EP0059909A1 - Procédé de déchaulage de peaux - Google Patents

Procédé de déchaulage de peaux Download PDF

Info

Publication number
EP0059909A1
EP0059909A1 EP82101530A EP82101530A EP0059909A1 EP 0059909 A1 EP0059909 A1 EP 0059909A1 EP 82101530 A EP82101530 A EP 82101530A EP 82101530 A EP82101530 A EP 82101530A EP 0059909 A1 EP0059909 A1 EP 0059909A1
Authority
EP
European Patent Office
Prior art keywords
liquor
deliming
descaling
acid
minutes
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
EP82101530A
Other languages
German (de)
English (en)
Other versions
EP0059909B1 (fr
Inventor
Erwin Dr. Hahn
Dietrich Dr. Lach
Kurt Dr. Schneider
Rainer Dr. Strickler
Rolf Streicher
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to AT82101530T priority Critical patent/ATE6164T1/de
Publication of EP0059909A1 publication Critical patent/EP0059909A1/fr
Application granted granted Critical
Publication of EP0059909B1 publication Critical patent/EP0059909B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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 invention relates to a process for deliming skins, in which cyclic carbonates of polyhydric aliphatic alcohols are used as "safety deliming agents". This avoids the disadvantages associated with overdosing of the known decalcifying agents.
  • Ashes of the skins for the purpose of depilation and skin disruption in the context of leather production are carried out in an alkaline medium, usually with the help of inorganic or organic sulfides.
  • Lime is usually used as the alkaline agent, usually alone, but occasionally also in a mixture with caustic soda or soda. Then the material must be freed from the liming chemicals, especially the lime, in preparation for further processing, that is, "descaled". This is usually done with acids or acidic salts, for example phthalic acid, sulfophthalic acid, formic acid, acetic acid, boric acid, aliphatic dicarboxylic acid mixtures, hydrochloric acid, sulfuric acid and their ammonium salts.
  • acids or acidic salts for example phthalic acid, sulfophthalic acid, formic acid, acetic acid, boric acid, aliphatic dicarboxylic acid mixtures, hydrochloric acid, sulfuric acid and their ammonium salts.
  • the amount of chemicals required for descaling depends heavily on the skins' content of lime and other basic compounds, e.g. Sodium sulfide and sodium hydroxide. Since this always fluctuates, exact dosing of the decalcifying chemicals is hardly possible in practice. It is therefore easy to overdose. As a result, the pH value drops to or even below the isoelectric point of the protein (pH approx. 5) at the start of decalcification. In the process of liming, protein substances that have gone into solution are precipitated, possibly together with other dissolved "dirt". They deposit on the surface of the skin material in a form that is difficult to remove, make it unsightly and interfere with later processing steps, especially when dyeing. The grip is also adversely affected.
  • ammonium salts as so-called "safety decalcifying agents".
  • these agents since the pH of aqueous ammonium salt solutions can be below 5, these agents also do not offer the desired safety.
  • the use of ammonium salts is also problematic from an ecological point of view. Ammonium salts are only partially broken down in sewage treatment plants and thus increase the COD value of the waste water.
  • butyrolactone as a deliming agent is known from DE-PS 804 827.
  • this internal ester hydrolyzes very slowly under the usual descaling conditions. The necessary descaling times are therefore very long. This is probably the reason why butyrolactone has not found its way into practice.
  • hydrolyzing esters are used under the descaling conditions. They overcome the above-mentioned disadvantages of conventional decalcifying agents by not dropping the pH below 5 and also being free of ammonium salts. However, they too cannot prevent hydrogen sulfide from being released when they are overdosed. Due to the high toxicity of hydrogen sulfide, this possibility represents a permanent latent danger to life for the personnel, apart from the unpleasant smell.
  • the invention was therefore based on the object of developing a deliming process which not only avoids the disadvantages of the usual deliming agents mentioned above, but also the development of hydrogen sulfide with certainty.
  • cyclic carbonates of polyhydric aliphatic alcohols preference is given to those whose equivalent weight (with respect to the carbonic acid component, not the alcohol component) is below 150, preferably below 100 and in particular below 60.
  • Suitable carbonates are Correspondingly, the carbonic diesters of polyhydric, that is to say more than one, preferably 2 to 3, in particular 2 hydroxyl groups, aliphatic alcohols having 2 to 6, preferably 2 to 3, carbon atoms, which optionally contain free hydroxyl groups, at least 2 hydroxyl groups to one another in 1, 3- or preferably the 1,2-position are arranged, for example the cyclic carbonates of 1,2-butanediol, 2,3-butanediol, neopentyl glycol, glycerol, the dicarbonate of pentaerythritol (spiro compound), preferably the cyclic carbonate of ethylene glycol and 1,2-propylene glycol.
  • the carbonic diesters of polyhydric that is to say more than one, preferably 2 to 3, in particular 2 hydroxyl groups, aliphatic alcohols having 2 to 6, preferably 2 to 3, carbon atoms, which optionally contain free hydroxyl groups, at least 2 hydroxyl groups
  • the carbonates are prepared in a known manner, e.g. by reacting the alcohols with phosgene or preferably epoxides with carbon dioxide.
  • the carbonate is hydrolyzed by the limestone contained in the liming so far until a pH value in the range of - depending on the carbonate excess - 7.8 to 7.5 is reached.
  • the lime is dissolved as calcium bicarbonate. Then the hydrolysis stops.
  • the pH did not fall below 7.5 in any experiment. This range is optimal, because on the one hand this ensures that no hydrogen sulfide escapes from the solution, on the other hand the pH is not higher than is absolutely necessary to avoid the formation of hydrogen sulfide. Too high pH values are also undesirable with regard to the grain smoothness and the feel of the leather as well as the safety of limescale removal.
  • the amounts used for the carbonate depend on the content of lime and other basic compounds (e.g. sodium sulfide and sodium hydroxide) in the skin material. They are of the order of 0.8 to 4%, preferably 1 to 2%, based on the weight of the wet hides.
  • the carbonates are preferably dissolved in water.
  • the emulsification or dispersion of insufficiently water-soluble carbonates can be carried out in a conventional manner with cationic, anionic or nonionic emulsifiers. It is in no way problematic.
  • Example 1 was repeated in exactly the same way, except that a commercially available product based on the ammonium salt of sulfophthalic acid was used as the deliming agent. After 5 minutes of walking, the pH of the decalcifying liquor was measured at 3.2, 15 minutes later it had risen to 7, and then after 40 minutes of walking adjust to the final pH of 8.6.
  • Example 2 100 parts of bare bark were always decalcified. The test results are summarized in the table.

Landscapes

  • 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)
  • Detergent Compositions (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Peptides Or Proteins (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Diaphragms For Electromechanical Transducers (AREA)
EP82101530A 1981-03-06 1982-02-27 Procédé de déchaulage de peaux Expired EP0059909B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82101530T ATE6164T1 (de) 1981-03-06 1982-02-27 Verfahren zum entkaelken von haeuten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3108428 1981-03-06
DE19813108428 DE3108428A1 (de) 1981-03-06 1981-03-06 Verfahren zum entkaelken von haeuten

Publications (2)

Publication Number Publication Date
EP0059909A1 true EP0059909A1 (fr) 1982-09-15
EP0059909B1 EP0059909B1 (fr) 1984-02-08

Family

ID=6126452

Family Applications (1)

Application Number Title Priority Date Filing Date
EP82101530A Expired EP0059909B1 (fr) 1981-03-06 1982-02-27 Procédé de déchaulage de peaux

Country Status (4)

Country Link
US (1) US4377387A (fr)
EP (1) EP0059909B1 (fr)
AT (1) ATE6164T1 (fr)
DE (2) DE3108428A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0210481A3 (en) * 1985-07-27 1987-08-12 Basf Aktiengesellschaft Method of deliming hides and use of sulphurous acid cyclic esters as deliming agents
RU2156304C1 (ru) * 1999-12-09 2000-09-20 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ обработки голья
RU2157409C1 (ru) * 1999-12-09 2000-10-10 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ обработки голья
EP4032989A1 (fr) 2021-01-22 2022-07-27 TFL Ledertechnik GmbH Composition de déchaulage et procédé de déchaulage destiné au déchaulage des peaux

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3425068B1 (fr) * 2017-07-06 2021-08-04 Stahl International B.V. Agent de déchaulage exempt d'ammonium et d'acide borique, ses utilisations, processus de détartrage
NL2027083B1 (en) * 2020-12-09 2022-07-07 Stahl Int B V Process for deliming of hides, skins or pelts

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE804827C (de) * 1948-10-02 1951-04-30 Basf Ag Entkaelken von Bloessen
DE2825081B1 (de) * 1978-06-08 1979-10-04 Basf Ag Verfahren zum Entkaelken von Haeuten

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE804827C (de) * 1948-10-02 1951-04-30 Basf Ag Entkaelken von Bloessen
DE2825081B1 (de) * 1978-06-08 1979-10-04 Basf Ag Verfahren zum Entkaelken von Haeuten

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0210481A3 (en) * 1985-07-27 1987-08-12 Basf Aktiengesellschaft Method of deliming hides and use of sulphurous acid cyclic esters as deliming agents
US4729768A (en) * 1985-07-27 1988-03-08 Basf Aktiengesellschaft Deliming of hides and use of cyclic esters of sulfurous acid as deliming agents
RU2156304C1 (ru) * 1999-12-09 2000-09-20 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ обработки голья
RU2157409C1 (ru) * 1999-12-09 2000-10-10 Центральный научно-исследовательский институт кожевенно-обувной промышленности Способ обработки голья
EP4032989A1 (fr) 2021-01-22 2022-07-27 TFL Ledertechnik GmbH Composition de déchaulage et procédé de déchaulage destiné au déchaulage des peaux
WO2022157273A1 (fr) 2021-01-22 2022-07-28 Tfl Ledertechnik Gmbh Composition de déchaulage et procédé de déchaulage de peaux

Also Published As

Publication number Publication date
US4377387A (en) 1983-03-22
ATE6164T1 (de) 1984-02-15
DE3108428A1 (de) 1982-09-23
DE3260040D1 (en) 1984-03-15
EP0059909B1 (fr) 1984-02-08

Similar Documents

Publication Publication Date Title
DD210078A5 (de) Verfahren zum umweltfreundlichen aeschern von rohhaeuten
DE102009018232B4 (de) Verfahren zur Gerbung von Tierhäuten
CH615224A5 (fr)
EP0059909B1 (fr) Procédé de déchaulage de peaux
DE69202522T2 (de) Verfahren zur Enthaarung von Tierhäuten.
DE2626429A1 (de) Verfahren zum gerben von haeuten
EP3924523B1 (fr) Adjuvants dans la fabrication du cuir pour le travail de rivière
DE2825081C2 (de) Verfahren zum Entkälken von Häuten
DE925605C (de) Entkaelkungsmittel
DE2063128A1 (de) Verfahren zur Herstellung von Phos phatidemulgatoren fur Ol in Wasser und Wasser in Ol Emulsionen durch partielle Hydrolyse von naturlichen und modifizier ten Pflanzenphosphatiden
EP0210481B1 (fr) Procédé de déchaulage des peaux et utilisation d'esters cycliques de l'acide sulfureux comme agents de déchaulage
AT258451B (de) Verfahren zur Herstellung von Chromledern
DE10221152B4 (de) Verfahren zur Herstellung sauberer Blößen in der Wasserwerkstatt
DE2424301C3 (de) Verfahren zum Chromgerben und Gerbmischung dafür
DE590234C (de) Verfahren zum Reinigen von Trinitrotoluol
DE703853C (de) Verfahren zur Herstellung gerbfertiger Hautbloessen
DE732574C (de) Verfahren zum Roesten von Flachs nach dem Warmwasserverfahren
DE2419326C3 (de) Verfahren zur Herabsetzung des Kalziumgehalts von natriumbasischer Sulfitablaugen
DE738962C (de) Verhefung von Laevoglucosan bzw. solches enthaltenden Stoffen
DE759631C (de) Verfahren zum Entfetten von Fellen und Haeuten
DE630250C (de) Verfahren zum AEschern tierischer Haeute im Fass
DE694936C (de) Gerbmittel
DE2758936A1 (de) Gerbmittel und verfahren zum gerben von haeuten
DE2730623C3 (fr)
DE656111C (de) Verfahren zur Aufbereitung von Abwaessern aus Wollwaeschereien

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT CH DE FR GB IT SE

17P Request for examination filed

Effective date: 19820929

ITF It: translation for a ep patent filed
GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19840119

Year of fee payment: 3

AK Designated contracting states

Designated state(s): AT CH DE FR GB IT LI SE

REF Corresponds to:

Ref document number: 6164

Country of ref document: AT

Date of ref document: 19840215

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3260040

Country of ref document: DE

Date of ref document: 19840315

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19870228

Ref country code: CH

Effective date: 19870228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19950130

Year of fee payment: 14

EAL Se: european patent in force in sweden

Ref document number: 82101530.2

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19960228

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19970124

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19970203

Year of fee payment: 16

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19980217

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19980226

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19980227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19980228

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19990225

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990227

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990227