispersant composition, to terminate the esterification leaving a moderate concentration of unreacted fatty acids.
  • the ester component is suitably a major component and the sulphonate component a minor component, and the acid number of the ester component (the percentage by weight of free fatty acids present, measured in accordance with test BS 684 1958) is desirably about 2- 8, preferably about 3-5.
  • Suitable alkyl aryl sulphonates have a long-chain (eg. C n ) alkyl group.
  • Preferred such sulphonates are alkyl benzene sulphonates and alkyl xylene sulphonates.
  • the dispersant when present, is itself a liquid at ambient temperature.
  • the dispersant may be present in an amount of from about 0.01 to about 1%, by weight of dry waste paper, preferably from about 0.05 to 0.5%, most preferably about 0.07 to 0.15%.
  • the optimal weight ratios of collector chemical to dispersant when present, will depend on the exact nature of the particular deinking process employed and on the nature of the paper and the ink printed thereon. Trial and error may easily be used to determine the optimal proportions in any given case. Typically, the weight ratios could be in the range 95:5 to 5:95, (collector chemical:dispersant) . It is believed that higher collector chemical: dispersant ratios (for example 80:20 by weight) may be preferred for newsprint and other coarse papers, containing lignin and hemicelluloses in substantial quantity, whilst lower ratios (for example 20:80 by weight) may be preferred for higher quality, so- called "woodfree" papers.
  • a further aspect of the present invention is provided by a composition
  • a composition comprising a collector chemical of the type defined herein and a dispersant, preferably an ester of an ethylene oxide/propylene oxide co-polymer and a fatty acid, as described above.
  • a method of recycling printed paper products comprising: subjecting the paper products to a mechanical treatment (pulping) in an aqueous medium until substantially broken down into fibres; adding to the medium, before, during or after the mechanical treatment, a collector chemical; passing a gas through the aqueous medium containing the fibres and the collector chemical and removing the ink-rich foam on the surface and/or removing ink by successive cycles of draining and rinsing; and recovering the cleansed paper pulp; characterised in that the collector chemical is the reaction product of an amine as defined above and a long-chain fatty acid as defined above.
  • the collector chemical is present in an amount from about 0.01 to about 2 wt%, for example from about 0.05 wt% to about 2 wt%, preferably from about 0.1 to about 1 wt%, most preferably from about 0.15 wt% to about 0.5 wt%, based on weight of dry waste paper.
  • the collector chemical can be added to the aqueous medium before, during, or after the completion of the mechanical treatment. Preferably it is added after the completion of the mechanical treatment, at the deinking stage, most preferably shortly before or substantially at the commencement of ink removal.
  • Example 1 A saponaceous material which is liquid at ambient temperature was prepared from the following materials:
  • the alkanolamine was added slowly with stirring to the tall oil fatty acids and stirred well for a further 15 minutes. After this period of stirring, the hexylene glycol was added in one batch and the reaction mixture stirred for a further 5 minutes.
  • the liquid amine soap thus prepared, of appearance a clear red or brown liquid showing a pH (5% aqueous) of 7.0 to 9.5 was then ready for use in the deinking of paper. The formation of the amine salt was confirmed by infra-red spectroscopy.
  • the flotation cell was started and allowed to run for 45 minutes at 45°C and an air flow of 2 litres/minute.
  • a liquid dispersant composition was prepared by heating together an ethylene oxide/propylene oxide random co-polymer (87 wt%) (EMKAROX VG 127 , Trade Mark, ICI Chemicals; RMM is c.1200) and distilled tallow fatty acids (13 wt%) .
  • the mixture was heated at 240°C at atmospheric pressure (in an alternative preparation, at 160°C in the presence of butyl titanate catalyst) until the free fatty acid value, determined by the test BS 684 1958, fell to 4.0 s - (approximately 6 hours).
  • To the reaction product (80 wt%) itself effective as a dispersant, was added a C 12 alkyl benzene sulphonate (20 wt%) .
  • a composition suitable for use in a flotation deinking process or especially, in a wash deinking process was prepared by adding the collector chemical of
  • Example 1 (90 wt%) to the dispersant composition of
  • Example 2 (10 wt%) .
  • a further composition was prepared by adding the collector chemical of Example 1 (80 wt%) to the dispersant composition of Example 2 (20 wt%) .
  • a further composition was prepared by adding the collector chemical of Example 1 (20 wt%) to the dispersant composition of Example 2 (80 wt%) .
  • paper products have been widely used in this specification as shorthand terms for cellulose fibre mats wet laid by a non-woven process and is intended to include materials such as tissue, card and the like.

Abstract

Dans un procédé de recyclage de papier imprimé, le collecteur chimique utilisé pour contribuer à enlever l'encre après la mise en pulpe du papier, comprend un produit saponacé formé par réaction d'un acide gras à longue chaîne, par exemple de l'huile de pin, et d'un amine, par exemple un triéthanolamine. Ce produit est, de façon appropriée, liquide à température ambiante et peut donc se transporter et s'utiliser sans inconvénient. Il est extrêmement actif. L'invention décrit également un agent de dispersion, un ester dérivé d'un copolymère d'oxyde de propylène et/ou d'oxyde d'éthylène et un acide gras à longue chaîne. L'usage combiné de cet agent de dispersion avec le produit chimique collecteur augmente son utilité.
PCT/GB1991/000434 1990-03-21 1991-03-21 Recyclage de produits fibreux WO1991014821A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP90303061.7 1990-03-21
EP90303061 1990-03-21
GB9011665.8 1990-05-24

Publications (1)

Publication Number Publication Date
WO1991014821A1 true WO1991014821A1 (fr) 1991-10-03

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Application Number Title Priority Date Filing Date
PCT/GB1991/000434 WO1991014821A1 (fr) 1990-03-21 1991-03-21 Recyclage de produits fibreux

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GB (1) GB9011665D0 (fr)
WO (1) WO1991014821A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015314A1 (fr) * 1994-11-12 1996-05-23 Stephenson Group Limited Recyclage de produits a base de fibres
US5658426A (en) * 1995-07-20 1997-08-19 Geo Specialty Chemicals, Inc. Alkoxylated lanolin derivatives as deinking agents
EP0861115A1 (fr) * 1995-10-17 1998-09-02 Henkel Corporation Composition demoussante/antimoussante
WO2002050369A1 (fr) * 2000-12-21 2002-06-27 Akzo Nobel N.V. Composition solide destinee au desencrage du papier de recyclage
EP2203105A1 (fr) 2007-10-05 2010-07-07 Dental Equipment, LLC Lampe à diode électroluminescente pour examen dentaire à chromaticité variable
WO2011020982A1 (fr) * 2009-08-03 2011-02-24 Stephenson Group Limited Recyclage de produits fibreux
EP2350382A1 (fr) 2008-10-17 2011-08-03 Stephenson Group Limited Recyclage de produits fibreux

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013505A (en) * 1972-03-09 1977-03-22 Vyzkumny Ustav Papieru A Celulosy Method of deinking printed wastepapers
EP0013758A1 (fr) * 1979-01-27 1980-08-06 Henkel Kommanditgesellschaft auf Aktien Procédé de désencrage de vieux papiers imprimés
GB2121071A (en) * 1982-06-01 1983-12-14 Ferguson And Menzies Limited Liquid soaps

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4013505A (en) * 1972-03-09 1977-03-22 Vyzkumny Ustav Papieru A Celulosy Method of deinking printed wastepapers
EP0013758A1 (fr) * 1979-01-27 1980-08-06 Henkel Kommanditgesellschaft auf Aktien Procédé de désencrage de vieux papiers imprimés
GB2121071A (en) * 1982-06-01 1983-12-14 Ferguson And Menzies Limited Liquid soaps

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015314A1 (fr) * 1994-11-12 1996-05-23 Stephenson Group Limited Recyclage de produits a base de fibres
US5968313A (en) * 1994-11-12 1999-10-19 Morton International, Inc. Process for deinking pulp fibers using ethoxylated lanolin
US5658426A (en) * 1995-07-20 1997-08-19 Geo Specialty Chemicals, Inc. Alkoxylated lanolin derivatives as deinking agents
EP0861115A1 (fr) * 1995-10-17 1998-09-02 Henkel Corporation Composition demoussante/antimoussante
EP0861115A4 (fr) * 1995-10-17 1998-12-02 Henkel Corp Composition demoussante/antimoussante
WO2002050369A1 (fr) * 2000-12-21 2002-06-27 Akzo Nobel N.V. Composition solide destinee au desencrage du papier de recyclage
EP2203105A1 (fr) 2007-10-05 2010-07-07 Dental Equipment, LLC Lampe à diode électroluminescente pour examen dentaire à chromaticité variable
EP2350382A1 (fr) 2008-10-17 2011-08-03 Stephenson Group Limited Recyclage de produits fibreux
EP2362015A1 (fr) 2008-10-17 2011-08-31 Stephenson Group Limited Recyclage de produits fibreux
WO2011020982A1 (fr) * 2009-08-03 2011-02-24 Stephenson Group Limited Recyclage de produits fibreux

Also Published As

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