EP2443280B1 - Alkaliperoxidbehandlung von abfällen in einer integrierten neutralalkali-papierfabrik - Google Patents

Alkaliperoxidbehandlung von abfällen in einer integrierten neutralalkali-papierfabrik Download PDF

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Publication number
EP2443280B1
EP2443280B1 EP10789951.0A EP10789951A EP2443280B1 EP 2443280 B1 EP2443280 B1 EP 2443280B1 EP 10789951 A EP10789951 A EP 10789951A EP 2443280 B1 EP2443280 B1 EP 2443280B1
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Prior art keywords
rejects
fiber
alkali
hydrogen peroxide
alkaline
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English (en)
French (fr)
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EP2443280A4 (de
EP2443280A1 (de
Inventor
Stanley A. Heimburger
Melford R. Lougheed
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Arkema Inc
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Arkema Inc
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    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • 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
    • D21C9/001—Modification of pulp properties
    • D21C9/002—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives
    • D21C9/005—Modification of pulp properties by chemical means; preparation of dewatered pulp, e.g. in sheet or bulk form, containing special additives organic 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
    • D21C9/001—Modification of pulp properties
    • D21C9/007—Modification of pulp properties by mechanical or physical means
    • 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
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the present invention is directed to processes producing mechanical pulps utilizing refiners for improving the quality of screen rejects, and most particularly to a mechanical pulp mill integrated with a neutral-alkaline papermaking process producing mechanical printing paper grades.
  • the rejects are treated with hydrogen peroxide, an alkali and an organic stabilizing agent to provide improved optical and physical properties of the refined rejects.
  • Mechanical pulping is a process of mechanically triturating wood into its fibers for the purpose of making pulp.
  • a key advantage of mechanical pulping is the high yield compared to chemical pulping which removes most or all of the lignin binding the cellulose fibers. Lignin is not removed from mechanically pulped wood, meaning scarce resources are more efficiently utilized.
  • Pulps made using conventional mechanical pulping methods are mainly used for newsprint and other printing papers destined for direct mail advertising, directories and some magazines and books, and are typically unsuitable for higher quality or more durable paper end products. This is due, in part, to the fact that mechanical pulps are generally more difficult to bleach, can revert in terms of brightness due to light and humidity exposure and typically have lower strength than chemical pulps.
  • SGW stone groundwood
  • PGW pressurized groundwood
  • RMP refiner mechanical pulp
  • TMP thermomechanical pulp
  • CMP chemi-thermomechanical pulp
  • SGW stone groundwood
  • PGW pressurized groundwood
  • RMP refiner mechanical pulp
  • TMP thermomechanical pulp
  • CMP chemi-thermomechanical pulp
  • the latter three can further be grouped generally under refiner pulping processes.
  • wood chips are ground between rotating metal disks. The process usually is carried out in two stages. The first stage is mainly used to separate the fibers, while the second stage is used to modify the fiber surface for improved fiber bonding in the paper making process.
  • the TMP process typically consists of two refining stages.
  • the first stage is pressurized, which allows the capture of thermal energy released as steam when mechanical energy is applied to the wood chips between the rotating refiner discs. Control of the steam pressure allows the primary refiner to operate at elevated temperatures and provides steam to heat and moisturize the wood chips before refining.
  • the second stage refiner may be atmospheric, but it is more common to pressurize that stage also in order to capture more energy and better control the process. Pulps made by the TMP and CTMP processes have higher strength, which makes them the more favored mechanical pulping processes. However, there is still potential for improvement.
  • the TMP process consumes a high quantity of electrical energy and the pulp produced by the TMP process tends to be darker than most other pulps due to thermal darkening of fiber during refining. Furthermore, the presence of large quantities of lignin in the refined fiber makes it highly susceptible to alkaline darkening.
  • alkaline peroxide treatment of mechanical pulp rejects has been shown to produce improved physical properties and higher brightness equal to or superior to those of sulphonation.
  • efficient alkaline peroxide treatments have been described as requiring a treatment time of from five to forty minutes or more to provide maximum improvements. See for example " HIGH ALKALINE PEROXIDE TREATMENT OF WHITE SPRUCE/LODGEPOLE PINE RMP REJECTS', S.G. Book, pp1-17, CPPA Pacific Coast Brach Mini-Conference April 1990 and " ALKALINE PEROXIDE TREATMENT OF SOUTHERN PINE TMP REJECTS", M.J. Sferrazza et al., pp 617- 629, 1988 Pulping Conference .
  • 4.4-8.9% by weight NaOH based on fiber was being utilized to treat rejects in order to achieve the physical strength improvements noted and caustic/ peroxide (C/P) ratios of 2-3:1 were utilized.
  • US Patent Publication No. 2009/0032207 discloses a mechanical or chem.-mechanical process for making pulp in which, after fibrillation, the pulp is bleached in alkaline conditions. Thereafter, the rejects are screened and bleached separately from the accepts and the bleached rejects mixed with the accepts.
  • US Patent Publication 2008/0035286 discloses an alkaline peroxide mechanical pulping process which includes a step of treating fiberized lignocellulosic material with alkali peroxide chemical for a time and under conditions sufficient to obtain a pulp of desired consistency.
  • Brightening is often carried out in a single step in the pulping process.
  • the bleaching process is conventionally carried out in a bleaching train in one or a plurality of vessels (bleach towers or stages) in a distinct section of the mill, as opposed to the pulping section of the mill.
  • Brightening can be carried out using oxidizing agents such as hydrogen peroxide and/or reducing agents such as sodium dithionite or sodium hydrosulfite.
  • hydrogen peroxide an oxidizing agent
  • sodium hydroxide is a strong alkali and provides the requisite high pH necessary to produce the active perhydroxyl ion, HOO - , thought to produce the bleaching effect in pulps.
  • the cost of sodium hydroxide has been increasing due to changes in availability and energy costs. Concern over the environment has also meant a decrease in the available sodium hydroxide supply. Therefore, different alkali sources and different methods have been tried to find suitable alternatives for bleaching liquors and bleaching processes with limited commercial success.
  • sodium silicate and one of various organic and inorganic stabilizing agents are typically applied to fiber during and prior to addition of hydrogen peroxide and alkali on the fiber.
  • These materials are beneficial largely due to their ability to control metal ions such as manganese, iron and copper that are contained in wood chips entering the pulping process. If untreated, these metal ions destroy hydrogen peroxide and perhydroxyl ion before it is able to brighten chromophores, making the process must less cost efficient and lowering brightening performance.
  • the present invention specifically excludes the use of sodium silicate for stabilization of peroxide and perhydroxyl ion.
  • the presence of silicates can result in the formation of scales (eg. calcium silicate, sodium carbonate) such as on refiner plates which can limit the ability of the refiner to refine rejects.
  • scales eg. calcium silicate, sodium carbonate
  • the present invention is especially directed to a method for treating mechanical pulps comprising the steps of:
  • said alkali is selected from the group consisting of sodium hydroxide, sodium carbonate or sodium bicarbonate.
  • said chelant is selected from the group consisting of aminopolycarboxylic acids, phosphonic acids, polycarboxylic acids, polyacrylates, polyaspartates, gluconates or citrates.
  • said alkali and hydrogen peroxide are added in combination with said rejects fiber ahead of refining.
  • said buffering agent is selected from the group consisting of precipitated calcium carbonate (PCC) or ground calcium carbonate.
  • said alkali and hydrogen peroxide are added in combination with said rejects fiber during refining.
  • the present invention is directed to an improved process for the treatment of mechanical pulping rejects fiber wherein an alkaline hydrogen peroxide treatment is employed that does not require retention time on fiber prior to high consistency refining and which is effective at low chemical treatment levels.
  • the use of zero retention time when adding alkaline treatment chemicals to thickened rejects prior to refining was found to be effective at caustic addition rates of less than or equal to 3.5% by weight in paper mills which operate at least one integrated neutral-alkaline papermaking machine and recycle water from this back to the mechanical pulp mill.
  • percentages are by weight unless specifically specified otherwise. Elimination of the requirement for retention of alkaline peroxide on rejects fiber prior to refining allows the present invention to be implimented with minimal capital cost.
  • Recycle of neutral-alkaline paper machine white water to the mechanical pulp mill and the buffering associated with it from precipitated calcium carbonate (PCC) or ground calcium carbonate (GCC) filler pigment minimizes operating chemical costs by reducing the alkali demand of the mechanical fiber. This results in lower addition of total alkali on the rejects.
  • the amount of hydrogen peroxide added when alkaline treating rejects is related to caustic additon so lower caustic requirements result in lower hydrogen peroxide requirements and makes the process more cost-effective.
  • C/P caustic to peroxide ratio
  • ATR alkaline peroxide treatment of rejects
  • alkali is meant to include any source of alkalinity such as sodium hydroxide or caustic soda (NaOH), sodium carbonate (Na 2 CO 3 ) and sodium bicarbonate (NaHCO 3 ).
  • Na 2 CO 3 and NaHCO 3 also provide buffer capacity to prevent wide swings in pH. When alkaline peroxide bleaching at high temperatures, better brightness is obtained with buffered systems. Buffering the system at lower pH (preferably between about 9 to about 10.5) prevents peroxide decomposition and darkening, but still provides adequate alkalinity to produce the desired species. The buffer releases alkalinity as necessary, and provides sufficient alkalinity for a slow and even production of the perhydroxyl ions.
  • the calcium carbonate functions as a buffer and would be expected to improve brightening during APTR that occurs in a high temperature refiner.
  • the components of the APTR liquor may be added separately or concurrently, concurrently meaning two or more components together such as a pre-mixed stream and separately meaning one at a time, as in individual streams.
  • a hydrogen peroxide stabilizer such as a suitable chelating agent may be included.
  • Chelating agents can include, but are not limited to aminopolycarboxylic acids, (e.g.) ethylenediaminetetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), phosphonic acids, (e.g.) ethylenediaminetetramethylene-phosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), nitrilotrimethylenephosphonic acid (NTMP), polycarboxylic acids, gluconates, citrates, polyacrylates, and polyaspartates or any combination thereof.
  • aminopolycarboxylic acids e.g.) ethylenediaminetetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTPA), nitrilotriacetic acid (NTA), phosphonic acids, (e.g.)
  • a chelating agent may be added to the bleaching liquor in an amount up to 0.5% by weight based on fiber but is preferably added at addition rates of from about 0.1-0.25% based on fiber.
  • chelating agents may be added separately or concurrently with one or more bleach liquor components at one or more chemical addition points in the refining system. Chelating agents are thought to bind metals to prevent the decomposition of hydrogen peroxide which can cause darkening of the produced paper.
  • neutral-alkaline it is meant a pH of about 7.0 to 7.5. Additionally, it was found that neutral-alkaline whitewater containing significant amounts of non-oxidized sulfur compounds leads to brightness gains during APTR that are lower than those where the neutral-alkaline whitewater does not contain these impurities.
  • APTR process described herein it can also be brightened in a conventional hydrogen peroxide bleach plant to produce a pulp having: a) superior optical and physical properties at a cost which is lower over an already achievable brightness range or b) equivalent optical and physical properties at an equivalent cost over a higher brightness range than currently achievable.
  • adverse effects on fiber properties such as yield and brightness losses are minimized between the mechanical pulp mill and the paper machine while simultaneously minimizing anionic charge loading to the paper machines and effluent BOD and COD loading.
  • rejects refiner specific energy versus freeness can be more closely controlled to realize operating savings.
  • Production trials were conducted at an integrated neutral-alkaline mechanical printing paper mill producing a range of paper grades having brightness specifications of 57.5-80% ISO and printing opacity specification of 91.5-96%. Fourteen trials were run which involved concurrently blending concentrated DTPA, NaOH and H 2 O 2 into dilution water and adding this liquor briefly though a dilution water nozzle into the eye of a TMP rejects refiner. A chelant (DTPA) was additionally added ahead of rejects screen thickening at a constant addition rate of 1.5 kg/BDt..
  • DTPA chelant
  • Figures 1-4 summarize the relationships observed after APTR on fiber from laboratory-prepared handsheets made from Refined Screen Rejects and brightened TMP Screened Stock samples.
  • Trials were conducted at an integrated neutral-alkaline mechanical printing paper mill producing a range of paper grades having brightness specifications of 58-84% ISO and printing opacity specification of 85-97%. During extended operating periods of 12 hours and separately, 7 days, APTR was evaluated by applying a liquor containing dilution water, DTPA, caustic soda and hydrogen peroxide onto feedstock for two rejects refiners operating in parallel.
  • the 12-hour evaluations allowed: a) comparing results from two different addition points around the refiners, b) evaluating a low (0.6) and a medium (1.0) C/P ratio at a constant hydrogen peroxide addition of 30 kg/BDt to determine effects on fiber quality at various locations in the TMP mill that the rejects refiners were operating in and c) determining how rejects refining specific energy was impacted by APTR.
  • the 7 day and 24 hour per day evaluation were at a 1.0 C/P with addition of 30 kg/BDt peroxide on rejects and a) allowed paper machine whitewater coming back to the TMP mill to completely turn over, b) evaluated downstream effects of APTR in bleaching of TMP on the paper machines on various paper grades and c) provided data showing specific energy reduction in rejects refining.
  • Table 2 summarizes laboratory data of accepts samples collected during a single week of primary, secondary and rejects screens when two APTR operating periods of 12 hours each in duration could be compared to three operating periods surrounding them when APTR was not operating.
  • Figures 5-7 illustrates the key benefits of APTR in the TMP mill during the 12 hour trials while Figures 8-10 summarize key results of continuous automated testing in the TMP mill and at the three downstream paper machines over the extended 7 day trial.
  • Trials were conducted at an integrated neutral-alkaline mechanical printing paper mill producing a limited number of paper grades having brightness specifications of 58-60% ISO and printing opacity specification of 85-95%.
  • APTR was evaluated by applying a liquor containing dilution water, DTPA, caustic soda and hydrogen peroxide into high-pressure dilution feed water added at the refining zone of one or two atmospheric refiners operating in series. These refiners process screened, cleaned TMP rejects that are subsequently bleached separately from additional TMP accepts/rejects with sodium hydrosulfite and utilized as a reinforcing fiber on two downstream paper machines.
  • Figures 11 and 12 illustrate the beneficial effects of APTR on brightness, tensile and other key pulp properties utilizing C/P ratios in the range of 0.35-0.40 in treatment liquor and DTPA applied into Unrefined Rejects prior to refining.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Paper (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Claims (10)

  1. Verfahren zur Behandlung von Holzstoffen, umfassend die Schritte:
    a) Bereitstellen von nadelholz- oder laubholzstämmigen Cellulosematerialien;
    b) Eintragen des Cellulosematerials in ein Hauptstrom-Refinermahlungssystem zur Verarbeitung eines Hauptstrom-Faserstoffs;
    c) Abtrennen von Rejekten aus dem Hauptstrom-Faserstoff mittels Sortierung oder Fraktionierung;
    d) Mischen eines aus einem Papierprozess zurückgeführten neutral-alkalischen Siebwasserstroms, der im Wesentlichen frei von oxidierbaren Schwefelspezies ist und eine Puffersubstanz enthält, wobei die Rejekte einen Rejektfaserstoff bilden;
    e) Zugeben einer Behandlungsflüssigkeit, die Wasserstoffperoxid und ein Alkali umfasst, zum Rejektfaserstoff, wobei die Menge an Alkali kleiner ist als 3,5 Gew.-% auf 100%-Basis bezogen auf Faserstoff, und das Verhältnis von Alkali zu Wasserstoffperoxid 0,35:1,0 bis 1,5:1,0 beträgt; und
    f) Zugeben eines Chelatbildners zum Rejektfaserstoff und zum neutral-alkalischen Siebwasserstrom zur Kontrolle von Metallionen, die schädlich für die Wasserstoffperoxidstabilität sind;
    g) Mahlen des behandelten Rejektfaserstoffs, wobei das Wasserstoffperoxid und ein Alkali getrennt oder gemeinsam vor oder während der Mahlung des Rejektfaserstoffs dem Rejektfaserstoff zugegeben werden.
  2. Verfahren nach Anspruch 1, wobei das Alkali aus der Gruppe bestehend aus Natriumhydroxid, Natriumcarbonat oder Natriumbicarbonat ausgewählt ist.
  3. Verfahren nach Anspruch 1 oder 2, wobei der Chelatbildner aus der Gruppe bestehend aus Aminopolycarbonsäuren, Phosphonsäuren, Polycarbonsäuren, Polyacrylaten, Polyaspartaten, Gluconaten oder Zitraten ausgewählt ist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der Chelatbildner der Flüssigkeit in einer Menge von bis zu 0,5 Gew.-% bezogen auf Faserstoff zugegeben wird, bevorzugt in Zugaberaten von 0,1 bis 0,25 Gew.-% bezogen auf Faserstoff zugegeben wird.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Alkali und das Wasserstoffperoxid in Kombination mit dem Rejektfaserstoff während der Mahlung zugegeben werden.
  6. Verfahren nach einem der vorhergehenden Ansprüche, wobei das Alkali und das Wasserstoffperoxid getrennt mit dem Rejektfaserstoff während der Mahlung zugegeben werden.
  7. Verfahren nach einem der Ansprüche 1 bis 6, wobei die Puffersubstanz aus der Gruppe bestehend aus gefälltem Calciumcarbonat (PCC) oder gemahlenem Calciumcarbonat ausgewählt ist.
  8. Verfahren nach einem der Ansprüche 1 bis 7, wobei der Pufferungs-pH-Wert zwischen 9 und 10,5 liegt.
  9. Verfahren nach einem der Ansprüche 1 bis 8, wobei das Verhältnis von Alkali zu Wasserstoffperoxid 0,35:1,0 bis 0,75:1,0 beträgt.
  10. Verfahren nach einem der Ansprüche 1 bis 8, wobei das Verhältnis von Alkali zu Wasserstoffperoxid 1,25:1,0 bis 1,5:1,0 beträgt.
EP10789951.0A 2009-06-15 2010-06-09 Alkaliperoxidbehandlung von abfällen in einer integrierten neutralalkali-papierfabrik Active EP2443280B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US18707309P 2009-06-15 2009-06-15
PCT/US2010/037880 WO2010147812A1 (en) 2009-06-15 2010-06-09 Alkaline peroxide treatment of rejects in an integrated neutral-alkaline paper mill

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EP2443280A1 EP2443280A1 (de) 2012-04-25
EP2443280A4 EP2443280A4 (de) 2014-08-13
EP2443280B1 true EP2443280B1 (de) 2020-12-09

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US (1) US20120097350A1 (de)
EP (1) EP2443280B1 (de)
CN (1) CN102459753A (de)
RU (1) RU2495177C2 (de)
WO (1) WO2010147812A1 (de)

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CN102776795B (zh) * 2012-08-03 2014-06-04 常州市春江化学有限公司 有机膦羧酸在纸浆漂白工艺中的应用
CA2824076A1 (en) 2012-08-21 2014-02-21 University Of New Brunswick System and method for reclaiming rejects in sulfite pulping

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RU2011142599A (ru) 2013-04-27
EP2443280A4 (de) 2014-08-13
EP2443280A1 (de) 2012-04-25
WO2010147812A1 (en) 2010-12-23
RU2495177C2 (ru) 2013-10-10
US20120097350A1 (en) 2012-04-26
CN102459753A (zh) 2012-05-16

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