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WO1993022491A1 - Produits chimiques de desencrage - Google Patents

Produits chimiques de desencrage Download PDF

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Publication number
WO1993022491A1
WO1993022491A1 PCT/US1992/003379 US9203379W WO9322491A1 WO 1993022491 A1 WO1993022491 A1 WO 1993022491A1 US 9203379 W US9203379 W US 9203379W WO 9322491 A1 WO9322491 A1 WO 9322491A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
wastepaper
acid
deinking
carboxylic acid
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US1992/003379
Other languages
English (en)
Inventor
Anthony Barrymore Cook
Gail Marie Howell
Jose Maria Rodriguez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Henkel Corp
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 Henkel Corp filed Critical Henkel Corp
Priority to AU22468/92A priority Critical patent/AU2246892A/en
Priority to BR9207120A priority patent/BR9207120A/pt
Priority to CA 2134079 priority patent/CA2134079A1/fr
Priority to EP19920914576 priority patent/EP0637347A1/fr
Priority to MX9302292A priority patent/MX9302292A/es
Priority to PCT/US1992/003379 priority patent/WO1993022491A1/fr
Priority claimed from CA 2134079 external-priority patent/CA2134079A1/fr
Publication of WO1993022491A1 publication Critical patent/WO1993022491A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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 process for regenerating wastepaper, and more specifically to the use of deinking chemicals prepared by reaction of epoxidized derivatives of C 10 -C 22 carboxylic acids with an alkoxylated polyhydroxy alcohol for the regeneration of wastepaper.
  • wastepaper is used in large quantities for the production of, for example, newsprint and hygiene paper. Brightness and color are important quality features for papers of this type.
  • the printing inks have to be removed from the printed wastepaper. This is normally done by deinking processes essentially comprising two steps, namely:
  • the second step can be carried out by washing or flotation (Ullmanns Encyclopaedie der ischen Chemie, 4th Edition. Vol. 17, pages 570-571 (1979)).
  • flotation which utilizes the difference in wetability between printing inks and paper fibers, air is forced or drawn through the fiber suspension. Small air bubbles attach themselves to the printing ink particles and form a froth at the surface of the water which is removed.
  • the deinking of wastepaper is normally carried out at alkaline pH values in the presence of alkali metal hydroxides, alkali metal silicates, oxidative bleaches and surfactants at temperatures in the range from 30 to 50°C.
  • Anionic and/or nonionic surfactants for example soaps, ethoxylated fatty alcohols and/or ethoxylated alkyl phenols are mainly used as surfactants (Wochenblatt fuer Textilfabrikation 17, 646 to 649 (1985) ) Discussion of Related Art:
  • DE-OS 31 01444 relates to a process for the deinking of wastepaper using a compound corresponding to the following general formula
  • R is a C 7 . 21 alkyl or alkenyl group
  • R 1 is a hydrogen atom or a c_,. 18 alkyl, alkenyl or acyl group
  • AO represents CmE 6 0 and C 4 H 8 0 groups or a mixture of C 2 H 4 0, C-.H 6 0 and C 4 H 8 0 groups
  • m is an integer of 1 to 100
  • n is an integer of 1 to 100.
  • DE 21 48 590 89., 131445J (1978) , and from DE 21 48 590.
  • the Japanese patent describes mixtures of castor oil with 10 to 400% ethylene oxide and ethoxylated nonylphenol which are suitable for the removal of printing inks from printed wastepaper.
  • the process disclosed in DE- PS 21 48 590 is concerned with organic materials, for example paper, which are bleached with sodium chlorite in the presence of organic compounds containing at least one ethylene oxide and/or propylene oxide unit.
  • Suitable organic compounds containing at least one alkylene oxide unit include inter alia ethoxylated castor oil.
  • DE 39 23 393 discloses a process for regenerating wastepaper containing printing ink using an alkoxylation product of a C 10 ⁇ C 22 carboxylic acid or derivative thereof containing an OH group in one or more of the 9, 10, 13 and 14 positions on the carboxylic acid moiety.
  • the alkoxylation product is obtained by epoxidizing unsaturated c ⁇ o ⁇ C 22 carboxylic acids or derivatives thereof, the oxirane ring of the epoxide is then opened by reaction with hydrogen or a protic compound to form hydroxy groups, and this material is then alkoxylated to the final product.
  • Japan 291952/88 (equivalent to European patent application number 89311550.1) is directed to a deinking composition
  • a deinking composition comprising a reaction product obtained by reacting a glyceride mixture derived from neutral oil and fat with ethylene oxide and propylene oxide.
  • the glyceride mixture contains 5 to 10%/wt of monoglycerides, 30 to 45%/wt of diglycerides, and 50 to 70%/wt of triglycerides.
  • the reaction product has a molar ratio of ethylene oxide to propylene oxide of between 1.8 to 2.2 wherein the mole number of added ethylene oxide is between 30 and 80 per mole of glycerides.
  • German patent application 40 32 050.2 filed October 9, 1990 relates to regenerating printed wastepaper using the reaction product of alkoxylated aliphatic alcohols, amines, carboxylic acids, and carboxylic amides with epoxidized triglycerides such as C. Q - C 22 carboxylic acid derivatives.
  • the present invention relates to a process for the regeneration of wastepaper wherein printed wastepaper is refined in known manner in the presence of deinking compounds obtained by reaction of epoxidized derivatives of C 10 -C 22 carboxylic acids with alkoxylated polyhydroxy alcohols, and the printing ink particles are subsequently removed from the fiber suspensions in known manner by flotation and/or washing.
  • the epoxidized derivatives of C 10 -C 22 carboxylic acids employed as reactants for the preparation of the deinking compounds according to the invention are obtained by epoxidation of derivatives of unsaturated C 10 -C 22 carboxylic acids.
  • unsaturated carboxylic acid derivatives can be epoxidized by reaction with peracetic acid in the presence of acidic catalysts or with performic acid formed in situ from formic acid and hydrogen peroxide.
  • the iodine values of the resulting epoxidation products are below 20, and preferably below 15.
  • Suitable unsaturated carboxylic acid derivatives include all naturally occurring or synthetically preparable carboxylic acid derivatives which are free from OH groups and contain carboxylic acid moieties with at least 1 or 2 double bond(s) in the 9- and/or 13-positions, for example 9c-dodecenoic acid, 9c- tetradecenoic acid, 9c-hexadecenoic acid, 9c-octadecenoic acid, 9t-octadecenoic acid, 9c,12c-octadecadienoic acid, 9c,12c,15c-octadecatrienoic acid, 9c-eicosenoic acid and/or 13c-eicosenoic acid derivatives, and/or mixtures thereof having at least a high content of such unsaturated carboxylic acid derivatives.
  • Unsaturated carboxylic acid derivatives containing C 16 -C 22 -carboxylic acid moieties having at least 1 or 2 double bond(s) in the 9- and/or 13- positions are preferred.
  • Suitable unsaturated carboxylic acid derivatives are, for example, unsaturated carboxylic acid esters, unsaturated carboxylic acid amides, unsaturated carboxylic acid mono- and/or di-G,_ 4 alkylamides and/or unsaturated carboxylic acid mono- and/or di-C 4 alkanolamides.
  • Unsaturated carboxylic acid alkyl esters having from 1 to 18 carbon atoms in the monohydric alcohol moiety and/or mono-, di- and/or triglycerides containing carboxylic acid moieties having at least 1 or 2 double bond(s) in the 9- and/or 13-positions are preferred.
  • Examples of unsaturated C 10 -C 22 carboxylic acid C_,-C 18 alkyl esters which are accessible in a per se known manner by esterifying the corresponding OH-group-free unsaturated carboxylic acids or by transesterification of the respective mono-, di- and/or tri-glycerides with ⁇ -C ⁇ - alkyl alcohols such as, for example, methanol, ethanol, propanol, butanol, isobutanol, 2-ethylhexanol, decanol and/or stearyl alcohol include palmitoleic acid methyl ester, oleic acid methyl ester, oleic acid ethyl ester, oleic acid isobutyl ester, oleic acid 2-ethylhexyl ester, oleic acid decyl ester, and C 10 -C 22 carboxylic acid C,,-C 18 - alkyl ester mixtures having at least a high
  • the mono-, di- and/or tri-glycerides containing C 10 —C 22 carboxylic acid moieties which are unsaturated and free from OH groups and have at least 1 or 2 double bond(s) in the 9- and/or 13-positions especially suitable are fats and/or oils of natural origin, the carboxylic acid contents of which are predominantly composed of unsaturated C 10 -C 22 -carboxylic acids which have at least 1 or 2 double bond(s) in the 9- and/or 13- positions, preferably predominantly of unsaturated C 16 -C 22 - carboxylic acids which have at least 1 or 2 double bond(s) in the 9- and/or 13-positions, such as olive oil, linseed oil, sunflower oil, safflower oil, soybean oil, peanut oil, cottonseed oil, rapeseed oil which is rich in erucic acid and/or low in erucic acid, palm oil, lard and/or tallow.
  • alkoxylated polyhydroxy alcohols examples include the alkoxylation products of glycol, glycerol, "neo" polyols such as tri ethylolpropane, trimethylolethane, pentaerythritol, and polymers of the latter, and carbohydrate-derived polyols such as sorbitol, mannitol, etc.
  • Ethoxylated sorbitol is a preferred alkoxylated sugar alcohol for reaction with epoxidized derivatives of C 10 -C 22 carboxylic acids to obtain the deinking chemicals in accordance with this invention.
  • the polyhydroxy alcohols are alkoxylated by known industrial methods, preferably with ethylene oxide, propylene oxide and/or butylene oxide and more preferably with ethylene oxide and/or propylene oxide, optionally in the presence of catalysts, for example potassium hydroxide and/or sodium methylate, at temperatures of 110 to 200°C and preferably at temperatures of 140 to 175°C and under pressures of 10 5 to 2*10° Pa (cf. for example "Chemische Technologie", Vol.
  • the alkylene oxide content of the alkoxylated polyhydroxy alcohols is from 4 to 600%, and is preferably from 40 to 120%, based on the non-alkoxylated compounds.
  • reaction products of epoxidized derivatives of C 10 - C 22 carboxylic acids with alkoxylated polyhydroxy alcohols are used in accordance with this invention by addition to paper stock suspensions in quantities of preferably 0.01 to 5% by weight and, more preferably, 0.1 to 0.8% by weight, based on air dry paper stock.
  • Air-dry paper stock means that an equilibrium state of internal moisture has established itself in the paper stock. This equilibrium state depends both on the temperature and on the relative humidity of the air.
  • the deinking result i.e., the removal of printing inks from printed wastepaper
  • the deinking chemicals of this invention in combination with, for example, C. Q -C 2Z fatty acids such as Olinor ® 4300, Olinor ⁇ 4010, and/or Olinor ® 4020 (all products of Henkel Corporation) , a soap, ethoxylated C 6 -C 22 fatty alcohols, ethoxylated alkylphenols, polymers such as polyacrylamides and/or polydimethylaminoethyl methacrylic acid, and/or copolymers of the type described, for example, in DE 38 39 479.
  • the total quantity of these optional constituents is between 0.01 and 5% by weight, based on air-dry paper stock.
  • water-dilutable and/or solvent-containing printing inks, and/or solvent free inks especially water- dilutable printing inks, for example rotary newsprint inks, book printing inks, offset printing inks, illustration intaglio printing inks, flexographic printing inks, laser printing inks and/or packaging intaglio printing inks, and/or xerographic inks may be removed from printed wastepaper, for example newspapers, magazines, computer paper, journals, brochures, forms, telephone directories and/or catalogues.
  • the deinked wastepaper obtained is distinguished by very high degrees of whiteness.
  • Printed wastepaper is refined in a pulper at 20°C to 80°C at a pulp concentration of, for example, 1 to 30% by weight in an aqueous solution typically containing 0 to 2.0% by weight 100% hydrogen peroxide,0 to 2.5% by weight NaOH, 0 to 4.0% by weight soda waterglass (silicate) having a solids content of about 35% by weight (37 to 40 ⁇ Be) , 0.01 to 5% by weight reaction products of epoxidized derivatives of C 10 -C 22 carboxylic acids with alkoxylated polyhydroxy alcohols according to the invention, and 0 to 1% by weight of the optional constituents mentioned above (all percentages by weight based on air-dry wastepaper) .
  • an aqueous solution typically containing 0 to 2.0% by weight 100% hydrogen peroxide,0 to 2.5% by weight NaOH, 0 to 4.0% by weight soda waterglass (silicate) having a solids content of about 35% by weight (37 to 40 ⁇ Be) , 0.01 to 5% by
  • the paper stock suspensions are stirred into water or water is added to them so that 0.6 to 1.6% by weight stock suspensions are obtained.
  • the detached printing ink particles are then removed from the stock suspensions in known manner by washing out or by flotation (Ullmanns Enzyklopadie der ischen Chemie, 4th Edition. Vol. 17, pages 570 to 571 (1979)). Flotation is preferably carried out in known manner, for example in a Denver flotation cell.
  • Example I To about 225 grams of ethoxylated sorbitol (40 moles of ethylene oxide per mole of sorbitol) heated to a temperature of about 160°C was added about 100 grams of soybean oil epoxide.
  • the soybean oil epoxide had a fatty acid composition of about 11.5% palmitic acid, 4.0% stearic acid, 24.5% oleic acid, 53% linoleic acid, and 7.0% linolenic acid; an epoxide content of about 7% by weight; an iodine value of about 0.8; and an acid value of about 0.3.
  • the mixture was reacted under a nitrogen gas purge at a temperature of about 200°C.
  • reaction temperature was increased to about 230"C, and about 0.32 gram of p-toluenesulfonic acid was added to the reaction mixture. After about three hours, the reaction was stopped. The product was found to have a residual oxirane content of about 0.20.
  • soybean oil epoxide About 100 grams of soybean oil epoxide were blended with about 225 grams of ethoxylated sorbitol (60 moles of ethylene oxide per mole of sorbitol) in a reaction flask.
  • the soybean oil epoxide had a fatty acid composition of about 11.5% palmitic acid, 4.0% stearic acid, 24.5% oleic acid, 53% linoleic and 7.0% linolenic acid; an epoxide content of about 7.0% by weight; an iodine value of about
  • linseed oil epoxide About 100 grams of linseed oil epoxide were blended with about 270.25 grams of ethoxylated sorbitol (40 moles of ethylene oxide per mole of sorbitol) in a reaction flask.
  • the linseed oil epoxide had a fatty acid composition of about 6% palmitic acid, 3.5% stearic acid, 20% oleic acid, 14.5% linoleic acid and 56% linolenic acid.
  • the linseed oil epoxide had an oxirane content of about 9.0% by weight; an iodine value of about 3.42; and an acid value of about 0.19.
  • the mixture was heated to about 230°C for about 10 hours under a nitrogen purge.
  • the product was found to have a residual oxirane content of about 0.51%.
  • Example I, II and III were evaluated for brightness gain, filler loss, fiber loss and total loss, and the values obtained were compared with those obtained using the deinking compositions of German Patent 39 23 393 and Japan Patent 291952/88.
  • a sample of the stock suspension was taken to form a pre-float pad.
  • the stock suspension was then floated for 8 minutes at 45°C in a Denver flotation cell at 1500 revolutions per minute and another sample of the stock suspension was taken to form a final pad.
  • the stock suspension samples were separated from the water on a Coors porcelain funnel and shaped into a sheet between two filter papers on a vacuum drying press and dried for 5 minutes.
  • the deinkability value (Brightness Gain) was calculated by subtracting the average brightness of the pre-float suspension pad from the average brightness of the after-float suspension pad according to the following formula:
  • A Average of 8 readings on the pre-float suspension pad.
  • B Average of 8 readings on the after-float suspension pad.
  • Brightness Gain A - B

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Toxicology (AREA)
  • Paper (AREA)

Abstract

De vieux papiers contenant de l'encre d'imprimerie sont raffinés en présence des produits de la réaction entre des dérivés époxydes d'acides carboxyliques C10-C22 et des alcools polyvalents alcoxylés, et les particules d'encre d'imprimerie détachées sont ultérieurement enlevées des suspensions de papier raffiné par flottation ou lavage.
PCT/US1992/003379 1992-04-23 1992-04-23 Produits chimiques de desencrage Ceased WO1993022491A1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AU22468/92A AU2246892A (en) 1992-04-23 1992-04-23 Deinking chemicals
BR9207120A BR9207120A (pt) 1992-04-23 1992-04-23 Processo para regeneração de papel residual contendo tinta de impressão
CA 2134079 CA2134079A1 (fr) 1992-04-23 1992-04-23 Produits chimiques de desencrage
EP19920914576 EP0637347A1 (fr) 1992-04-23 1992-04-23 Produits chimiques de desencrage
MX9302292A MX9302292A (es) 1992-04-23 1992-04-23 Productos quimicos removedores de tinta.
PCT/US1992/003379 WO1993022491A1 (fr) 1992-04-23 1992-04-23 Produits chimiques de desencrage

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CA 2134079 CA2134079A1 (fr) 1992-04-23 1992-04-23 Produits chimiques de desencrage
PCT/US1992/003379 WO1993022491A1 (fr) 1992-04-23 1992-04-23 Produits chimiques de desencrage

Publications (1)

Publication Number Publication Date
WO1993022491A1 true WO1993022491A1 (fr) 1993-11-11

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PCT/US1992/003379 Ceased WO1993022491A1 (fr) 1992-04-23 1992-04-23 Produits chimiques de desencrage

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AU (1) AU2246892A (fr)
WO (1) WO1993022491A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002057538A3 (fr) * 2001-01-16 2002-09-26 Novozymes North America Inc Désencrage neutre avec une composition de désencrage comprenant une lipase et un ester d'acide gras
WO2005047594A1 (fr) * 2003-11-12 2005-05-26 Kemira Chemicals, Inc. Melanges de desencrage pour systemes faiblement alcalins

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991011424A1 (fr) * 1990-01-26 1991-08-08 Henkel Kommanditgesellschaft Auf Aktien Composes alcoxyles prepares a partir de derives d'acide carboxylique epoxydes
WO1992006240A1 (fr) * 1990-10-09 1992-04-16 Henkel Kommanditgesellschaft Auf Aktien Utilisation de composes contenant des chaines polyethers et extraits de derives d'acide carboxylique epoxyde afin d'eliminer les encres d'impression de vieux papiers et/ou d'eaux de recyclage de papier

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991011424A1 (fr) * 1990-01-26 1991-08-08 Henkel Kommanditgesellschaft Auf Aktien Composes alcoxyles prepares a partir de derives d'acide carboxylique epoxydes
WO1992006240A1 (fr) * 1990-10-09 1992-04-16 Henkel Kommanditgesellschaft Auf Aktien Utilisation de composes contenant des chaines polyethers et extraits de derives d'acide carboxylique epoxyde afin d'eliminer les encres d'impression de vieux papiers et/ou d'eaux de recyclage de papier

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002057538A3 (fr) * 2001-01-16 2002-09-26 Novozymes North America Inc Désencrage neutre avec une composition de désencrage comprenant une lipase et un ester d'acide gras
WO2005047594A1 (fr) * 2003-11-12 2005-05-26 Kemira Chemicals, Inc. Melanges de desencrage pour systemes faiblement alcalins
US7169257B2 (en) * 2003-11-12 2007-01-30 Kemira Chemicals, Inc. Method of deinking waste paper using a reduced alkali system
EP1694906A4 (fr) * 2003-11-12 2009-09-16 Kemira Chemicals Inc Melanges de desencrage pour systemes faiblement alcalins

Also Published As

Publication number Publication date
AU2246892A (en) 1993-11-29

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