EP0439108A1 - Verfahren zum Entkälken von Häuten in der Gerberei-Industrie und Vorrichtung zur Ausführung desselben - Google Patents

Verfahren zum Entkälken von Häuten in der Gerberei-Industrie und Vorrichtung zur Ausführung desselben Download PDF

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Publication number
EP0439108A1
EP0439108A1 EP91100732A EP91100732A EP0439108A1 EP 0439108 A1 EP0439108 A1 EP 0439108A1 EP 91100732 A EP91100732 A EP 91100732A EP 91100732 A EP91100732 A EP 91100732A EP 0439108 A1 EP0439108 A1 EP 0439108A1
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EP
European Patent Office
Prior art keywords
hides
bath
drum
process according
deliming
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.)
Granted
Application number
EP91100732A
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English (en)
French (fr)
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EP0439108B1 (de
Inventor
Edoardo Meregalli
Massimo Beccalli
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Sol SpA
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Sol SpA
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Publication date
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    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing

Definitions

  • the present invention relates to a process for deliming hides in the tanning industry and to an apparatus for carrying out said process.
  • the technological cycle to which hides are subjected during tanning generally comprises a first step of desalination in which the dry hides are washed in water so as to remove the salt used for their preservation.
  • the desalination step is followed by a soaking step in which the hides are treated with water and additives, such as for example surface-active substances, enzymes and sodium sulphide, so as to soften them and prepare them for subsequent treatments.
  • the hides are then treated with water, sodium sulphide and slaked lime. This step, termed lime pit, relaxes the hides and depilates them, making them soft.
  • the hides are subjected to fleshing to eliminate the fleshy and gelatinous subcutaneous parts.
  • the fleshing step is followed by a deliming step in which the hides, after a first wash with water, are generally treated with ammonium sulphate in water to prepare them for the subsequent steeping treatment.
  • the deliming step is performed in order to eliminate from the hides the residual lime which would prevent the successful outcome of the steeping step.
  • the steeping step which is again performed in a water bath with appropriate enzymes, has the effect of completely relaxing the hides and preparing them for the subsequent tanning step.
  • the technological tanning cycle then continues with the steps of actual tanning (chrome or vegetable tanning) and of dyeing and drying of the hides.
  • One or more of the described steps can be avoided for some types of hide.
  • the ammonium sulphate which performs an acidifying action by penetrating in the hides, has in fact the disadvantage of developing ammonia, with consequent problems of toxicity for personnel.
  • the waste water which derives from this treatment furthermore has a high content of sulphates and ammonia and as such is highly polluting for the environment.
  • deliming agents such as dicarboxylic acids, formic acid, acetic acid, which do not produce the same harmful effects, have been proposed and used but have considerably higher costs.
  • the carrying out of deliming by introducing a constant and high flow-rate of CO2 in the bath in which the hides are immersed does not allow to correspondingly reduce the treatment times.
  • a CO2 flow-rate higher than a certain limit which varies according to the type of hide and to the treatments already performed an extremely rapid reduction of the pH is in fact caused, but a rapid acidification of the grain of the hide, i.e. of its surface portion, is also caused, and this entails a blocking effect against the penetration of CO2 inside the hide. This blocking effect hinders the continuation of the process of neutralization of the lime which is present inside the hide.
  • a deliming treatment performed in this manner one would obtain satisfactory pH values but a deliming which is markedly insufficient for the successful outcome of the subsequent treatments.
  • the aim of the present invention is to solve the above described problems by providing a process for deliming hides in the tanning industry which, by using CO2 as deliming agent, allows to reduce the treatment time with respect to known processes which use CO2, thus also reducing the operating costs of the treatment facilities.
  • an object of the invention is to provide a process which, at the end of the treatment, gives the hides a degree of acidity which is ideal for the successful outcome of the subsequent steeping treatment.
  • Another object of the invention is to provide a process which allows to obtain a high yield in the use of the amount of CO2 employed.
  • a further object of the invention is to provide an apparatus for carrying out the process according to the invention which can be applied with modest investments to the production facilities which are currently in use in the tanning industry.
  • the process according to the invention can be performed with a deliming apparatus which comprises a drum intended to contain a treatment bath and the hides to be treated, said drum being supported so as to be rotatable about its own axis, which is arranged substantially horizontally, and being actuatable with a rotary motion about said axis to mix said hides, characterized in that it comprises means for introducing CO2 into said drum.
  • figures 1 to 3 are schematic views of three embodiments of the apparatus for carrying out the process according to the invention
  • figures 4 and 5 are respective diagrams of the trend of the pH and of the amount of CO2 introduced into the environment which contains the hides to be treated as a function of time in the process according to the invention.
  • the deliming process according to the invention substantially consists in using CO2 as deliming agent, similarly to known processes, but differently from said known processes the flow-rate, in relation to a unit mass of hide to be treated, of the CO2 which is introduced into the environment which contains the hides to be treated is increased at least once during the treatment time.
  • the treatment preferably comprises a first step of introduction of a flow-rate of CO2 which is substantially comprised, depending on the characteristics of the hides to be treated and on the previously undergone treatments, between 0.1 g/min per Kg of hides and 0.4 g/min per Kg of hides and a second step of introduction of a flow-rate of CO2 which is substantially comprised, again depending on the hides to be treated and on the previously performed treatments, between 0.3 g/min per Kg of hides and 0.6 g/min per Kg of hides.
  • the first step can have a duration comprised between 1/10 and 3/4 of the total duration of the treatment, which can vary from 30 minutes to 3 hours.
  • the introduction of CO2 preferably occurs by injection into a water-based bath in which the hides are immersed.
  • Figures 4 and 5 plot, by way of example, the diagrams of the trend of the pH and of the amount of CO2 as a function of the treatment time in the deliming of 2,500 kg of fatted calf hide with a thickness of approximately 4 mm performed according to the invention.
  • a flow-rate of CO2 which in this case is equal to 0.2 g CO2/min per Kg of hide is introduced in the bath which contains the hides.
  • a rapid reduction of the pH is achieved though a degree of acidity such as to block deliming is not reached on the surface of the hides.
  • the process according to the invention obtains a rapid reduction of the pH, but said reduction is not so rapid as to cause the blocking of the deliming.
  • the pH has a value comprised between 6.5 and 8.5 to allow the successful outcome of the subsequent steeping treatment and not to damage the hide with excessively acid values.
  • the pH value is preferably comprised between 7.0 and 7.3.
  • the process according to the invention can be performed in drums 1 of a known type, which are supported so as to be rotatable about their own axis 1a which is arranged horizontally, and in which a water-based bath, with the hides 2 to be treated, is introduced.
  • the desired amount of CO2 is conveyed by a distributor 3 to two feed ducts 4a and 4b which are connected to ducts 5a and 5b which in turn pass through the bases of the drum at the axis 1a and feed delivery nozzles 6a and 6b which are immersed in the bath.
  • a plurality of delivery nozzles 6a and 6b is preferably provided in the drum 1, said nozzles being distributed around the axis 1a of the drum and fixed to the walls of said drum between agitators 7 which are fixed in a known manner to the internal surface of the drum.
  • each nozzle is fed by a duct 5a or 5b and said ducts 5a and 5b are in turn connected to the feed ducts 4a and 4b by means of rotary couplings 8a, 8b of a known type which provide a selective connection, feeding CO2 only to the nozzles which, during the rotation of the drum, are in each instance immersed in the bath.
  • the introduction of CO2 can also occur above the free surface of the bath by adequately pressurizing the interior of the drums
  • the reaction between the CO2 and the lime of the hides is performed by the continuous mixing obtained with the rotation of the drum about its own axis
  • the introduction of CO2 in the water of the bath can also be performed indirectly, as illustrated by way of example in figures 2 and 3, by adding CO2 to a preset amount of the bath liquid drawn from the drum 1 and subsequently reintroduced in said drum with the aid of pumps 9 and 10.
  • the recirculation of the liquid of the bath can be performed with the aid of a tank 11 which collects the liquid which flows out of an appropriately perforated portion of the drum.
  • a known CO2 distributor 12 is arranged on the delivery duct of the pump 9 which leads into the drum.
  • the recirculation of the liquid of the bath can also be obtained by immersing the inlet of the suction duct of the pump 10 into the bath and arranging the outlet of its delivery duct inside the drum.
  • the CO2 is introduced into the delivery duct of the pump 10 by means of a known distributor 13.
  • the delivery and suction ducts of the pump 10 pass through openings which are defined on the bases of the drum at the axis 1a so as not to interfere with the rotation of the drum.
  • Another advantage which derives from the process according to the invention is that it is possible to perform the deliming with sufficiently high temperatures, so as to obtain a better result in the subsequent steeping treatment.
  • a further advantage of the process according to the invention is that it can be performed, with easily executable modifications, in known deliming facilities.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
EP91100732A 1990-01-23 1991-01-22 Verfahren zum Entkälken von Häuten in der Gerberei-Industrie und Vorrichtung zur Ausführung desselben Expired - Lifetime EP0439108B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT1913190 1990-01-23
IT01913190A IT1238336B (it) 1990-01-23 1990-01-23 Procedimento per la decalcinazione di pelle nell'industria conciaria e impianto per la sua esecuzione

Publications (2)

Publication Number Publication Date
EP0439108A1 true EP0439108A1 (de) 1991-07-31
EP0439108B1 EP0439108B1 (de) 1996-12-11

Family

ID=11155077

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91100732A Expired - Lifetime EP0439108B1 (de) 1990-01-23 1991-01-22 Verfahren zum Entkälken von Häuten in der Gerberei-Industrie und Vorrichtung zur Ausführung desselben

Country Status (3)

Country Link
EP (1) EP0439108B1 (de)
DE (1) DE69123466T2 (de)
IT (1) IT1238336B (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2684314A1 (fr) * 1991-11-07 1993-06-04 Sio Srl Dispositif pour introduire du gaz dans des zones determinees, dans des equipements ou machines rotatives.
EP0624654A2 (de) * 1993-05-11 1994-11-17 Linde Aktiengesellschaft Verfahren zur Herstellung von Leder aus Tierhäuten
DE19507572A1 (de) * 1995-03-03 1996-09-12 Helmut Geihsler Verfahren zur Zurichtung von tierischen Häuten oder Fellen
JP2016518487A (ja) * 2013-04-11 2016-06-23 ゼロス・リミテツド 固体粒子および化学配合物を使用して、動物の繊維でできた基材を処理する方法
US10287642B2 (en) 2014-10-10 2019-05-14 Xeros Limited Animal skin substrate treatment apparatus and method
US10301691B2 (en) 2014-10-03 2019-05-28 Xeros Limited Method for treating an animal substrate
US10808289B2 (en) 2014-10-10 2020-10-20 Xeros Limited Animal skin substrate treatment apparatus and method
DE102019127040A1 (de) * 2019-10-08 2021-04-08 Air Liquide Deutschland Gmbh Entkälken von Leder

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2147542A (en) * 1937-01-27 1939-02-14 Ruby Kid Co Treating skins, hides, and pelts
WO1988010317A1 (en) * 1987-06-16 1988-12-29 Aga Aktiebolag Process for the treatment of hides

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2147542A (en) * 1937-01-27 1939-02-14 Ruby Kid Co Treating skins, hides, and pelts
WO1988010317A1 (en) * 1987-06-16 1988-12-29 Aga Aktiebolag Process for the treatment of hides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DAS LEDER, vol. 40, no. 12, December 1989, pages 251-256, Darmstadt, DE; K.H. MUNZ et al.: "Entkälken mit Kohlendioxid (Teil 1)" *

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2684314A1 (fr) * 1991-11-07 1993-06-04 Sio Srl Dispositif pour introduire du gaz dans des zones determinees, dans des equipements ou machines rotatives.
EP0624654A2 (de) * 1993-05-11 1994-11-17 Linde Aktiengesellschaft Verfahren zur Herstellung von Leder aus Tierhäuten
EP0624654A3 (de) * 1993-05-11 1995-07-05 Linde Ag Verfahren zur Herstellung von Leder aus Tierhäuten.
DE19507572A1 (de) * 1995-03-03 1996-09-12 Helmut Geihsler Verfahren zur Zurichtung von tierischen Häuten oder Fellen
US5900027A (en) * 1995-03-03 1999-05-04 Geihsler; Helmut Process for preparing animal hides or pelts
JP2016518487A (ja) * 2013-04-11 2016-06-23 ゼロス・リミテツド 固体粒子および化学配合物を使用して、動物の繊維でできた基材を処理する方法
US9845516B2 (en) 2013-04-11 2017-12-19 Xeros Limited Method for treating a substrate made of animal fibers with solid particles and a chemical formulation comprising a colourant
US10745769B2 (en) 2013-04-11 2020-08-18 Xeros Limited Method for treating a substrate made of animal fibers with solid particles and a chemical formulation
US10301691B2 (en) 2014-10-03 2019-05-28 Xeros Limited Method for treating an animal substrate
US10287642B2 (en) 2014-10-10 2019-05-14 Xeros Limited Animal skin substrate treatment apparatus and method
US10808289B2 (en) 2014-10-10 2020-10-20 Xeros Limited Animal skin substrate treatment apparatus and method
DE102019127040A1 (de) * 2019-10-08 2021-04-08 Air Liquide Deutschland Gmbh Entkälken von Leder

Also Published As

Publication number Publication date
EP0439108B1 (de) 1996-12-11
DE69123466D1 (de) 1997-01-23
DE69123466T2 (de) 1997-04-24
IT1238336B (it) 1993-07-12
IT9019131A0 (it) 1990-01-23
IT9019131A1 (it) 1991-07-24

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