Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/22—Organic complexes
• • 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
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3932—Inorganic compounds or complexes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
  • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
  • D21C9/10—Bleaching ; Apparatus therefor
  • D21C9/1026—Other features in bleaching processes
  • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
  • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
  • B01J2531/72—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
  • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
  • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
  • B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
• • 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 invention concerns the use of bleaching solutions.
• Raw cotton (gin output) is dark brown in colour due to the natural pigment in the plant.
• the cotton and textile industries recognise a need for bleaching cotton prior to its use in textiles and other areas.
• the object of bleaching such cotton fibres is to remove natural and adventitious impurities with the concurrent production of substantially whiter material.
• bleach used in the cotton industry.
• One type is a dilute alkali or alkaline earth metal hypochlorite solution.
• the second type of bleach is a peroxide solution, e.g., hydrogen peroxide solutions.
• This bleaching process is typically applied at high temperatures, i.e. 80 to 95° C. Controlling the peroxide decomposition due to trace metals is key to successfully using hydrogen peroxide.
• Mg-silicates or sequestering agents such as EDTA or analogous phosphonates are applied to reduce decomposition.
• a problem with the above types of treatment is that the cotton fibre is susceptible tendering.
• Wood pulp produced for paper manufacture either contains most of the originally present lignin and is then called mechanical pulp or it has been chiefly delignified, as in chemical pulp.
• Mechanical pulp is used for e.g. newsprint and is often more yellow than paper produced from chemical pulp (such as for copy paper or book-print paper). Further, paper produced from mechanical pulp is prone to yellowing due to light- or temperature-induced oxidation. Whilst for mechanical pulp production mild bleaching processes are applied, to produce chemical pulp having a high whiteness, various bleaching and delignification processes are applied. Widely applied bleaches include elemental chlorine, hydrogen peroxide, chlorine dioxide and ozone.
• the azacyclic molecules have been known for several decades, and their complexation chemistry with a large variety of metal ions has been studied thoroughly.
• the azacyclic molecules often lead to transition-metal complexes with enhanced thermodynamic and kinetic stability with respect to metal ion dissociation, compared to their open-chain analogues.
• United States Application 2001/0025695 discloses the use of a manganese transition metal catalyst of 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me 3 -TACN); the transition metal catalyst has as a non-coordinating counter ion PF 6 ⁇ .
• United States Application 2001/0025695A1 also discloses a manganese transition metal catalyst of 1,2,-bis-(4,7,-dimethyl-1,4,7,-triazacyclonon-1-yl)-ethane (Me 4 -DTNE); the transition metal catalyst has as a non-coordinating counter ion ClO 4 ⁇ .
• the solubility, in water at 20° C., of the Me4-DTNE complex having non-coordinating counter ion ClO 4 ⁇ is about 16 gram/Liter.
• the solubility, in water at 20° C., of the Me4-DTNE complex having non-coordinating counter ion PF 6 ⁇ is about 1 gram/Liter.
• US 2002/0066542 discloses the use of a manganese transition metal complex of Me 3 -TACN in comparative experiments and makes reference to WO 97/44520 with regard to the complex; the non-coordinating counter ion of the manganese transition metal complex of Me 3 -TACN is PF 6 ⁇ .
• the X groups as listed in paragraph [021] of US 2002/0066542 are coordinating.
• EP 0458397 discloses the use of a manganese transition metal complex of Me 3 -TACN as bleaching and oxidation catalysts and use for paper/pulp bleaching and textile bleaching processes.
• Me 3 -TACN complexes having the non-coordinating counter ion perchlorate, tetraphenyl borate (BPh 4 ⁇ ) and PF 6 ⁇ are disclosed.
• the solubility, in water at 20° C., of the Me 3 -TACN complex having non-coordinating counter ion ClO 4 ⁇ is between 9.5 to 10 gram/Liter.
• the solubility, in water at 20° C., of the Me 3 -TACN complex having non-coordinating counter ion BPh 4 ⁇ is less then 0.01 gram/Liter.
• WO 95/27773 discloses the use of manganese transition metal catalysts of 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me 3 -TACN); the transition metal catalysts have as a non-coordinating counter ion ClO 4 ⁇ and PF 6 ⁇ .
• 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) has been used in dishwashing for automatic dishwashers, SUNTM, and has also been used in a laundry detergent composition, OMO PowerTM.
• the ligand (Me 3 -TACN) is used in the form of its manganese transition-metal complex, the complex having a counter ion that prevents deliquescence of the complex.
• the counter ion for the commercialised products containing manganese Me 3 -TACN is PF 6 ⁇ .
• the Me 3 -TACN PF 6 ⁇ salt has a water solubility of 10.8 g per litre at 20° C.
• the perchlorate (ClO 4 ⁇ ) counter ion is acceptable from this point of view because of its ability to provide a manganese Me 3 -TACN that does not appreciably absorb water.
• One advantage of the PF 6 ⁇ or ClO 4 ⁇ counter ions for the manganese Me 3 -TACN complex is that the complex may be easily purified by crystallisation and recrystallisation from water.
• the non-deliquescent PF 6 ⁇ salt permits processing, e.g., milling of the crystals, and storage of a product containing the manganese Me 3 -TACN.
• these anions provide for storage-stable metal complexes.
• highly deliquescent water soluble counterions are used, but these counterions are replaced with non-deliquescent, much less water soluble counter ions at the end of the synthesis.
• a drawback of using PF 6 ⁇ is its significant higher cost compared to other highly soluble anions.
• U.S. Pat. Nos. 5,516,738 and 5,329,024 disclose the use of a manganese transition metal catalyst of 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) for epoxidizing olefins; the transition metal catalyst has as a non-coordinating counter ion ClO 4 ⁇ .
• Me 3 -TACN 1,4,7-Trimethyl-1,4,7-triazacyclononane
• U.S. Pat. No. 5,329,024 also discloses the use of the free Me 3 -TACN ligand together with manganese chloride in epoxidizing olefins.
• WO 2002/088063 to Lonza AG, discloses a process for the production of ketones using PF 6 ⁇ salts of manganese Me 3 -TACN.
• WO 2005/033070 discloses the addition of an aqueous solution of Mn(II)acetate to an aqueous solution of Me 3 -TACN followed by addition of a organic substrate followed by addition of hydrogen peroxide.
• the invention is particularly applicable to industrial bleaching of paper/pulp, cotton-textile fibres, and the removal or degradation of starches.
• a transition metal catalyst that is significantly water soluble the synthesis negates the preparation of significantly water insoluble salts and hence reduces cost.
• the transition metal catalyst may be shipped in solution or as a solid form of transition metal catalyst which is easily dissolved in water.
• the present invention provides a method of catalytically treating a substrate, the substrate being a cellulose-containing substrate or starch containing substrate, with a preformed transition metal catalyst salt, the preformed transition metal catalyst salt having a non-coordinating counter ion, the method comprising the following steps:
• the preformed transition metal catalyst salt is a mononuclear or dinuclear complex of a Mn (III) or Mn(IV) transition metal catalyst for catalytically treating the substrate with hydrogen peroxide, the non-coordinating counter ion of said transition metal selected to provide a preformed transition metal catalyst salt that has a water solubility of at least 30 g/l at 20° C. and wherein the ligand of the transition metal catalyst is of formula (I):
• R is independently selected from: hydrogen, C1-C6-alkyl, CH 2 CH 2 OH, and CH 2 COOH, or one of R is linked to the N of another Q via an ethylene bridge;
• R1, R2, R3, and R4 are independently selected from: H, C1-C4-alkyl, and C1-C4-alkylhydroxy, and the substrate is bought into contact with a mixture of the aqueous solution of the preformed transition metal catalyst salt and the hydrogen peroxide.
• the dinuclear complex may have two manganese in same or differing oxidation states.
• R is preferably C1-C6-alkyl, most preferably Me, and/or one of R is an ethylene bridge linking the N of Q to the N of another Q.
• the reaction vessel may be part of a continuous flow apparatus or a vessel used in a batch process. Preferably pulp and cotton are treated in a continuous flow process. Steps (ii) and (iii) provide a mixture of the aqueous solution of the preformed transition metal catalyst salt and the hydrogen peroxide; the substrate is bought into contact with this mixture and hence is treated with such within the reaction vessel.
• the preformed transition metal catalyst salt is one which has been provided by bringing into contact the free ligand or protonated salt of the free ligand and a manganese salt in solution followed by oxidation to form a Mn (III) or Mn(IV) transition metal catalyst.
• Preferred protonated salts of the ligand are chloride, acetate, sulphate, and nitrate.
• the protonated salts should not have undesirable counterions such as perchlorate or PF 6 ⁇ .
• the contact and oxidation step is preferably carried out in an aqueous medium, at least 24 hours before use, preferably at least 7 days before use.
• the rate of formation of the transition metal catalyst depends upon the ligand.
• the formation of a transition metal catalyst from Me 3 -TACN ligand is typically complete within 5 min.
• the formation of a transition metal catalyst from Me 4 -DTNE ligand requires about 20 to 30 min for optimal complexation.
• an aqueous solution of H 2 O 2 /NaOH may be slowly added to form a desired Mn(IV)/Mn(IV) or Mn(IV)/Mn(III) species.
• This second step, the oxidation step provides a sufficiently stable complex for storage.
• the present invention provides the preformed transition metal catalyst salt as defined herein, wherein the preformed transition metal catalyst salt has been formed by a contact and oxidation step that is carried out at least 24 hours previously, preferably 7 days previously, and is stored in a closed, preferably sealed, container.
• the present invention also extends to the substrate treated with preformed transition metal catalyst and hydrogen peroxide.
• the solubility, in water at 20° C., of the Me 3 -TACN complex having non-coordinating counter ion acetate is more than 70 gram/Liter.
• the solubility, in water at 20° C., of the Me 3 -TACN complex having non-coordinating counter ion sulphate is more than 50 gram/Liter.
• the solubility, in water at 20° C., of the Me 3 -TACN complex having non-coordinating counter ion chloride is 43 gram/Liter.
• the preformed transition metal catalyst salt is a dinuclear Mn(III) or Mn(IV) complex with at least two O 2 ⁇ bridges.
• the method of treating paper/pulp, cotton-textile fibres, or starch containing substrate is most applicable to industrial processes. Other examples of such processes are laundry or mechanical dish washing applications, fine chemical synthesis. Most preferably the method is applied to wood pulp, raw cotton, or industrial laundering. In this regard, the wood pulp is bleached which has not been processes into a refined product such as paper. The raw cotton is in most cases treated/bleached after preparation of the raw cotton cloths or bundled fibres.
• the method of treatment is employed in an aqueous environment such that the liquid phase of the aqueous environment is at least 80 wt % water, more preferably at least 90 wt % water and even more preferably at least 95 wt % water. After treatment of the substrate the reactants may be recycled back into the reaction vessel.
• poly-cotton may also advantageously be treated in the form of a thread or a woven garment.
• Another preferred utility is in the industrial bleaching market of laundry, for example, the bleaching of large amounts of soiled white bed linen as generated by hospitals and gaols.
• R is independently selected from: hydrogen, CH 3 , C 2 H 5 , CH 2 CH 2 OH and CH 2 COOH; least preferred of this group is hydrogen.
• R is Me and/or one of R is an ethylene bridge linking the N of Q to the N of another Q.
• R1, R2, R3, and R4 are independently selected from: H and Me.
• Preferred ligands are 1,4,7-Trimethyl-1,4,7-triazacyclononane (Me 3 -TACN) and 1,2,-bis-(4,7-dimethyl-1,4,7,-triazacyclonon-1-yl)-ethane (Me 4 -DTNE) of which Me 3 -TACN is most preferred.
• the manganese ion is most preferably Mn(III) or Mn(IV), most preferably Mn(IV).
• the water solubility of the preformed transition metal catalyst salt is at least 30 g/l at 20° C., more preferably at least 50 g/l at 20° C. Even more preferably the water solubility of the preformed transition metal catalyst salt is at least 70 g/l at 20° C. and most preferably the salt is deliquescent.
• the high solubility provides for concentrates whilst avoiding precipitation or crystallisation of the preformed transition metal catalyst salt.
• the preformed transition metal catalyst salt (cationic) used in the method is most preferably a single species.
• the aqueous solution used comprises at least 90% of a single species.
• the non-coordinating counter ions may, for example, be a mixture of acetate and chloride.
• the non-coordinating anion of the transition metal catalyst salt is preferably selected from the group consisting of chloride, acetate, sulphate, and nitrate. Most preferably the salt is acetate. The salt is other than the perchlorate.
• Co-ordinating counter ions for the transition metal complexes are O 2 ⁇ and/or carboxylate (preferably acetate). It is preferred that the transition metal complexes have at least one O 2 ⁇ coordinating counter ion. In particular, for Me 3 -TACN three O 2 ⁇ co-ordinating counter ions are preferred or one O 2 ⁇ co-ordinating counter ion and two carboxylate co-ordinating counter ions are preferred, with two acetate moieties as co-ordinating counter ions being most preferred. For Me 4 -DTNE two O 2 ⁇ coordinating counter ions and one acetate co-ordinating counter ion are preferred.
• the transition metal catalyst salt is present in a buffer system that maintains the solution in the pH range 2 to 7, and preferably in the pH range 4 to 6.
• the buffer systems is preferably phosphate or carboxylate containing buffers, e.g., acetate, benzoate, citrate.
• the buffer system most preferably keeps the transition metal catalyst salt in the range pH 4.5 to 5.5.
• the catalyst solution may also be provided in a reduced volume form such that it is in a concentrate, solid or slurry which is then dispatched to its place of use. Removal of solvent is preferably done by reduced pressure rather than the elevation of temperature.
• the solution, solid or slurry is stored over an inert atmosphere, e.g., nitrogen or argon, with little or no headspace at 4° C.
• an inert atmosphere e.g., nitrogen or argon
• a preformed transition metal catalyst salt concentration range of 0.1 to 10% is desirable, more desirable is between 0.5 and 8%, and most desirable is between 0.5 and 2%.
• the concentrate or solid or solid most preferably has the pH means as described above before reduction of water volume.
• the substrate is contacted with between from 0.1 to 100 micromolar of the preformed transition metal catalyst and from 5 to 1500 mM of hydrogen peroxide.
• the preformed transition metal catalyst salt and hydrogen peroxide are mixed just before introduction to the substrate.
• Mn 2 O 3 (Me 3 -TACN) 2 complexes with different anions examples on the syntheses of Mn 2 O 3 (Me 3 -TACN) 2 complexes with different anions are provided.
• Synthesis of the Mn 2 O 3 (Me 3 -TACN) 2 PF 6 salt is disclosed in U.S. Pat. No. 5,153,161, U.S. Pat. No. 5,256,779, and U.S. Pat. No. 5,274,147.
• the solubility of the Mn 2 O 3 (Me 3 -TACN) 2 PF 6 salt in water at 20° C. is 1.08% (w/w).
• the mixture was filtered through a G4 glass frit, washed with water and the collected red filtrate and wash diluted to 50.00 ml in a graduated flask. From this solution a 1000 ⁇ dilution was made and from the absorption in the UV/Vis spectrum at 244, 278, 313, 389 and 483 nm the concentration in the stock was calculated and the yield (based on extinction of the PF 6 analogue in water)
• the mixture was filtered through a G4 glass frit, washed with water and the collected red filtrate and wash diluted to 50.00 ml in a graduated flask. From this solution a 1000 ⁇ dilution was made and from the absorption in the UV/Vis spectrum at 244, 278, 313, 389 and 483 nm the concentration in the stock was calculated and the yield (based on extinction of PF 6 analogue in water)
• Softwood chemical mill pulp obtained after the D0 bleaching stage (abbreviated as softwood D0 pulp) was used.
• the bleaching experiments were conducted on small scale in 100 ml vessels using the pulps at 5% consistency (i.e., 5% oven dry wood pulp; 95% aqueous bleaching liquor).
• the mixture contained 2.5 microM of the catalyst (as chloride, sulfate, acetate and PF 6 salts—see Table), 1 kg/t of MgSO 4 , 8 kg/t of NaOH and 10 kg/t of H 2 O 2 (kg/t: kg chemicals per ton oven dry pulp).
• the mixture was manually stirred to ensure good distribution of the bleaching chemicals.
• the vessel was placed in a water bath and stirred regularly at 50° C. for 1 h.

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• 2006
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