EP0141355B1 - Process for bleaching ground wood pulp - Google Patents
Process for bleaching ground wood pulp Download PDFInfo
- Publication number
- EP0141355B1 EP0141355B1 EP84112648A EP84112648A EP0141355B1 EP 0141355 B1 EP0141355 B1 EP 0141355B1 EP 84112648 A EP84112648 A EP 84112648A EP 84112648 A EP84112648 A EP 84112648A EP 0141355 B1 EP0141355 B1 EP 0141355B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- acid
- salts
- bleaching
- phosphonic
- aminoethane
- 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.)
- Expired
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- 238000004061 bleaching Methods 0.000 title claims abstract description 29
- 229920001131 Pulp (paper) Polymers 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 150000002978 peroxides Chemical class 0.000 claims abstract description 11
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims abstract description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims abstract description 6
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000003009 phosphonic acids Chemical class 0.000 claims abstract description 6
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000174 gluconic acid Substances 0.000 claims abstract description 5
- 235000012208 gluconic acid Nutrition 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 150000004760 silicates Chemical class 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 9
- 235000011007 phosphoric acid Nutrition 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 6
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 5
- QXVJRDMNUOAUNI-UHFFFAOYSA-N [1-[bis(hydroxymethyl)amino]-1-phosphonoethyl]phosphonic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)N(CO)CO QXVJRDMNUOAUNI-UHFFFAOYSA-N 0.000 claims description 5
- 229940090960 diethylenetriamine pentamethylene phosphonic acid Drugs 0.000 claims description 5
- DUYCTCQXNHFCSJ-UHFFFAOYSA-N dtpmp Chemical compound OP(=O)(O)CN(CP(O)(O)=O)CCN(CP(O)(=O)O)CCN(CP(O)(O)=O)CP(O)(O)=O DUYCTCQXNHFCSJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 5
- KONBRAAEGUYPQV-UHFFFAOYSA-N 2-phosphonobutane-1,1,2-tricarboxylic acid Chemical compound CCC(P(O)(O)=O)(C(O)=O)C(C(O)=O)C(O)=O KONBRAAEGUYPQV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- PJXKZTFOBRSZOY-UHFFFAOYSA-N 2-[carboxymethyl(1,1-diphosphonoethyl)amino]acetic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)N(CC(O)=O)CC(O)=O PJXKZTFOBRSZOY-UHFFFAOYSA-N 0.000 claims description 3
- -1 alkaline earth metal salts Chemical class 0.000 claims description 3
- 229960004585 etidronic acid Drugs 0.000 claims 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 3
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 229940116254 phosphonic acid Drugs 0.000 claims 3
- 229910052783 alkali metal Inorganic materials 0.000 claims 2
- 150000001340 alkali metals Chemical class 0.000 claims 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 8
- 235000019353 potassium silicate Nutrition 0.000 description 7
- 239000000126 substance Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 239000004471 Glycine Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000007844 bleaching agent Substances 0.000 description 2
- 230000000368 destabilizing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 2
- 238000004076 pulp bleaching Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- VPTUPAVOBUEXMZ-UHFFFAOYSA-N (1-hydroxy-2-phosphonoethyl)phosphonic acid Chemical compound OP(=O)(O)C(O)CP(O)(O)=O VPTUPAVOBUEXMZ-UHFFFAOYSA-N 0.000 description 1
- VPRHJIQBWBXGNE-UHFFFAOYSA-N 3-(1,1-diphosphonoethylamino)propanoic acid Chemical compound OP(=O)(O)C(P(O)(O)=O)(C)NCCC(O)=O VPRHJIQBWBXGNE-UHFFFAOYSA-N 0.000 description 1
- UVKTVGIDMKVNQD-UHFFFAOYSA-N CCO.OP(O)=O.OP(O)=O Chemical compound CCO.OP(O)=O.OP(O)=O UVKTVGIDMKVNQD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000029142 excretion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- TVZISJTYELEYPI-UHFFFAOYSA-N hypodiphosphoric acid Chemical compound OP(O)(=O)P(O)(O)=O TVZISJTYELEYPI-UHFFFAOYSA-N 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 125000002081 peroxide group Chemical group 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- D21C9/1026—Other features in bleaching processes
- D21C9/1042—Use of chelating agents
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
Definitions
- the present invention relates to auxiliaries for stabilizing peroxide-containing bleaching solutions used for wood pulp bleaching.
- the bleaching of the wood pulp necessary for use as a raw material in paper production is generally carried out with the aid of hydrogen peroxide and / or dithionite or hydrosulfite.
- the bleaching can be carried out in one or two stages.
- the bleaching result is influenced by the type of wood and wood pretreatment, the amount of bleach, the water quality, the dosage and the type of additives.
- the average increase in whiteness for a one-step bleaching is 8-10 points, for a two-step bleaching 16-19 points.
- DE-A 22 26 784 discloses bleach stabilizers for textile materials in which an alkaline, aqueous peroxide solution stabilized with sodium silicate additionally with a combination of nitrilotriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and a water-soluble magnesium or calcium salt , among others Magnesium hypophosphate is added to prevent decomposition of the peroxide on the one hand and the failure of silicates on the other (p. 4, paragraph 3).
- DE-A 22 09 358 also includes cold bleaching liquors, i.e. Textile bleaches described in which perborate solutions, u. a. Contain sodium and magnesium silicate as stabilizers, may additionally contain polyaminocarboxylic acids, phosphonic acids and sodium triphosphate.
- perborate solutions u. a. Contain sodium and magnesium silicate as stabilizers
- polyaminocarboxylic acids phosphonic acids
- sodium triphosphate sodium triphosphate.
- glycolurils in particular tetraacetylglycoluril, appears to be essential. These products cannot be used as wood bleaches because of their surfactant content.
- Gluconic acid citric acid, N, N-dihydroxyethylene glycine, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid or the corresponding salts of these acids are used as the second component.
- Orthophosphoric acid or polyphosphoric acid or the corresponding alkali and alkaline earth metal salts can be used as the phosphoric acid component.
- a bleaching formulation can have the following composition:
- test sheets produced on a sheet formation system and the degree of whiteness measured according to TAPPI.
- the bleaching solution consisted of 1.9% H 2 0 2 , 1.7% NaOH and the respective stabilizer.
- the pH of the bleaching solution was 11.0.
- the stability of the bleaching solution was checked using permanganate titration.
- the fabric density was 20%
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Paper (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Gegenstand der vorliegenden Erfindung sind Hilfsmittel zur Stabilisierung von zur Holzschliffbleiche eingesetzten peroxidhaltigen Bleichlösungen.The present invention relates to auxiliaries for stabilizing peroxide-containing bleaching solutions used for wood pulp bleaching.
Das für den Einsatz als Rohstoff bei der Papierherstellung notwendige Bleichen des Holzschliffes erfolgt im allgemeinen mit Hilfe von Wasserstoffperoxid und/oder Dithionit bzw. Hydrosulfit. Die Bleiche kann hierbei sowohl ein- als auch zweistufig durchgeführt werden.The bleaching of the wood pulp necessary for use as a raw material in paper production is generally carried out with the aid of hydrogen peroxide and / or dithionite or hydrosulfite. The bleaching can be carried out in one or two stages.
Das Bleichergebnis wird beeinflusst von Holzart und Holzvorbehandlung, der Bleichmittelmenge, der Wasserqualität, der Dosierweise und der Art der Zusatzmittel. Die durchschnittliche Weissesteigerung bei einer Einstufenbleiche beträgt 8-10 Punkte, bei einer Zweistufenbleiche 16-19 Punkte.The bleaching result is influenced by the type of wood and wood pretreatment, the amount of bleach, the water quality, the dosage and the type of additives. The average increase in whiteness for a one-step bleaching is 8-10 points, for a two-step bleaching 16-19 points.
Stand der Technik ist, dass die zur Erzielung der gewünschten Weissesteigerung notwendige Stabilisierung der Bleichlösung im Falle von Wasserstoffperoxid mit Hilfe von Wasserglas vorgenommen wird. Der Einsatz von Wasserglas führt jedoch zu verfahrenstechnischen Problemen, da hierdurch Ablagerungen in den Maschinenteilen und Schwierigkeiten bei der Abwasserklärung hervorgerufen werden. Diese Probleme erfordern zu ihrer Minderung einen erhöhten Einsatz an chemischen Hilfsmitteln, was durch die ebenfalls dem Stand der Technik entsprechende Kreislaufschliessung wieder zu neuen Problemen führt. Weiterhin ist die Dosierung von Wasserglas problematisch, was wiederum teilweise seine Ursache in der Qualität des verwendeten Wassers hat.State of the art is that the stabilization of the bleaching solution necessary to achieve the desired increase in whiteness in the case of hydrogen peroxide is carried out with the aid of water glass. However, the use of water glass leads to procedural problems, since this causes deposits in the machine parts and difficulties in the waste water treatment. These problems require an increased use of chemical auxiliaries to reduce them, which leads to new problems due to the state-of-the-art circuit closure. The metering of water glass is also problematic, which in turn is partly due to the quality of the water used.
Aus der DE-A 25 00 209 ist es bekannt, zur Verhütung der Harzausscheidung bei der Herstellung von Papier, dem zu verarbeitenden harzhaltigen Zellstoff oder Holzschliff eine Kombination von Phosphonsäuren, Aminopolycarbonsäuren oder Hydroxysäuren und Ortho- oder Polyphosphorsäure zuzusetzen. Ein Einfluss dieser Stoffe auf die Bleichlösung ist nicht beschrieben.From DE-A 25 00 209 it is known to add a combination of phosphonic acids, aminopolycarboxylic acids or hydroxy acids and ortho- or polyphosphoric acid to prevent resin excretion in the manufacture of paper, the resin-containing pulp to be processed or wood pulp. An influence of these substances on the bleaching solution is not described.
Aus der DE-A 22 26 784 sind Bleichstabilisierungsmittel für Textilmaterialien bekannt, bei denen eine mit Natriumsilikat stabilisierte, alkalische, wässrige Peroxidlösung zusätzlich mit einer Kombination aus Nitrilotriessigsäure, 1-Hydroxy- ethyliden-1,1-diphosphonsäure und einem wasserlöslichen Magnesium- oder Calciumsalz, u.a. Magnesiumhypophosphat versetzt wird, um einerseits die Zersetzung des Peroxids und andererseits den Ausfall von Silikaten zu verhindern (S. 4, Abs. 3).DE-A 22 26 784 discloses bleach stabilizers for textile materials in which an alkaline, aqueous peroxide solution stabilized with sodium silicate additionally with a combination of nitrilotriacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid and a water-soluble magnesium or calcium salt , among others Magnesium hypophosphate is added to prevent decomposition of the peroxide on the one hand and the failure of silicates on the other (p. 4, paragraph 3).
Auch in der DE-A 22 09 358 sind Kaltbleichflotten, d.h. Textilbleichmittel beschrieben, in denen Perboratlösungen, die u. a. Natrium- und Magnesiumsilikat als Stabilisatoren enthalten, zusätzlich noch Polyaminocarbonsäuren, Phosphonsäuren und Natriumtriphosphat enthalten können. Wesentlich scheint der Zusatz von Glykolurilen, insbesondere Tetraacetylglykoluril, zu sein. Als Holzbleichmittel sind diese Produkte wegen des Tensidgehaltes nicht verwendbar.DE-A 22 09 358 also includes cold bleaching liquors, i.e. Textile bleaches described in which perborate solutions, u. a. Contain sodium and magnesium silicate as stabilizers, may additionally contain polyaminocarboxylic acids, phosphonic acids and sodium triphosphate. The addition of glycolurils, in particular tetraacetylglycoluril, appears to be essential. These products cannot be used as wood bleaches because of their surfactant content.
Es ist bis jetzt nicht gelungen, Produkte zur Verfügung zu stellen, die einen vollständigen Ersatz von Wasserglas bei der Holzschliffbleiche mit Peroxid erlauben. Ziel der vorliegenden Erfindung war es daher, Produkte zu entwickeln, die einen vollständigen Ersatz des Wasserglases bei der Peroxidbleiche von Holzschliff erlauben und die darüber hinaus auch bei der Dithionitbleiche bleichunterstützend wirken.So far, it has not been possible to provide products that allow a complete replacement of water glass in wood pulp bleaching with peroxide. The aim of the present invention was therefore to develop products which allow a complete replacement of the water glass in the peroxide bleaching of wood pulp and which also have a bleaching support in the case of dithionite bleaching.
Es war naheliegend, für den genannten Einsatzzweck die als Peroxidstabilisatoren bekannten Produkte einzusetzen. Völlig unerwartet zeigte sich jedoch, dass diese Produkte trotz ihrer ausgezeichneten Stabilisierwirkung gegenüber Peroxid nur unzureichende Bleicheffekte ergaben.It was obvious to use the products known as peroxide stabilizers for the purpose mentioned. However, it was completely unexpected that these products, despite their excellent stabilizing effect against peroxide, gave only insufficient bleaching effects.
Überraschenderweise gelang die Lösung der gestellten Aufgabe durch Verwendung einer Kombination von
- 1. Phosphonsäuren,
- 2. Gluconsäure, Citronensäure, N,N-Dihydro- xyethylenglycin, DTPA, EDTA, NTA bzw. deren Gemische
- 3. Phosphorsäuren bzw. deren Salzen.
- 1. phosphonic acids,
- 2. Gluconic acid, citric acid, N, N-dihydroxyethylene glycine, DTPA, EDTA, NTA or mixtures thereof
- 3. Phosphoric acids or their salts.
Diese Substanzen üben für sich ungenügende Bleichwirkung aus, bzw. sie zeigen eine nur geringe Stabilisierung der Peroxidlösung. Zum Teil wirken sie sogar destabilisierend.These substances exert inadequate bleaching action or show only a slight stabilization of the peroxide solution. In some cases, they even have a destabilizing effect.
Als Phosphonsäuren können verwendet werden:
- N,N-Bis(carboxy-methyl)-1-amino-ethan-1,1- diphosphonsäure;
- N-2-Carboxyethyi-1-amino-ethan-1,1-diphosphonsäure;
- N,N-Bis(hydroxy-methyl)-1-amino-ethan-1,1-di-phosphonsäure;
- 1,2,1-Tricarboxybutan-2-phosphonsäure;
- Diethylentriaminpentamethylenphosphonsäure (DTPMP);
- Hydroxyethandi-phosphonsäure (HEDP); Aminotrismethylenphosphonsäure (ATMP) bzw. die entsprechenden Salze dieser Säuren.
- N, N-bis (carboxymethyl) -1-amino-ethane-1,1-diphosphonic acid;
- N-2-carboxyethyl-1-amino-ethane-1,1-diphosphonic acid;
- N, N-bis (hydroxy - methyl) -1-amino-ethane-1,1-di-phosphonic acid;
- 1,2,1-tricarboxybutane-2-phosphonic acid;
- Diethylenetriaminepentamethylenephosphonic acid (DTPMP);
- Hydroxyethane di-phosphonic acid (HEDP); Aminotrismethylenephosphonic acid (ATMP) or the corresponding salts of these acids.
Als 2. Komponente werden Gluconsäure, Citronensäure, N,N-Dihydroxyethylenglycin, Diethylentriaminpentaessigsäure, Ethylendiamintetraessigsäure, Nitrilotriessigsäure bzw. die entsprechenden Salze dieser Säuren verwendet.Gluconic acid, citric acid, N, N-dihydroxyethylene glycine, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid or the corresponding salts of these acids are used as the second component.
Als Phosphorsäurekomponente können Orthophosphorsäure bzw. Polyphosphorsäure oder die entsprechenden Alkali- und Erdalkalisalze eingesetzt werden.Orthophosphoric acid or polyphosphoric acid or the corresponding alkali and alkaline earth metal salts can be used as the phosphoric acid component.
Als besonders geeignet haben sich die genannten Komponenten in Mischungsverhältnissen von 8/1/1 bis 1/1/8 bis 1/8/1 erwiesen.The components mentioned in mixing ratios of 8/1/1 to 1/1/8 to 1/8/1 have proven particularly suitable.
Durch die gemeinsame Verwendung dieser Substanzen entsteht ein synergistischer Effekt, der insbesondere deshalb überrascht, da einzelne Komponenten oder diese in Zweierkombination nur ungenügende Bleichwirkung ausüben, bzw. destabilisierend auf das Oxidationsmittel wirken. Die nachfolgenden Beispiele erläutern die erfindungsgemässen Zusammenhänge näher.The joint use of these substances creates a synergistic effect, which is particularly surprising because individual components or these in combination of two only have an insufficient bleaching effect or have a destabilizing effect on the oxidizing agent. The following examples explain the relationships according to the invention in more detail.
Eine Bleichrezeptur kann nach dem heutigen Stand der Technik folgende Zusammensetzung haben:
Bei den Versuchen wurde wie folgt verfahren:The test was carried out as follows:
20 g Holzschliff otro wurden mit 20 ml Bleichlösung 3 h bei 60°C gebleicht. Danach wurde mit20 g of wood pulp otro were bleached with 20 ml of bleaching solution at 60 ° C. for 3 h. After that, with
Schwefelsäure auf pH 5 abgesäuert, auf einer Blattbildungsanlage Prüfblätter hergestellt und der Weissgrad nach TAPPI gemesen. Die Bleichlösung bestand aus 1,9% H202, 1,7% NaOH und dem jeweiligen Stabilisator. Der pH-Wert der Bleichlösung betrug 11,0. Die Stabilität der Bleichlösung wurde mittels Permanganattitration überprüft. Die Stoffdichte lag bei 20%
Die voranstehenden Beispiele zeigen eindeutig, dass mit den erfindungsgemässen Bleichhilfsmitteln wesentlich bessere Stabilisierwirkungen undWeissgradgewinneaismitdenjeweiiigenEinzelkomponenten erzielt werden. Darüber hinaus kann Wasserglas vollständig ersetzt werden, wobei z.T. sogar eine höhere Weisse erzielt wird. Desweiteren konnte bei diesen Versuchen gezeigt werden, dass sowohl bei Verwendung von Wasserglas als auch bei alleinigem Einsatz der Einzelkomponenten eine wesentlich höhere Menge als beim Einsatz der erfindungsgemässen Kombination eingesetzt werden muss. Somit wird bei Einsatz der erfindungsgemässen Produkte die Belastung des Kreislaufwassers mit Chemikalien herabgesetzt. Dies führt zusammen mit den oben beschriebenen Vorteilen insgesamt zu störungsfreiem Betrieb und damit gesteigerter Effektivität.The above examples clearly show that the bleaching aids according to the invention achieve significantly better stabilizing effects and whiteness gains with the individual components. In addition, water glass can be completely replaced, some of which even a higher whiteness is achieved. Furthermore, it was possible to show in these experiments that both when using water glass and when using the individual components alone, a significantly higher amount than when using the combination according to the invention must be used. Thus, when the products according to the invention are used, the load on the circulating water with chemicals is reduced. Together with the advantages described above, this leads overall to trouble-free operation and thus increased effectiveness.
Claims (6)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT84112648T ATE34790T1 (en) | 1983-10-21 | 1984-10-19 | METHOD OF BLEACHING WOOD Pulp. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3338260A DE3338260C1 (en) | 1983-10-21 | 1983-10-21 | Process and means for bleaching groundwood |
| DE3338260 | 1983-10-21 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0141355A1 EP0141355A1 (en) | 1985-05-15 |
| EP0141355B1 true EP0141355B1 (en) | 1988-06-01 |
Family
ID=6212408
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP84112648A Expired EP0141355B1 (en) | 1983-10-21 | 1984-10-19 | Process for bleaching ground wood pulp |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0141355B1 (en) |
| AT (1) | ATE34790T1 (en) |
| DE (2) | DE3338260C1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11207863B2 (en) | 2018-12-12 | 2021-12-28 | Owens Corning Intellectual Capital, Llc | Acoustic insulator |
| US11666199B2 (en) | 2018-12-12 | 2023-06-06 | Owens Corning Intellectual Capital, Llc | Appliance with cellulose-based insulator |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3531563A1 (en) * | 1985-09-04 | 1987-03-05 | Benckiser Knapsack Gmbh | WOOD FABRICS |
| GB8826431D0 (en) * | 1988-11-11 | 1988-12-14 | Albright & Wilson | Phosphate composition |
| DE4224607A1 (en) * | 1992-07-25 | 1994-01-27 | Benckiser Knapsack Ladenburg | New biodegradable ether carboxylate stabilising agent - useful for oxidative or reductive bleaching of TMP, CTMP, mechanical wood pulp or chemical pulp and for de-inking waste paper |
| ATE165636T1 (en) * | 1993-10-26 | 1998-05-15 | Akzo Nobel Nv | AMINOALKAN-DIPHOSPHONIC ACIDS FOR BLEACHING PULP |
| DE19528843A1 (en) * | 1995-08-04 | 1997-02-06 | Cht R Beitlich Gmbh | Process for the stabilization of alkaline peroxide-containing bleaching liquors for the bleaching of cellulose and other fibrous materials |
| FI115641B (en) * | 1996-02-19 | 2005-06-15 | Kemira Oyj | Bleaching process for high yields |
| FI115470B (en) * | 1996-02-19 | 2005-05-13 | Kemira Oyj | Process for the treatment of chemical cellulose material |
| SE9604413D0 (en) * | 1996-11-29 | 1996-11-29 | Eka Chemicals Ab | Chemical composition |
| SE9604414D0 (en) * | 1996-11-29 | 1996-11-29 | Eka Chemicals Ab | Chemical composition |
| GB0721587D0 (en) | 2007-11-02 | 2007-12-12 | Innospec Ltd | Process for bleaching pulp |
| EP2225175B1 (en) | 2007-12-13 | 2012-12-12 | Akzo Nobel N.V. | Stabilized hydrogen peroxide solutions |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1052797B (en) * | 1951-08-08 | 1959-03-12 | Scott Paper Co | Process for bleaching wood pulp |
| DE1052798B (en) * | 1952-09-11 | 1959-03-12 | Scott Paper Co | Process for bleaching wood pulp |
| US3766078A (en) * | 1971-06-03 | 1973-10-16 | Monsanto Co | Processes for stabilizing peroxy solutions |
| DE2209358A1 (en) * | 1972-02-27 | 1973-09-13 | Henkel & Cie Gmbh | Bleaching agent - contg diphenyl-distyryl type brightener |
| DE2500209B2 (en) * | 1975-01-03 | 1977-03-03 | Benckiser-Knapsack Gmbh, 6802 Ladenburg | METHOD AND MEANS OF PREVENTION OF RESIN PRECIPITATION IN PAPER MANUFACTURING |
| US4294575A (en) * | 1979-01-02 | 1981-10-13 | Monsanto Company | Peroxide stabilization |
| GB2072643B (en) * | 1980-04-01 | 1983-06-08 | Interox Chemicals Ltd | Aqueous h2 o2 bleach compositions |
-
1983
- 1983-10-21 DE DE3338260A patent/DE3338260C1/en not_active Expired
-
1984
- 1984-10-19 EP EP84112648A patent/EP0141355B1/en not_active Expired
- 1984-10-19 AT AT84112648T patent/ATE34790T1/en active
- 1984-10-19 DE DE8484112648T patent/DE3471705D1/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11207863B2 (en) | 2018-12-12 | 2021-12-28 | Owens Corning Intellectual Capital, Llc | Acoustic insulator |
| US11666199B2 (en) | 2018-12-12 | 2023-06-06 | Owens Corning Intellectual Capital, Llc | Appliance with cellulose-based insulator |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0141355A1 (en) | 1985-05-15 |
| DE3338260C1 (en) | 1985-07-25 |
| ATE34790T1 (en) | 1988-06-15 |
| DE3471705D1 (en) | 1988-07-07 |
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