US20030024664A1 - Eop & Ep process for bleaching of chemical pulp - Google Patents
Eop & Ep process for bleaching of chemical pulp Download PDFInfo
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- US20030024664A1 US20030024664A1 US10/086,191 US8619102A US2003024664A1 US 20030024664 A1 US20030024664 A1 US 20030024664A1 US 8619102 A US8619102 A US 8619102A US 2003024664 A1 US2003024664 A1 US 2003024664A1
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- chemical pulp
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/147—Bleaching ; Apparatus therefor with oxygen or its allotropic modifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- Pulping is the changing of wood chips or other wood particulate matter to fibrous form. Chemical pulping includes partial removal of lignin and other materials associated with the wood.
- Bleaching is the treatment of the partially delignified cellulosic fibers with chemicals to remove or alter the coloring matter associated therewith. Bleaching brightens the fibers in order to reflect white light more truly.
- caustic soda NaOH
- CaOH chemical oxygen demand
- E op bleaching typically utilizes hydrogen peroxide, oxygen, caustic soda and magnesium sulfate as the bleaching chemicals.
- E p bleaching typically utilizes hydrogen peroxide and caustic soda as the bleaching chemicals.
- Conventional E op and E p bleaching suffer from the drawback of increased COD which is described above.
- This invention is directed to an E op and an E p process for bleaching chemical pulp which overcome drawbacks associated with conventional bleaching.
- the subject process comprises providing a bleached chemical pulp produced by bleaching sequences in which E op and/or the E p aqueous bleaching solutions employed therein include magnesium hydroxide in place of a substantial portion of the NaOH, and as a total replacement for any magnesium sulfate.
- the E op aqueous bleaching solution can comprise a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate.
- the E op aqueous chemical solution for bleaching chemical pulp can comprise an E op aqueous bleaching solution consisting essentially of a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide.
- chemical pulp is bleached with an E op aqueous bleaching solution to form an E op bleached chemical pulp.
- the E op aqueous bleaching solution of this invention can be employed in a D-E op -D-E p -D bleaching sequence.
- the subject invention is also directed to a bleaching sequence which includes the E p bleaching of chemical pulp.
- the E p aqueous bleaching solution can comprise a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate.
- an E p aqueous bleaching solution can be provided consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide.
- the E p aqueous bleaching solution of the subject invention can be provided for bleaching E op bleached pulp to form an E p bleached chemical pulp.
- the E p aqueous bleaching solution of this invention can also be employed in a D-E op -D-E p -D bleaching sequence.
- the amount of sodium hydroxide in the E op and/or aqueous bleaching solution is preferably not more than about 8% by weight, more preferably not more than about 5% by weight, and most preferably not more than about 3% by weight, based on the O.D. weight of said chemical pulp.
- the ratio of sodium hydroxide to magnesium hydroxide in said E op aqueous bleaching solution is not more than about 5:1 (based on an OH ⁇ molar ratio), preferably not more than about 3:1 (based on an OH ⁇ molar ratio), and most preferably not more than about 1:2 (based on an OH ⁇ molar ratio).
- the ratio of sodium hydroxide to magnesium hydroxide in said E p aqueous bleaching solution it is not more than about 1:1 (based on an OH ⁇ molar ratio), preferably not more than about 1:3 (based on an OH ⁇ molar ratio). Most preferably about 100% magnesium hydroxide is employed without substantially any sodium hydroxide.
- both the E op and E p bleaching processes of this invention preferably contemplates that the pulp viscosity of a final bleached chemical pulp is at least substantially the same as the pulp viscosity of a final bleached chemical pulp which is bleached with the same total amount of an E op aqueous bleaching solution comprising a peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the one hand, and/or an E p aqueous bleaching solution comprising a peroxide compound and sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the other hand.
- Pulp viscosity is measured in centipoises using the 0.5% CED viscosity test method described in TAPPI T-230.
- the preferred E op process generates a bleach effluent which has a COD which is less than the COD of a bleach effluent from an E op process which employs an E op aqueous bleaching solution comprising the peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
- the COD of the bleach effluent produced using the E op aqueous bleaching solution of the present invention is preferably at least about 5%, more preferably at least about 8%, and most preferably at least about 10%, less than the COD generated by an E op stage which uses an E op aqueous bleaching solution comprising said peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
- COD is measured in mg/L using a HACH test kit.
- the bleached chemical pulp of a bleach sequence containing the subject process preferably has a final ISO brightness (% ISO) of which is at least substantially the same as the final ISO brightness (% ISO) of bleached chemical pulp which is bleached with the same bleach sequence but with an E op aqueous bleaching solution comprising a peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the one hand, and/or an E p aqueous bleaching solution comprising a peroxide compound and sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the other hand.
- ISO brightness is measured using the test method described in TAPPI T-452.
- the process of this invention also produces a bleached chemical pulp having a preferred wet zero span tensile strength which is at least substantially the same as the wet zero span tensile strength of bleached chemical pulp which is bleached with the same total amount of an E op aqueous bleaching solution comprising a peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the one hand, and/or an E p aqueous bleaching solution comprising a peroxide compound and sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the other hand.
- Wet zero span tensile strength is measured in km using a Pulmac wet zero-span tensile apparatus.
- E op and E p bleaching are typically part of a broader overall chemical pulp bleaching sequence.
- these additional chemical pulp bleaching stages are conducted employing conventional bleaching technology utilizing bleaching chemicals such as ClO 2 , O 2 , Cl 2 and peroxide.
- FIG. 1 is a schematic diagram comparing pulp brightness for various levels of bleaching solution in an E op bleaching process.
- FIG. 2 is a schematic diagram comparing pulp viscosity for various levels of bleaching solution in an E op bleaching process.
- FIG. 3 is a schematic diagram comparing pulp wet zero-span tensile strength for various levels of bleaching solution in an E op bleaching process.
- FIG. 4 is a schematic diagram comparing pulp COD for various levels of bleaching solution in an E op bleaching process.
- an aqueous slurry containing magnesium hydroxide was employed as a partial substitution for caustic soda and a complete replacement for magnesium sulfate in the extraction-oxygen-peroxide stage (E op ) of the bleaching of northeast softwood kraft pulp. More specifically, laboratory experiments examined the bleachability of the pulp through a complete DE op DE p D bleach sequence with complete replacement of magnesium sulfate and partial substitution of NaOH on an OH ⁇ molar basis using CellGuardTMOP (see description of CellGuardTMOP below) in the E op stage. Three magnesium hydroxide substitution levels were evaluated in the E op stage: 0%, 25%, and 50% of the OH ⁇ derived from CellGuardTMOP and the balance from NaOH.
- an aqueous slurry containing magnesium hydroxide was also employed as a partial substitution for caustic soda and a complete replacement for magnesium sulfate in the extraction-peroxide stage (E p ) of the bleaching of northeast softwood kraft pulp. More specifically, laboratory experiments examined the bleachability of the pulp through a complete D E op D E p D bleach sequence with complete replacement of magnesium sulfate and partial substitution of NaOH on an OH ⁇ molar basis using CellGuardTMOP (see description of CellGuardTMOP below) in both the E op and E p stages. Four magnesium hydroxide substitution levels were evaluated in the E p stage: 0%, 25%, 50%, 75% and 100% of the OH ⁇ derived from CellGuardTMOP and the balance, if any, from NaOH.
- Bleaching experiments for the E op stage were performed in a 2-liter, medium consistency oxygen reactor equipped with a mixer.
- the oxygen reactor was treated with nitric acid to passivate the surface to avoid contamination from metals.
- the D 0 , D 1 , E p , and D 2 stages were performed by traditional bag bleaching methods.
- the brownstock kraft pulp to be bleached had a kappa number of 29.2, a brightness of 26.9% ISO, and viscosity of 48.0 cps. This kraft pulp was bleached under the conditions outlined in Tables I-III. Chemical dosages were based on the weight of oven-dried pulp.
- the experimental procedure for each stage is summarized as follows:
- Martin Marietta Magnesia Specialties, LLC is the manufacturer of CellGuardTMOP Magnesium Hydroxide Slurry for use in pulp bleaching.
- the CellGuardTMOP Magnesium Hydroxide Slurry which is produced from a dolomitic lime and magnesium brine process, contains 62% by weight Mg(OH) 2 solids suspended in water.
- the purity of the magnesium hydroxide is over 98% with low levels of transition metals.
- This product has a fine particle size (3 microns as measured by Micromeritics Sedigraph 5100) which promotes high reactivity and excellent suspension stability.
- FIG. 1 compares pulp brightness for the various levels of CellGuardTMOP substitution in the E op stage.
- the data shows the increasing trend in brightness with each subsequent bleaching stage for all substitution cases.
- the control sample which employed 100% OH ⁇ from NaOH (or 0% OH ⁇ from CellGuardTMOP) and MgSO 4 , yielded an increase in brightness from 62.1% ISO after the E op stage to a final pulp brightness of 90.8% ISO after the D 2 stage.
- FIG. 1 shows that the brightness after the E op stage was 59.7% ISO. Even with the use of a mild alkali in the extraction stage which lowers the bleaching pH to 10.1 for 25% substitution and 9.3 for 50% substitution, comparable final brightness was achieved as evidence by the final 89.9% ISO brightness result after the D 2 stage.
- the control sample's final viscosity was 16.5 cps
- the 25% and 50% substitution samples with CellGuardTMOP produced pulps with respective viscosities of 17.5 cps and 18.6 cps.
- CellGuardTMOP Magnesium Hydroxide in the E op stage, a one to two point increase in pulp viscosity over the conventional E op stage was achieved.
- Fiber strength was maintained in both CellGuardTMOP substitution cases as shown in FIG. 3.
- Wet zero-span tensile strength for all cases ranged from 10.9-11.0 km for the E op stage, 10.2-10.6 for the D 1 stage, and 10.3-10.4 km for the D 2 stage.
- High chemical oxygen demand (COD) is generated in the E op stage where the most of the extraction occurs (see FIG. 4). Partially substituting the NaOH charge with a weak alkali such as Mg(OH) 2 reduces the organic loading in the effluent from the E op stage. The higher substitution rate with CellGuardTMOP yielded a noticeable reduction in COD when compared to the control sample. The control sample generated 4635 mg/L COD versus 4105 mg/L COD for the 50% substitution case, which represents an 11% reduction. Lower COD loading can contribute to reduced effluent treatment costs downstream.
- COD chemical oxygen demand
- CellGuardTMOP Magnesium Hydroxide Slurry for caustic soda and eliminating magnesium sulfate in the E op stage, a strong alkali is present to facilitate lignin removal while a mild alkali is added to promote peroxide bleaching and cellulose protection.
- CellGuardTMOP can replace up to 50% of the caustic soda requirement in the E op stage producing final pulp from the D 2 stage with similar brightness, permanganate number, and wet zero-span tensile strength as pulp bleached with a 100% caustic soda charge.
- CellGuardTMOP At 50% substitution of caustic soda, the use of CellGuardTMOP improves the pulp viscosity by 12% and reduces the COD after the E op stage by 11%. Since only 0.73 kg of magnesium hydroxide provides the equivalent amount of hydroxyl ions as 1 kg of caustic soda, CellGuardTMOP reduces bleaching costs in many cases. At no added cost beyond the amount required for caustic soda replacement, CellGuardTMOP also eliminates the need for magnesium sulfate for further reduction in chemical costs.
- Pulp samples from the E op , D 1 , and D 2 stages were also tested for viscosity and K#.
- the final ISO brightness, viscosity and K# of the bleached chemical pulp of the process of the present invention is comparable or greater than the final ISO brightness, viscosity and K# of bleached chemical pulp which is bleached with the same total amount of an E p aqueous bleaching solution comprising said peroxide compound and sodium hydroxide, but in the absence of magnesium hydroxide.
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Abstract
The subject process comprises providing chemical pulp and an Eop and/or Ep aqueous bleaching solution. The Eop aqueous bleaching solution comprises a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate. Alternatively, the Eop aqueous chemical solution for bleaching chemical pulp comprises an Eop aqueous bleaching solution consisting essentially of a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide. In any case, the chemical pulp is bleached with the Eop aqueous bleaching solution to form a bleached chemical pulp. The Ep aqueous bleaching solution comprises a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate. Alternatively, the Ep aqueous bleaching solution consists essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide. In any case, the chemical pulp is bleached with the Eop and/or Ep aqueous bleaching solution to form a bleached chemical pulp as part of an overall chemical pulp bleaching sequence.
Description
- This application claims priority from Provisional Application Serial No. 60/271,987 filed on Feb. 27, 2001.
- Historically the treatment of wood chips to form a chemical pulp has been divided into two processes. The first process is pulping and the second process is bleaching.
- Pulping is the changing of wood chips or other wood particulate matter to fibrous form. Chemical pulping includes partial removal of lignin and other materials associated with the wood.
- Bleaching is the treatment of the partially delignified cellulosic fibers with chemicals to remove or alter the coloring matter associated therewith. Bleaching brightens the fibers in order to reflect white light more truly.
- Throughout the evolution of pulp bleaching, caustic soda (NaOH) has been used as the primary alkali source in bleaching of chemical pulp. Caustic soda is a highly soluble alkali that readily provides an optimum reaction pH and facilitates the dissolution of lignin from pulp in pulp bleaching. Since caustic soda is a strong base, carbohydrate degradation can occur resulting in a decrease in pulp viscosity and an increase in chemical oxygen demand (COD).
- In conventional pulp bleaching, a D-Eop-D-Ep-D bleaching sequence is often employed for brightening chemical pulp. Eop bleaching typically utilizes hydrogen peroxide, oxygen, caustic soda and magnesium sulfate as the bleaching chemicals. Ep bleaching typically utilizes hydrogen peroxide and caustic soda as the bleaching chemicals. Conventional Eop and Ep bleaching suffer from the drawback of increased COD which is described above.
- Accordingly, there is a need for a Eop and Ep bleaching sequences which overcome the above-described drawback.
- This invention is directed to an Eop and an Ep process for bleaching chemical pulp which overcome drawbacks associated with conventional bleaching.
- The subject process comprises providing a bleached chemical pulp produced by bleaching sequences in which Eop and/or the Ep aqueous bleaching solutions employed therein include magnesium hydroxide in place of a substantial portion of the NaOH, and as a total replacement for any magnesium sulfate. The Eop aqueous bleaching solution can comprise a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate. Alternatively, the Eop aqueous chemical solution for bleaching chemical pulp can comprise an Eop aqueous bleaching solution consisting essentially of a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide. In any case, chemical pulp is bleached with an Eop aqueous bleaching solution to form an Eop bleached chemical pulp. The Eop aqueous bleaching solution of this invention can be employed in a D-Eop-D-Ep-D bleaching sequence. The subject invention is also directed to a bleaching sequence which includes the Ep bleaching of chemical pulp. The Ep aqueous bleaching solution can comprise a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate. Stated another way, an Ep aqueous bleaching solution can be provided consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide. In certain bleaching sequences, for example, the Ep aqueous bleaching solution of the subject invention can be provided for bleaching Eop bleached pulp to form an Ep bleached chemical pulp. The Ep aqueous bleaching solution of this invention can also be employed in a D-Eop-D-Ep-D bleaching sequence.
- In the Eop and/or Ep processes of the present invention, the amount of sodium hydroxide in the Eop and/or aqueous bleaching solution is preferably not more than about 8% by weight, more preferably not more than about 5% by weight, and most preferably not more than about 3% by weight, based on the O.D. weight of said chemical pulp.
- Furthermore, the ratio of sodium hydroxide to magnesium hydroxide in said Eop aqueous bleaching solution is not more than about 5:1 (based on an OH− molar ratio), preferably not more than about 3:1 (based on an OH− molar ratio), and most preferably not more than about 1:2 (based on an OH− molar ratio). As for the ratio of sodium hydroxide to magnesium hydroxide in said Ep aqueous bleaching solution, it is not more than about 1:1 (based on an OH− molar ratio), preferably not more than about 1:3 (based on an OH− molar ratio). Most preferably about 100% magnesium hydroxide is employed without substantially any sodium hydroxide.
- Both the Eop and Ep bleaching processes of this invention preferably contemplates that the pulp viscosity of a final bleached chemical pulp is at least substantially the same as the pulp viscosity of a final bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising a peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the one hand, and/or an Ep aqueous bleaching solution comprising a peroxide compound and sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the other hand. Pulp viscosity is measured in centipoises using the 0.5% CED viscosity test method described in TAPPI T-230.
- Also, the preferred Eop process generates a bleach effluent which has a COD which is less than the COD of a bleach effluent from an Eop process which employs an Eop aqueous bleaching solution comprising the peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide. More specifically, the COD of the bleach effluent produced using the Eop aqueous bleaching solution of the present invention is preferably at least about 5%, more preferably at least about 8%, and most preferably at least about 10%, less than the COD generated by an Eop stage which uses an Eop aqueous bleaching solution comprising said peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide. COD is measured in mg/L using a HACH test kit.
- Moreover, the bleached chemical pulp of a bleach sequence containing the subject process preferably has a final ISO brightness (% ISO) of which is at least substantially the same as the final ISO brightness (% ISO) of bleached chemical pulp which is bleached with the same bleach sequence but with an Eop aqueous bleaching solution comprising a peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the one hand, and/or an Ep aqueous bleaching solution comprising a peroxide compound and sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the other hand. ISO brightness is measured using the test method described in TAPPI T-452.
- The process of this invention also produces a bleached chemical pulp having a preferred wet zero span tensile strength which is at least substantially the same as the wet zero span tensile strength of bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising a peroxide compound, oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the one hand, and/or an Ep aqueous bleaching solution comprising a peroxide compound and sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide, on the other hand. Wet zero span tensile strength is measured in km using a Pulmac wet zero-span tensile apparatus.
- Eop and Ep bleaching are typically part of a broader overall chemical pulp bleaching sequence. Thus, there can be one or more additional chemical pulp bleaching stages that occur prior to Eop and Ep bleaching, as well as one or more additional chemical pulp bleaching stages that occur subsequent to Eop and Ep bleaching. Usually, these additional chemical pulp bleaching stages are conducted employing conventional bleaching technology utilizing bleaching chemicals such as ClO2, O2, Cl2 and peroxide.
- The foregoing and other objects, features and advantages of the invention will become more apparent from the detailed description of a preferred embodiment of the invention below which proceeds with reference to the accompanying drawings.
- FIG. 1 is a schematic diagram comparing pulp brightness for various levels of bleaching solution in an Eop bleaching process.
- FIG. 2 is a schematic diagram comparing pulp viscosity for various levels of bleaching solution in an Eop bleaching process.
- FIG. 3 is a schematic diagram comparing pulp wet zero-span tensile strength for various levels of bleaching solution in an Eop bleaching process.
- FIG. 4 is a schematic diagram comparing pulp COD for various levels of bleaching solution in an Eop bleaching process.
- As set forth in Tables I-III, an aqueous slurry containing magnesium hydroxide was employed as a partial substitution for caustic soda and a complete replacement for magnesium sulfate in the extraction-oxygen-peroxide stage (Eop) of the bleaching of northeast softwood kraft pulp. More specifically, laboratory experiments examined the bleachability of the pulp through a complete DEopDEpD bleach sequence with complete replacement of magnesium sulfate and partial substitution of NaOH on an OH− molar basis using CellGuard™OP (see description of CellGuard™OP below) in the Eop stage. Three magnesium hydroxide substitution levels were evaluated in the Eop stage: 0%, 25%, and 50% of the OH− derived from CellGuard™OP and the balance from NaOH.
- In Table III, an aqueous slurry containing magnesium hydroxide was also employed as a partial substitution for caustic soda and a complete replacement for magnesium sulfate in the extraction-peroxide stage (Ep) of the bleaching of northeast softwood kraft pulp. More specifically, laboratory experiments examined the bleachability of the pulp through a complete D Eop D Ep D bleach sequence with complete replacement of magnesium sulfate and partial substitution of NaOH on an OH− molar basis using CellGuard™OP (see description of CellGuard™OP below) in both the Eop and Ep stages. Four magnesium hydroxide substitution levels were evaluated in the Ep stage: 0%, 25%, 50%, 75% and 100% of the OH− derived from CellGuard™OP and the balance, if any, from NaOH.
- Bleaching experiments for the Eop stage were performed in a 2-liter, medium consistency oxygen reactor equipped with a mixer. The oxygen reactor was treated with nitric acid to passivate the surface to avoid contamination from metals. The D0, D1, Ep, and D2 stages were performed by traditional bag bleaching methods. The brownstock kraft pulp to be bleached had a kappa number of 29.2, a brightness of 26.9% ISO, and viscosity of 48.0 cps. This kraft pulp was bleached under the conditions outlined in Tables I-III. Chemical dosages were based on the weight of oven-dried pulp. The experimental procedure for each stage is summarized as follows:
- D0 Stage.
- Standard conditions as set forth in Tables I-III were employed for the D0 stage. The kappa factor was adjusted with 2.44% ClO2 to reach the desired kappa number out of the D0 stage. The pulp was then washed to pH 7.5.
- Eop Stage.
- After the D0 stage, the pulp was extracted with a conventional Eop stage which employed 1.7% NaOH and 0.1% MgSO4. For comparison purposes in Tables I and II, bleaching experiments using CellGuard™OP as a replacement for MgSO4 and as a partial substitute for NaOH were conducted. Caustic soda replacement was based on an OH− molar basis. For example, at 25% substitution where 25% of the OH− comes from Mg(OH)2, the respective alkali dosages used were 1.275% NaOH and 0.31% CellGuard™OP. Caustic soda contains 42.51% by weight OH− ions while magnesium hydroxide contains 58.32% by weight OH− ions. For the Eop stage in Tables I-III, bleaching occurred at 138 kPa of O2 pressure for 20 minutes followed by bleaching at atmospheric pressure for the remaining 40 minutes.
- Martin Marietta Magnesia Specialties, LLC is the manufacturer of CellGuard™OP Magnesium Hydroxide Slurry for use in pulp bleaching. The CellGuard™OP Magnesium Hydroxide Slurry, which is produced from a dolomitic lime and magnesium brine process, contains 62% by weight Mg(OH)2 solids suspended in water. The purity of the magnesium hydroxide is over 98% with low levels of transition metals. This product has a fine particle size (3 microns as measured by Micromeritics Sedigraph 5100) which promotes high reactivity and excellent suspension stability.
TABLE I CONDITIONS FOR EACH BLEACHING STAGE Pulp Consistency Time Temp Pressure Chemical Stage % (min) (° C.) (kPa) % on O.D. pulp D 0 12 45 60 — 2.44% ClO2 Eop 12 60 70 138 kPa of O2 for 0.5% H2O2 20 min, then 1.7% NaOH or atm Mg(OH)2/NaOH 0.1% MgSO4 (for Control only) D 112 180 80 — 1.2% ClO2 Ep 12 40 70 — 0.15% H2O2 0.5 % NaOH D 2 12 100 80 — 0.6% ClO2 - D1-Ep-D2 Stages (Tables I and II)
- Standard conditions were employed for the D1-Ep-D2 stages shown in Tables I and II. The pulp and filtrate following each bleaching stage were tested for ISO brightness and end pH, respectively. The pH of the residual liquor was determined using a pH meter and appropriate buffer solutions to calibrate the pH meter. Pulp samples from the Eop, D1, and D2 stages were tested for viscosity and wet zero-span tensile strength. The respective filtrates were analyzed for chemical oxygen demand (COD).
- After the D0 stage and washing step, the kappa number decreased from 29.2 to 11.9. Pulp brightness increased from 26.9% ISO to 35.9% ISO. The effects of CellGuard™OP substitution in the Eop stage on each of the pulp parameters were measured. Table II contains a summary of results for each bleaching test performed.
- FIG. 1 compares pulp brightness for the various levels of CellGuard™OP substitution in the Eop stage. The data shows the increasing trend in brightness with each subsequent bleaching stage for all substitution cases. The control sample, which employed 100% OH− from NaOH (or 0% OH− from CellGuard™OP) and MgSO4, yielded an increase in brightness from 62.1% ISO after the Eop stage to a final pulp brightness of 90.8% ISO after the D2 stage.
- At 25% substitution with CellGuard™OP in the Eop stage, brightness after this bleaching step (60.1% ISO) was lower than the control. However, equivalent final pulp brightness after the D2 stage resulted in 90.5% ISO at the same ClO2 and H2O2 charge in the D1 and Ep stages respectively as the control sample.
- At 50% substitution with CellGuard™OP, FIG. 1 shows that the brightness after the Eop stage was 59.7% ISO. Even with the use of a mild alkali in the extraction stage which lowers the bleaching pH to 10.1 for 25% substitution and 9.3 for 50% substitution, comparable final brightness was achieved as evidence by the final 89.9% ISO brightness result after the D2 stage.
- At the end of the Eop stage, the control sample yielded a pulp viscosity of 27.8 cps. As shown in FIG. 2, both the 25% and 50% substitution runs with CellGuard™OP produced higher viscosity results of 28.6 cps and 29.3 cps respectively after the Eop stage. These results indicate that CellGuard™OP serves a dual role as a peroxide activator and cellulose protector. In a conventional Eop system where NaOH and MgSO4 are utilized, CellGuard™OP Mg(OH)2 can reduce the NaOH consumption and eliminate MgSO4. As seen in FIG. 2, the control sample's final viscosity was 16.5 cps, the 25% and 50% substitution samples with CellGuard™OP produced pulps with respective viscosities of 17.5 cps and 18.6 cps. By utilizing CellGuard™OP Magnesium Hydroxide in the Eop stage, a one to two point increase in pulp viscosity over the conventional Eop stage was achieved.
- Fiber strength was maintained in both CellGuard™OP substitution cases as shown in FIG. 3. Wet zero-span tensile strength for all cases ranged from 10.9-11.0 km for the Eop stage, 10.2-10.6 for the D1 stage, and 10.3-10.4 km for the D2 stage.
- High chemical oxygen demand (COD) is generated in the Eop stage where the most of the extraction occurs (see FIG. 4). Partially substituting the NaOH charge with a weak alkali such as Mg(OH)2 reduces the organic loading in the effluent from the Eop stage. The higher substitution rate with CellGuard™OP yielded a noticeable reduction in COD when compared to the control sample. The control sample generated 4635 mg/L COD versus 4105 mg/L COD for the 50% substitution case, which represents an 11% reduction. Lower COD loading can contribute to reduced effluent treatment costs downstream.
- By employing partial substitution of CellGuard™OP Magnesium Hydroxide Slurry for caustic soda and eliminating magnesium sulfate in the Eop stage, a strong alkali is present to facilitate lignin removal while a mild alkali is added to promote peroxide bleaching and cellulose protection. CellGuard™OP can replace up to 50% of the caustic soda requirement in the Eop stage producing final pulp from the D2 stage with similar brightness, permanganate number, and wet zero-span tensile strength as pulp bleached with a 100% caustic soda charge.
- At 50% substitution of caustic soda, the use of CellGuard™OP improves the pulp viscosity by 12% and reduces the COD after the Eop stage by 11%. Since only 0.73 kg of magnesium hydroxide provides the equivalent amount of hydroxyl ions as 1 kg of caustic soda, CellGuard™OP reduces bleaching costs in many cases. At no added cost beyond the amount required for caustic soda replacement, CellGuard™OP also eliminates the need for magnesium sulfate for further reduction in chemical costs.
TABLE II RESULTS OF PARTIAL SUBSTITUTION OF CAUSTIC SODA WITH MAGNESIUM HYDROXIDE SLURRY IN THE EOP STAGE OF A DEopDEpD BLEACH SEQUENCE ISO Chemical Time Temp Pressure End Brightness K WetZero-Span COD Stage (% on pulp)1 (min) (° C.) (kPa) PH (%) Viscosity(cp) No. (km) (mg/l) Brown- 26.9 48.0 29.2 as 12.5 stock kappa) D0 Stage D0 0.22 kf 45 60 2.32 35.9 7.4 (2.44% ClO2) (11.9 as kappa) Control Eop 0.5% H2O2 60 70 138 kPa 11.3 62.1 27.8 3.1 10.9 4635 NaOH + 1.7% NaOH O2 for MgSO4 0.1% MgSO4 20 min, 0% Mg(OH)2 then atm D1 1.2% ClO2 180 80 2.3 80.2 21.4 1.1 10.2 1352 Ep 0.15% H2O2 40 70 11.4 86.0 0.5% NaOH D2 0.6% ClO2 100 80 3.3 90.8 16.5 0.6 10.3 176 25% Eop 0.5% H2O2 60 70 138 kPa 10.1 60.1 28.6 3.4 10.8 4555 Substitution 1.275% NaOH O2 for CellGuard ™ 0.31% 20 min, in Eop Mg(OH)2 then atm D1 1.2% ClO2 180 80 2.3 78.9 22.1 1.3 10.3 1326 Ep 0.15% H2O2 40 70 11.4 85.3 0.5% NaOH D2 0.6% ClO2 100 80 3.3 90.5 17.5 0.6 10.2 50% Eop 0.5% H2O2 60 70 138 kPa 9.3 59.7 29.3 3.5 11.0 4105 Substitution 0.85% NaOH O2 for CellGuard ™ 0.62% 20 min, in Eop Mg(OH)2 then atm D1 1.2% ClO2 180 80 2.3 76.3 22.0 1.4 10.6 1420 Ep 0.15% H2O2 40 70 11.3 83.9 0.5% NaOH D2 0.6% ClO2 100 80 3.2 89.9 18.6 0.7 10.4 184 - Eop-D1-Ep-D2 Stages (Table III)
- Standard conditions were employed for the D1 and D2 stages of bleaching processes shown in Table III. In the experiments involving substitution of magnesium hydroxide for NaOH in the Ep stage, magnesium hydroxide was substituted for all of the magnesium sulfate and a portion of the NaOH (25%, 50%, 75% or 100%). The Eop stage employed a 50% substitution of magnesium hydroxide for NaOH, and 100% substitution for all of the magnesium sulfate, in all the bleaching experiments. The pulp and filtrate following each bleaching stage were tested for ISO brightness and end pH, respectively. The pH of the residual liquor was determined using a pH meter and appropriate buffer solutions to calibrate the pH meter. Pulp samples from the Eop, D1, and D2 stages were also tested for viscosity and K#. As seen in Table III, the final ISO brightness, viscosity and K# of the bleached chemical pulp of the process of the present invention is comparable or greater than the the final ISO brightness, viscosity and K# of bleached chemical pulp which is bleached with the same total amount of an Ep aqueous bleaching solution comprising said peroxide compound and sodium hydroxide, but in the absence of magnesium hydroxide.
TABLE III RESULTS OF SUBSTITUTION OF CAUSTIC SODA AND MAGNESIUM SULFATE WITH MAGNESIUM HYDROXIDE SLURRY In Eop and Ep Stages of a DEop DEpD Bleach Sequence ISO Chemical Time Pressure K# Brightness Viscosity Stage % (min) TEMP (psig) Kappa 25 ml % cp BS Brownstock 30.4 26.1 51.9 D D 0.22 kf 13.7 8.6 34.3 48.2 After washing (2.54% CIO2) To 7.5 pH CONTROL Eop 0.5% H2O2 60 70 138 Kpa 3.5 61.6 41.9 NaOH + 100% OH- 1.7% NaOH O2 for MgSO4 from NaOH 0.1 % MgSO 420 min. Sequence 0% Mg(OH)2 then atm Eop & Ep stages D1 1.2% CIO2 180 80 1.3 79.6 29.8 NaOH only Ep 0.15% H2O2 40 70 86.4 100% OH- 0.48% NaOH from NaOH 0% Mg(OH)2 D2 0.6 % CIO 2100 80 0.6 90.7 22.0 Mg(OH)2 Eop 0.5% H2O2 60 70 138 Kpa 4.0 54.9 42.6 Substitution 50% OH- 0.85% NaOH O2 for Sequence from Mg(OH)2 0.62 % Mg 20 min. Eop (OH)2 then atm 50% D1 1.2% CIO2 180 80 1.6 74.9 32.9 Substitution Ep 0.15% H2O2 40 70 84.0 Ep Control 0.48% NaOH Varying 0% Mg(OH)2 Substitution D2 0.6 % CIO 2100 80 0.7 90.3 24.6 Ep 0.15% H2O2 40 70 83.6 25% OH- 0.36% NaOH from Mg(OH)2 0.09% Mg (OH)2 D2 — 100 80 0.7 90.2 24.6 Ep 0.6 % CIO 240 70 83.1 50% OH- 0.15% H2O2 from Mg(OH)2 0.24% NaOH 0.18% Mg D2 (OH)2 100 80 0.8 89.9 25.2 Ep 0.6 % CIO 240 70 81.5 75% OH- 0.15% H2O2 from Mg(OH)2 0.12% NaOH D2 0.26 % Mg 100 80 89.5 25.3 (OH)2 Ep 0.6 % CIO 240 70 78.8 100% OH- 0.15% H2O2 100 80 0.8 88.6 24.0 from Mg(OH)2 0% NaOH D2 0.35% Mg (OH)2 0.6% CIO2
Claims (35)
1. An Eop process for bleaching chemical pulp, which comprises:
providing said chemical pulp;
providing an Eop aqueous bleaching solution comprising a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate; and
bleaching said chemical pulp with said Eop aqueous bleaching solution to form Eop bleached chemical pulp.
2. The process of claim 1 , wherein the amount of sodium hydroxide in said Eop aqueous bleaching solution is at not more than about 8% by weight, based on the O.D. weight of said Eop chemical pulp.
3. The process of claim 1 , wherein the ratio of sodium hydroxide to magnesium hydroxide in said Eop aqueous bleaching solution is not more than about 5:1 (based on an OH− molar ratio).
4. The process of claim 1 , wherein the pulp viscosity of a final bleached chemical pulp is at least substantially the same as the final pulp viscosity of bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
5. The process of claim 1 , wherein the final pulp brightness of said Eop bleached chemical pulp produced from the Eop bleached chemical pulp is at least substantially the same as the final pulp brightness of bleached chemical pulp which is bleached with same bleach sequence containing the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
6. The process of claim 1 , wherein the COD of bleach effluent from an Eop stage using said Eop aqueous bleaching solution is less than the COD of bleach effluent from an Eop stage which uses the same total amount of an Eop aqueous bleaching solution comprising said peroxide, an oxygen-containing material compound, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
7. The process of claim 1 , which further includes the step of providing an Ep aqueous bleaching solution comprising a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate; and bleaching said Eop bleached chemical pulp with said Ep aqueous bleaching solution to form Ep bleached chemical pulp.
8. The process of claim 1 , which further includes the step of providing an Ep aqueous bleaching solution consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide; and bleaching said Eop bleached chemical pulp with said Ep aqueous bleaching solution to form Ep bleached chemical pulp.
9. The process of claim 1 , wherein the wet zero span tensile strength of said Eop bleached chemical pulp is at least substantially the same as the wet zero span tensile strength of bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
10. The process of claim 1 , wherein the COD in the bleach effluent of said bleached Eop chemical pulp is at least about 5% less than the COD in beach effluent of said bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
11. An Eop process for bleaching chemical pulp, which comprises:
providing said chemical pulp;
providing an Eop aqueous bleaching solution consisting essentially of a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide; and
bleaching said chemical pulp with said Eop aqueous bleaching solution to form said bleached chemical pulp.
12. The process of claim 11 , wherein the amount of sodium hydroxide in said Eop aqueous bleaching solution is at not more than about 8% by weight, based on the O.D. weight of said Eop chemical pulp.
13. The process of claim 11 , wherein the ratio of sodium hydroxide to magnesium hydroxide in said Eop aqueous bleaching solution is not more than about 5:1 (based on an OH− molar ratio).
14. The process of claim 11 , wherein the pulp viscosity of a final bleached chemical pulp produced from the Eop bleached chemical pulp is at least substantially the same as the final pulp viscosity of bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
15. The process of claim 11 , wherein the final pulp brightness of said Eop bleached chemical pulp is at least substantially the same as the final pulp brightness of bleached chemical pulp which is bleached with same bleach sequence containing the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
16. The process of claim 11 , wherein the COD of bleach effluent from an Eop stage using said Eop aqueous bleaching solution is less than the COD of bleach effluent from an Eop stage which uses the same total amount of an Eop aqueous bleaching solution comprising said peroxide, an oxygen-containing material compound, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
17. The process of claim 11 , which further includes the step of providing an Ep aqueous bleaching solution comprising a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate; and bleaching said Eop bleached chemical pulp with said Ep aqueous bleaching solution to form Ep bleached chemical pulp.
18. The process of claim 11 , which further includes the step of providing an Ep aqueous bleaching solution consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide; and bleaching said Eop bleached chemical pulp with said Ep aqueous bleaching solution to form Ep bleached chemical pulp.
19. The process of claim 11 , wherein the wet zero span tensile strength of said Eop bleached chemical pulp is at least substantially the same as the wet zero span tensile strength of bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
20. The process of claim 11 , wherein the COD in the bleach effluent of said bleached Eop chemical pulp is at least about 5% less than the COD in beach effluent of said bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, g v; an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
21. An Eop aqueous chemical solution for bleaching chemical pulp, which comprises an Eop aqueous bleaching solution consisting essentially of a peroxide compound, an oxygen-containing material, sodium hydroxide and magnesium hydroxide.
22. The Eop aqueous bleaching solution of claim 21 , wherein the amount of sodium hydroxide in said Eop aqueous bleaching solution is at not more than about 8% by weight, based on the O.D. weight of said chemical pulp.
23. The Eop aqueous bleaching solution of claim 21 , wherein the ratio of sodium hydroxide to magnesium hydroxide in said Eop aqueous bleaching solution is not more than about 5:1 (based on an OH− molar ratio).
24. The Eop aqueous bleaching solution of claim 21 , wherein the pulp viscosity of the final chemical pulp produced using said Eop aqueous bleaching solution is at least substantially the same as the pulp viscosity of final bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide, an oxygen-containing material compound, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
25. The Eop aqueous bleaching solution of claim 21 , wherein the pulp brightness of Eop bleached chemical pulp produced using said Eop aqueous bleaching solution is at least substantially the same as the pulp final brightness of bleached chemical pulp which is bleached with a bleaching sequence containing the same total amount of an Eop aqueous bleaching solution comprising said peroxide, an oxygen containing compound, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
26. The Eop aqueous bleaching solution of claim 21 , wherein the COD of bleach effluent produced using said Eop aqueous bleaching solution is less than the COD of bleach effluent which is produced by the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
27. The Eop aqueous bleaching solution of claim 21 , wherein the ratio of sodium hydroxide to magnesium hydroxide in said Eop aqueous bleaching solution is not more than about 3:1 (based on an OH− molar ratio).
28. The Eop aqueous bleaching solution of claim 21 , wherein the ratio of sodium hydroxide to magnesium hydroxide in said Eop aqueous bleaching solution is not more than about 1:2 (based on an OH− molar ratio).
29. The Eop aqueous bleaching solution of claim 21 , wherein the wet zero span tensile strength of Eop bleached chemical pulp produced using said Eop aqueous bleaching solution is at least substantially the same as the wet zero span tensile strength of bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
30. The Eop aqueous bleaching solution of claim 21 , wherein COD in the bleach effluent of said bleached Eop chemical pulp is at least about 5% less than the COD in the bleach effluent of said bleached chemical pulp which is bleached with the same total amount of an Eop aqueous bleaching solution comprising said peroxide compound, an oxygen-containing material, sodium hydroxide, with or without magnesium sulfate, in the absence of magnesium hydroxide.
31. An Ep process for bleaching chemical pulp, which comprises:
providing said chemical pulp;
providing an Ep aqueous bleaching solution comprising a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate; and
bleaching said chemical pulp with said Ep aqueous bleaching solution to form said bleached chemical pulp.
32. An Ep process for bleaching chemical pulp, which comprises:
providing said chemical pulp;
providing an Ep aqueous bleaching solution consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide; and
bleaching said chemical pulp with said Ep aqueous bleaching solution to form said bleached chemical pulp.
33. An Ep aqueous chemical solution for bleaching chemical pulp, which comprises an Ep aqueous bleaching solution consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide.
34. A process for bleaching chemical pulp, which comprises:
providing said chemical pulp;
providing an Eop aqueous bleaching solution;
bleaching said chemical pulp with said Eop aqueous bleaching solution to form Eop bleached chemical pulp;
providing an Ep aqueous bleaching solution comprising a peroxide compound, sodium hydroxide and magnesium hydroxide, in the absence of magnesium sulfate; and
bleaching said Eop bleached chemical pulp with said Ep aqueous bleaching solution to form Ep bleached chemical pulp.
35. A process for bleaching chemical pulp, which comprises:
providing said chemical pulp;
providing an Eop aqueous bleaching solution;
bleaching said chemical pulp with said Eop aqueous bleaching solution to form Eop bleached chemical pulp;
providing an Ep aqueous bleaching solution consisting essentially of a peroxide compound, sodium hydroxide and magnesium hydroxide; and
bleaching said Eop bleached chemical pulp with said Ep aqueous bleaching solution to form Ep bleached chemical pulp.
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US10/086,191 US20030024664A1 (en) | 2001-02-27 | 2002-02-27 | Eop & Ep process for bleaching of chemical pulp |
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US27198701P | 2001-02-27 | 2001-02-27 | |
US10/086,191 US20030024664A1 (en) | 2001-02-27 | 2002-02-27 | Eop & Ep process for bleaching of chemical pulp |
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US10/086,191 Abandoned US20030024664A1 (en) | 2001-02-27 | 2002-02-27 | Eop & Ep process for bleaching of chemical pulp |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110042022A1 (en) * | 2008-03-25 | 2011-02-24 | University Of Brunswick | Process of chlorine dioxide bleaching of chemical pulps using magnesium hydroxide or magnesium oxide |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3657065A (en) * | 1968-06-13 | 1972-04-18 | South African Pulp Paper | Delignification and bleaching of cellulose pulp with oxygen gas in an allsaline medium in the presence of a protector |
US4568420A (en) * | 1984-12-03 | 1986-02-04 | International Paper Company | Multi-stage bleaching process including an enhanced oxidative extraction stage |
US4734161A (en) * | 1985-05-29 | 1988-03-29 | Atochem | Process for a two stage peroxide bleaching of pulp |
-
2002
- 2002-02-27 CA CA002373562A patent/CA2373562A1/en not_active Abandoned
- 2002-02-27 US US10/086,191 patent/US20030024664A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3657065A (en) * | 1968-06-13 | 1972-04-18 | South African Pulp Paper | Delignification and bleaching of cellulose pulp with oxygen gas in an allsaline medium in the presence of a protector |
US4568420A (en) * | 1984-12-03 | 1986-02-04 | International Paper Company | Multi-stage bleaching process including an enhanced oxidative extraction stage |
US4568420B1 (en) * | 1984-12-03 | 1999-03-02 | Int Paper Co | Multi-stage bleaching process including an enhanced oxidative extraction stage |
US4734161A (en) * | 1985-05-29 | 1988-03-29 | Atochem | Process for a two stage peroxide bleaching of pulp |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20110042022A1 (en) * | 2008-03-25 | 2011-02-24 | University Of Brunswick | Process of chlorine dioxide bleaching of chemical pulps using magnesium hydroxide or magnesium oxide |
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