EP0120132A1 - Process for bleaching raw paper materials - Google Patents
Process for bleaching raw paper materials Download PDFInfo
- Publication number
- EP0120132A1 EP0120132A1 EP83112505A EP83112505A EP0120132A1 EP 0120132 A1 EP0120132 A1 EP 0120132A1 EP 83112505 A EP83112505 A EP 83112505A EP 83112505 A EP83112505 A EP 83112505A EP 0120132 A1 EP0120132 A1 EP 0120132A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bleaching
- sulfinic acid
- dithionite
- whiteness
- formamidine sulfinic
- 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.)
- Granted
Links
- 238000004061 bleaching Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- NYYSPVRERVXMLJ-UHFFFAOYSA-N 4,4-difluorocyclohexan-1-one Chemical compound FC1(F)CCC(=O)CC1 NYYSPVRERVXMLJ-UHFFFAOYSA-N 0.000 claims description 25
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 19
- 229920001131 Pulp (paper) Polymers 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 11
- 102100031260 Acyl-coenzyme A thioesterase THEM4 Human genes 0.000 claims description 9
- 101000638510 Homo sapiens Acyl-coenzyme A thioesterase THEM4 Proteins 0.000 claims description 9
- 150000002978 peroxides Chemical class 0.000 claims description 7
- 239000010893 paper waste Substances 0.000 claims description 6
- 238000005188 flotation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000010802 sludge Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- 239000002023 wood Substances 0.000 description 12
- 239000007844 bleaching agent Substances 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 241000218657 Picea Species 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 description 2
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 2
- 241000018646 Pinus brutia Species 0.000 description 2
- 235000011613 Pinus brutia Nutrition 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000294754 Macroptilium atropurpureum Species 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 239000013055 pulp slurry Substances 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000009895 reductive bleaching Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/1084—Bleaching ; Apparatus therefor with reducing compounds
Definitions
- the invention relates to a method for bleaching paper raw materials such as wood pulp, thermomechanical and chemothermomechanical wood pulp (generally referred to as TMP or CTMP) and waste paper.
- TMP thermomechanical and chemothermomechanical wood pulp
- a two-stage process makes economic sense for bleaching to very high whiteness levels.
- the state of the art here is bleaching with hydrogen peroxide and then dithionite treatment.
- a disadvantage of this process is the high capital requirement for the necessary installations, such as high thickeners, thick matter mixers and towers for peroxide bleaching and other units for dithionite bleaching.
- thermomechanical or chemothermomechanical wood pulp With thermomechanical or chemothermomechanical wood pulp, the effectiveness of the dithionite is significantly reduced. Obviously, the high temperature load in the refiner creates condensation products from the lignin of the wood, which cannot be reduced with discolouration using dithionite. In addition, there is a reduction in the basic white content.
- thiourea dioxide for bleaching wood pulps with a low cellulose content, preferably in combination with sodium bisulfite (Na2s20-5).
- the pH range from 5.5 - 8.0 is described as suitable.
- US Pat. No. 3,481,828 relates to improving the effectiveness of thiourea dioxide (formamidine sulfinic acid) in bleaching by adding zinc salts.
- the application relates to a process for reducing bleaching of paper raw materials such as wood pulp, TMP and CTMP and waste paper at a temperature of 50-130 ° C, preferably 70-100 ° C, a consistency of 2-20% by weight, preferably 3-6% by weight .%, a residence time of 1 - 120 min, preferably 2 - 60 min, in an alkaline, aqueous slurry with formamidine sulfinic acid, which is characterized in that the pH at the beginning of the bleaching reaction is between 9.7 and 12, preferably between 10 , 3 and 10.6, and after completion is between 7 and ⁇ 9, preferably between 7.1 and 8.5.
- the concentration of formamidine sulfinic acid amounts to 0.05-3% by weight, preferably 0.25-1.5% by weight, based on the substance (atro).
- thermomechanical TMP
- CTMP chemothermomechanical
- Wood pulp or pulp are preferred with 0.01 to 1.0% by weight of a complexing agent, e.g. DTPA (di-alkylene-triamine-penta-acetic acid) treated.
- DTPA di-alkylene-triamine-penta-acetic acid
- TMP and CTMP can be bleached with formamidine sulfinic acid during the passage through the refiner, even at the elevated temperatures prevailing, without additional equipment.
- the normal residence time in the refiner is generally sufficient for a good one Bleaching effect. If a two-stage refiner is used, it is advisable to bleach in the second stage. Of course, there is also the possibility to carry out the bleaching step in a conventional bleaching tower.
- Pretreatment of the wood chips with sodium sulfite and sodium hydroxide solution or sodium bisulfite when producing TMP or CTMP does not prevent bleaching with formamidine sulfinic acid.
- a special washing stage is not necessary here.
- Transferred to the production of wood pulp bleaching with formamidine sulfinic acid can be carried out in an alkaline medium in a grinder. If waste paper is used as a raw material, it is advisable to bleach during the flotation-de-inking process, which follows the rules of technology, before flotation. Compliance with the prescribed pH values is crucial for the successful implementation of the process. They are adjusted with NaOH. Although higher initial values are possible, they do not lead to an improvement in the white content.
- the process according to the invention can be carried out either alone or in combination with conventional bleaching processes. It is advantageous, for example, to post-treat wood bleached with dithionite or to sand wood with formamidine sulfinic acid. Losses do not occur because both are reducing agents.
- dithionite bleaching can be added to the process according to the invention or the process according to the invention can be repeated again to increase the white content.
- Example 1 TMP bleach with dithionite or formamidine sulfinic acid
- TMP from spruce wood chips with a basic whiteness of 53.0% remission and pretreated with 0.5% DTPA is treated with 1.2% Na 2 S 2 O 4 (all quantities on dry substance) at 5% consistency, p H 5 , 5 , 70 ° C, 1 hour residence time and bleached to a whiteness of 60.9% remission under an N 2 atmosphere.
- a whiteness of 61.5 is achieved with only 0.5% formamidine sulfinic acid and 0.4% NaOH, the initial pH being 10.5 and the final pH 7.8.
- With 1.2% formamidine sulfinic acid and 0.8% NaOH the white content of the TMP can even be increased to 65.9% remission.
- Spruce wood sanding with a basic whiteness of 62.8% remission is reduced to 71 by 1% Na 2 S 2 O 4 at pH 5.5, 70 ° C, 4.5% consistency and 1 hour , 8% remission brightened.
- 1% formamidine sulfinic acid and 0.6% NaOH With 1% formamidine sulfinic acid and 0.6% NaOH, a whiteness of 76.1 is accessible from an initial pH of 10.4. The final pH is 7.7.
- the formamidine sulfinic acid can advantageously be used to further increase the whiteness of a wood pulp pre-bleached with dithionite. It is a washing stage is not necessary.
- the bleaching sequence of dithionite-formamidine sulfinic acid thus offers a technically uncomplicated possibility of improving the whiteness level beyond the level accessible with dithionite. As with peroxide-dithionite bleaching, this does not have to involve a considerable amount of equipment.
- Spruce wood with a basic whiteness of 64.3% remission is pretreated in the grinding circuit with 0.3% DTPA and then at pH 5.5, 65 ° C, 4.5% consistency and 1 hour residence time with 1.3% Na 2 S 2 O 4 bleached. The result is a white content of 71.9% remission.
- the pH of the pulp slurry is raised to 10.6 with 0.5% NaOH and formamidine sulfinic acid (0.5%) is added at the same time. The consistency drops to 4.2%. After 90 minutes the pH of the stock suspension is 7.5 and the whiteness has risen to 75.3% remission.
- a mixture of 30% pine and 70% spruce wood chips is mixed with 1.5% sodium hydroxide and Impregnated with 2% sodium sulfite and ground in a two-stage refiner system.
- a CTMP with a white content of 57.6% remission is obtained. If you add 1% formamidine sulfinic acid to the stream from the second refiner stage, the final whiteness is 68.3% remission.
- the pH is 10.2 at the beginning and 8.5 at the end
- a mixture of 30% pine and spruce wood chips provides TMP with a whiteness of 54.8 without the use of additional chemicals. If, on the other hand, 0.8% sodium hydroxide solution and 1.2% formamidine sulfinic acid are mixed in before the second refiner stage (pH: 10.3), a whiteness of 66.5% remission is obtained at a final pH of 7.5. After thickening to 20% consistency, a final whiteness of 77.3% remission is achieved with 1.5% H 2 0 29 1.0% NaOH and 3.5% water glass at 60 ° C. after a residence time of 2 hours. The additional use of dithionite (0.75% Na 2 S 2 O 4 ) enables a further increase in whiteness to 80.1% remission.
- a second application of the method according to the invention with 0.5% formamidine sulfinic acid and 0.4% sodium hydroxide solution is also possible. This gives a final whiteness of 81.9% remission (initial pH value: 9.7; final pH value 7.7). Without the use of formamidine sulfinic acid in the refiner, peroxide bleaching only results in an increase in whiteness to 67.2% remission.
- a mixture of newspapers and magazines (1: 1) with a white content of 44% remission is mixed with 0.8% sodium hydroxide solution, 0.5% soap ( S erfax), 0.1% dispersant (lame ink) and 0.2 % DTPA and 0.5% formamidine sulfinic acid at 5% consistency and 60 ° C.
- the pH is 9.8. After an hour's stay, the pH drops to 7.7. It is diluted to 2% consistency, deflated and floated at 1% consistency. After thickening and acidification, the de-intact fabric reaches a white content of 62.5% remission.
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Die Erfindung betrifft ein Verfahren zum Bleichen von Papierrohstoffen wie Holzschliff, thermomechanischem und chemothermomechanischem Holzstoff (im allgemeinen als TMP bzw. CTMP bezeichnet) und Altpapier.The invention relates to a method for bleaching paper raw materials such as wood pulp, thermomechanical and chemothermomechanical wood pulp (generally referred to as TMP or CTMP) and waste paper.
Hohe Zellstoff- undHolzpreise verstärken die Tendenz zur Verwendung dieser Rohstoffe auch in bisher holzfrei produzierten Papierqualitäten, da bei ihrer Herstellung kaum Holz verloren geht, und auch die Verfahrenskosten gegenüber dem chemischen Aufschlußverfahren zur Gewinnung von zellulosereichen, holzfreien Papierrohstoffen deutlich niedriger liegen.High pulp and wood prices reinforce the tendency to use these raw materials in paper grades that have previously been produced wood-free, since hardly any wood is lost in their production, and the process costs compared to the chemical pulping process for the production of cellulose-rich, wood-free paper raw materials are significantly lower.
Eine der entscheidenden Voraussetzungen für die Verwendung von Holzschliff, TMP und CTMP auf diesem Gebiet stellt jedoch die Erzielung eines ausreichend hohen Weißgehaltes dar, der nur über Bleichverfahren zugänglich ist.However, one of the decisive requirements for the use of wood pulp, TMP and CTMP in this area is the achievement of a sufficiently high white content, which is only accessible via bleaching processes.
Für eine Vielzahl von Anwendungen ist ein geringfügiger Weißgehaltsanstieg ausreichend. Hier hat sich die technisch und chemisch sehr einfache Dithionitbleiche gut bewährt. Bei einem durchschnittlichen Grundweißgehalt des Holzschliffes von 60 bis 66 % Remission bei 457 nm (Elrepho) ist ein Anstieg auf 70 bis 74 % mit der Dithionitbleiche möglich. In den meisten Fällen ist eine Steigerung des Weißgehaltes um 8 bis 12 Punkte mit 1-1,5 % Na2S2 0 4 möglich. Höhere Einsatzmengen des Reduktionsmittels sind ohne Einfluß auf den Weißgehaltsgewinn, sie können im Gegenteil sogar wegen der Disproportionierung des Dithionits in Thiosulfat und Sulfit zu einem Verlust an Weiße führen. Generell ist der Weißgewinn in Punkten geringer, wenn die Grundweiße höher ist. Zur Bleiche auf sehr hohe Weißgehalte ist ein zweistufiges Verfahren wirtschaftlich sinnvoll. Stand der Technik ist hier zunächst die Bleiche mit Wasserstoffperoxid und daran anschließend eine Dithionitbehandlung. Damit kann sowohl Holzschliff als auch TMP oder CTMP auf Weißgehalte über 80 % Remission gebleicht werden, wobei die zweistufige Bleichvariante der einstufigen Peroxidbleiche wegen der erheblich geringeren Chemikalienkosten überlegen ist. Nachteilig für dieses Verfahren ist jedoch der hohe Kapitalbedarf für die notwendigen Installationen, wie z.B. Hocheindicker, Dickstoff-mischer und -turm für die Peroxidbleiche und weitere Aggregate für die Dithionitbleiche.A slight increase in white content is sufficient for a large number of applications. Here the technically and chemically very simple dithionite bleach has proven itself. With an average ground whiteness of the pulp of 60 to 66% remission at 457 nm (Elrepho), an increase to 70 to 74% is possible with the dithionite bleach. In most cases an increase of the W is eißgehaltes possible by 8 to 12 points with 1-1.5% Na 2 S 2 0. 4 Higher amounts of the reducing agent have no effect on the whiteness gain; on the contrary, they can even lead to a loss of whiteness due to the disproportionation of the dithionite in thiosulfate and sulfite. In general, the white gain is lower in points if the basic white is higher. A two-stage process makes economic sense for bleaching to very high whiteness levels. The state of the art here is bleaching with hydrogen peroxide and then dithionite treatment. This means that both wood pulp as well as TMP or CTMP can be bleached for whiteness levels above 80% remission, whereby the two-stage bleaching variant is superior to the one-stage peroxide bleaching because of the considerably lower chemical costs. A disadvantage of this process, however, is the high capital requirement for the necessary installations, such as high thickeners, thick matter mixers and towers for peroxide bleaching and other units for dithionite bleaching.
Oft entsteht der Wunsch nach einer höheren Weiße des erzeugten Faserstoffes, wenn bereits eine Anlage zur Bleiche mit Dithionit installiert ist. Für den erwünschten 4 bis 5 Punkte höheren Weißgehalt (z.B. 78 % Remission), muß dann die aufwendige Peroxidbleiche installiert werden, für die man zusätzlich z.B. Hocheindicker, Dickstoffmischer und -turm benötigt.Often there is a desire for a higher whiteness of the fiber material produced if a bleaching plant with dithionite is already installed. For him If you wanted 4 to 5 points higher whiteness (eg 78% remission), then the complex peroxide bleaching must be installed, for which you also need, for example, high thickener, thick matter mixer and tower.
Bei thermomechanischem oder chemothermomechanischem Holzstoff ist die Wirksamkeit des Dithionits deutlich herabgesetzt. Offensichtlich entstehen durch die hohe Temperaturbelastung im Refiner Kondensationsprodukte aus dem Lignin des Holzes, die mit Dithionit nicht unter Entfärbung reduziert werden können. Zusätzlich erfolgt eine Verringerung des Grundweißgehaltes.With thermomechanical or chemothermomechanical wood pulp, the effectiveness of the dithionite is significantly reduced. Obviously, the high temperature load in the refiner creates condensation products from the lignin of the wood, which cannot be reduced with discolouration using dithionite. In addition, there is a reduction in the basic white content.
Bei mäßiger Hackschnitzelqualität und erhöhtem Rindengehalt erhält man mit einer Dithionitbleiche dann nicht einmal die für Zeitungsdruckpapier notwendige Weiße von 60 % Remission.With moderate wood chip quality and increased bark content, dithionite bleaching does not even give the whiteness of 60% remission required for newsprint.
Aus der DE-OS 1 546 252 ist bekannt, zum Bleichen von Holzpulpen mit niedrigem Zellulosegehalt Thioharnstoffdioxid einzusetzen, vorzugsweise in Kombination mit Natriumbisulfit (Na2s20-5). Der pH-Bereich von 5,5 - 8,0 wird als geeignet beschrieben. Die US-PS 3 481 828 betrifft die Verbesserung der Wirksamkeit von Thioharnstoffdioxid (Formamidinsulfinsäure) bei der Bleiche durch Zusatz von Zinksalzen.From DE-OS 1 546 252 it is known to use thiourea dioxide for bleaching wood pulps with a low cellulose content, preferably in combination with sodium bisulfite (Na2s20-5). The pH range from 5.5 - 8.0 is described as suitable. US Pat. No. 3,481,828 relates to improving the effectiveness of thiourea dioxide (formamidine sulfinic acid) in bleaching by adding zinc salts.
Dieses Verfahren ist aber wegen der damit verursachten Belastung des Abwassers mit Zinkionen nicht mehr tragbar.However, this process is no longer viable because of the pollution of the wastewater with zinc ions.
Wie aus den vorangegangenen Ausführungen verständlich wird, besteht ein Bedarf für ein relativ einfaches Bleichverfahren, das sowohl als Ergänzung zu den bekannten Verfahren. als auch in besonderen Fällen ausschließlich mit gutem Erfolg angewandt werden kann.As can be understood from the foregoing, there is a need for a relatively simple bleaching process that complements both known methods. as well as in special cases can only be used with good success.
Gegenstand der Anmeldung ist ein Verfahren zum reduzierenden Bleichen von Papierrohstoffen wie Holzschliff, TMP und CTMP und Altpapier bei einer Temperatur von 50 - 130°C, vorzugsweise 70 - 100°C einer Stoffdichte von 2 - 20 Gew.%, vorzugsweise 3 - 6 Gew.%, einer Verweilzeit von 1 - 120 min, vorzugsweise 2 - 60 min, in einer alkalischen, wässrigen Aufschlämmung mit Formamidinsulfinsäure, das dadurch gekennzeichnet ist, daß der pH-Wert zu Beginn der Bleichreaktion zwischen 9,7 und 12, vorzugsweise zwischen 10,3 und 10,6, und nach der Beendigung zwischen 7 und <9, vorzugsweise zwischen 7,1 und 8,5 liegt.The application relates to a process for reducing bleaching of paper raw materials such as wood pulp, TMP and CTMP and waste paper at a temperature of 50-130 ° C, preferably 70-100 ° C, a consistency of 2-20% by weight, preferably 3-6% by weight .%, a residence time of 1 - 120 min, preferably 2 - 60 min, in an alkaline, aqueous slurry with formamidine sulfinic acid, which is characterized in that the pH at the beginning of the bleaching reaction is between 9.7 and 12, preferably between 10 , 3 and 10.6, and after completion is between 7 and <9, preferably between 7.1 and 8.5.
Die Konzentration der Formamidinsulfinsäure beläuft sich auf 0,05 - 3 Gew.%, vorzugsweise 0,25 - 1,5 Gew.%, bezogen auf Stoff(atro).The concentration of formamidine sulfinic acid amounts to 0.05-3% by weight, preferably 0.25-1.5% by weight, based on the substance (atro).
Bei den gemäß Erfindung bleichbaren Papierrohstoffen handelt es sich vor allem um thermomechanischen-(TMP), chemothermomechanischen (CTMP) Holzstoff und Holzschliff, aber auch um Altpapier.The paper raw materials which can be bleached according to the invention are primarily thermomechanical (TMP), chemothermomechanical (CTMP) wood pulp and wood pulp, but also waste paper.
Holzstoff bzw. Holzschliff werden vor dem Bleichen bevorzugt mit 0,01 bis 1,0 Gew.% eines Komplexbildners z.B. DTPA (Di-alkylen-triamin-penta-essigsäure) behandelt.Wood pulp or pulp are preferred with 0.01 to 1.0% by weight of a complexing agent, e.g. DTPA (di-alkylene-triamine-penta-acetic acid) treated.
Ohne zusätzlichen apparativen Aufwand kann man TMP und CTMP während des Durchgangs durch den Refiner mit Formamidinsulfinsäure auch bei den dort herrschenden erhöhten Temperaturen bleichen. Die normale Verweilzeit im Refiner reicht im allgemeinen für einen guten Bleicheffekt aus. Wird ein zweistufiger Refiner verwendet, ist es zweckmäßig, in der zweiten Stufe zu bleichen. Die Möglichkeit, den Bleichschritt in einem konventionellen Bleichturm vorzunehmen, besteht natürlich auch.TMP and CTMP can be bleached with formamidine sulfinic acid during the passage through the refiner, even at the elevated temperatures prevailing, without additional equipment. The normal residence time in the refiner is generally sufficient for a good one Bleaching effect. If a two-stage refiner is used, it is advisable to bleach in the second stage. Of course, there is also the possibility to carry out the bleaching step in a conventional bleaching tower.
Eine Vorbehandlung der Hackschnitzel mit Natriumsulfit und Natronlauge oder Natriumbisulfit bei der Erzeugung von TMP bzw. CTMP steht einer Bleichbehandlung mit Formamidinsulfinsäure nicht im Wege. Eine besondere Waschstufe ist hier im Gegensatz zu Verfahren, die eine Nachbehandlung mit H202 vorschreiben, nicht notwendig. Auf die Herstellung von Holzschliff übertragen, kann man die Bleiche mit Formamidinsulfinsäure in alkalischem Medium im Schleifer durchführen. Setzt man Altpapier als Rohstoff ein, bleicht man zweckmäßigerweise während des Flotations-de-inking-Prozesses, der nach den Regeln der Technik abläuft, vor dem Flotieren. Die Einhaltung der vorgeschriebenen pH-Werte ist ausschlaggebend für eine erfolgreiche Durchführung des Verfahrens. Sie werden mit NaOH eingestellt. Es sind zwar auch höhere Anfangswerte möglich, sie führen jedoch nicht zu einer Verbesserung der Weißgehalte.Pretreatment of the wood chips with sodium sulfite and sodium hydroxide solution or sodium bisulfite when producing TMP or CTMP does not prevent bleaching with formamidine sulfinic acid. In contrast to processes which prescribe post-treatment with H 2 0 2 , a special washing stage is not necessary here. Transferred to the production of wood pulp, bleaching with formamidine sulfinic acid can be carried out in an alkaline medium in a grinder. If waste paper is used as a raw material, it is advisable to bleach during the flotation-de-inking process, which follows the rules of technology, before flotation. Compliance with the prescribed pH values is crucial for the successful implementation of the process. They are adjusted with NaOH. Although higher initial values are possible, they do not lead to an improvement in the white content.
Das erfindungsgemäße Verfahren kann sowohl allein als auch in Kombination mit herkömmlichen Bleichverfahren durchgeführt werden. Es ist beispielsweise von Vorteil, mit Dithionit vorgebleichten Holzstoff oder Holzschliff mit Formamidinsulfinsäure nachzubehandeln. Verluste treten nicht auf, da es sich in beiden Fällen um Reduktionsmittel handelt.The process according to the invention can be carried out either alone or in combination with conventional bleaching processes. It is advantageous, for example, to post-treat wood bleached with dithionite or to sand wood with formamidine sulfinic acid. Losses do not occur because both are reducing agents.
Ebenso kann man zur Erhöhung des Weißgehaltes an das erfindungsgemäße Verfahren eine Dithionitbleiche anschließen oder aber auch das erfindungsgemäße Verfahren noch einmal wiederholen.Likewise, dithionite bleaching can be added to the process according to the invention or the process according to the invention can be repeated again to increase the white content.
Bei ausreichender Eindickung des erfindungsgemäß gebleichten Papierrohstoffs ist es möglich, eine Peroxidbleiche gemäß den Regeln der Technik anzuschließen.With sufficient thickening of the paper raw material bleached according to the invention, it is possible to connect peroxide bleaching in accordance with the rules of the art.
Die anschließenden Beispiele dienen der Erläuterung der Erfindung.The following examples serve to illustrate the invention.
Alle Weißgehalte wurden mit einem Zeiss Elrepho bei 457 nm bestimmt.All white levels were determined using a Zeiss Elrepho at 457 nm.
TMP aus Fichtenholzhackschnitzeln mit einer Grundweiße von 53,0 % Remission und mit 0,5 % DTPA vorbehandelt, wird mit 1,2 % Na2S2O4 (alle Mengenangaben auf atro Stoff) bei 5 % Stoffdichte, pH 5,5, 70°C, 1 Stunde Verweilzeit und unter N2-Atmosphäre auf eine Weiße von 60,9 % Remission gebleicht. Unter gleichen Rahmenbedingungen wird mit nur 0,5 % Formamidinsulfinsäure und 0,4 % NaOH eine Weiße von 61,5 erreicht, wobei der Anfangs-pH 10,5, der End-pH 7,8 betrug. Mit 1,2 % Formamidinsulfinsäure und 0,8% NaOH läßt sich der Weißgehalt des TMP sogar auf 65,9 % Remission steigern.TMP from spruce wood chips with a basic whiteness of 53.0% remission and pretreated with 0.5% DTPA is treated with 1.2% Na 2 S 2 O 4 (all quantities on dry substance) at 5% consistency, p H 5 , 5 , 70 ° C, 1 hour residence time and bleached to a whiteness of 60.9% remission under an N 2 atmosphere. Under the same general conditions, a whiteness of 61.5 is achieved with only 0.5% formamidine sulfinic acid and 0.4% NaOH, the initial pH being 10.5 and the final pH 7.8. With 1.2% formamidine sulfinic acid and 0.8% NaOH, the white content of the TMP can even be increased to 65.9% remission.
Fichtenholzschliff mit einer Grundweiße von 62,8 % Remission (vorbehandelt mit 0,3 % DTPA) wird durch 1 % Na2S2O4 bei pH 5,5, 70°C, 4,5 % Stoffdichte und 1 Stunde Verweilzeit auf 71,8% Remission aufgehellt. Mit 1 % Formamidinsulfinsäure und 0,6 % NaOH wird von einem Anfangs-pH von 10,4 ausgehend eine Weiße von 76,1 zugänglich. Der End-pH beträgt 7,7.Spruce wood sanding with a basic whiteness of 62.8% remission (pretreated with 0.3% DTPA) is reduced to 71 by 1% Na 2 S 2 O 4 at pH 5.5, 70 ° C, 4.5% consistency and 1 hour , 8% remission brightened. With 1% formamidine sulfinic acid and 0.6% NaOH, a whiteness of 76.1 is accessible from an initial pH of 10.4. The final pH is 7.7.
Die Formamidinsulfinsäure kann vorteilhaft zur weiteren Steigerung des Weißgehaltes eines mit Dithionit vorgebleichten Holzstoffes verwandt werden. Dabei ist eine Waschstufe nicht erforderlich. Die Bleichfolge Dithionit-Formamidinsulfinsäure bietet somit eine technisch unkomplizierte Möglichkeit zur Verbesserung des Weißeniveaus über das mit Dithionit zugängliche Niveau hinaus. Dabei muß nicht wie bei der Peroxid-Dithionitbleiche ein erheblicher apparativer Aufwand getrieben werden.The formamidine sulfinic acid can advantageously be used to further increase the whiteness of a wood pulp pre-bleached with dithionite. It is a washing stage is not necessary. The bleaching sequence of dithionite-formamidine sulfinic acid thus offers a technically uncomplicated possibility of improving the whiteness level beyond the level accessible with dithionite. As with peroxide-dithionite bleaching, this does not have to involve a considerable amount of equipment.
Nachbleiche eines mit Dithionit vorgebleichten HolzschliffsAfter bleaching of a wood pulp pre-bleached with dithionite
Fichtenholzschliff mit einer Grundweiße von 64,3 % Remission wird im Schleifereikreislauf mit 0,3 % DTPA vorbehandelt und danach bei pH 5,5, 65°C, 4,5 % Stoffdichte und 1 Stunde Verweilzeit mit 1,3 % Na2S2O4 gebleicht. Es resultiert ein Weißgehalt von 71,9 % Remission. Der pH-Wert der Holzschliffaufschlämmung wird mit 0,5 % NaOH auf 10,6 angehoben und gleichzeitig Formamidinsulfinsäure (0,5 %) zugesetzt. Dabei sinkt die Stoffdichte auf 4,2 %. Nach 90 Minuten beträgt der pH-Wert der Stoffsuspension 7,5 und der Weißgehalt ist auf 75,3 % Remission gestiegen.Spruce wood with a basic whiteness of 64.3% remission is pretreated in the grinding circuit with 0.3% DTPA and then at pH 5.5, 65 ° C, 4.5% consistency and 1 hour residence time with 1.3% Na 2 S 2 O 4 bleached. The result is a white content of 71.9% remission. The pH of the pulp slurry is raised to 10.6 with 0.5% NaOH and formamidine sulfinic acid (0.5%) is added at the same time. The consistency drops to 4.2%. After 90 minutes the pH of the stock suspension is 7.5 and the whiteness has risen to 75.3% remission.
Weiterhin kann mit Formamidinsulfinsäure im Refiner gebleicht werden. Die Gegenwart von Natriumsulfit neben Natronlauge beeinträchtigt den Bleicheffekt der Formamidinsulfinsäure nicht. Sinnvoll ist die Anwendung in der zweiten Refinerstufe.It can also be bleached with formamidine sulfinic acid in the refiner. The presence of sodium sulfite in addition to sodium hydroxide solution does not impair the bleaching effect of formamidine sulfinic acid. It makes sense to use it in the second refiner stage.
Bleiche mit Formamidinsulfinsäure im RefinerBleach with formamidine sulfinic acid in the refiner
Eine Mischung aus 30 % Kiefern und 70 % Fichtenholzhackschnitzeln wird mit 1,5 % Natronlauge und 2 % Natriumsulfit imprägniert und in einer zweistufigen Refineranlage aufgemahlen. Man erhält einen CTMP mit einem Weißgehalt von 57,6 % Remission. Setzt man dem Stoffstrom von der zweiten Refinerstufe 1 % Formamidinsulfinsäure zu resultiert eine Endweiße von 68,3 % Remission. Dabei liegt der pH-Wert zu Anfang bei 10,2 und am Ende bei 8,5A mixture of 30% pine and 70% spruce wood chips is mixed with 1.5% sodium hydroxide and Impregnated with 2% sodium sulfite and ground in a two-stage refiner system. A CTMP with a white content of 57.6% remission is obtained. If you add 1% formamidine sulfinic acid to the stream from the second refiner stage, the final whiteness is 68.3% remission. The pH is 10.2 at the beginning and 8.5 at the end
Eine Mischung aus 30 % Kiefern- und Fichtenholzhackschnitzeln liefern ohne den Einsatz zusätzlicher Chemikalien TMP mit einer Weiße von 54,8. Mischt man dagegen 0,8 % Natronlauge und 1,2 % Formamidinsulfinsäure vor der zweiten Refinerstufe ein (pH:10,3),so erhält man bei einem End-pH-Wert von 7,5 einen Weißgehalt von 66,5 % Remission. Nach einer Eindickung auf 20 % Stoffdichte wird mit 1,5 % H2029 1,0 % NaOH und 3,5 % Wasserglas bei 60°C nach einer Verweilzeit von 2 Stunden eine Endweiße von 77,3 % Remission erreicht. Durch die zusätzliche Anwendung von Dithionit (0,75 % Na2S2O4) ist eine weitere Weißesteigerung auf 80,1 % Remission möglich. Ebenfalls möglich ist eine zweite Anwendung des erfindungsgemäßen Verfahrens mit 0,5 % Formamidinsulfinsäure und 0,4 % Natronlauge. Dabei erhält man eine Endweiße von 81,9 % Remission (Anfangs-pH-Wert: 9,7; End-pH-Wert 7,7). Ohne die Anwendung von Formamidinsulfinsäure im Refiner ergibt die Peroxidbleiche lediglich einen Weißeanstieg auf 67,2 % Remission.A mixture of 30% pine and spruce wood chips provides TMP with a whiteness of 54.8 without the use of additional chemicals. If, on the other hand, 0.8% sodium hydroxide solution and 1.2% formamidine sulfinic acid are mixed in before the second refiner stage (pH: 10.3), a whiteness of 66.5% remission is obtained at a final pH of 7.5. After thickening to 20% consistency, a final whiteness of 77.3% remission is achieved with 1.5% H 2 0 29 1.0% NaOH and 3.5% water glass at 60 ° C. after a residence time of 2 hours. The additional use of dithionite (0.75% Na 2 S 2 O 4 ) enables a further increase in whiteness to 80.1% remission. A second application of the method according to the invention with 0.5% formamidine sulfinic acid and 0.4% sodium hydroxide solution is also possible. This gives a final whiteness of 81.9% remission (initial pH value: 9.7; final pH value 7.7). Without the use of formamidine sulfinic acid in the refiner, peroxide bleaching only results in an increase in whiteness to 67.2% remission.
Eine Mischung von Zeitungen und Illustrierten (1:1) mit einem Weißgehalt von 44 % Remission wird mit 0,8 % Natronlauge, 0,5 % Seife (Serfax), 0,1 % Dispergiermittel (Lame-ink) und 0,2 % DTPA sowie 0,5 % Formamidinsulfinsäure bei 5 % Stoffdichte und 60°C aufgeschlagen. Der pH-Wert liegt bei 9,8. Nach einer Stunde Verweilzeit sinkt der pH-Wert auf 7,7. Es wird auf 2 % Stoffdichte verdünnt, entstippt und bei 1 % Stoffdichte flotiert. Der de-inkte Stoff erreicht nach Eindicken und Ansäuern einen Weißgehalt von 62,5 % Remission. Führt man das Verfahren mit Wasserstoffperoxid als Bleichchemikalie durch, so wird mit 0,5 % H2O2, 1 % NaOH, 2 % Wasserglas und 0,5 % Seife, 0,1 % Dispergiermittel sowie 0,2 % DTPA bei 5 % Stoffdichte und 40°C analog zur obigen Verfahrensweise nach der Flotation eine Endweiße von 61,8 % Remission erhalten.A mixture of newspapers and magazines (1: 1) with a white content of 44% remission is mixed with 0.8% sodium hydroxide solution, 0.5% soap ( S erfax), 0.1% dispersant (lame ink) and 0.2 % DTPA and 0.5% formamidine sulfinic acid at 5% consistency and 60 ° C. The pH is 9.8. After an hour's stay, the pH drops to 7.7. It is diluted to 2% consistency, deflated and floated at 1% consistency. After thickening and acidification, the de-intact fabric reaches a white content of 62.5% remission. If the process is carried out using hydrogen peroxide as a bleaching chemical, 0.5% H 2 O 2 , 1% NaOH, 2% water glass and 0.5% soap, 0.1% dispersant and 0.2% DTPA at 5% Fabric density and 40 ° C analogous to the above procedure after flotation to obtain a final whiteness of 61.8% remission.
Claims (9)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT83112505T ATE23376T1 (en) | 1983-03-19 | 1983-12-13 | PROCESS FOR BLEACHING PAPER RAW MATERIALS. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3309956A DE3309956C1 (en) | 1983-03-19 | 1983-03-19 | Process for bleaching paper raw materials |
| DE3309956 | 1983-03-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0120132A1 true EP0120132A1 (en) | 1984-10-03 |
| EP0120132B1 EP0120132B1 (en) | 1986-11-05 |
Family
ID=6194000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP83112505A Expired EP0120132B1 (en) | 1983-03-19 | 1983-12-13 | Process for bleaching raw paper materials |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0120132B1 (en) |
| AT (1) | ATE23376T1 (en) |
| DE (2) | DE3309956C1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0360993A2 (en) * | 1988-09-17 | 1990-04-04 | Sulzer-Escher Wyss Gmbh | Process for increasing the brightness of waste paper by recirculating neutral water |
| EP0379858A2 (en) * | 1989-01-27 | 1990-08-01 | Degussa Aktiengesellschaft | Process for bleaching fibre stock for making paper |
| US10974348B2 (en) | 2016-06-02 | 2021-04-13 | Priefert Mfg. Co, Inc. | Method for forming a brazed joint |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3616816A1 (en) * | 1986-05-17 | 1987-11-19 | Degussa | METHOD FOR REMOVING BULK COLORED PAPER AND SELF-COPYING PAPER |
| GB9214041D0 (en) * | 1992-07-02 | 1992-08-12 | Morton Int Inc | Process for de-inking recycled paper pulp |
| AT407762B (en) * | 1994-03-22 | 2001-06-25 | Brueggemann L Kg | Bleaching agent for bleaching secondary fibrous materials for papermaking |
| DE19920338A1 (en) * | 1999-05-03 | 2000-11-16 | Voith Sulzer Papiertech Patent | Bleaching control of a paper fiber pulp suspension uses measurements before and after bleaching with intermediate measurements to control the bleaching stage for optimum whiteness and max use of the bleaching chemicals |
| DE102007007654A1 (en) * | 2007-02-13 | 2008-08-14 | Voith Patent Gmbh | FAS bleach |
| DE102020111675A1 (en) * | 2020-04-29 | 2021-11-04 | Kübler & Niethammer Papierfabrik Kriebstein AG | Process for producing a label paper from detached wet labels |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1546252A1 (en) * | 1964-12-16 | 1970-04-30 | Fmc Corp | Process for bleaching wood pulps with a low cellulose content |
| GB1404315A (en) * | 1971-09-15 | 1975-08-28 | Albright & Wilson | Production of bleached high yield pulp |
| DE3118192A1 (en) * | 1981-05-08 | 1982-11-25 | Basf Ag, 6700 Ludwigshafen | Process for de-inking waste paper |
-
1983
- 1983-03-19 DE DE3309956A patent/DE3309956C1/en not_active Expired
- 1983-12-13 EP EP83112505A patent/EP0120132B1/en not_active Expired
- 1983-12-13 AT AT83112505T patent/ATE23376T1/en active
- 1983-12-13 DE DE8383112505T patent/DE3367421D1/en not_active Expired
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1546252A1 (en) * | 1964-12-16 | 1970-04-30 | Fmc Corp | Process for bleaching wood pulps with a low cellulose content |
| GB1404315A (en) * | 1971-09-15 | 1975-08-28 | Albright & Wilson | Production of bleached high yield pulp |
| DE3118192A1 (en) * | 1981-05-08 | 1982-11-25 | Basf Ag, 6700 Ludwigshafen | Process for de-inking waste paper |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0360993A2 (en) * | 1988-09-17 | 1990-04-04 | Sulzer-Escher Wyss Gmbh | Process for increasing the brightness of waste paper by recirculating neutral water |
| EP0360993A3 (en) * | 1988-09-17 | 1991-11-06 | Sulzer-Escher Wyss Gmbh | Process for increasing the brightness of waste paper by recirculating neutral water |
| EP0379858A2 (en) * | 1989-01-27 | 1990-08-01 | Degussa Aktiengesellschaft | Process for bleaching fibre stock for making paper |
| EP0379858A3 (en) * | 1989-01-27 | 1991-01-16 | Degussa Aktiengesellschaft | Process for bleaching fibre stock for making paper |
| US10974348B2 (en) | 2016-06-02 | 2021-04-13 | Priefert Mfg. Co, Inc. | Method for forming a brazed joint |
| US12017305B2 (en) | 2016-06-02 | 2024-06-25 | Priefert Mfg. Co., Inc. | System of elongated tubes and a joint |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3367421D1 (en) | 1986-12-11 |
| DE3309956C1 (en) | 1984-07-12 |
| ATE23376T1 (en) | 1986-11-15 |
| EP0120132B1 (en) | 1986-11-05 |
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