WO2013178875A1 - Procédé de traitement d'un matériau fibreux et nouvelle composition - Google Patents

Procédé de traitement d'un matériau fibreux et nouvelle composition Download PDF

Info

Publication number
WO2013178875A1
WO2013178875A1 PCT/FI2013/050551 FI2013050551W WO2013178875A1 WO 2013178875 A1 WO2013178875 A1 WO 2013178875A1 FI 2013050551 W FI2013050551 W FI 2013050551W WO 2013178875 A1 WO2013178875 A1 WO 2013178875A1
Authority
WO
WIPO (PCT)
Prior art keywords
polymer
mol
bleaching
phosphonate
salt
Prior art date
Application number
PCT/FI2013/050551
Other languages
English (en)
Inventor
Jonas Konn
Reijo Aksela
Minna Sankari
Irene LIU
Anna ILOMÄKI
Original Assignee
Kemira Oyj
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
Priority claimed from CN201210171492.1A external-priority patent/CN102767106B/zh
Priority claimed from FI20125578A external-priority patent/FI126957B/en
Application filed by Kemira Oyj filed Critical Kemira Oyj
Publication of WO2013178875A1 publication Critical patent/WO2013178875A1/fr

Links

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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/08—Removal of fats, resins, pitch or waxes; Chemical or physical purification, i.e. refining, of crude cellulose by removing non-cellulosic contaminants, optionally combined with bleaching
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1047—Conserving the bleached pulp
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds
    • 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
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds

Definitions

  • the present invention relates to a process for the treatment of fiber material, especially a cellulosic fiber material in the presence of a phosphonate and a polymer and optionally a chelating agent.
  • the invention further relates to a composition comprising a phosphonate and a polymer and optionally a chelat- ing agent.
  • the composition is used in alkaline peroxide bleaching of mechanical and chemi-mechanical pulps.
  • the type of metals and their complexes formed, their activity state, interactions and the local environment will affect the chemistry involved in peroxide decomposition.
  • the peroxide needs a special stabilizer to prevent this decomposition.
  • the optimal behaviour of a stabilizer in the peroxide bleaching combines complexing and deactivating of detrimental metal ions.
  • chelating agents are used as pretreatment for removing harmful metal ions.
  • Transition metal ions such iron and manganese are re- moved before pulp is bleached with hydrogen peroxide.
  • Chelating agents, such as polyaminopolycarboxylat.es, are commonly used for sequestering the transition metals.
  • Phosphonates are used to inhibit calcium carbonate scale formation in water systems. Although phosphonates are very effective at controlling calcium car- bonate scale formation, and certain phosphonates exhibit excellent calcium tolerance, i.e. the ability to inhibit calcium carbonate scale in water having a propensity toward scale deposition, they can produce insoluble phosphonate- calcium complexes or calcium phosphate scale upon degradation, especially in waters having high calcium concentrations and pH. The use of phosphonate products for stabilizing peroxide bleaching normally requires high dosages of phosphonate.
  • EP 0628539 A1 relates to control of scale formation and corrosion with modified polyepoxysuccinic acid in aqueous systems.
  • the method is effective at inhibiting the formation and deposition of calcium scales in circulating aqueous systems at conditions of high pH, high calcium concentration and high M- alkalinity.
  • the method provides a method for inhibiting scale formation as well as inhibiting and controlling corrosion of metals, particularly ferrous-based metals in contact with aqueous systems.
  • the treatment controls calcium scale formation without forming undesirable inhibitor-calcium precipitates.
  • Alkaline silicate (waterglass) is a commodity used to enhance peroxide bleach- ing efficiency of mechanical and chemi-mechanical pulps. It is relatively cost- effective, rather easy to apply and universally available.
  • silicate can act as a peroxide stabilizer, a metal ion sequestrant, a buffering agent and as a metal surface passivator. With regard to peroxide stabilization, surface pas- sivation and metal ion sequestration are the most important functions.
  • silicate is beneficial in peroxide bleaching, it generates detrimental effects in the pulping processes. Scaling caused by silicate may be an issue for the case when a mechanical or a chemi-mechanical plant is integrated with a chemical pulp mill in such a way that effluent containing silicates is directed to the recovery cycle of the chemical pulp mill. Also, when a chemi- thermomechanical pulp (CTMP) or alkaline peroxide mechanical pulp (APMP) mill has its own evaporation plant, the silicate precipitates are troublesome as they tend to precipitate on evaporation units decreasing the heat transfer capacity.
  • CMP chemi- thermomechanical pulp
  • APMP alkaline peroxide mechanical pulp
  • silicates when in form of the water carry-over, enter the paper making process, they will disturb the papermaking process in severe ways, such as by precipitating on hot surface and causing holes in the paper reel. Therefore, a partial or total replacement of water glass would be advantageous and at the same time decrease the precipitation problems connected with the use of water glass.
  • the Applicant's prior application WO 2005/080673 discloses a stabilizing composition and a process for treatment of fibre material.
  • the fibre material is treated with a composition comprising i) co-polymer of 3-allyloxy-2- hydroxypropane-sulfonic acid (AHPS) and an unsaturated carboxylic acid, and ii) a chelating agent.
  • AHPS 3-allyloxy-2- hydroxypropane-sulfonic acid
  • a chelating agent ii)
  • the Applicant's prior application WO 2005/108673 discloses a stabilizing composition and a process for treatment of fibre material.
  • the fibre material is treated with a composition comprising i) co-polymer of AHPS and an unsatu- rated carboxylic acid, ii) a chelating agent, and iii) an alkaline earth metal compound, such as magnesium sulphate.
  • the Applicant's prior application EP 21 18363 discloses a composition and a process for treatment of fibre material.
  • the fibre material is treated with a composition comprising i) co-polymer of AHPS and an unsaturated carboxylic acid, ii) a chelating agent, and iii) a poly-alpha-hydroxyacrylic acid or an alkaline salt thereof or the corresponding polylactone thereof.
  • the composition may additionally comprise polycarboxylic acid polymer.
  • US 5820636 disclose a process for the continuous pretreatment of cellulosic textile material.
  • the process comprises a) a pre-cleaning step, b) a bleaching step with hydrogen peroxide in an alkaline-aqueous liquor.
  • the bleaching step b) comprises customary surfactants and other customary auxiliaries, wherefore the treatment bath additionally comprises from 1 to 10 wt-%, based on the weight of the textile material, (i) either of an aminopolycarboxylic acid, of a hy- droxyalkyl- or amino-phosphonic acid, of a polycarboxylic acid, of a polyhy- droxycarboxylic acid or of an inorganic polymetaphosphate, or a mixture thereof, as complexing agent for polyvalent metal ions, or (ii) of a water-soluble polymer of monoethylenically unsaturated mono- or dicarboxylic acids or anhydrides, or a mixture thereof, or (ii
  • the combination of the phosphonate and the polycarboxylic acid polymer and optionally the chelating agent may be used as an anti-scaling agent in bleaching processes.
  • composition comprising the phosphonate and the polycarboxylic acid polymer and optionally the chelating agent has a multifunction property. That is, by using the composition very good bleaching performance, partial or total replacement of water glass and anti-scaling effect are achieved.
  • the composition is very effectively being used as a stabilizer and/or as anti- scaling agent in alkaline peroxide bleaching of mechanical and chemi- mechanical pulps of a fiber material in an aqueous medium.
  • the composition has multi-functionality, simultaneously acting as a stabilizer and as an anti- scaling agent.
  • the present invention makes it possible to partially or totally replace water glass in bleaching by using the provided combination of the phosphonate and the polycarboxylic acid polymer and optionally the chelating agent.
  • the present invention provides a process for treating of fiber material comprising the step of contacting the fiber material in an aqueous medium with a phosphonate and a polycarboxylic acid polymer and optionally a chelating agent.
  • the present invention provides a composition comprising the phosphonate and the polycarboxylic acid polymer and optionally the chelating agent.
  • composition and process according to the invention are in one embodi- ment being used as a pretreatment of mechanical pulp, for example thermo- mechanical pulp (TMP) and groundwood (GW), and chemi-mechanical pulp, for example chemi-thermomechanical pulp (CTMP), alkaline peroxide mechanical pulp (APMP) and pre-conditioning refiner chemical alkaline peroxide mechanical pulp (P-RC APMP), or similar processes which are bleached with alkaline peroxide.
  • mechanical pulp for example thermo- mechanical pulp (TMP) and groundwood (GW)
  • chemi-mechanical pulp for example chemi-thermomechanical pulp (CTMP), alkaline peroxide mechanical pulp (APMP) and pre-conditioning refiner chemical alkaline peroxide mechanical pulp (P-RC APMP), or similar processes which are bleached with alkaline peroxide.
  • TMP thermo- mechanical pulp
  • GW groundwood
  • chemi-mechanical pulp for example chemi-thermomechanical pulp (CTMP), alkaline peroxide mechanical pulp
  • the composition is used as an anti-scaling agent.
  • the composition is used as an anti-scaling agent in bleaching of a fiber material in an aqueous medium.
  • the alkaline peroxide bleaching process for mechanical and chemi-mechanical pulps according to the invention is practiced as a single stage of bleaching or in a two-stage process, where the pre-bleached pulp is entering the second stage.
  • Any consistency may be used, but for example in bleached chemi- thermomechanical pulp (BCTMP) process it is preferred to use medium consistency in the first stage and high consistency in the second stage.
  • BCTMP bleached chemi- thermomechanical pulp
  • P-RC APMP high consistency is preferred choice.
  • the bleaching may be preceded by a pretreatment with a chelating agent in order to reduce the amount of transition metals entering the bleaching process.
  • the composition is suitable as an anti-scaling agent in bleaching of a fibre material in an aqueous medium. As papermaking operations more frequently take place in closed-loops and with as low water usage as possible, silicate and other components build up in the process. These components may cause deposits on the paper machine. In order to prevent this, the composition is used as an anti-scaling agent.
  • the composition can be used as total or partial replacement of water glass in those processes, where water glass is commonly used.
  • the effect of the combination of the phosphonate and the polycarboxylic acid polymer and the optional chelating agent in pre- treatment depends on that the phosphonate very strongly chelate transition metal ions, such as for example iron and manganese ions.
  • the polycarboxylic acid polymer used according to the invention in turn, binds very strongly alkaline earth metal ions, especially calcium ions.
  • the concentration of the alkaline earth metal ions is in very big excess in relation to the transition metal ions, as is often the case when for example white water from papermaking process is recycled to the pulping and bleaching operation, the phosphonate are also consumed for binding the alkaline earth metal ions.
  • a very strong calcium binder the amount of a conventional chelating agent can be reduced.
  • the phosphonate and the polycarboxylic acid polymer and the optional chelating agent may be added into pulp either mixed together or separately.
  • the phosphonate and the polycarboxylic acid polymer are mixed with peroxide and the resulting composition is mixed with alkaline, and the resulting mixture is added into pulp.
  • the phosphonate and the polycarboxylic acid polymer are mixed with peroxide, and the optional chelat- ing agent is mixed with alkaline, such as sodium hydroxide (NaOH). Said two mixtures are then added into pulp, or first mixed together, and resulting mixture is added into pulp.
  • alkaline such as sodium hydroxide (NaOH).
  • the phosphonate and the polycarboxylic acid polymer and optionally the chelating agent will work together which is surprising, because the polymer itself cannot stabilize very well alkaline hydrogen perox- ide solution and also gives general poor bleaching performance.
  • the phos- phonates stabilize quite well the alkaline hydrogen peroxide solution.
  • the chelating agents stabilize quite well the above mentioned alkaline peroxide, but cannot give a good bleaching result.
  • the common chelating agents will bind the soluble manganese ions in the alkaline peroxide solutions, but since iron is then in solid form, either colloidal or in precipitated form, chelating agents cannot any more bind the solid compounds. The same is valid for the solid forms of manganese compounds.
  • the phosphonates are suitable for stabilizing the alkaline hydrogen peroxide solutions and bind metal ions in the alkaline peroxide solutions.
  • phosphonates that contain impurities, such as phosphate or phosphite may be involved in the formation of precipitates, such as phosphate precipitates.
  • the phosphate precipitates are calcium-phosphate precipitates.
  • the polycarboxylic acid polymer of the present invention in turn binds the calcium ions. Less calcium-phosphate precipitates are formed and thus the pro- cess is more stable.
  • composition according to the invention is anticipated to bind to the solid surfaces or inactivates the catalytic effect of the solid particles.
  • the common chelating agents cannot, when used alone, give a good bleaching performance for chemical pulps, small vis- cosity loss and high brightness gain and a sufficient amount of residual peroxide, and for mechanical pulps high brightness gain and a sufficient amount of residual peroxide, which indicates that peroxide has mainly been consumed for bleaching and not for decomposition processes. Therefore there is synergetic effect between the phosphonate, the polycarboxylic acid polymer and the optional the chelating agent used according to the invention.
  • One special feature of the invention is that by using this composition or the components of the composition, the dewatering properties will improve consid- erably compared to using water glass. Wash presses before and after high consistency bleaching has lower energy demand when using the components of the composition of the present invention. Thus, dewatering of pulp with silicate free bleaching is more efficient, for example less drying energy is needed than with silicate. Hence, less energy is needed in the dewatering processes on paper machine and in dewatering presses and screws, for example. At the same time the production throughput is increased. This may be due to water glass being in colloidal form during the bleaching. The colloids are reason that the dewatering properties of the pulps are inferior. Another reason for the negative effect on dewatering could be the fact that water glass disturbs the function of micropar- ticle silica in a papermaking process.
  • a process for the treatment of fibre material comprising the step of contacting the fibre material in an aqueous medium with a phosphonate and a polycarboxylic acid polymer and optionally a chelating agent.
  • the process for the treatment of fibre material comprises the step of contacting the fibre material in an aqueous medium with following components (A) a phosphonate having formula II
  • R 4 , R 5 , R6, R7 and Rs are independently a hydrogen atom or an alkyl chain having 1 to 6 carbon atoms and containing one or more phosphonic group(s) or a salt thereof, and
  • Ri is a hydrogen atom or an alkyl group containing 1 to 12 atoms
  • R 2 is a -COOM or CH 2 COOM
  • M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, monium ion or a mixture thereof,
  • R3 sulphonic acid, its alkali or earth alkaline metal salt or its C1 -C10 alkyl ester
  • n, m and k are molar ratios of corresponding monomers, wherein n is from 0 to 0.95, m is from 0 to 0.9 and k is from 0 to 0.8, and (n+m+k) equals 1 , and the weight average molecular weight is between 500 and 20000000 g/mol, and optionally (C) a chelating agent provided that the chelating agent is not a phosphonate.
  • R 4 , R 5 , R6, R7 and Rs are independently a hydrogen atom or an alkyl chain having 1 to 6 carbon atoms and containing one or more phosphonic group(s) or a salt thereof, and a polycarboxylic acid polymer having following formula I
  • Ri is a hydrogen atom or an alkyl group containing 1 to 12 atoms
  • R 2 is a -COOM or CH 2 COOM
  • M is a hydrogen atom, an alkali metal ion, an alkaline earth metal ion, an am- monium ion or a mixture thereof,
  • R3 sulphonic acid, its alkali or earth alkaline metal salt or its C1 -C10 alkyl ester, n, m and k are molar ratios of corresponding monomers, wherein n is from 0 to 0.95, m is from 0 to 0.9 and k is from 0 to 0.8, and (n+m+k) equals 1 , and the weight average molecular weight is between 500 and 20000000 g/mol, and optionally
  • the above said alkali metal ion is preferably sodium or potassium ion, and the alkaline earth metal ion is preferably a magnesium ion.
  • the phosphonate (A) has ability to function as a sequestrant and as an anti- scaling agent.
  • the phosphonate has to be relatively pure. Impurities, such as phosphites and phosphates in the phosphonate may form deposits with calcium. That is, the impurities function as scaling agents. Precipitation effect of the impurities is not significant if the impurities are present in less than 3 wt-%, calculated of the weight of the phosphonate.
  • the phosphonate has high molecular weight and is multidentate.
  • the phosphonate (A) is a phosphonate having formula II
  • R 4 , R 5 , R6, R 7 and Rs are independently a hydrogen atom or an alkyl chain having 1 to 6 carbon atoms and containing one or more phosphonic group(s) or a salt thereof.
  • the alkyl chain is preferably methylene (-CH 2 -) or ethylene (-CH 2 CH 2 -).
  • R 4 , R 5 , R6, R7 and Rs represent the same group.
  • Examples of the phosphonates according to the above formula II are polyam- inopolymethylenephosphonic acids.
  • the polyaminopolymethylenephosphonic acids are made conventionally from the corresponding polyamine, formaldehyde and phosphonic acid. With the higher amines a full substitution with acetic acid groups or methylenphosphon- ic acid groups will become more and more difficult.
  • the polyaminopolymeth- ylenephosphonic acids are also commercially available.
  • Preferred polyaminopolymethylenephosphonic acids are
  • DTPMP Diethylenetriaminepenta(methylene phosphonic acid)
  • TTHMP Triethylenetetraminehexa(methylenephosphonic) acid
  • the most preferred polyaminopolymethylenephosphonic acid is DTPMP.
  • the DTPMP is a multidentate compound having high molecular weight.
  • the component (B) is a polycarboxylic acid polymer or an alkaline salt thereof.
  • the component (B) has pH buffering capacity and acts furthermore as an anti- scaling agent.
  • the polycarboxylic acid polymer of the present invention is prepared by co- polymerizing monomers by any known method in the art. Examples of suitable monomers are acrylic acid, methacrylic acid, unsaturated carboxylic acid or di- carboxylic acid, such as maleic acid or itaconic acid, and sodium allyl sul- fonate.
  • maleic acid or itaconic acid as one of the monomers in order to increase the calcium binding ability of the polymer.
  • the maleic acid and itaconic acid, as one of the monomers of the polymer have a high affinity towards calcium, that is, complexing ability.
  • Said monomers are more cost effective than for example poly-alfa-hydroxyacrylate (PHAS).
  • Increase in molecular weight (MW) increases total polyelectrolytic charge and therefore interac- tion with Ca 2+ , but at very high MW the complex stability becomes less effective due to high level of dispersion producing more linear polymer shape.
  • Polymer of acrylic acid, maleic acid and sodium allyl sulphonate monomers enhances passivation of colloidal metal oxides more effectively.
  • n, m and k are molar ratios of corresponding monomers, wherein n is from 0 to 0.95, m is from 0 to 0.9 and k is from 0 to 0.8, and (n+m+k) equals 1 .
  • n is from 0 to 0.8
  • m is from 0 to 0.7
  • k is from 0.2 to 0.6
  • (n+m+k) equals 1 .
  • n is from 0.0 to 0.65
  • m is from 0 to 0.5 and k is from 0.35 to 0.5
  • (n+m+k) equals 1 .
  • the weight average molecular weight of the polymer is between 500 and 20000000 g/mol, preferably between 1000 and 1000000 g/mol, more preferably between 2000 g/mol and 500000 g/mol, and most preferably between 3000 g/mol and 100000 g/mol.
  • the weight average molecular weight is lower than about 500 g/mol, the efficiency of the polymer becomes too low. If the average molecular weight is higher than 20000000 g/mol, handling and dosage become a problem due to high viscosity of the polymer solution.
  • a cross linker may be used in an amount of 0 to 20 % by mole, preferably 0 to 10 % by mole, of the total monomer content.
  • Suitable cross linkers are, for example methylenebisacryl- amide, ethylene glycol divinyl ether, di(ethylene glycol) divinyl ether, tri- (ethylene glycol) divinyl ether and vinyl or allyl terminated polymers, but are not limited to these.
  • a chain transfer agent may be used in an amount of 0 to 20 % by mole, preferably 0 to 10 % by mole, of the total monomer content.
  • Suitable chain transfer agents are, for example thiols (such as butylmercaptan) and alcohols (such as isopropanol), but are not lim- ited to these.
  • the optional chelating agent (C) may be any chelating agent known in the art provided that the chelating agent is not a phosphonate.
  • the chelating agent removes metal ions which catalyze decomposition of hydrogen peroxide, such as transition metals, iron, manganese and copper. Adding chelating agent al- lows the peroxide to be used more efficiently.
  • the optional chelating agent (C) acts furthermore as a sequestrant. Chelating agent can contribute to brightness gain by sequestering iron ions, for example as EDTA complexes, which are less colored than complexes between iron and lignin.
  • the chelating agent (C) is preferably a chelating agent having formula III
  • p is 0 or an integer of 1 to 10, preferably p is 1 R 9 , Rio, Ri 1 , Ri2 and R13 are independently a hydrogen atom or an alkyl chain having 1 to 6 carbon atoms and containing one or more active chelating lig- ands, such as carboxylic or hydroxyl group(s) or a salt thereof.
  • the alkyl chain is preferably methylene (-CH 2 -) or ethylene (-CH 2 CH 2 -).
  • R9, R10, R11 , R12 and R13 preferably represent the same group.
  • chelating agents according to the above formula II are poly- aminopolycarboxylic acids.
  • the polyaminopolycarboxylic acids are preferably produced by the conventional route from the polyamine and formaldehyde and sodium cyanide or hy- drocyanic acid.
  • the more preferable route for small scale production is to use a haloacetic acid, especially monochloroacetic acid as a reactant.
  • the polyaminopolycarboxylic acids are also commercially available.
  • Preferred polyaminopolycarboxylic acids are:
  • DTPA Diethylenetriaminepentaacetic acid
  • THA Triethylenetetraaminehexaacetic acid
  • polyaminopolycarboxylic acid is DTPA. It has high binding capability and a wide operating range. Furthermore, pH of DTPA is suitable for the bleaching processes.
  • Another preferred chelating agent is a compound having following general formula IV
  • r is an integer of 3 to 10
  • Ri 4 , Ri 5 , Ri6 and Ri 7 are independently a hydrogen atom or an alkyl chain having 1 to 6 carbon atoms and containing one or more active chelating lig- ands, such as carboxylic or hydroxyl group(s) or a salt thereof.
  • the alkyl chain is preferably methylene -CH 2 - or ethylene -CH 2 CH 2 -.
  • Ri 4 , Ri 5 and Ri 7 preferably represent the same group.
  • a further preferred chelating agent is a compound having following general formula V OOUn i1 ⁇ 2 CO Rn v
  • alkyl chain containing 1 -30 carbon atoms and 1 -10 carboxylic acid groups attached to said chain, or alkali or alkaline earth metal salt thereof,
  • Rig and R20 are hydrogen, an alkali metal ion or an alkaline earth metal ion or an alkyl group containing 1 -30 carbon atoms,
  • t is 0 or 1
  • s is 0 or 1 .
  • N-bis- or tris-[(1 ,2-dicarboxy-ethoxy)ethyl]amines of formula IV are the following compounds
  • a preferred N-bis-(1 ,2-dicarboxy-ethyl)amine of formula V is iminodisuccinic acid (ISA) having following formula
  • the bleaching result depends highly on the metal concentrations and on the process conditions, such as raw material, water circulation and processes itself. Therefore optional bleaching result is usually obtained after tailoring the right stabilizer formulation for each process. For this reason, in one embodiment of the present invention, bleaching efficiency is enhanced by an additional component (D).
  • the step of contacting the fibre material in an aqueous medium according to the present invention further comprises contacting the fibre material with component (D).
  • composition of the present invention optionally comprises the component (D).
  • the component (D) is selected from the group comprising a homopolymer of a sulphonate monomer, preferably a homopolymer of 3-allyloxy-2-hydroxy- propane sulfonic acid (AHPS), a homopolymer of acrylic acid, a co-polymer of acrylic acid with a sulphonate monomer, preferably with AHPS, a co-polymer of AHPS with acrylic acid and a second sulphonate monomer, a salt thereof, or a mixture thereof.
  • a homopolymer of a sulphonate monomer preferably a homopolymer of 3-allyloxy-2-hydroxy- propane sulfonic acid (AHPS), a homopolymer of acrylic acid, a co-polymer of acrylic acid with a sulphonate monomer, preferably with AHPS, a co-polymer of AHPS with acrylic acid and a second sulphonate monomer, a salt thereof, or a mixture thereof.
  • the components (A), (B), (C) and (D) may be prepared by any known method in the literature.
  • the components (A), (B), (C) and (D) are moreover commercially available.
  • the components (A), (B), (C) and (D) of the invention are in form of alkaline salts, especially if the components are added separately.
  • the composition according to the invention is made by mixing the alkaline salts. It is preferred that the pH of the product is between 2 and 12.
  • the weight ratio of the components (A):(B):(C) is 1 to 95 : 1 to 95 : 1 to 85, preferably 5 to 90 : 5 to 90 : 5 to 80, more preferably 15 to 80 : 15 to 75 : 15 to 70, most preferably 20 to 70 : 20 to 65 : 20 to 60, and at best 40 to 60 : 20 to 30 : 20 to 35, calculated as active substance.
  • the normal content of the component (D) in the mixture is 0-10 % by weight, preferably 0-6 % by weight, calculated as active substance.
  • the total amount, calculated as product, of the components (A), (B), optionally the component (C) and optionally the component (D), added separately or as a mixture, is from 0.1 to 10 kg per ton of dry fiber material, more preferably from 0.5 to 7 kg per ton of dry fiber material, and most preferably 0.5 to 5 kg per ton of dry fiber material.
  • the fiber material is preferably a cellulosic fiber material, especially a mechanical and/or chemi-mechanical pulp.
  • the cellulosic fiber material may also be chemical pulp.
  • the normal content of active materials in the mixture is at least 10%, preferably at least 15%, and more preferably at least 20% by weight, but also more diluted solutions can be used in the application process if the dosage is increased.
  • the treatment comprises bleaching the fiber material with an alkaline peroxide solution in the presence of the phosphonate and the polycarboxylic acid polymer and optionally the chelating agent.
  • the peroxide bleaching of mechanical pulps with the process according to the invention can comprise all kind of mechanical pulps, e.g. stone groundwood pulp (SGW), pressure groundwood (PGW), thermo-mechanical pulp (TMP), but also chemically treated high-yield pulps, such as chemi-thermomechanical pulp (CTMP).
  • SGW stone groundwood pulp
  • PGW pressure groundwood
  • TMP thermo-mechanical pulp
  • CTMP chemically treated high-yield pulps, such as chemi-thermomechanical pulp (CTMP).
  • CTMP chemi-thermomechanical pulp
  • the invention is furthermore being practiced in refiner bleaching of mechanical pulps and in alkaline peroxide mechanical pulp (APMP, or P-RC APMP), in which wood chips are impregnated with alkaline peroxide solution before and/or during refining.
  • APMP alkaline peroxide mechanical pulp
  • P-RC APMP alkaline peroxide mechanical pulp
  • the residence time in the bleaching can vary within a wide range, from 30 to 240 minutes, preferably from 45 to 180 minutes and most preferably from 60 to 120 minutes.
  • the residence time will also depend on the temperature used in the bleaching.
  • the composition according to the invention is used as a mixture or the ingredients are added separately.
  • the bleaching of mechanical pulps can be carried out at a temperature of from 30°C to 95°C, preferably at a temperature of from 50°C to 90°C. In the case of APMP process, the temperature can occasionally raise up to 150°C in the refiner and up to 100°C in the bleaching tower.
  • the bleaching can be carried out at a consistency of choice, such as about 20 % or higher, but it is most preferably to carry out the bleaching at a high consistency, such as about 30% or higher.
  • Bleaching can also be carried in two stages with a washing/dewatering stage between the stages. The stages can be carried out at a consistency of choice, but it is most preferably to use medium consistency in the first stage and a high consistency in the second stage. This makes it possible to remove the detrimental substances efficiently.
  • the ratio between the alkali and hydrogen peroxide can vary in a wide range, depending on raw materials and degree of bleaching.
  • alternative alkali sources like sodium carbonate, can be utilized.
  • magnesium hydroxide and magnesium carbonate and/or sodium carbonate are being used as whole or partial displacement of the common alkali, sodium hydroxide.
  • P-RC APMP Preconditioning followed by Refiner Chemical treatment Alkaline Peroxide Mechanical Pulping (results disclosed in Example 2)
  • the reaction temperature was 95°C, reaction time 45 minutes, consistency 20%.
  • Chemical charges were: H2O2 55 kg/tp, NaOH 24 kg/tp, chelating agent (DTPA) 2 kg/tp (as commercial product) and composition (phosphonate and polycarboxylic acid polymer) dosages were 3 kg/tp (as product).
  • DTPA and composition phosphonate and polycarbox- ylic acid polymer were diluted 1 :10 with deionized water. Pulp was preheated in microwave oven for about 1 min in order to reach the reaction temperature. Mixing of chemicals into pulp was done either by hand in a plastic beaker. Chemicals were mixed in following order into the pulp: DTPA and NaOH were mixed in a beaker with some hot distilled water (beaker 1 ). Composition (phos- phonate and polycarboxylic acid polymer) was mixed with peroxide in a beaker with some hot distilled water (beaker 2). The content of beakers 1 and 2 were added simultaneously into the pulp and mixed properly.
  • CTMP Chemi-thermomechanical pulp (results disclosed in Example 3)
  • An industrial CTMP aspen/spruce, 75/25 pulp taken after main high consistency refiner was bleached in laboratory using different compositions.
  • the pulp contained Fe ⁇ 10 mg/kg, Mn 3 mg/kg and Ca 362 mg/kg.
  • the reaction temperature was 80°C, reaction time 120 minutes, consistency 25%.
  • the pulp was bleached in laboratory using different compositions. Initial brightness of the pulp was 75.7 %ISO. Chemical charges were: H2O2 38 kg/tp, NaOH 19 kg/tp, composition (phosphonate and polycarboxylic acid polymer) dosages were 1 .7 kg/tp as product. Bleaching trials were carried out in plastic bags similarly as in the APMP bleaching, but chemicals were mixed into pulp using a Quantum Mark IV mixer. Laboratory sheets were prepared using a KCL type sheet former. The sheets were air dried until next day when measuring optical properties (ISO brightness). 3. CTMP: Chemi-thermomechanical pulp (results disclosed in Example 4)
  • the pulp contained Fe ⁇ 10 mg/kg, Mn 1 1 mg/kg and Ca 495 mg/kg.
  • the reaction tem- perature was 85°C, reaction time 120 minutes, consistency 20%.
  • the pulp was bleached in laboratory using different compositions. Initial brightness of the pulp was 65.2 %ISO. Chemical charges were: H 2 O 2 50 kg/tp, NaOH 28 kg/tp, composition (phosphonate and polycarboxylic acid polymer) dosages were 1 .7 kg/tp as product. Bleaching trials were carried out in plastic bags similarly as in the APMP bleaching, but chemicals were mixed into pulp using a Quantum Mark IV mixer. Laboratory sheets were prepared using a KCL type sheet former. The sheets were air dried until next day when measuring optical properties (ISO brightness). Peroxide stability test
  • the efficiency of the stabilizing composition was evaluated by assessing the peroxide degradation in water solutions containing iron and manganese ions by residual peroxide titrations.
  • the iron and manganese content was 2 ppm each.
  • the pH was set to 10 by adding NaOH.
  • An Erlenmeyer with predeter- mined water amount to obtain 200ml_ in total volume was preheated in a water bath to target treatment temperature.
  • 0.565 ml of pre-made Fe solution (0.25g (NH4) 2 Fe (SO 4 ) 2 x 6 H 2 O diluted to 50 g with deionized water) and 0.410 ml of Mn solution (3g MnSO 4 x H 2 O diluted to 1000 g with deionized water) was added.
  • Example 1 Then the evaluated stabilizer (diluted to 1 :10) was added before adding 0.3 ml NaOH (as 10% solution). Finally was added 1 .0 ml H 2 O 2 (as 50%). The residual peroxide was determined by thiosulfate titration after 5, 10, 15, 30, 60, and 90 minutes to evaluate the efficiency of the stabilizing compositions. Results are disclosed in Example 5 and 6.
  • Example 1 Then the evaluated stabilizer (diluted to 1 :10) was added before adding 0.3 ml NaOH (as 10% solution). Finally was added 1 .0 ml H 2 O 2 (as 50%). The residual peroxide was determined by thiosulfate titration after 5, 10, 15, 30, 60, and 90 minutes to evaluate the efficiency of the stabilizing compositions. Results are disclosed in Example 5 and 6. Example 1
  • compositions according to present invention are listed in Table 1 .
  • Table 1 Stabilizing compositions, disclosed as wt-% of active components in the compositions.
  • Ref1 and Ref2 are according to WO 2008/092988.
  • PLAC is polylactone of poly-alpha-hydroxyacrylic acid.
  • Phosphonate is DTPMP.
  • Chelating agent is DTPA.
  • MAH-AA is a copolymer of monomers maleic acid anhydride and acrylic acid having a monomer ratio and molecular weight according to polycarboxylic acid polymer component (B) of the present invention.
  • MAH-SAS is a copolymer of monomers maleic acid anhydride and sodium allyl sulfonate having monomer ratio and molecular weight according to polycar- boxylic acid polymer component (B) of the present invention.
  • AH PS is a copolymer of monomers acrylic acid and 3-allyloxy-2- hydroxypropanesulfonic acid having molecular weight of 3000-5000 g/mol.
  • Blend 2 is according to the present invention (Example 1 ).
  • Blend 2 product resulted in higher residual peroxide and ISO brightness compared to the Ref 1 (according to WO 2008/092988) and mere phosphonate product (Ref 3).
  • Blend 2 product resulted in higher residual peroxide and ISO brightness compared to mere phosphonate product (Ref 3).
  • Example 5 Peroxide stability tests were carried out as described above. The treatment temperature was 50°C and the stabilizing composition dosage was 70 ppm as active substance. The results of the tests are set forth in Table 5. Compositions of the stabilizers are according to the present invention (Example 1 ).
  • Blend 4 3.07 3.04 3.00 2.68 2.23 1 .78
  • Blend 8 2.91 2.78 2.67 2.34 1 .79 1 .13
  • Peroxide stability tests were carried out as described above.
  • the treatment temperature was 90°C and the stabilizer dosage was 140 ppm (as product).
  • the results of the tests are set forth in Table 6.
  • Compositions of the stabilizers are according to the present invention.

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)

Abstract

Cette invention concerne un procédé de traitement d'un matériau fibreux comprenant la mise en contact du matériau avec les composants suivants : (A) un phosphonate, et (B) un polymère ayant la formule (I) suivante dans laquelle R1 est un atome d'hydrogène ou un groupe alkyle contenant de 1 à 12 atomes de carbone, R2 est -COOM ou CH2COOM, M est un atome d'hydrogène, un ion métal alcalin, un ion métal alcalino-terreux, un ion ammonium ou un mélange de ceux-ci, R3 = acide sulfonique, son sel de métal alcalin ou de métal alcalino-terreux ou son ester d'alkyle C1-C10, n, m et k sont les rapports molaires des monomères correspondants, n valant de 0 à 0,95, m de 0 à 0,9 et k de 0 à 0,8, et (n+m+k) étant égal à 1, et éventuellement (C) un agent de chélation, à condition que l'agent de chélation ne soit pas un phosphonate. Cette invention concerne également une composition stabilisante comprenant les composants (A) et (B), et éventuellement le composant (C).
PCT/FI2013/050551 2012-05-29 2013-05-21 Procédé de traitement d'un matériau fibreux et nouvelle composition WO2013178875A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CN201210171492.1A CN102767106B (zh) 2012-05-29 2012-05-29 用于处理纤维材料的方法和新型组合物
FI20125578 2012-05-29
FI20125578A FI126957B (en) 2012-05-29 2012-05-29 Method for treating fibrous material and novel composition
CN201210171492.1 2012-05-29

Publications (1)

Publication Number Publication Date
WO2013178875A1 true WO2013178875A1 (fr) 2013-12-05

Family

ID=48576442

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI2013/050551 WO2013178875A1 (fr) 2012-05-29 2013-05-21 Procédé de traitement d'un matériau fibreux et nouvelle composition

Country Status (1)

Country Link
WO (1) WO2013178875A1 (fr)

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010067A (en) * 1975-01-03 1977-03-01 Benckiser-Knapsack Gmbh Process of preventing formation of resinous deposits in the manufacture of paper and the like
US4056430A (en) * 1974-02-22 1977-11-01 Benckiser-Knapsack Gmbh Process of preventing formation of resinous deposits in the manufacture of paper and the like, and compositions
EP0460797A1 (fr) * 1990-05-04 1991-12-11 Betz Europe, Inc. Procédé pour inhiber la formation de tartre dans les systèmes aqueux
EP0628539A1 (fr) 1993-06-09 1994-12-14 Betz Europe, Inc. Dérivés de l'acide polyepoxysuccinique et leur utilisation pour l'inhibition de la formation de tertre et pour le contrôle de la corrosion dans des systèmes aqueux
US5820636A (en) 1993-05-21 1998-10-13 Basf Aktiengesellschaft Continuous pretreatment of cellulosic textile material
EP0959175A1 (fr) * 1998-05-20 1999-11-24 Degussa-Hüls Aktiengesellschaft Compositions comprenant de l'acide formamidine sulfinique
WO2005080672A2 (fr) * 2004-02-24 2005-09-01 Kemira Oyj Procede de reduction de la teneur en produits d'extraction de pates a haut rendement, et procede de production de pates blanchies a haut rendement
WO2005080673A2 (fr) 2004-02-25 2005-09-01 Kemira Oyj Procede de traitement d'un materiau fibreux et nouvelle composition
US20050217813A1 (en) * 2004-03-31 2005-10-06 Shevchenko Sergey M Methods to enhance brightness of pulp and optimize use of bleaching chemicals
WO2005108673A1 (fr) 2004-05-12 2005-11-17 Kemira Oyj Composition et procede pour le traitement d'une matiere fibreuse
WO2008092988A1 (fr) 2007-02-02 2008-08-07 Kemira Oyj Nouvelle composition et procédé pour le traitement d'un matériau fibreux
WO2010106077A1 (fr) * 2009-03-17 2010-09-23 Dequest Ag Composition pour inhiber la formation de tartre de sel de calcium

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4056430A (en) * 1974-02-22 1977-11-01 Benckiser-Knapsack Gmbh Process of preventing formation of resinous deposits in the manufacture of paper and the like, and compositions
US4010067A (en) * 1975-01-03 1977-03-01 Benckiser-Knapsack Gmbh Process of preventing formation of resinous deposits in the manufacture of paper and the like
EP0460797A1 (fr) * 1990-05-04 1991-12-11 Betz Europe, Inc. Procédé pour inhiber la formation de tartre dans les systèmes aqueux
US5820636A (en) 1993-05-21 1998-10-13 Basf Aktiengesellschaft Continuous pretreatment of cellulosic textile material
EP0628539A1 (fr) 1993-06-09 1994-12-14 Betz Europe, Inc. Dérivés de l'acide polyepoxysuccinique et leur utilisation pour l'inhibition de la formation de tertre et pour le contrôle de la corrosion dans des systèmes aqueux
EP0959175A1 (fr) * 1998-05-20 1999-11-24 Degussa-Hüls Aktiengesellschaft Compositions comprenant de l'acide formamidine sulfinique
WO2005080672A2 (fr) * 2004-02-24 2005-09-01 Kemira Oyj Procede de reduction de la teneur en produits d'extraction de pates a haut rendement, et procede de production de pates blanchies a haut rendement
WO2005080673A2 (fr) 2004-02-25 2005-09-01 Kemira Oyj Procede de traitement d'un materiau fibreux et nouvelle composition
US20050217813A1 (en) * 2004-03-31 2005-10-06 Shevchenko Sergey M Methods to enhance brightness of pulp and optimize use of bleaching chemicals
WO2005108673A1 (fr) 2004-05-12 2005-11-17 Kemira Oyj Composition et procede pour le traitement d'une matiere fibreuse
WO2008092988A1 (fr) 2007-02-02 2008-08-07 Kemira Oyj Nouvelle composition et procédé pour le traitement d'un matériau fibreux
EP2118363A1 (fr) 2007-02-02 2009-11-18 Kemira OYJ Nouvelle composition et procédé pour le traitement d'un matériau fibreux
WO2010106077A1 (fr) * 2009-03-17 2010-09-23 Dequest Ag Composition pour inhiber la formation de tartre de sel de calcium

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PRESLEY, J.R; HILL, R.T.: "The Technology of Mechanical Pulp Bleaching", TAPPI PRESS, pages: 463

Similar Documents

Publication Publication Date Title
AU2008211802B2 (en) New composition and process for the treatment of fibre material
CA2564015C (fr) Composition et procede pour le traitement d'une matiere fibreuse
CA2554056C (fr) Procede de traitement d'un materiau fibreux et nouvelle composition
US7867357B2 (en) Polymer composition for peroxide bleaching of cellulosic fibre material and processes for peroxide bleaching
US7754048B2 (en) Bleaching of cellulosic fibre material with peroxide using polymers as a stabiliser
CN102767106B (zh) 用于处理纤维材料的方法和新型组合物
FI126957B (en) Method for treating fibrous material and novel composition
WO2013178875A1 (fr) Procédé de traitement d'un matériau fibreux et nouvelle composition
KR20130007285A (ko) 질소와 인 성분이 함유되지 않은 친환경 킬레이트제의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13726806

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13726806

Country of ref document: EP

Kind code of ref document: A1