EP0235832A1 - Verfahren und Vorrichtung für die Entfettung von Rohhäuten und so erhaltene Rohhäute - Google Patents

Verfahren und Vorrichtung für die Entfettung von Rohhäuten und so erhaltene Rohhäute Download PDF

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Publication number
EP0235832A1
EP0235832A1 EP87200091A EP87200091A EP0235832A1 EP 0235832 A1 EP0235832 A1 EP 0235832A1 EP 87200091 A EP87200091 A EP 87200091A EP 87200091 A EP87200091 A EP 87200091A EP 0235832 A1 EP0235832 A1 EP 0235832A1
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EP
European Patent Office
Prior art keywords
skins
degreasing
bath
raw
fats
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
EP87200091A
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English (en)
French (fr)
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EP0235832B1 (de
Inventor
Christine Godawa
Michel Delmas
Antoine Gaset
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.)
CHAMBRE SYNDICALE DE L'INDUSTRIE DU CUIR DE MAZAMET
CHAMBRE SYNDICALE DES PATRONS MEGISSIERS (Syndicat Professionnel)
Original Assignee
CHAMBRE SYNDICALE DE L'INDUSTRIE DU CUIR DE MAZAMET
CHAMBRE SYNDICALE DES PATRONS MEGISSIERS (Syndicat Professionnel)
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Priority to AT87200091T priority Critical patent/ATE44048T1/de
Publication of EP0235832A1 publication Critical patent/EP0235832A1/de
Application granted granted Critical
Publication of EP0235832B1 publication Critical patent/EP0235832B1/de
Expired legal-status Critical Current

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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
    • C14C1/00—Chemical treatment prior to tanning
    • C14C1/08—Deliming; Bating; Pickling; Degreasing
    • 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

Definitions

  • the invention relates to an improved process and installation for degreasing raw hides rendered, having a moisture content which is generally of the order of 60%; it applies to raw hides coming directly from rendering or raw hides having undergone certain preliminary treatments, such as fleshing, pickling, stripping. It extends to the degreased raw skins obtained, skins of sheep, cattle, pigs, mestizos, goats ...
  • the raw skins coming from rendering are very wet, especially if they have undergone preliminary treatments, in particular fleshing. They contain interstitial fats, sometimes in very large quantities linked to the origin of the skins, and residual surface fats, in smaller quantities if the skins have undergone prior fleshing. Interstitial fats are made up of reserve fats between cells and cell-building fats. It is essential in the skin treatment industries to extract these fats to allow correct implementation of subsequent treatments (tanning, dyeing) and obtaining good quality leathers.
  • the present invention proposes to provide a new deep degreasing process for wet raw skins coming from rendering.
  • An object of the invention is to provide a degreasing process which lends itself to extremely easy recovery of fats without being polluted by other products.
  • Another objective is to avoid charging the skin with an organic solvent or a surfactant so as not to modify its characteristics.
  • Another objective is to reduce the cost of the treatment, on the one hand, thanks to a complete recovery of the basic products, on the other hand, thanks to a valorization of the fats allowing either to resell them, or to use them then for the skin nourishment, if any, after appropriate treatment.
  • the method according to the invention for separating wet raw skins from rendering, interstitial fats and residual surface fats consists in putting said raw skins in their wet state in the presence of a liquid bath based on fluorocarbon compound (s), in particular trichloro-1,1,2 trifluoro-1,2 , 2 ethane or monofluorotrichloromethane, for a time necessary for the separation of said greases, generally between 15 minutes and 2 hours.
  • This treatment is carried out cold in a temperature range which can range from 10 ° C. to 30 ° C. It is possible to choose liquid compounds in this temperature range and to use pure baths of these compounds; in this case, if monofluorotrichloromethane is used, the temperature will be limited to 23 ° C, the boiling point of this body.
  • the skins obtained can be very easily rid of all of the fluorocarbon compound simply by isolating them from the liquid phase and by heating them in air at a temperature of 35 ° C to 55 ° C. This heating can be obtained by circulation hot air. It should be noted that, in a draft, the skins can withstand the temperatures mentioned above without any damage.
  • the fluorocarbon compounds are thus entirely removed due to their volatile nature and can be entirely recovered by simple condensation of the vapors. In addition, any residual traces are naturally removed very quickly during subsequent handling or mixing of the skins.
  • fluorocarbon compounds are also known to have fat-solubilizing properties.
  • 1,1,2-trifluoro-1,2,2 ethane has already been used for degreasing dry clothes or furs tanned (Japanese patent No. 77.64401), or to extract laboratory oils homogenates soybeans, or to degrease components in the electronics industries.
  • the eliminated fats are superficial fats, directly accessible.
  • their dissolution is always done dry and most often using another means (heating, activation with ultrasound ).
  • they have been subjected to extensive drying beforehand, so that their moisture content is negligible.
  • the fats and the fluorocarbon compound can be easily separated and recovered, by subjecting the bath resulting from the degreasing treatment to a distillation of the compound.
  • the fluorocarbon compound can thus be recycled, while the recovered fats are clean and usable in many industrial sectors: cosmetology, soap, detergent ...
  • cosmetology soap, detergent ...
  • some of these fats can be used on site to then nourish the skins after tanning, after having undergone if necessary an appropriate treatment.
  • the invention extends to an installation allowing the degreasing of the skins by implementing the method defined above.
  • This installation is of the type comprising a rotating barrel provided with a door for introducing the skins and means for emptying the bath.
  • said barrel is associated with a closed loop comprising air heating means, circulation means and a steam condenser.
  • the invention also extends to degreased raw skins of quality corresponding to that obtained by implementing the above method. These skins are characterized in that they are free from traces of hydrophobic bodies or foreign surfactants.
  • This installation comprises a rotating barrel 1 intended to receive a liquid bath of one or more fluorocarbon compounds.
  • This barrel is provided on either side with two hollow shafts 2 and 3 placed in fixed bearings 4 and 5.
  • the barrel is externally provided with a toothed crown 6 engaged with a gear system associated with an electric motor 7.
  • the barrel has a door 8 for introducing the skins and means for draining the bath, constituted in the example by a drain hole on which a stop valve 9 is mounted.
  • this barrel is internally provided with pegs 10 driving the skins in rotation and ensuring their mixing in the bath.
  • the barrel 1 is associated with a closed loop which enters it by one of the hollow shafts 2 by means of a rotary joint 11, and which exits therefrom by the other hollow shaft 3 by means of a another rotating joint 12.
  • This loop comprises a gas / liquid separation enclosure 13, making it possible to send the liquid to a conduit 14 provided with a valve, and the vapors to a conduit 15 also provided with a valve.
  • the conduit 15 is equipped with a condenser 16 associated with a separator 17. This separator makes it possible to separate any traces of water present in the fluorocarbon compound.
  • an air circulator 18 At the outlet of the condenser 16 is arranged an air circulator 18 and an air heater 19.
  • the circulator 18 and the heater 19 make it possible, by opening a valve 20, to circulate air at a temperature between 35 ° C and 55 ° C in order to clear the skins of the residual fluorocarbon compound and recovering this compound in the condenser 16.
  • the barrel 1 preferably comprises on the side of the shaft 3 a double wall 21, partially formed by a grid in order to allow possible recovery of the bath by the hollow shaft, without being hindered by the skins.
  • the volume of liquid fluorocarbon compound placed in the barrel will be between 0.25 and 4 liters per kilogram of skin.
  • Examples 1 to 5 were implemented on a pilot installation having a barrel of capacity of the order of 0.55 m3 into which 2 dozen were introduced. skins.
  • Example 6 was implemented on an industrial-size installation having a barrel with a capacity of the order of 5 m3 into which 10 dozen skins were introduced.
  • a bath of trichloro-1,1,2 trifluoro-1,2,2 ethane (7.5 1 per dozen skins, or 0.75 1 per kg of skin) is then introduced into the barrel.
  • the barrel is rotated for 1 hour at room temperature (20 ° C). The residual bath is recovered.
  • a circulation of hot air (50-55 ° C) for half an hour makes it possible to evaporate the solvent remaining on the skins; the latter is recovered after condensation. During this operation, the barrel continues to rotate. It takes about 175 joules to recover one gram of solvent. It takes about 5 times more energy to heat the skins and take into account the various heat losses.
  • the operation makes it possible on the one hand to rid the skins of all traces of solvent and on the other hand to recover almost all of the 1,12,2-trichloro-1,2,2-trihane ethane and to recycle it. Separation of 1,12,2-trichloro-1,2,2-trifluoroethane and fats.
  • 1,1,2 trichloro-1,2,2 trihane is a compound with high vapor pressure and low latent heat of vaporization (147 kJ / kg). Distillation is therefore a separation process which is both inexpensive in energy and efficient, which makes it possible to collect 1,1,2-trichloro-1,2,2-trifluoroethane and pure fat.
  • the traces of solvent remaining in the fats can be easily removed by entrainment under a stream of air or nitrogen.
  • the amount of fat recovered is 600 g (i.e. 30 g / kg of skin).
  • Skin samples were taken before and after degreasing. The humidity percentage has been determined.
  • the fat content of these skins was determined by quantitative analysis, which made it possible to calculate the degreasing efficiency.
  • the quantitative analysis includes grinding the sample, extracting the fat with a chloroform-methanol mixture, and weighing the fat after evaporation of the solvents. The efficiency is 82%.
  • the fatty acid composition of the fats extracted was determined qualitatively and quantitatively by gas chromatography. It includes for the main constituents: oleic acid, palmitic acid and stearic acid.
  • the acidity of these fats is 5.6% in oleic acid.
  • the quantity of fat extracted is comparable and even slightly higher than that obtained by the hydrocarbon-surfactant method.
  • composition and the content of free fatty acids are comparable to those obtained after a degreasing of hydrocarbon-surfactant.
  • the extracted fats are pure and usable, subject to any suitable transformations (deacidification %) for the subsequent stages of leather nourishment.
  • the efficiency is 76% and the quality of the finished product is satisfactory.
  • the experimental procedure is identical to that followed in Example 1, but the quantity of 1,1,2-trichloro-1,2,2-trifluoroethane is 10 1 per dozen of skin (i.e. 0.91 1 / kg of skin).
  • the skins 22 kg have a higher fat content, about 30% relative to the weight of dry leather, in the oily areas of the skin. Their water content is around 60%.
  • the barrel rotation time is 2 hours.
  • the efficiency is 77% and the quality of the finished product is satisfactory.
  • the amount of fat recovered is 980 g (i.e. 45 g / kg of skin).
  • the experimental procedure is identical to that followed in Example 1, but the amount of 1,1,2-trichloro-1,2,2-trifluoroethane is 20 liters per dozen of skin (i.e. 2 1 / kg of skin) .
  • the barrel rotation time is 30 minutes.
  • the efficiency is 78% and the quality of the finished product is satisfactory.
  • Example 4 The experimental procedure is identical to that followed in Example 4 with regard to the degreasing and recovery phase of the 1,1,2,2-trifluoro-1,2,2 ethane trichloro absorbed on the skins, but a bath is used. which comes from a previous implementation: in this example, the bath is composed of the residual bath and 1,1,2-trichloro-1,2,2-trihane-ethane, recovered after a test carried out according to example 4.
  • the efficiency is 76% and the quality of the finished product is satisfactory.
  • Direct recycling can be done multiple times.
  • the experimental procedure is identical to that followed in Example 1, but the quantity of skin is greater: 10 dozen, or approximately 100 kg. The efficiency is 79%.
  • the experimental procedure is identical to that followed in Example 3, but we use lamb skins called "country".
  • the skins 25 kg have a fat content of around 25% in fatty areas. Their texture is different from that of New Zealand lambskins.
  • the efficiency is 75% and the quality of the finished product is satisfactory.

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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)
  • Glass Compositions (AREA)
  • Processing Of Solid Wastes (AREA)
  • Detergent Compositions (AREA)
  • Meat, Egg Or Seafood Products (AREA)
  • Soy Sauces And Products Related Thereto (AREA)
EP87200091A 1986-02-12 1987-01-22 Verfahren und Vorrichtung für die Entfettung von Rohhäuten und so erhaltene Rohhäute Expired EP0235832B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT87200091T ATE44048T1 (de) 1986-02-12 1987-01-22 Verfahren und vorrichtung fuer die entfettung von rohhaeuten und so erhaltene rohhaeute.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8602277 1986-02-12
FR8602277A FR2594141B1 (fr) 1986-02-12 1986-02-12 Procede et installation perfectionnee pour le degraissage de peaux brutes et peaux brutes obtenues

Publications (2)

Publication Number Publication Date
EP0235832A1 true EP0235832A1 (de) 1987-09-09
EP0235832B1 EP0235832B1 (de) 1989-06-14

Family

ID=9332309

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Application Number Title Priority Date Filing Date
EP87200091A Expired EP0235832B1 (de) 1986-02-12 1987-01-22 Verfahren und Vorrichtung für die Entfettung von Rohhäuten und so erhaltene Rohhäute

Country Status (4)

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EP (1) EP0235832B1 (de)
AT (1) ATE44048T1 (de)
DE (1) DE3760248D1 (de)
FR (1) FR2594141B1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5098446A (en) * 1989-10-13 1992-03-24 Minnesota Mining And Manufacturing Company Use of fluorochemicals in leather manufacture

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR462280A (fr) * 1912-11-18 1914-01-23 Joseph Filhol Procédé pour le dégraissage des peaux
US1338307A (en) * 1919-06-20 1920-04-27 Krouse Charles Clement Art of tanning
FR717000A (fr) * 1931-05-13 1931-12-30 Procédé et installation pour le dégraissage des peaux et autres applications similaires
FR2318930A1 (fr) * 1975-07-19 1977-02-18 Boehme Chem Fab Kg Procede de traitement du cuir et des peaux

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5264401A (en) * 1975-11-18 1977-05-27 Tokyo Hooruseeru Kk Process for processing fur

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR462280A (fr) * 1912-11-18 1914-01-23 Joseph Filhol Procédé pour le dégraissage des peaux
US1338307A (en) * 1919-06-20 1920-04-27 Krouse Charles Clement Art of tanning
FR717000A (fr) * 1931-05-13 1931-12-30 Procédé et installation pour le dégraissage des peaux et autres applications similaires
FR2318930A1 (fr) * 1975-07-19 1977-02-18 Boehme Chem Fab Kg Procede de traitement du cuir et des peaux

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 87, 1977, page 79, résumé no. 86351w, Columbus, Ohio, US; & JP-A-77 64 401 (TOKYO HORU SEIRU K.K.) 27-05-1977 *

Also Published As

Publication number Publication date
FR2594141A1 (fr) 1987-08-14
FR2594141B1 (fr) 1989-02-24
EP0235832B1 (de) 1989-06-14
ATE44048T1 (de) 1989-06-15
DE3760248D1 (en) 1989-07-20

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