WO1998017857A1 - Extraction de metaux de fluides de traitement dans une usine de pate a papier - Google Patents

Extraction de metaux de fluides de traitement dans une usine de pate a papier Download PDF

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Publication number
WO1998017857A1
WO1998017857A1 PCT/SE1997/001749 SE9701749W WO9817857A1 WO 1998017857 A1 WO1998017857 A1 WO 1998017857A1 SE 9701749 W SE9701749 W SE 9701749W WO 9817857 A1 WO9817857 A1 WO 9817857A1
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WO
WIPO (PCT)
Prior art keywords
organophilic
extraction
hydroxy
procedure according
chelating agent
Prior art date
Application number
PCT/SE1997/001749
Other languages
English (en)
Inventor
Arne Elofson
Arne Nordgren
Original Assignee
Hampshire Chemical Ab
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 Hampshire Chemical Ab filed Critical Hampshire Chemical Ab
Priority to AU47976/97A priority Critical patent/AU4797697A/en
Publication of WO1998017857A1 publication Critical patent/WO1998017857A1/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
    • D21C11/00—Regeneration of pulp liquors or effluent waste waters
    • D21C11/0007—Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for
    • 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
    • D21C1/00—Pretreatment of the finely-divided materials before digesting
    • 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
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/22—Other features of pulping 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

Definitions

  • the present invention relates to a procedure in the manufacture of lignocellulose for removing non-process metal ions by extraction with a combination of an organophilic chelating agent and an organic solvent.
  • ECF Elementally Chlorine Free
  • TCF Total Chlorine Free
  • a key factor for attaining this in TCF production is that the levels of transition metal ions in the pulp in the above- mentioned chlorine free bleaching steps are low, preferably near zero level in at least the peroxide step (P) since especially manganese gives serious disturbances in bleaching with peroxide by catalysing certain side reactions wherein free radicals are involved, which attack the hydrocarbon chains .
  • P peroxide step
  • An often used method is the so-called ignox method (EKA Nobel) which is described in SE-A-8902058.
  • non-process metal ions commonly named non-process metal ions
  • NPE non-process metal ions
  • Ca, Mg, Al, Ba and K which have been desorbed from the pulp by the acidic pH value in the Q step of the bleach plant and in optional acidic Z steps, and which together with different anions, such as sulphate, phosphate, oxalate, silicate and carbonate, can form sparingly soluble salts and form problematic incrusts in the form of barium sulphate and calcium oxalate in the bleach plant, calcium carbonate in digesters, while in the chemical recovery sodium aluminum silicate can be formed in black liquor evaporators and calcium carbonate in the surrounding equipment of the green liquor preparation, such as in pumps and pipelines.
  • NPE non-process metal ions
  • the pH lowering in the Q step must be carried out in order that the manganese ions shall be able to form complexes effectively but at the same time it causes an undesirable release of fibre adsorbed calcium and magnesium ions.
  • Hampox-Q process which uses a higher pH level and thus releases less calcium and magnesium ions, the situation can be improved but incrust problems cannot be excluded.
  • the incrust formation can be reduced in the evaporators by passing the filtrates not to the weak liquor, but to the wash liquor, which goes to the melt dissolver and then to the green liquor clarification where the transition metal ions can be expelled but then incompletely since the ligand instead of a complete degradation such as in the soda recovery unit is subjected to a gradually splitting with a certain degree of retained complex forming ability in the green liquor preparation (melt solution, green liquor clarification) , white liquor preparation (causticizing, white liquor clarification) , impregnation, cooking, discharging etc., by means of which optionally some non-process metal ions can be returned and built up in the system to a balance level which depends on the ratio in rapidity between addition and degradation of the complexes in the soda recovery unit and other parts of the system.
  • the present invention relates to a procedure in the manufacture of lignocellulose to remove non-process elements (NPE) in the form of : a) incrust forming alkaline earth metals, preferentially calcium, magnesium and barium, b) other incrust forming metals, preferentially aluminum, c) transition metals, preferentially iron, manganese and copper, wherein extraction is carried out with a combination of an organophilic chelating agent and an organic solvent, which extraction is carried out in at least one position in at least one stage in a chemical process such as in the kraft process, the sulphite process or in the manufacture of semi- chemical, chemi-mechanical, mechanical and recycled pulps.
  • NPE non-process elements
  • the organophilic chelating agent i.e. a chelating agent with one or more lipophilic groups, is selected from organophilic derivatives of aminocarboxylic acids, hydroxy alkyl amino- carboxylic acids, hydroxy carboxylic acids, aminophosphonic acids, phosphonic acids, hydroxy benzyl aminocarboxylic acids, hydroxy alkyl benzyl aminocarboxylic acids, hydroxy sulpho benzyl aminocarboxylic acids, hydroxy carboxy benzyl aminocarboxylic acids or mixtures thereof.
  • Suitable chelating agents are an organophilic derivative of DTPA, EDTA, DTPMPA, monomeric or oligomeric forms of N,N-bis (2-hydroxy-5-sulphobenzyl) glycine, N,N-bis- (2-hydroxy-5-alkylbenzyl) glycine, N,N-bis (2-hydroxy-5- carboxybenzyl) glycine or mixtures thereof.
  • the total amount of chelating agents which is added is calculated according to the amount of metal ions in the pulp which shall be subjected to complex forming and e.g. it can be from 1 to 10 kgs/ton absolute dry pulp but since the chelating agents are recovered and recirculated after "make up" with new chelating agents this is not the same as the consumption but the consumption can be of the order of one tenth of the dosage.
  • the amount of organic solvent can be determined within wide limits the lower limit being determined by the solubility of the organophilic chelating agent and of the complex and, furthermore, by the type of extraction equipment, and for instance can be up to the order five to ten times the amount of pulp which is subjected to extraction in the extraction zone in integrated extraction in some washing apparatus, for instance a diffuser, while in differentiated extraction of the white water flow in an extractor alongside of the pulp flow can be set lower, how much depends on the type of extractor.
  • the upper limit should for practical and economical reasons of course not be set higher than what is necessary for an effective extraction.
  • the organic solvent can belong to the group of terpenes, for instance terpentine from the mill's own terpentine recovery or be some other suitable solvent which has restricted solubility or is sparingly soluble in water.
  • Figure 1 shows integrated extraction in a diffuser with an organic solvent and an organophilic chelating agent in the pulp flow
  • Figure 2 shows differentiated extraction with an organic solvent and an organophilic chelating agent with the use of an extractor on the white water system.
  • NPE are removed in an integrated extraction, preferably on the brown side, by means of an organophilic chelating agent dissolved in an organic solvent, whereby fibre adsorbed and water dissolved NPE are transferred to the organic phase in the form of a metal ion complex.
  • the stability of complexes of the category transition metal ions is maintained by maintainance of reductive conditions by the addition of a suitable reducing agent as is described in our copending patent application relating to "Process in preparing cellulose pulp" in treatment with water soluble chelating agents.
  • the extraction can be carried out for instance in an diffuser such as is shown in Figure 1.
  • Suitable reducing agents is one or a combination of reducing agents selected from hydrogen sulphide, sulphide, sulphur dioxide, hydrogen sulphite, sulphite, boron hydride, dithio- nite, tetrathionite, dithionate, tetrathionate, thiosulphate, hypophosphite, orthophosphite etc. where the counterion to the anions in said examples can belong to the groups alkali or alkaline earth metals, usually sodium, magnesium and calcium, an especially suitable reducing agent is for instance sodium dithionite.
  • the organic phase with the dissolved complexes passes together with the wash liquor out from the diffuser to the white water system from which the organic phase with the dissolved complex is separated from the liquor phase in a separator.
  • the organic phase with the organophilic metal ion complex is extracted with diluted acid, for instance sulphuric acid, the metal ion in the complex being released from the ligand (chelating agent) and passes over into the acid phase while the ligand remains dissolved in the organic phase.
  • the organic phase with the ligand (chelating agent) is recirculated to the diffuser after "make up" with organophilic chelating agent and the procedure is repeated in a circle process.
  • the acid phase is neutralized with for instance sodium hydroxide, and any remaining organic solvent in the neutralized acid phase is separated in the turpentine decanting before it goes to the external purification.
  • the extraction can be carried out differentiated in an extractor on the white water system, i.e. alongside of the pulp flow, such as is illustrated in Figure 2, and then the white water after having been freed from NPE can be recirculated to the extractor.
  • This second embodiment of the invention means a process which is simpler from a process technical point of view since the organic solvent will not enter the main flow of the pulp.
  • the extraction of organosolve soluble resinous substances and NPE will be inferior since the organic solvent and the dissolved organophilic chelating agent respectively will not come into direct contact with the fibre.
  • this process is less suitable for fibre adsorbed Mn, which must be lowered to zero level in order not to disturb in the bleaching process.
  • the process is suitable for removal of NPE in the form of alkaline earth metals, Ca, Mg and Ba. In this context no reducing agent is necessary which, however, as can be seen from what has been stated above, is the case as regards transition metals.
  • Two phase extraction according to the invention can in addition to craft pulp also be used in the manufacture of other chemical pulps such as sulphite pulp and in the production of semi-chemical, chemi- mechanical and mechanical pulps such as GW, PGW, SPGW, TMP, RMP and CTMP and recycle fibre pulps, on the whole when there is a need to remove metal ions from a system in order to solve incrust problems or if there are other reasons for removing metal ions .
  • the different forms of extraction according to the invention can be carried out batchwise or continuously in counter- current.
  • stainless tanks with agitators can be used, which are used alternately while continuous differential counter-current extraction, also according to the gravitation principle, consists of a tower or column with a zone for mechanical dispersing of the liquid phases and another zone where separation takes place.
  • More advanced continuous apparatuses for differential counter- current extraction are based on the centrifugal principle. Suitable such are for instance Podbielniak, Quadronics, (Liquid Dynamics) , Luwestra (Centriwestra) or De Laval extractors .

Abstract

L'invention concerne un procédé utilisé dans la fabrication de la lignocellulose, qui consiste à extraire les éléments ne faisant pas partie du procédé, se présentant sous la forme, entre autres, de métaux alcalino-terreux formant des incrustations et de métaux de transition. L'extraction combinée à un agent de chélation organophilique et à un solvant organique s'effectue au cours de la production de pâtes à papier chimique ou mécanique, et de pâtes à partir de fibres recyclées.
PCT/SE1997/001749 1996-10-21 1997-10-17 Extraction de metaux de fluides de traitement dans une usine de pate a papier WO1998017857A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU47976/97A AU4797697A (en) 1996-10-21 1997-10-17 Removal of metals from treatment fluids in a cellulose pulp mill

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE9603859-1 1996-10-21
SE9603859A SE507483C2 (sv) 1996-10-21 1996-10-21 Avlägsnande av metalljoner genom extraktion med en kombination av en organofil komplexbildare och ett organiskt lösningsmedel vid framställning av pappersmassa

Publications (1)

Publication Number Publication Date
WO1998017857A1 true WO1998017857A1 (fr) 1998-04-30

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/SE1997/001749 WO1998017857A1 (fr) 1996-10-21 1997-10-17 Extraction de metaux de fluides de traitement dans une usine de pate a papier

Country Status (3)

Country Link
AU (1) AU4797697A (fr)
SE (1) SE507483C2 (fr)
WO (1) WO1998017857A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998053893A1 (fr) * 1997-05-30 1998-12-03 Hampshire Chemical Ab Agents d'extraction et leur procede d'utilisation
WO2008060519A2 (fr) * 2006-11-15 2008-05-22 International Paper Company Procédé de blanchiment amélioré avec au moins une étape d'extraction
WO2009151366A1 (fr) * 2008-06-13 2009-12-17 Hans Magnus Norgren Produit chimique et procédé destiné à chélater des ions métalliques renfermés dans l’eau et à séparer/récupérer le chélate formé

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994001615A1 (fr) * 1992-07-09 1994-01-20 Kvaerner Pulping Technologies Ab Procede de blanchiment de pulpe combine a l'adsorption de metaux
WO1994012720A1 (fr) * 1992-12-02 1994-06-09 Kvaerner Pulping Technologies Ab Procede de blanchiment de pate de cellulose, sans substances chimiques contenant du chlore
WO1994021857A1 (fr) * 1993-03-24 1994-09-29 Kamyr, Inc. Traitement des effluents d'installations de blanchiment
US5571378A (en) * 1993-11-23 1996-11-05 Hampshire Chemical Ltd. Process for high-pH metal ion chelation in pulps

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994001615A1 (fr) * 1992-07-09 1994-01-20 Kvaerner Pulping Technologies Ab Procede de blanchiment de pulpe combine a l'adsorption de metaux
WO1994012720A1 (fr) * 1992-12-02 1994-06-09 Kvaerner Pulping Technologies Ab Procede de blanchiment de pate de cellulose, sans substances chimiques contenant du chlore
WO1994021857A1 (fr) * 1993-03-24 1994-09-29 Kamyr, Inc. Traitement des effluents d'installations de blanchiment
US5571378A (en) * 1993-11-23 1996-11-05 Hampshire Chemical Ltd. Process for high-pH metal ion chelation in pulps

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998053893A1 (fr) * 1997-05-30 1998-12-03 Hampshire Chemical Ab Agents d'extraction et leur procede d'utilisation
WO2008060519A2 (fr) * 2006-11-15 2008-05-22 International Paper Company Procédé de blanchiment amélioré avec au moins une étape d'extraction
WO2008060519A3 (fr) * 2006-11-15 2008-08-14 Int Paper Co Procédé de blanchiment amélioré avec au moins une étape d'extraction
WO2009151366A1 (fr) * 2008-06-13 2009-12-17 Hans Magnus Norgren Produit chimique et procédé destiné à chélater des ions métalliques renfermés dans l’eau et à séparer/récupérer le chélate formé
US8658814B2 (en) 2008-06-13 2014-02-25 Chemseq International Ab Chemical and method for chelating metal ions included in water and separating/recovering of formed chelate
EP2297397A4 (fr) * 2008-06-13 2015-08-26 Hans Magnus Norgren Produit chimique et procédé destiné à chélater des ions métalliques renfermés dans l eau et à séparer/récupérer le chélate formé

Also Published As

Publication number Publication date
SE9603859D0 (sv) 1996-10-21
SE9603859L (sv) 1998-04-22
SE507483C2 (sv) 1998-06-15
AU4797697A (en) 1998-05-15

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