US3909194A - Bleaching of textiles with chlorine monoxide - Google Patents

Bleaching of textiles with chlorine monoxide Download PDF

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Publication number
US3909194A
US3909194A US360974A US36097473A US3909194A US 3909194 A US3909194 A US 3909194A US 360974 A US360974 A US 360974A US 36097473 A US36097473 A US 36097473A US 3909194 A US3909194 A US 3909194A
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fabric
chlorine monoxide
moisture content
bleaching
terminal
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US360974A
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Norman Liebergott
Henry I Bolker
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Pulp and Paper Research Institute of Canada
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Pulp Paper Res Inst
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/28—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen in an inert solvent
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/22—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents
    • D06L4/23—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using inorganic agents using hypohalogenites
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/29—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen in a gaseous environment

Definitions

  • the process comprises contacting the textile material at a suitable moisture content (eg. in the range of about 80 to about 20% by weight), with chlorine monoxide which is in admixture with an inert gaseous or liquid solvent.
  • the chlorine monoxide being present in an amount of about 0.1 to about 1.0% on the weight of the dry fabric. If the chlorine monoxide is in gaseous form, it is generally at a partial pressure of about 1 to about 253 Torr, and the contact time is less than about 1 second up to about 300 seconds.
  • the terminal pH is selectively adjusted to about 1 to about 13.
  • the present invention relates to the bleaching of textiles. More particularly, it relates to the bleaching of raw, natural fibers and synthetic fibers, either alone or together, in open-width or in rope form.
  • bleaching includes bleaching per se as well as other related operations designed to purify fibers and fabrics by removing natural and processing soils and colours.
  • the bleaching process may de-size, caustic'scour, and acid sour goods, in addition actually to bleaching them.
  • the condition of the fibers, their sensitivity to bleaching chemicals and to mechanical handling, and the intended use of the goods all contribute to determine the type of bleaching process selected.
  • Natural raw-fiber stock, yarn, knitgoods, and woven piece goods are bleached for white finishing, printing, and dye bottoms. Although most synthetic fibers require bleaching only for special uses, blends of natural and synthetic fibers are often bleached to whiten the natural fibers. Occasionally, bleaching may be necessary to redress the colour of a synthetic fiber which has yellowed during heatsetting. With blends, the bleaching process selected is that least damaging to the most sensitive fiber in the blend. Chlorine bleaches and strongly alkaline solutions damage wool and other protein fibers, notably silk.
  • Raw wool requires a washing-scouring-acid bleaching (or alkaline peroxide) bleaching operation to remove the natural water-soluble, saponifiable, and oxidizable impurities.
  • Wool yarns, knits, and woven fabrics are commonly bleached by steeping in hydrogen peroxide solutions at a maximum pH of about 9.6 and a temperature of about 1 16 to about 120F.
  • Cotton is comparatively resistant to bleaching chemicals and temperatures, but control of bath conditions is necessary for optimum bleaching with minimum fiber degradation For example, neutral chlorine bleaches damage cotton; chlorine bleaches are therefore used at alkaline pH.
  • the man-made cellulosic fibers are more sensitive to alkalies and high temperatures than is cotton; cellulose acetate is more sensitive than rayon. Most acrylic fibers and fabricsare scoured in mildly alkaline detergent solutions containing perborates and silicates.
  • Acrylic-cotton blends can be bleached batchwise or continuously in hydrogen peroxide-sodium silicate formulations having a pH of about 9.0 to about 10.0.
  • Acrylic-wool blends can be bleached using the standard wool-bleaching techniques.
  • Nylon and nylon blends containing over about 50% nylon are usually bleached with sodium chlorite or with peracetic acid.
  • Nylon-cotton blends can be bleached with hypochlorite or peroxide bleaches. Most polyester fibers are white as produced, but require a scour to remove the processing oils and waxes.
  • Polyestercotton-nylon blends are scoured similarly to cotton. Polyester fabrics and polyester blends may be bleached using chlorite bleaches or peroxide bleaches.
  • acid sodium chlorite bleaches are often recommended for synthetics and synthetic-cotton blends.
  • hypochlorite bleaches an antichlor should follow the sodium chlorite bleach to ensure against yellowing of the bleached fibers upon subsequent exposure to high temperatures, such as those commonly used in drycleaning and pressing.
  • mildly alkaline peroxide solutions are often used to bleach syntheticcotton blends.
  • the absorbency of the cotton (which consumes the chemicals) prevents degradation of the synthetic fibers by the solutions.
  • peroxide bleaching Since peroxide bleaching is applicable to all natural fibers, it is particularly suited to the processing of fabric blends. Peroxide bleaches are chemically less reactive than hypochlorite bleaches and therefore cause less fiber degradation and less injury to dyed yarns. As a result, peroxide bleaching gives permanently white bleached goods with good absorbency and excellent appearance, hand, loft, and elasticity.
  • Alkaline peroxide solutions tend to yellow some synthetic fibers, particularly acrylic fibers.
  • Peracetic acid and sodium chlorite bleaches which have found some use in commercial bleaching in the past decade, have little degrading action on most synthetics and have good bleaching action on their blends with cellulosic fibers.
  • a preliminary wash, wetting-out", or scour normally precedes the actual bleaching operation as an integral part of the overall process of fabric preparation.
  • kiers dolly washers, or other machines equipped to' move the goods through the chemicals solutions or to circulate the solutions through the goods.
  • Continuous bleaching systems have drive mechanisms coupled with suitably designed units for each step to permit quasi-automation of the consecutive steps.
  • a continuous scouring and peroxide-bleaching system generally uses stainless-steel equipment 'designed to process fabric in either rope or in open-width form. Standard washers are used in a continuous line, tight-strand washers for high-speed rope operation or slack washers for low-speed operation. Saturators for rope processing are actually single-strand washers equipped with a small entrance chute at one end and a set of squeeze rolls at the other. For open-width processing, a multiple-bowl or open-type washer is satisfactory.
  • the J-box the preferred storageconveyor device, provides for holding the goods hot, either after preheating or by steaming during stor age. Since heating accelerates peroxide decomposition, direct heating of a peroxide saturator solution is uneconomical in a continuous system. Therefore the cloth is first saturated, then heated and stored in a J-box or similar device long enough to permit effective bleaching. The washing step between the caustic and the bleaching steps must be thorough for good-quality work at moderate costs.
  • .I-box for the caustic soda scour and a second J-box for the hydrogen peroxide bleach.
  • Each J-box provides for about one hour retention time and heats the saturated cloth to a temperature of from about 205F. to about 212F.
  • the conventional sequence for cotton cloth in rope form is: singe; quench with an enzyme solution; lay in bins at least four hours; rinse; saturate with caustic soda; steam in a .I-box for about 1 to about 1 /2 hours; rinse; saturated with hydrogen peroxide bleach solution; steam in J-box one hour; rinse; and finally pile in white bins.
  • Another system is the so-called continuous kier system in which the dry cloth enters the saturator and then passes into a J-box where it is steamed as it moves down the straight section of the J. Diluted bleach solution enters the J-box at the top of the curve, circulates through the cloth, and leaves near the exit end of the .l-box. This circulation through the cloth is similar to the flow of solution in a kier.
  • This system although relatively rapid, suffers the general deficiencies of the use of the J-box as a conveyor-storage device.
  • An object of a broad aspect of this invention is to provide an improved simple process for the bleaching of a raw, natural fiber, such as, for example, cotton, linen, jute, hemp, etc., alone or in combination with a synthetic fiber such as, for example, polyamides, (e.g. the nylons, for example Nylon 66, Nylon 6, Nylon 4, Nylon 610 [Trademarked Tynex], Nylon 11 [Trademarked Rilsan], Nylon 12, and Nylon 9), polyesters isoprene and their copolymers), etc., in open-width or in rope form, so that one reagent could be employed (e.g.
  • polyethylene terephthalate [trademarked Terylene and Dacron]
  • rayon modified rayon
  • acetates e.g. cellulose acetate [trademarked Acele] and cellulose triacetate [trade marked Arnel]
  • acrylic fibers e.g. a long chain synthetic polymer composed of at least 85% by weight acrylonitrile units, for example, the synthetic acrylicfibers known by the trade marks of Acrilan, Creslan, Orlon and Zefran
  • polyolefins e.g. polyethylene, polypropylene, polybutenes, polyfor all blends of fabric.
  • An object of another aspect of this invention is to provide an improved textile bleaching process using some of the existing equipment, such as the .I-box, to conduct the treatment of bleaching with a gaseous bleaching agent under atmospheric conditions, or at a partial pressure of from about 1 to about 253 Torr.
  • An object of yet another aspect of this invention is the provision of a textile bleaching process which is operable in the acid, neutral or alkaline range, thereby substantially eliminating the need for changing chemicals for different combinations of natural and synthetic fibers, and consequently simplifying the bleaching of 2 textiles.
  • An object of yet another aspect of this invention is the provision of such a process in which the saturating step with the bleaching agent may be obviated.
  • a process for the bleaching of a raw, natural fiber, alone or in combination with a synthetic fiber, in open-width or rope form which comprises contacting the material, at a suitable moisture content (generally in the range of about 80 to about with gaseous chlorine monoxide (generally in the range of about 0.1 to about 1.0%
  • the fabric, in contact with the gaseous chlorine monoxide, is generally at a moisture content from about 80 to about 20%, for a contact time of from a fraction of a second up to about 300 seconds, at ambient temperature, and at a terminal pH selected to be a narrow range within the limits of about I to about 13.
  • the fabric is we treated with an alkaline material (i.e. NaOH or Na CO in such a manner that the terminal pI-I, after addition of the chlorine monoxide, will be a selected one within the limits of about 1 to about 13.
  • the terminal pH after the treatment with chlorine monoxide, has a significant effect on the brightness of the fabric obtained, but not a significant effect on the fluidity. Thus, it was found that the highest brightness values were obtained in the alkaline range for the particular blend of fabric used in these experiments.
  • Brightness or Whiteness measure on an Elrepho reflectometer using a blue filter at 457 nm.
  • EXAMPLE 1 A starch-sized, cream-coloured cotton/polyester fabric (/50), characterized by an Elrepho brightness of 56.2 and a fluidity of 2.5, was soaked in tap water to bring the moisture content of the fabric to EXAMPLE la A portion of the fabric was passed into a reaction vessel. Chlorine monoxide, diluted with air to a partial pressure of 200 Torr, was passed into the reaction vessel until 02% chlorine monoxide, based on the oven dry weight of fiber, was added to the fabric in twenty seconds. The terminal pH of the fabric was 4.7 after the twenty second treatment. The bleached fabric was removed, washed with water, air dried, and the brightness and fluidity measured.
  • the brightness was 73 on the Elrepho meter, and the fabrid had a fluidity of 3.9.
  • EXAMPLE 1b Another portion of the prepared, open-width fabric was sprayed with a solution containing 1.5% Na CO on the weight of dry fabric. The moisture content of the web was 75%. The web was placed into a reaction flask. Chlorine monoxide, diluted with air to a partial pressure of 200 Torr, was passed into the reaction flask until 0.2% chlorine monoxide, based on the oven dry weight of fiber, was added to the fabric in twenty seconds. The terminal pH of the fabric was 6.6 after the twenty second treatment. The bleached fabric was washed with water, air dried, and the brightness and fluidity measured.
  • the brightness was 78, and the fluidity was 4.1.
  • EXAMPLE 1c Another portion of the unbleached, open-width fabric was sprayed with a solution containing 5% Na CO on the weight of dry fiber, and the moisture content of the fiber was 75%.
  • the fabric was placed in a reaction chamber. Chlorine monoxide, diluted with air to a partial pressure of 200 Torr, was passed into the reaction chamber until 0.2% chlorine monoxide, based on the oven dry weight of fiber, was added to the fiber in twenty seconds time.
  • the bleached fabric was washed with water, air dried, and the brightness and fluidity measured.
  • the brightness was 81.0 and the fluidity was 4.0.
  • EXAMPLE 1d Another portion of the unbleached, open-width fabric was sprayed with a solution containing 7% 1 ⁇ Ia CO on the weight of dry fiber, and the moisture content of the fiber was 75%.
  • the fabric was placed in a reaction chamber. Chlorine monoxide, diluted with air to a partial pressure of 200 Torr, was passed into the reaction chamber until 0.2% chlorine monoxide, based on the oven dry weight of fiber, was added to the fiber in twenty seconds time.
  • the bleached fabric was washed with water, air dried, and the brightness and fluidity measured.
  • the brightness was 87 and the fluidity was 3.9.
  • EXAMPLE 2 A starch-sized, cotton/polyester fabric was de-sized by soaking at one percent consistency in a solution con taining 10% NaOH on the weight of dry fabric, at 70F. The fabric was then pressed to a moisture content of 30%.
  • EXAMPLE 2a A portion of the de-sized fabric was passed into a reaction vessel. Chlorine monoxide, diluted with air to a partial pressure of 5 Torr, was passed into the reaction vessel until 0.2% chlorine monoxide, based on the oven dry weight of fiber, was added to the fabric in one minute. The terminal pH of the fabric was 6.2 after the one minute treatment. The bleached fabric was removed, washed with water, air dried, and the brightness and fluidity measured.
  • the brightness was 83.9 and the fluidity was 4.1.
  • EXAMPLE 2b Another portion of the de-sized fabric was sprayed with a solution containing 1% NaOH on the dry weight of fabric.
  • the moisture content of the fabric was 25%.
  • the fabric was placed in a reaction flask. Chlorine monoxide, diluted with air in a partial pressure of 5 Torr, was passed into the reaction flask until 0.2% chlorine monoxide, based on the oven dry weight of fiber, was added to the fabric in one minute.
  • the terminal pH of the fabric was 9.8 after the one minute treatment.
  • the bleached fabric was washed with water, air dried, and the brightness and fluidity measured.
  • the brightness was 92, and the fluidity was 4.3.
  • Starch-sized, cream-coloured cotton/polyester fabric (50/50) characterized by an Elrepho brightness of 56.2 was used in the following test:
  • Portions of the fabric were passed into a solution of carbon tetrachloride containing 8.9 g/l of chlorine monoxide and left to reside for retention times of 1 minute, 5 minutes, 15 minutes and 30 minutes.
  • the treated fabrics were removed after each respective time period from the chlorine monoxide carbon tetrachloride solution, washed copiously with water, air dried, and the brightness measured. The brightnesses obtained are listed below.
  • Example 3 Although the solvent used in Example 3 was carbon tetrachloride, it is known that chlorine monoxide is readily soluble in various organic liquids.
  • suitable solvents are those which are inert to the textile being bleached, and include trichloroethylene, tetrachloroethylene, and the fluorocarbon solvents known by the Trade Mark of Freon.
  • the brightness was 82.0 and the fluidity was 3.1.
  • Test Aii Using acidified sodium chlorite, a portion of the desized cotton/polyester fabric of Example 1 was treated with a sodium chlorite solution under the following conditions:
  • the brightness was 67.1 and the fluidity was 3.9.
  • the fabric was a cotton/polyester fabric, having an initial Elrepho brightness of 56.2 and an initial fluidity of 2.5.
  • bleaching with carbon monoxide is as effective as bleaching with hydrogen peroxide, but is more effective than bleaching with acidified sodium chlorite, and the bleaching takes place in the order of seconds, i.e. one minute or less (when gaseous chlorine monoxide is used) and in the order of minutes, i.e. 30 minutes (when chlorine monoxide in a liquid solvent is used), instead of two hours.
  • the brightness was 88.1.
  • Test Bii A partially delignified sulphite pulp, having a Kappa No. of 1.0, and an Elrepho brightness of 57.5, was formed into a handsheet having a moisture content of and a basic weight of 40 lbs. per 3,000 square feet. It was then treated with chlorine monoxide at a partial pressure of 210 Torr, for 1 minute, until the amount added was 0.6% based on oven-dried pulp. The terminal pH was 3.0. The brightness was then measured.
  • the brightness was only 72.3.
  • the process of claim 1 including an alkaline pretreatment with NaOH or Na CO- 15.
  • the process of claim 1 including a de-size washing step and a caustic soda scour step prior to the chlorine monoxide contacting step, and a washing step and a drying step subsequent to the chlorine monoxide contacting step.
  • the fabric is a blend of cotton and polyester, having a moisture content of about 70%; wherein the chlorine monoxide is diluted with air to a partial pressure of about 200 Torr; wherein the amount of chlorine monoxide is about 0.2%; wherein the contacting time is about 20 seconds; and wherein the terminal pH is about 4.7.
  • the fabric is a blend of cotton and polyester; wherein the fabric is treated with a solution containing about 1.5% Na CO wherein the moisture content is about 75%; wherein the chlorine monoxide is diluted with air to a partial pressure of about 200 Torr; wherein the amount of chlorine monoxide is about 0.2%; wherein the contacting time is about 20 seconds; and wherein the terminal pH is about 6.6.
  • the fabric is a blend of cotton and polyester; wherein the fabric is treated with a solution containing about 5% Na CO wherein the moisture content is about 75%; wherein the chlorine monoxide is diluted with air to a partial pressure of about 200 Torr; wherein the amount of chlorine monoxide is about 0.2%; wherein the contacting time is about 20 seconds; and wherein the terminal pH is about 8.2.
  • the fabric is a blend of cotton and polyester; wherein the fabric is treated with a solution containing about 7% Na CO wherein the moisture content is about 75%; wherein the chlorine monoxide is diluted with air to a partial pressure of about 200 Torr; wherein the amount of chlorine monoxide is about 0.2%; wherein the contacting time is about 20 seconds; and wherein the terminal pH is about 9.8.
  • the fabric is a blend of cotton and polyester; wherein the fabric is desized by soaking at one percent consistency in a solution containing about 10% NaOH at about F; wherein the fabric has a moisture content of about 30%; wherein the chlorine monoxide is diluted with air to a partial pressure of about 5 Torr; wherein the amount of chlorine monoxide is about 0.2%; wherein the contacting time is about 60 seconds; and wherein the terminal pH is about 6.2.
  • the fabric is a blend of cotton and polyester; wherein the fabric is desized by soaking at one percent consistency in a solution containing about 10% NaOH at about 70F; wherein the fabric is further treated with a solution containing about 1% NaOH; wherein the moisture content of the fabric is about 25%; wherein the chlorine monoxide is diluted with air to a partial pressure of about 5 Torr; wherein the amount of chlorine monoxide is about 0.2%; wherein the contacting time is about 60 seconds; and wherein the terminal pH is about 9.8.
  • the fabric is a blend of cotton and polyester, having a moisture content of about 70%; wherein the chlorine monoxide is dissolved in carbon tetrachloride to a concentration of about 8.9 g/l; and wherein the contacting time is about 1 minute to about 30 minutes.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US360974A 1972-05-30 1973-05-16 Bleaching of textiles with chlorine monoxide Expired - Lifetime US3909194A (en)

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JP (1) JPS5030193B2 (enrdf_load_html_response)
AR (1) AR198223A1 (enrdf_load_html_response)
BR (1) BR7303981D0 (enrdf_load_html_response)
CA (1) CA989112A (enrdf_load_html_response)
DE (1) DE2327771C3 (enrdf_load_html_response)
FR (1) FR2186566B1 (enrdf_load_html_response)
GB (1) GB1416502A (enrdf_load_html_response)
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291559A (en) * 1961-10-13 1966-12-13 Olin Mathieson Process of bleaching cellulose with chlorine dioxide wherein chlorine dioxide is continuously replenished
US3560330A (en) * 1966-02-25 1971-02-02 Stora Kopparbergs Bergslags Ab Multistage cellulose pulp bleaching with chlorine and chlorine dioxide
US3579419A (en) * 1967-04-24 1971-05-18 Pulp Paper Res Inst Treatment of fluffed pulp fibers with gaseous chlorine
US3585147A (en) * 1969-10-01 1971-06-15 Int Dioxcide Inc Stabilized chlorine dioxide solutions containing a chloride and processes of making and using same
US3619349A (en) * 1968-12-16 1971-11-09 Pulp Paper Res Inst Bleaching of shredded or fluffed cellulosic pulp with gaseous chlorine monoxide
US3655505A (en) * 1965-06-25 1972-04-11 Pulp Paper Res Inst Two-stage purification of fibrous cellulose material employing gaseous chlorine dioxide in one stage and a peroxygen compound in the other
US3720577A (en) * 1970-05-25 1973-03-13 Int Paper Co Chlorine dioxide-peracetic acid-chlorine dioxide pulp bleaching sequence
US3802958A (en) * 1968-11-07 1974-04-09 Mo Och Domsjoe Ab Chlorination of cellulose pulp

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3291559A (en) * 1961-10-13 1966-12-13 Olin Mathieson Process of bleaching cellulose with chlorine dioxide wherein chlorine dioxide is continuously replenished
US3655505A (en) * 1965-06-25 1972-04-11 Pulp Paper Res Inst Two-stage purification of fibrous cellulose material employing gaseous chlorine dioxide in one stage and a peroxygen compound in the other
US3560330A (en) * 1966-02-25 1971-02-02 Stora Kopparbergs Bergslags Ab Multistage cellulose pulp bleaching with chlorine and chlorine dioxide
US3579419A (en) * 1967-04-24 1971-05-18 Pulp Paper Res Inst Treatment of fluffed pulp fibers with gaseous chlorine
US3802958A (en) * 1968-11-07 1974-04-09 Mo Och Domsjoe Ab Chlorination of cellulose pulp
US3619349A (en) * 1968-12-16 1971-11-09 Pulp Paper Res Inst Bleaching of shredded or fluffed cellulosic pulp with gaseous chlorine monoxide
US3585147A (en) * 1969-10-01 1971-06-15 Int Dioxcide Inc Stabilized chlorine dioxide solutions containing a chloride and processes of making and using same
US3720577A (en) * 1970-05-25 1973-03-13 Int Paper Co Chlorine dioxide-peracetic acid-chlorine dioxide pulp bleaching sequence

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JPS5030193B2 (enrdf_load_html_response) 1975-09-29
FR2186566B1 (enrdf_load_html_response) 1977-02-11
DE2327771B2 (de) 1977-08-25
IT1008540B (it) 1976-11-30
AR198223A1 (es) 1974-06-07
CA989112A (en) 1976-05-18
BR7303981D0 (pt) 1974-07-25
IL42335A (en) 1976-07-30
DE2327771A1 (de) 1973-12-13
FR2186566A1 (enrdf_load_html_response) 1974-01-11
JPS4947678A (enrdf_load_html_response) 1974-05-08
DE2327771C3 (de) 1978-04-27
GB1416502A (en) 1975-12-03

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