EP0103992A1 - Chloration de matériau fibreux - Google Patents

Chloration de matériau fibreux Download PDF

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Publication number
EP0103992A1
EP0103992A1 EP83304817A EP83304817A EP0103992A1 EP 0103992 A1 EP0103992 A1 EP 0103992A1 EP 83304817 A EP83304817 A EP 83304817A EP 83304817 A EP83304817 A EP 83304817A EP 0103992 A1 EP0103992 A1 EP 0103992A1
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EP
European Patent Office
Prior art keywords
solution
water
chlorine
wool
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP83304817A
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German (de)
English (en)
Inventor
Francois Albertus Barkhuysen
Nicolaas Jacobus Janse Van Rensburg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South African Inventions Development Corp
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South African Inventions Development Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South African Inventions Development Corp filed Critical South African Inventions Development Corp
Publication of EP0103992A1 publication Critical patent/EP0103992A1/fr
Withdrawn legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/10—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics
    • D06B3/20—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics with means to improve the circulation of the treating material on the surface of the fabric
    • D06B3/201—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics with means to improve the circulation of the treating material on the surface of the fabric the treating material being forced through the textile material
    • D06B3/203—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of fabrics with means to improve the circulation of the treating material on the surface of the fabric the treating material being forced through the textile material by suction, e.g. by means of perforated drums
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof
    • D06M11/09—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof with free halogens or interhalogen compounds

Definitions

  • THIS invention relates to the chlorination of fibrous material, particularly wool and the like, for the purpose of rendering such material shrinkresistant.
  • wool is intended to include wool in the form of slivers as well as loose stock.
  • wool sliver in turn, is intended to include combed sliver, card sliver, top sliver, roving, yarn and thread while the term loose stock is intended to include scoured wool, carbonised wool, broken top etc.
  • chlorination is very broad and includes the use of chlorine in various chemical forms according to a wide variety of treatments. These include aqueous chlorination treatments, chlorination in organic solvents, and dry gaseous chlorination. Of these, the aqueous chlorination processes are by far the most popular for the oxidative treatment of wool.
  • This process is based on the use of an alkali metal hypochlorite, particularly sodium hypochlorite, from which compound a suitable chlorinating agent can be prepared by acidifying a solution of it with an acid, such as sulphuric acid, according to the following reaction:
  • hypochlorite solution does not contain hypochlorous acid only, but that it comprises a mixture of hypochlorous acid and free chlorine, as is illustrated by the following equilibrium reaction:
  • the material to be treated is made to pass around a hollow rotatable cylinder onto which the material is sucked and which is at least partly submerged in the treatment liquor contained in the chlorination bowl of the apparatus.
  • the cylinder is perforated over its entire cirumference so that suction applied to its inside causes the treatment liquor to pass from outside the cylinder through the material and via the perforations to the inside of the cylinder.
  • the suction is usually effected by means of a suitable impeller operative within the cylinder or by means of a suitable pump located elsewhere in the system.
  • the chlorination of wool with an acidified hypochlorite solution in a suction drum generally produces acceptable results, the process also suffers from a number of significant drawbacks.
  • the temperature of the liquor in the bowl generally increases during the treatment, mainly due to the neutralisation reaction between NaOC1 and H 2 SO 4 , as well as due to the fact that any excess free alkali present in the sodium hypochlorite solution has to be neutralised by the sulphuric acid.
  • the pH of commercially available sodium hypochlorite solutions is usually above 11 and that these solutions usually contain between 0,3 and 1,2% NaOH (mass/mass).
  • the aforesaid increase in temperature not only results in an increase in the degree of yellowness of the wool, but also gives rise to a loss of chlorine to the atmosphere.
  • concentration of the sodium hypochlorite stock solutions tends to vary from batch to batch and also tends to decrease on storage and should accordingly be determined daily in order to calculate the amount of hypochlorite which has to be fed to the chlorination bowl.
  • the wool to be treated is made to enter the aqueous chlorine solution at an angle of not more than from the vertical and is then immersed to a depth of at least one meter in the solution. It is claimed that with this apparatus a very uniform degree of chlorination of the wool is possible and the explanation which is given for this is that as the wool is progressively drawn into the solution the air in the material is gradually driven out and, due to the progressive increase in hydrostatic pressure and the resulting capillary action, the solution is progressively drawn into the material.
  • the Kroy apparatus is completely different from the suction drums which are in common use in the industry and in order to utilise the claimed benefits of the new process it is necessary to replace these drums at great cost with the new type of apparatus.
  • a method of chlorinating a fibrous material includes the step of forcing a solution comprising free chlorine which is dissolved in a liquid medium to pass through the material in a manner so that the solution can react uniformly with substantially every fibre in the material.
  • Applicant believes that by forcing the solution in this manner to react with substantially every fibre in the material, the chlorine in the solution is given the maximum opportunity to react with the material so that there is substantially no unspent chlorine left in the solution emerging from the other side of the material. This, accordingly, reduces the amount of chlorine available for escaping from the solution during the treatment process. Furthermore, because the solution reacts uniformly with substantially every fibre in the material, a very uniform degree of chlorination is possible.
  • the method includes the step of locating and holding the material in the path of the solution in a manner to substantially prevent channeling.
  • the solution is forced to pass through the material by means of suction applied to one side of the material.
  • the suction is that provided in a suction drum of conventional construction in which the material is passed through a chlorination bowl charged with the solution.
  • the method according to the invention can accordingly be carried out with substantially the same apparatus which is conventionally used for the shrinkresist treatment of wool and the like using acidified hypochlorite as the chlorinating agent.
  • the chlorine solution is prepared by passing chlorine gas into water under conditions which ensure that substantially all of the gas is dissolved in the water.
  • the dissolution of the gas is enhanced by passing the chlorine gas into the water under conditions of vigorous agitation.
  • chlorine gas is dispersed into the water in the form of small bubbles.
  • the chlorine gas is passed into the water at such a level below the surface of the water where maximum use can be made of the hydrostatic pressure and any turbulance in the water for enchancing the dissolution of the gas in the water.
  • the solution is prepared by dispersing chlorine gas into water contained in a suction drum in the form of small bubbles at a point in close proximity to the impeller of the apparatus.
  • the gas is released approximately one to two cm from the impeller shaft at a point where the impeller of the apparatus causes severe turbulance in the water.
  • apparatus for carrying out the aforesaid method includes a suction drum of conventional construction in which the material to be treated can be drawn over a hollow rotatable cylinder which is perforated over at least part of its cirumference and which includes an impeller which is operative in the cylinder to cause a solution of chlorine gas in water contained in the chlorination bowl of the apparatus to be sucked via the perforations in the cylinder through the material while the latter is located on the drum
  • the apparatus may include a chlorinating means located outside the suction drum for providing the free chlorine solution.
  • the apparatus may include means for dispersing chlorine gas in the form of small bubbles in the cylinder.
  • the suction in the cylinder of the apparatus is preferably caused by an impeller operative in the cylinder, the dispersing means being located in the cylinder in a position in close proximity to the impeller.
  • the dispersing means may comprise a fine mesh through which the gas is introduced to the water.
  • Such mesh may, for example, be of a suitable metal, such as stainless steel, or a suitable synthetic resinous material, or sinter glass etc.
  • the dispersing means may comprise a tube for passing the chlorine gas into the water, the end of the tube being closed off and the tube being provided with a plurality of fine holes extending through the wall of the tube in positions spaced a small distance from the said closed off end.
  • the dispersing means may comprise a plurality of small bored tubes, with or without dispensing devices such as those disclosed above, for passing the chlorine gas into the water.
  • wetting of the material can be facilitated by the use of a suitable wetting agent.
  • the processing speed i.e. the speed of the material through the chlorinating liquor, and thus the contact time of the material in the chlorinating liquor, will be determined by a number of parameters, such as, the diameter of the suction drum; the rate at which the chlorinating liquor is passed through the wool; the concentration of chlorine in the bowl and the rate of addition of chlorine to the bowl; the fibre diameter and/or material thickness; maximum speed of the plant; capacity of the dryer; etc.
  • Applicant has found that a processing speed of between 0,1 m/min and lOm/min, or even higher, is possible with the process according to the invention.
  • the temperature of the chlorinating solution in the suction drum can vary between 5 °C and 40°C without having any significant adverse effects on the shrinkresistance being obtained with material being treated.
  • the temperature of the solution in the bowl increased from 23 C, in the case of acidified hypochlorite to 38 C, while in the case of chlorine gas in water it only increased to 28 C.
  • the pH of the chlorinating solution in the present invention depends mainly on the concentration of chlorine in the bowl, and remains fairly constant when no material is passed through the bowl and while there is no change made to the concentration of the solution, applicant has found that when material is' passed through the bowl the pH of the liquor tends to decrease, probably as a result of the reaction between the chlorine and hypochlorous acid in the solution and the material.
  • the pH of the chlorinating solution therefore generally tends to decrease slowly as the time of treatment increases and it seems to reach equilibrium conditions at a pH value of between 1,0 and 2,8. In practice acceptable results have been obtained at pH values varying from 0,5 to 5,0.
  • the level of chlorination i.e. the amount of chlorine applied to the material, depends on the properties of the material used, the presence of grease and foreign matter, such as lubricants and oils on the fibre, as well as on the level of shrinkresistance required.
  • the level of the chlorination has been found generally to vary between 0,4% and 5,0% C1 2 (on mass of material). At higher C1 2 levels applicant has found that a very lustrous product is formed,probably because most of the scales of the fibres are removed. If it is required to enhance the formation of such a product, the of the chlorine upper level could be increased to 10%. It is also possible to operate at a lower level than the stated 0,4%.
  • chlorination process according to the invention can be used as oxidative shrinkproofing treatment only, or it can be followed by a subsequent resin treatment.
  • Any resin or polymer having the properties required for continuous material treatment can be used, e.g. the acid colloid of melamine type resins, polyamide-epichlorohydrins, polyurethanes, polyacrylates, certain silicones such as polysiloxanes, certain cationic polyamides, etc.
  • some water should preferably be added to the bowl during continuous treatments.
  • Such added water could be utilised for introducing chemicals such as, for example, a wetting agent, to the reaction medium.
  • a suction drum 1 which includes a chlorination bowl 2 in which a hollow elongated cylinder 3 is located for rotation at a predetermined variable speed in the direction of arrow A about its longitudinal axis 4 by means of a motor or the like (not shown).
  • Cylinder 3 includes over its entire circumference a plurality of perforations 5 by means of which bowl 2 communicates with the bore of cylinder 3.
  • impeller 7 forces chlorinating liquor 11 to move rapidly away from, it and out of tube 6 thus causing a suction action in the bore of cylinder 3 which causes the liquor to pass from bowl 2 via perforations 5 into the bore of cylinder 3. While impeller 7 is in operation, there is accordingly a constant flow of liquor 11 from bowl 2 to the inside of cylinder 3. At the same time impeller 7 causes extensive turbulance in the liquor contained inside cylinder 3 especially in the immediate proximity of impeller 7.
  • tube 6 leads into the cavity defined by the double wall at the end of bowl 2, from where the chlorinating liquor 11 is returned , in conventional manner, to the inside of bowl 2 via the apertures on the inside member of the double walls.
  • water may be added to the liquor so returned to bowl 2 and such fresh water may, for example, be used to convey such other chemicals as may be required to be introduced to the bowl.
  • a pair of rollers 9 and 10 serves as the web 12 conveying means for a continuous of adjacently disposed longitudinally extending fibres of wool which may comprise wool slivers (or loose wool supported on a suitable netting or the like) which passes around the lower outside half of cylinder 3.
  • Drum 1, cylinder 3, tube 6, impeller 7 and rollers 9 and 10 are preferably of a suitable corrosion resistant material such as stainless steel, for example.
  • Bowl 2 is filled with chlorinating liquor 11 to a level at which cylinder 3 is substantially completely submerged.
  • End 14 of tube 13 is closed off with a fine wire mesh 15 of stainless steel.
  • the apertures 16 of mesh 15 are of such a size that gas issuing through them will be dispersed as fine bubbles into chlorinating liquor 11.
  • chlorine gas is introduced into the water in the bore of cylinder 3 as a continuous stream at a predetermined flow rate via apertures 16 in wire mesh 15.
  • each fibre of material in web 12 is contacted by chlorinating liquor 11 thus allowing the latter a substantial period of time for reacting with each of such fibres.
  • the suction caused to web 12 also serves to locate and to hold the material on the cylinder in the path of the chlorinating liquor in this manner preventing channelling of the material.
  • the material 12 may be treated on the upstream side of ro.ller 9 in any of the conventional manners required for rendering such material in a form suitable for chlorination and that the material 12 on the downstream side of roller 10 may be subjected to such further treatment as may be required such as rinsing, dechlorination, resin application etc.
  • Bowl 2 of suction drum 1 was filled with water at 15,5 "C after which 0,1% (mass/volume) * Alcopol 650 (Allied Colloids Ltd), a wetting agent which is resistant towards oxidising agents, was added. Chlorine gas was then fed as 15 and a flow a continuous stream via wire mesh meter (not shown) to give a chlorine content in the bowl of approximately 0,1% (mass/volume).
  • the wool was then passed through squeeze rollers into a resin bowl containing 2,0% (mass/volume) acid colloid prepared from Cassurit HML (Hoechst Ltd) and 1,0% (mass/volume) Polythem N-40 (Textile Chemicals Ltd) as softening agent.
  • the wool 12 was then passed through squeeze rollers (at a wet pick-up of 60%) into a dryer where it was dried and the resin cured.
  • the slivers 12 were then converted into yarn, and a fabric was knitted from the yarn. This fabric showed a percentage area shrinkage of about 1,0% when washed for 3 hours in a Cubex machine, indicating an excellent degree of shrinkresistance.
  • the wool 12 was then passed through squeeze rollers into a bowl containing 0,2-0,5% softening agent (while a softening agent solution was simultaneously pumped into the bowl at a rate of 0,5% softener (on mass of wool).
  • the wool 12 was then passed through squeeze rollers into a drier where the wool was dried and the polymer cured.
  • the slivers 12 were converted into yarn, and a fabric was knitted from the yarn. This fabric showed a percentage area shrinkage of less then 3,0% when washed for 3 hours in a Cubex * machine, indicating an excellent degree of shrinkresistance.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
EP83304817A 1982-08-20 1983-08-19 Chloration de matériau fibreux Withdrawn EP0103992A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
ZA826068 1982-08-20
ZA826068 1982-08-20
ZA834453 1983-06-17
ZA834453 1983-06-17

Publications (1)

Publication Number Publication Date
EP0103992A1 true EP0103992A1 (fr) 1984-03-28

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EP83304817A Withdrawn EP0103992A1 (fr) 1982-08-20 1983-08-19 Chloration de matériau fibreux

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EP (1) EP0103992A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112095259A (zh) * 2020-08-21 2020-12-18 常熟市新光毛条处理有限公司 一种巴素兰羊毛条连续处理工艺

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB417719A (en) * 1933-03-11 1934-10-11 Wool Ind Res Association Improvements in or relating to the treatment of wool and like fibres or materials made therefrom to render them unshrinkable
GB559263A (en) * 1942-05-05 1944-02-11 John Brandwood Improvements in or relating to the gaseous treatment of wool and analogous fibres
FR982839A (fr) * 1948-03-15 1951-06-15 Bradford Dyers Ass Ltd Procédé pour réduire le pouvoir feutrant des fibres de laine
BE696613A (fr) * 1966-04-07 1967-10-05
GB1200086A (en) * 1966-09-29 1970-07-29 Vepa Ag Apparatus for the continuous treatment of wool

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB417719A (en) * 1933-03-11 1934-10-11 Wool Ind Res Association Improvements in or relating to the treatment of wool and like fibres or materials made therefrom to render them unshrinkable
GB559263A (en) * 1942-05-05 1944-02-11 John Brandwood Improvements in or relating to the gaseous treatment of wool and analogous fibres
FR982839A (fr) * 1948-03-15 1951-06-15 Bradford Dyers Ass Ltd Procédé pour réduire le pouvoir feutrant des fibres de laine
BE696613A (fr) * 1966-04-07 1967-10-05
GB1200086A (en) * 1966-09-29 1970-07-29 Vepa Ag Apparatus for the continuous treatment of wool

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TEXTILE RESEARCH JOURNAL, December 1957, pages 961-965 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112095259A (zh) * 2020-08-21 2020-12-18 常熟市新光毛条处理有限公司 一种巴素兰羊毛条连续处理工艺

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SU370757A1 (ru) СССР)Опубликовано 15.11.1973. Бюллетень № 11 Дата опубликовани описани 18.IV. 1973М. Кл. В 05с 3/152УДК 677.057.252.2(088.8)

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PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

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Effective date: 19840924

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Inventor name: BARKHUYSEN, FRANCOIS ALBERTUS

Inventor name: VAN RENSBURG, NICOLAAS JACOBUS JANSE