BLEACHING OF LIGNOCELLULOSIC MATERIAL WITH ACTIVATED OXYGEN

Abstract: A chemical pulp that contains reactants able to generate a dioxirane within the pulp. The reactants comprise of carbonyl compound, preferably a ketone, and oxygen donor in proportions suitable to produce a dioxirane having a molecular diameter of less than 140 angstrom units. A process of bleaching a chemical pulp is also described. The process comprises mixing the pulp with the reactants able to generate a dioxirane within the pulp.

Description: TtT.T.APHTNG OF IGNOCELLU OSIC MATERIAL WITH ACTIVATED OXYGEN This invention relates to a process of bleaching a chemical pulp and to the pulp. For the last three decades, chemical pulps, particularly those produced by the kraft process, have bee bleached to the brightness level required for market pulps about 90% ISO, by conventional processes such as CEDED, where C stands for chlorination, E for caustic extraction, and D for chlorine dioxide treatment. Effluents from thes conventional bleaching processes cannot be concentrated an burned in a kraft recovery boiler due to their high conten of chlorinated organic material, typically about five kilogram per air-dried ton of pulp. Instead, these mill effluents have to be post-treated and discharged into waterways. In response to the need for reducing the adverse impa of pulp mill effluents on the environment, technologies to reduce the use of elemental chlorine in chemical pulp bleaching have been evaluated and many retrofitted, where feasible, into pulp mills. These technologies, are: (1) modified continuous cooking (MCC) ; (2) rapid displacement heating (RDH) ; (3) oxygen delignification and (4) high chlorine dioxide substitution. The first three methods reduce the residual lignin content in the pulp to the chlorination stage. The fourth method is a direct substitution of elemental chlorine by chlorine dioxide to reduce the elemental chlorine charge. The aforementioned technologies available today have the object of reducing t use of elemental chlorine. However, the complete elimination of elemental chlorine and chlorine-containing compounds in the bleaching of chemical pulps is highly desirable. Our co-pending application PCT/CA90/00052 teaches the use of dioxiranes in pulp bleaching. However, the process of the co-pending application, although producing excellent results in bleaching, can be inefficient in the generation of dioxirane. The published method for the preparation of isolated dioxirane (Murray, R. . and Jeyaraman, R., J. Org. Chem. 5fJ, 2847, 1985) is not practical for large-scale production. For this reason, in-situ-generated dimethyldioxirane was employed to oxidize aromatic amines under phase-transfer conditions using only a slight excess of monoperoxysulphate to complete the required oxidation transformation (Zabrowski, D.L., Moormann, A.E. and Beck, Jr. .R., Tetrahedron Letters, 29., (36):4501, 1988). Montgomery, R.E. reported that ketones catalysed a number of reactions with monoperoxysulphate (Montgomery, R.E., J. A er. Chem. Soc, .96., (25):7820, 1974). U.S. Patent 3,822,114 to Montgomery, R.E. discloses a bleaching process for activation of peroxygen bleaching agents which comprise conjointly dissolving in aqueous solution containing peroxygen bleaching agents, certain aldehyde or ketone bleaching activators, and buffering compounds. Montgomery's process is applied to the instant bleaching activation process for the purpose of bleaching stains on fabrics and hard surfaces and for reducing dye transfer in conventional laundering solutions. Montgomery does not disclose delignification of lignocellulosic pulps to produce bleached pulps for papermaking with market pulp brightness and good strengths, particularly, the selectivity in residual lignin removal for chemical pulp bleaching. The present invention seeks to improve our prior process by providing economies in the use of the bleaching agents. Accordingly, and in its broadest aspect, the present invention is a chemical pulp that contains reactants able to generate a dioxirane within the pulp. In a process aspect, this invention relates to a process of bleaching pulp that comprises mixing the pulp with reactants able to generate a dioxirane within the pulp. It is believed that dioxirane is the oxidizing moiety for bleaching of cellulose in the present invention. It is however possible that concurrently other moieties heretofore not identified may be present and responsible for some of the bleaching effect claimed. The in-situ-generated dioxirane is designated as A throughout this application. In drawings which illustrate embodiments of the present invention. Figure 1 is a graph of tensile breaking lengths for pulps bleached in accordance with the present invention after different stages of refining. Figure 2 is a graph of tear indices for the same conditions as Figure 1, Figure 3 is a graph of zero-span breaking lengths for the same conditions as Figure 1, Figure 4 is a graph of tensile breaking lengths for pulps bleached in accordance with different aspects of the present invention than shown in Figure 1, after different stages of refining, Figure 5 is a graph of tear indices for the same conditions as Figure 4, Figure 6 is a graph of zero-span breaking lengths for the same conditions as Figure 4. Preferably the reactants comprise a ketone and an oxygen donor in proportions suitable to produce a water- soluble dioxirane which has a molecular diameter of less than 140, preferably less than about 50, angstrom units. The molecular diameter allows the dioxirane to make proper contact with the pulp by allowing the dioxirane to permeate the pores of the pulp. The ketone may be aliphatic or aromatic. An appropriate ketone is acetone. A preferred dioxirane is dimethyldioxirane. The pulp bleached with dioxirane and other non-chlorine containing compounds preferably contains less than 120 parts per million (pp ) of chlorine element content and a brightness of at least about 70% Elrepho. In a particular preferred embodiment, the dioxirane- treated pulps have a Kappa number of less than 10. In a further aspect the invention is a process of bleaching a chemical pulp that comprises mixing the pulp with reactants able to generate a dioxirane within the pulp. In this process aspect, the reactants preferably comprise a ketone and an oxygen donor in proportions suitable to produce a water-soluble dioxirane which has a molecular diameter of less than about 50 angstrom units, The ketone may be aliphatic or aromatic. The ketone may be impregnated into a pulp slurry followed by application of the oxygen donor. Alternatively the ketone and the oxygen donor are applied simultaneously to the pulp. Preferably, the ketone is acetone added in the amount of at least 4% by weight based on oven-dried pulp. The oxygen donor is preferably a monoperoxysulphate. However, suitable oxygen donors include peroxymonocarbonate, peracetic acid, perbenzoic acid, perboric acid and perphosphoric acid. The oxygen donor may be added in a series of stages. It may be added in powdered form into the pulp slurry or in solution in which the donor can be dissolved in an aqueous buffer solution of controlled pH. The pH of the pulp slurry may be within the range from 6.0 to 14, preferably about 7.2. Adjustment of the pH can be carried out by the addition of, for example, sodium bicarbonate, sodium carbonate, sodium hydroxide, sodium acetate or other appropriate buffers and bases. The ketone, the oxygen donor and the pH control reagent may be added in any order or portionally premixed together before their additions into the pulp and preferably the pH control agent is the last one added. The pulp may be at a consistency in the range from 3 to 35%, preferably about 12%. The temperature of the process may be in the range of 5 to 80°C, preferably from 20 to 60°C. The time required for the treatment is in the range of 5 to 90 minutes, preferably about 30 minutes. The pulp may be treated with chelating agent, that is ethylenediaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTPA) or other chelating agent, and preferably should be treated before the bleaching stage of the present invention. The charge of chelating agent may vary from between 0.1 to 3.0% based on the weight of on oven-dried pulp and is preferably about 0.2-0.6%. The pulps of the present invention can be further treated by a subsequent caustic extraction. The caustic charge, usually of sodium hydroxide, may vary from between about 1 to 5% based on the weight of oven-dried pulp and is preferably about 2%. This caustic extraction can be reinforced by oxygen, hydrogen peroxide or both. The caustic-extracted pulps of the present invention can be bleached to a brightness of greater than 85% Elrepho by a chelating treatment followed by hydrogen peroxide brightening. During the chelating treatment, ethylenediaminetetraacetic acid (EDTA) , diethylenetriaminepentaacetic acid (DTPA) or other chelating agent is used as chelant, preferably EDTA. The charge of EDTA may vary from about 0.2 to 3% based on the weight of on oven-dried pulp and is preferably about 0.2-1.5%. The dioxirane bleaching may be carried out in combination with, either before or after, oxygen delignification, preferably after oxygen delignification. All prebleaching referred to in the application designated as C is considered to be: (C50% + D50%) , as available chlorine. The following examples illustrate but do not limit the invention: Example 1 Hemlock pulp, sample 1, produced by a kraft process to a Kappa number of 31.5 was treated with in-situ-generated dioxirane (designated by A) by impregnating the pulp slurry with acetone, 16% on oven-dried pulp, for 10 minutes before the addition of the powdered form of monoperoxysulphate at an active oxygen charge of 0.9% on oven-dried pulp at 25°C for 30 minutes. The pulp consistency in the said in-situ- dioxirane bleaching stage was 13.6%. This in-situ- dioxirane-treated pulp was further extracted with 3.0% sodium hydroxide charge on oven-dried pulp at 74°C and 12% pulp consistency for two hours. Example 2 A second sample of the same unbleached hemlock pulp of Example 1 was oxygen-delignified (0 2 ). The pulp was heated to 110°C followed by the addition of sodium hydroxide, 1.8% charge on oven-dried pulp, and magnesium sulphate, 0.75% charge on oven-dried pulp, before the introduction of oxygen at a pressure of 90 psig. The resulting pulp slurry at a 10% pulp consistency was kept under the conditions for 30 minutes. Example 3 A third sample of the same unbleached hemlock pulp of Example 1 was bleached by a conventional chlorination stage using 3.0% available chlorine on oven-dried pulp at 20°C and 3% pulp consistency for one hour. The resulting chlorinated pulp was subsequently extracted, using 2.0% sodium hydroxide charge on oven-dried pulp at 74°C and 12% pulp consistency for two hours. The results, listed in Table 1, illustrate that the in- situ-dioxirane treatment is substantially more effective on Kappa number reduction than oxygen delignification at about the same level of viscosity drop. The viscosity of the in- situ-dioxirane treated pulp has been maintained at a level close to that of the pulp bleached via a conventional CE bleaching sequence at about the same level of Kappa number reduction. Table 1. Kappa number and viscosity of hemlock pulps bleached by in-situ dioxirane treatment, oxygen delignification, and a conventional CE sequence. Example 4 A fourth sample of the unbleached hemlock pulp of Example 1 was treated with the in-situ-generated dioxirane. An aliquot of this in-situ-dioxirane treated hemlock pulp was further extracted with a 3.0% sodium hydroxide charge on oven-dried pulp under the exact conditions employed in Example 1. The results, shown in Table 2, demonstrate that the in- situ-generated dioxirane reacts with the residual lignin in kraft pulp in a way similar to elemental chlorine and renders the residual lignin more soluble in dilute alkali; hence, the caustic extraction reduces the residual lignin content even further. Table 2. Further Kappa number reduction achieved in the caustic extraction stage following the said in- situ-dioxirane treatment in the bleaching of hemlock pulps. Unbleached 31.5 0 33.5 E . 4 A-Treated 0.9 20.6 35.0 28.3 Ex. 4 AE-Bleached 13.7 57.0 26.0 Example 5 A first sample of the oxygen-delignified hemlock pulp prepared as described in Example 2 was treated with in- situ-generated dioxirane at an 0.9% active oxygen charge on oven-dried pulp at 25°C and 13.6% pulp consistency for 30 minutes. An aliquot of this in-situ-generated dioxirane treated hemlock pulp was further delignified by caustic extraction using 2.0% sodium hydroxide charge on oven-dried pulp at 74°C, and 12% pulp consistency for two hours. Example 6 A fifth sample of the unbleached hemlock pulp of Example 1 was treated with in-situ-generated dioxirane at an 0.9% active oxygen charge on oven-dried pulp at 25°C and 13.6% pulp consistency for 30 minutes. An aliquot of this in-situ-dioxirane treated hemlock pulp was further delignified by an oxygen-reinforced extraction, E 0 , at 2.0% sodium hydroxide charge and 0.5% magnesium sulphate charge respectively on oven-dried pulp. This E 0 stage was carried out at 12% pulp consistency and 60°C for 40 minutes. The oxygen pressure was kept at 20 psig for the first 10 minutes and then reduced to atmospheric pressure. The results, shown in Table 3, demonstrate that the in- situ-dioxirane treatment in combination with oxygen delignification can reduce the residual lignin content to more than 50% in Kappa number reduction while retaining satisfactory viscosity in the bleached pulps. Table 3. Kappa number and viscosity of the bleached hemlock pulps employing a combination of in-situ-dioxirane treatment and oxygen delignification. Example 7 A sixth sample of the hemlock pulp of Example 1 treated with in-situ-generated dioxirane at 2.7% active oxygen charge on oven-dried pulp was followed by a caustic extraction using 3.23% sodium hydroxide charge on oven-dried pulp. Both treatments were carried out under the same conditions as described in Example 1 and the resulting pulp was further bleached to a brightness of 90% Elrepho via a conventional DED sequence. The chlorine dioxide treatment was carried out at 1% charge on oven-dried pulp for each D stage, 6% pulp consistency, and 74°C for three hours. The caustic extraction was achieved at 1% sodium hydroxide charge on oven-dried pulp, 74°C, and 12% pulp consistency for two hours. Example 8 A seventh sample of the same hemlock pulp of Example 1 was bleached to a brightness of 90.1% Elrepho by a conventional CE^D.E-D- process. Chlorination was carried out at 6.0% available chlorine on oven-dried pulp, 20°C, and 3% pulp consistency for one hour; chlorine dioxide treatments, D. and D 2 both used 1% charge on oven-dried pulp, were carried out at 74°C and 6% pulp consistency for three hours; caustic extractions, E, and E 2 were accomplished by using 3.6% and 1.0% sodium hydroxide charges for E, and E 2 respectively, were carried out at 74°C and 12% pulp consistency for two hours for each stage. Example 9 A second sample of the same oxygen-delignified hemlock pulp described in Example 2 was further bleached to a brightness of 91.8% Elrepho via CE ^ D-E ^ D^. Where the conditions for the conventional CE.D ^ E ^ D ^ were the same as those applied to Example 8 with 4.8%, 1.0% and 1.0% charges on oven-dried pulp for the order of C, D,, AND D„ stages and 2.88% and 1.0% sodium hydroxide charges on oven-dried pulp for E, and E~ respectively. A complete replacement of elemental chlorine in bleaching chemical pulps to 90% Elrepho brightness, which satisfies market pulp specifications, was achieved by the invention bleaching sequence, AEDED. The strengths of the pulp produced by the invention bleaching process are comparable to those of a pulp bleached by conventional bleaching processes such as CEDED and O2CEDED shown in Table 4. Table 4. Optical and strength properties of hemlock pulps bleached by the in-situ-dioxirane treatment of the invention and conventional processes. Pulp AEDED CEDED 0 2 CEDED Properties (Ex. 7) (Ex. 8) (Ex. 9) Brightness (% Elrepho) Burst Index (kPa.m 2 /g) Tensile Index (N.m/g) Tear Index (mN.irr/g) Zero-Span Tensile (km) Bulk (cm 3 /g) Example 10 An eighth sample of the same unbleached hemlock pulp of Example 1 was treated with in-situ-generated dioxirane by multiple addition of monoperoxysulphate on acetone- impregnated pulp. The overall active oxygen charge, 0.9% on oven-dried pulp, was divided into three portions, 0.25%, 0.25% and 0.45% and added in order at twenty-minute intervals. The overall time for the in-situ-dioxirane treatment was one hour. An aliquot of this in-situ- dioxirane treated hemlock pulp was further extracted using a 3% sodium hydroxide charge on oven-dried pulp at 74°C and 12% pulp consistency for two hours. Example 11 A third sample of the same oxygen-delignified hemlock pulp as described in Example 2 was treated with in-situ- generated dioxirane by multiple additions of active oxygen charge on oven-dried pulp. « An aliquot of the in-situ- dioxirane-treated hemlock pulp was then extracted with a 3% sodium hydroxide charge on oven-dried pulp under the exact conditions employed in Example 10. The results, shown in Table 5, illustrate that the single and multiple modes of the addition of monoperoxysulphate are equally effective in Kappa number reduction at the same active oxygen charge during the said in-situ-dioxirane treatment and caustic extraction stages. Table 5. Kappa number and viscosity of hemlock pulps bleached by single or multiple addition modes of active oxygen in the in-situ-dioxirane treatment. Example 12 A ninth sample of the unbleached hemlock pulp of Example 1 was delignified via multistage in-situ-dioxirane treatments and caustic extractions such as A,-E,-A 2 -E 2 . The in-situ-dioxirane treatments were carried out at 0.45% active oxygen charge on oven-dried pulp at each stage, 25°C, and 13.6% pulp consistency for 30 minutes and the caustic extractions were performed at 2% sodium hydroxide charge on oven-dried pulp at each stage, 74°C, and 12% pulp consistency for two hours. Example 13 A fourth sample of the same oxygen-delignified hemlock pulp of Example 2 was bleached via exactly the same multistage sequence as that employed for the Example 12. The results, shown in Table 6, demonstrate that multistage treatment of the said in-situ-dioxirane treatment followed by caustic extraction is slightly more effective in the reduction of Kappa number compared to a single stage treatment at the same active oxygen charge on oven-dried pulp. This multistage treatment of the unbleached hemlock pulp employing the said in-situ-dioxirane treatment followed by caustic extraction effectively delignifies the hemlock pulp to more than 50% in Kappa number reduction while the viscosity of the treated pulp is retained above 20 mPa.s. However, in the case of the oxygen-delignified hemlock pulp bleached by a multistage treatment via in-situ-dioxirane treatment and caustic extraction, a major loss of pulp viscosity evidently occurred during the oxygen delignification stage. Table 6. Kappa number and viscosity of hemlock pulps bleached via single or multi-stage in-situ- dioxirane treatment and caustic extraction. Example 14 A tenth sample of the same unbleached hemlock pulp of Example 1 was treated with in-situ-generated dioxirane under the exact conditions employed in Example 1 except that the charge of acetone, (16% on oven-dried pulp used in Example 1) , was 4%. The increase in the acetone charge from 4 to 16% on oven-dried pulp resulted in a 24% increase in Kappa number reduction during the AE bleaching. The degree of delignification depends on the quantity of dioxirane generated in the pulp slurry by the reaction of acetone with monoperoxysulphate. Example 15 An eleventh sample of the unbleached hemlock pulp of Example 1 was delignified via the in-situ-dioxirane treatment followed by caustic extraction. Conditions in both stages were the same as those described in Example 7. An aliquot of the AE-Bleached hemlock pulp was further bleached with hydrogen peroxide using 1.88% available oxygen charge (calculated as one available oxygen per hydrogen peroxide molecule) on oven-dried pulp. Sodium hydroxide, 2.5%, sodium silicate, 3%, and magnesium sulphate, 0.5%, on oven-dried pulp were added in the hydrogen peroxide treatment (P) which was carried out at 60°C and 14% pulp consistency for one hour and forty minutes. Example 16 An aliquot of the hemlock pulp from Example 11 was bleached by hydrogen peroxide using 1.88% available oxygen charge on oven-dried pulp under the same conditions used in Example 15. Both in-situ-dioxirane-t eated hemlock pulps with or without oxygen delignification can be bleached to a brightness of more than 70% Elrepho without the use of chlorine-containing compounds, as shown in Table 8. Table 8. Kappa number, viscosity and optical property of hemlock pulps bleached via in-situ-dioxirane treatment, oxygen delignification, and caustic extraction without the use of chlorine-containing compounds. Example 17 A twelfth sample of the unbleached hemlock pulp of Example 1 was delignified via the in-situ-dioxirane treatment using 3.0% active oxygen and 16.3% acetone charges respectively at 25 C, 13.6% pulp consistency for 45 minutes. Example 18 A thirteenth sample of the unbleached hemlock pulp of Example 1 was delignified under the same conditions as those employed in Example 17 except the bleaching temperature was 30°C. Example 19 A fourteenth sample of the unbleached hemlock pulp of Example 1 was delignified under the same conditions as those employed in Example 17 except the bleaching temperature was 40°C. Example 20 A fifteenth sample of the unbleached hemlock pulp of Example 1 was delignified under the same conditions as those employed in Example 17 except the bleaching temperature was 50°C. Example 21 A sixteenth sample of the unbleached hemlock pulp of Example 1 was delignified under the same conditions as those employed in Example 17 except the bleaching temperature was 60°C. The results, shown in Table 9, demonstrate that the same degree of Kappa number reduction was achieved by the present invention under the described conditions at a temperature range from 25 to 60 C. The pulps bleached by the present invention showed the same zero-span tensile and viscosity in the temperature range investigated. Table 9. Kappa number, viscosity and zero-span tensile of hemlock pulps bleached by the in-situ-dioxirane treatment at varying temperatures. Example 22 A seventeenth sample of the unbleached hemlock pulp of Example 1 was delignified via the in-situ-dioxirane treatment using 3.0% active oxygen and 16.3% acetone charges respectively at 25 C, 13.6% pulp consistency for 15 minutes. Example 23 An eighteenth sample of the unbleached hemlock pulp of Example 1 was delignified under the same conditions as those used in Example 22 except the residence time was 30 minutes. Example 24 A nineteenth sample of the unbleached hemlock of pulp of Example 1 was delignified under the same conditions as those used in Example 22 except the residence time was 45 minutes. The residence time required for a complete consumption of active oxygen does not exceed 45 minutes at an 3.0% active oxygen and 16.3% acetone charges on oven-dried pulp, as shown in Table 10. Almost complete consumption was observed at as short as 15 minutes. The Kappa number reduction and the viscosity of pulps bleached via the invention under conditions investigated are the same for a residence time of 15, 30 and 45 minutes. Table 10. Kappa number and viscosity of hemlock pulps bleached by the invention and the active oxygen consumption for varying residence times. Example 25 A twentieth sample of the unbleached hemlock pulp of Example 1 was deliberately contaminated with metal ions of Cu +2 (82 ppm), Fe +3 (111 ppm) and Mn +2 (199 ppm) . The resulting pulp was bleached by the invention using 0.9% active oxygen and 4.9% acetone charges respectively at 25 C and 13.6% pulp consistency for 45 minutes. The in-situ- dioxirane-treated pulp was further extracted with 1% sodium hhyyddrrooxxiiddee cchhaarrggee oonn oovveenn--dd:ried pulp at 74 C and 12% pulp consistency for two hours. Example 26 An aliquot of the metal-ion contaminated pulp of Example 25 was treated with EDTA at 0.26% charge on oven- dried pulp at 60 C and 3.5% pulp consistency for 30 minutes and then dewatered to about 30% pulp consistency by filtration under slight vacuum. The EDTA-treated pulp was bleached by the invention and then extracted with sodium hydroxide, both under exactly the same conditions used in Example 25. Example 27 An aliquot of the metal-ion contaminated pulp of Example 25 was treated with EDTA, dewatered, bleached by the invention and then extracted with sodium hydroxide using exactly the same conditions employed in Example 26 except 2.6% EDTA charge on oven-dried pulp was used as the chelating treatment. The EDTA-treated pulps bleached by the invention show a greater Kappa number reduction than the untreated pulp and resulted in better pulp viscosity, as shown in Table 11. Table 11. Kappa number and viscosity of hemlock pulps bleached by the invention with or without EDTA treatment. Example 28 A twenty first sample of the unbleached hemlock pulp of Example 1 was delignified by the invention using 0.9% active oxygen and 4.9% acetone charges respectively on oven-dried pulp at 25 C and 20% pulp consistency for 30 minutes. Example 29 A twenty second sample of the unbleached hemlock pulp of Example 1 was bleached under exactly the same conditions used in Example 28 except the pulp consistency was 13.6%. Example 30 A twenty third sample of the unbleached hemlock pulp of Example 1 was bleached under exactly the same conditions used in Example 28 except the pulp consistency was 12%. Example 31 A twenty fourth sample of the unbleached hemlock pulp of Example 1 was bleached under exactly the same conditions used in Example 28 except the pulp consistency was 8%. Example 32 A twenty fifth sample of the unbleached hemlock pulp of Example 1 was bleached under the exactly same conditions used in Example 28 except the pulp consistency was 3%. The degree of Kappa number reduction is significantly affected by the pulp consistency. A medium pulp consistency, 10-15%, is desirable for bleaching using the invention. The results of Kappa number reduction agree with the consumption of active oxygen at varying pulp consistencies, as illustrated in Table 12. Table 12. Kappa number of hemlock pulps bleached by the invention at varying pulp consistencies and the active oxygen consumption at the end of 30 minutes residence time. Example 33 A twenty sixth sample of the unbleached hemlock pulp of example 1 was bleached via the invention using 0.9% active oxygen and 4.9% acetone charges respectively at 25 C and 13.6% pulp consistency for 45 minutes. Example 34 A twenty seventh sample of the unbleached hemlock pulp of example 1 was bleached under the conditions exactly the same as those employed in Example 33 except that 9.4% 1,1,1- trifluoroacetone was used in place of 4.9% acetone. Example 35 A twenty eighth sample of the unbleached hemlock pulp of Example 1 was bleached via the invention under the conditions exactly the same as those employed in Example 34 except that active oxygen and 1,1,1-trifluoroacetone used were 2.0% and 21% respectively on oven-dried pulp. Example 36 A twenty ninth sample of the unbleached hemlock pulp of Example 1 was bleached via the invention under the conditions exactly the same as those used in Example 33 except that 7.2% 3-pentanone was used in place of 4.9% acetone on oven-dried pulp. All three ketones, acetone, 3-pentanone, and 1,1,1- trifluoroacetone, used in the invention provide good selectivity in pulp delignification, in particular when 1,1,1-trifluoroacetone is used, as illustrated in Table 13. Table 13. Kappa number, viscosity, zero-span tensile of hemlock pulps bleached by the invention using different ketones. The active oxygen consumption was measured. Example 37 A thirtieth sample of the unbleached hemlock pulp was delignified by the invention using 0.9% active oxygen, 4.9% acetone and 20% sodium bicarbonate charges respectively on oven-dried pulp at 25 C and 13.6% pulp consistency for 45 minutes. Example 38 A thirty first sample of the unbleached hemlock pulp was delignified by the invention under exactly the same conditions used in Example 37 except that 7% sodium carbonate was used in place of 20% sodium bicarbonate. Example 39 A thirty second sample of the unbleached hemlock pulp was delignified by the invention under exactly the same conditions used in Example 37 except that 5% sodium carbonate and 1.5% sodium hydroxide were used in place of 20% sodium bicarbonate. Example 40 A thirty third sample of the unbleached hemlock pulp was delignified by the invention using exactly the same conditions used in Example 37 except that 1% sodium carbonate and 4.5% sodium hydroxide were used in place of 20% sodium bicarbonate. Example 41 A thirty fourth sample of the unbleached hemlock pulp was delignified by the invention using exactly the same conditions used in Example 37 except that 5.3% sodium hydroxide was used in place of 20% sodium bicarbonate. The pH of in-situ-dioxirane bleaching can be controlled by either a single or a combination of buffers and base, namely, sodium bicarbonate, sodium carbonate and sodium hydroxide to achieve the same degree of Kappa number reduction at a given active oxygen charge (0.9% on oven- dried pulp), as shown in Table 14. Table 14. Kappa number of hemlock pulps delignified by the invention using one or a combination of the following buffers and base, namely, NaHC0 3 , Na2C03 and NaOH. The active oxygen consumption and the end pH were monitored. Pulp Ex. 37 Ex. 38 Ex. 39 Ex. 40 Ex. 41 Identity Buffer/ Na 2 C0 3 / Na C0 3 / Base NaHC0 3 Na C0 3 NaOH NaOH NaOH Example 42 A Canadian mixed softwood kraft pulp, sample 1, produced by a kraft process and oxygen-delignified to a Kappa number of 12.6 was bleached by the invention using 0.9% active oxygen and 4.9% acetone charges respectively at 25 C and 13.6% pulp consistency for 45 minutes. The in- situ-dioxirane-treated pulp was further delignified by oxygen-/peroxide-reinforced caustic extraction (E ) using 0.68% NaOH, 0.5% MgS0 4 and 0.4% DTPA charges respectively on oven-dried pulp at 60 C and 12% pulp consistency for 40 minutes. During E stage the oxygen pressure was kept at 20 psig for the first 10 minutes and then released to atmospheric pressure. Example 43 A second sample of the same mixed softwood pulp as Example 42 was delignified by a conventional chlorination stage using 4% available chlorine on oven-dried pulp at 20 C and 3% pulp consistency for one hour. The resulting pulp was subsequently extracted, E , under the same conditions employed in Example 42. The 0 2 AE -bleached pulp achieved a brightness of 68.2% Elrepho while the 0 2 CE -bleached pulp obtained a brightness of 65.7% Elrepho. Both pulps produced from Example 42 and 43 were refined by a PFI mill. A PFI mill is a laboratory scale device for beating (refining) pulps. The results shown in Figures 1,2 and 3 demonstrate identical beating responses in tensile, tear and zero-span strengths. Example 44 A third sample of the same mixed softwood kraft pulp of Example 42 was bleached by the invention under the conditions exactly the same as those employed in Example 42 except a 1.5% active oxygen was used in place of 0.9% at the in-situ-dioxirane treatment and a 0.51% NaOH charge in place of 0.68% at the Eop stag J e. This AEop-bleached p.ulp was treated with 1.2% EDTA on oven-dried pulp at 50 C, pH 7 and 3.5% pulp consistency for 30 minutes and then washed thoroughly with deionized water. The resulting pulp was further bleached with hydrogen peroxide using 2.5% H 2 0 2 , 0.5% MgS0 4 , 0.2% DTPA and 2.5% NaOH at 90°C and 10% pulp consistency for four hours. Example 45 An aliquot of the sample of Example 43 was treated with EDTA under exactly the same conditions employed in Example 43. This CE -delignified pulp was further bleached by a conventional D.ED 2 sequence using 0.5 and 0.3% CIO- and 0.5% NaOH charges on oven-dried pulp for D, and D 2 and E stages respectively. Each of the chlorine dioxide stages was carried out at 74 C and 6% pulp consistency for three hours; the extraction stage was carried out at 74 C and 12% pulp consistency for two hours. The O-AE QP-bleached pulp achieved a brightness of 89.7% Elrepho while the O^CE D,ED 2 -bleached pulp accomplished a brightness of 92.6% Elrepho. The former exhibits significantly improved tensile breaking length with lower tear index than the latter at given revolutions, as shown in Figure 4 and 5 respectively. Both pulps demonstrated comparable zero-span tensile strength up to 6,000 revolutions of PFI beating, as shown in Figure 6. Example 46 A sample of aspen kraft pulp of 16.4 Kappa number was treated with in-situ-generated dioxirane at 2.7% active oxygen and 32% acetone charges on oven-dried pulp at 25°C and 13.6% pulp consistency for 30 minutes. An aliquot of the in-situ-dioxirane-treated aspen pulp was extracted at 0.45% sodium hydroxide charge on oven-dried pulp at 74°C and 12% pulp consistency for three hours and then further bleached with hydrogen peroxide using 0.94% available oxygen, 2.5% sodium hydroxide, 3% sodium silicate, 0.5% magnesium sulphate charges on oven-dried pulp respectively at 60°C and 14% pulp consistency for one hour and forty minutes. Example 47 A second sample of the same aspen kraft pulp was oxygen-delignified using 1% sodium hydroxide and 0.5% magnesium sulphate on oven-dried pulp, and 100 psig oxygen pressure at 100 β C and 12% pulp consistency for 40 minutes. This oxygen-delignified aspen kraft pulp was then treated with in-situ-generated dioxirane at 0.9% active oxygen and 8% acetone charges on oven-dried pulp at 25°C for 30 minutes. An aliquot of the oxygen-delignified and in-situ- dioxirane-treated aspen pulp was extracted and further bleached with hydrogen peroxide using 0.94% available oxygen charge on oven-dried pulp under exactly the same conditions employed in Example 46. The results, shown in Table 15, demonstrate that in- situ-dioxirane treatment is effective in delignifying aspen kraft pulp while retaining good viscosity and strength properties. Table 15. Strength and optical properties of aspen kraft pulps bleached via in-situ-dioxirane treatment, oxygen delignification, and conventional bleaching process. The process of the present invention is applicable to pulps produced by kraft, sulphite, soda-AQ, organosol or others processed from softwood or hardwood species. The lignocellulosic materials may be processed to have residual lignin contents equivalent to 15 to 35 and 8 to 25 Kappa numbers for softwood and hardwood respectively. The process of the present invention, is able to bleach a pulp to a brightness of about 90% ISO without the use of elemental chlorine and to a brightness of above 89% Elrepho without the use of any chlorine containing compounds, for example, the sequence combining all or several of the following bleaching stages, namely caustic extraction, treatment according to the present invention with a dioxirane generated in-situ, oxygen delignification, chelating treatment, hydrogen peroxide treatment, ozone treatment, or other bleaching stages using chlorine-free compounds. The pulps produced are bleached pulps of a desirable brightness level with strength properties comparable to those of pulps produced by a conventional CEDED process and superior to those pulps produced via extensive oxygen delignification. Acetone is exemplified but the dioxiranes can be generated by contacting a range of ketones with oxygen donors. The oxygen donors can be inorganic or organic compounds which give off one or more oxygen atoms during the reaction. They are, for example, monoperoxysulphate, peroxymonocarbonate, and peracetic, perbenzoic, perboric, and perphosphoric acid and their derivatives. The in-situ- dioxirane treatment can be applied in any sequences with oxygen delignification, caustic extraction, hydrogen peroxide bleaching, ozone treatment, chlorine dioxide treatment, chelating treatment and other conventional bleaching sequences.

Claims: WE CLAIM: 1. A chemical pulp that contains reactants able to generate a dioxirane within the pulp. 2. A pulp as claimed in claim 1 in which the reactants comprise a carbonyl compound and an oxygen donor in proportions suitable to produce a dioxirane having a molecular diameter of less than 140 angstrom units. 3. A pulp as claimed in claim 2 in which the dioxirane has a molecular diameter of less than about 50 angstrom units. 4. A pulp as claimed in claim 2 in which the carbonyl compound is a ketone. 5. A pulp as claimed in claim 4 in which the ketone is acetone. 6. A pulp as claimed in claim 4 in which the ketone is 3- pentanone. 7. A pulp as claimed in claim 2 in which the dioxirane is dimethyldioxirane. 8. A pulp as claimed in claim 2 in which the oxygen donor is a monoperoxysulphate. 9. A pulp as claimed in claim 2 in which the oxygen donor is selected from peroxymonocarbonate, peracetic acid, perboric acid, perphosphoric acid, perbenzoic acid, and their derivatives. 10. A pulp as claimed in claim 2 when further bleached with non-chlorine containing compounds. 11. A pulp as claimed in claim 2 containing less than 120 parts per million (ppm) chlorine element content. 12. A pulp as claimed in claim 10 having a brightness of at least about 70% Elrepho. 13. A pulp as claimed in claim 10 having a brightness of about 89% Elrepho. 14. A pulp as claimed in claim 13 having pulp strengths comparable to those of pulp produced by a conventional bleaching process. 15. A pulp as claimed in claim 10 having a Kappa number of about 4. 16. A process of bleaching a chemical pulp that comprises mixing the pulp with reactants able to generate a dioxirane within the pulp. 17. A process as claimed in claim 16 in which the reactants comprise a carbonyl compound and an oxygen donor in proportions suitable to produce a dioxirane having a molecular diameter of less than 140 angstrom units. 18. A process as claimed in claim 17 in which the dioxirane has a molecular diameter of less than about 50 angstrom units. 19. A process as claimed in claim 17 in which the carbonyl compound is a ketone. 20. A process as claimed in claim 19 in which the ketone is acetone. 21. A process as claimed in claim 17 in which the carbonyl compound is impregnated into a pulp slurry followed by the application of the oxygen donor. 22. A process as claimed in claim 17 in which the carbonyl compound and the oxygen donor are applied to the pulp simultaneously. 23. A process as claimed in claim 20 in which the acetone is added in the amount of at least about 4% by weight based on oven-dried pulp. 24. A process as claimed in claim 17 in which the oxygen donor is monoperoxysulphate. 25. A process as claimed in claim 17 in which the oxygen donor is selected from peroxymonocarbonate, peracetic acid, perboric acid, perphosphoric acid, perbenzoic acid and their derivatives. 26. A process as claimed in claim 17 in which the oxygen donor is added in a series of stages. 27. A process as claimed in claim 17 including the additional step of carrying out a caustic extraction on the pulp using sodium hydroxide in an amount from 0.5 to 5% by weight based on oven-dried pulp. 28. A process as claimed in claim 27 in which the dioxirane treatment and caustic extraction are applied sequentially in a multi-stage sequence. 29. A process as claimed in claim 28 in which the bleaching sequence is A.E.A^ j , where A indicates a bleaching treatment using in-situ-generated dimethyldioxirane. 30. A process as claimed in claim 17 in which the dioxirane is generated in sufficient amount to provide an active oxygen charge within the pulp varying from 0.2 to 4.0% by weight based on oven-dried pulp. 31. A process as claimed in claim 17 in which the pulp is at a temperature within the range from 20°C to 80°C. 32. A process as claimed in claim 17 carried out for a time within the range of 5 to 90 minutes. 33. A process as claimed in claim 17 in which the pH of the pulp is within the range from 6 to 14. 34. A process as claimed in claim 33 in which the pH adjustment of the pulp is carried out by the addition of sodium bicarbonate. 35. A process as claimed in claim 33 in which pH adjustment of the pulp is carried out by the addition of sodium carbonate, sodium hydroxide, sodium acetate or a buffer. 36. A process as claimed in claim 17 in which the pulp is at a consistency in the range from 3 to 35%. 37. A process as claimed in claim 36 in which the pulp is at a consistency of about 12%. 38. A process as claimed in claim 17 carried out in combination with oxygen delignification, either before or after the oxygen delignification. 39. A process as claimed in claim 17 including an additional bleaching steps carried out in sequence with the dioxirane treatment. 40. A process as claimed in claim 39 in which the bleaching agent for the additional bleaching step selected from chlorine dioxide, hydrogen peroxide, ozone and oxygen. 41. A process as claimed in claim 17 in which the pulp is treated with a chelating agent. 42. A process as claimed in claim 41 wherein the pulp is treated with a chelating agent before the bleaching process. 43. A process as claimed in claim 41 wherein the chelating agent is selected from EDTA and DTPA. 44. A process as claimed in claim 41 wherein the charge of chelating agent is in the range of about 0.1 to 3.0% based on the weight of oven-dried pulp.

Inventors: HUNT KENNETH, LEE CHUNG-LI, MURRAY ROBERT W, HUNT, KENNETH, LEE, CHUNG-LI, MURRAY, ROBERT W.
Applicants: PULP PAPER RES INST, UNIV MISSOURI, PULP AND PAPER RESEARCH INSTITUTE OF CANADA, THE CURATORS OF THE UNIVERSITY OF MISSOURI
Application year: 1992
Main classification: D21C9
IPC codes: D21C9