EP0015478B1 - Tannins au chrome stables au vieillissement - Google Patents

Tannins au chrome stables au vieillissement Download PDF

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Publication number
EP0015478B1
EP0015478B1 EP80100936A EP80100936A EP0015478B1 EP 0015478 B1 EP0015478 B1 EP 0015478B1 EP 80100936 A EP80100936 A EP 80100936A EP 80100936 A EP80100936 A EP 80100936A EP 0015478 B1 EP0015478 B1 EP 0015478B1
Authority
EP
European Patent Office
Prior art keywords
mol
tanning agents
formic acid
content
chrome tanning
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.)
Expired
Application number
EP80100936A
Other languages
German (de)
English (en)
Other versions
EP0015478B2 (fr
EP0015478A1 (fr
Inventor
Herbert Dr. Knopf
Heinrich Dr. Spahrkäs
Wolfhard Dr. Luck
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.)
Bayer AG
Original Assignee
Bayer AG
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
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Application filed by Bayer AG filed Critical Bayer AG
Publication of EP0015478A1 publication Critical patent/EP0015478A1/fr
Application granted granted Critical
Publication of EP0015478B1 publication Critical patent/EP0015478B1/fr
Publication of EP0015478B2 publication Critical patent/EP0015478B2/fr
Expired legal-status Critical Current

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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
    • C14C3/00—Tanning; Compositions for tanning
    • C14C3/02—Chemical tanning
    • C14C3/04—Mineral tanning
    • C14C3/06—Mineral tanning using chromium compounds

Definitions

  • the present invention relates in particular to age-resistant chrome tanning agents, the solubility of which is retained in water even over a long period of time.
  • Tanning agents of this type are characterized by a mild tanning effect and good dyeability of the leather produced with them. They are easily soluble in water, but lose this property when stored for a long time. This is disadvantageous for practical use, since chrome tanning agents are generally added to the tanning drums in powder form without prior dissolution. Tannins of the type mentioned which have been stored for a long time then dissolve too slowly or only incompletely in the time available for tanning.
  • powdered chrome tanning agents with a formate content of 1.8-2.6 mol / mol Cr 2 0 3 and a basicity of at least 42%, preferably about 50%, which, before drying, have a sulfate content of at least 1, 8 moles of SO 3 / Cr 2 O 3 have been adjusted and then spray-dried, and their solubility is maintained even after prolonged storage.
  • the present invention therefore relates to age-resistant spray-dried chrome tanning agents with a formate content of about 1.8-2.6 mol / mol Cr 2 0 3 and a basicity of at least 42%, which are characterized in that they have a sulfate content of at least 1.8 Have moles of SO 3 / moles of Cr 2 0 3 .
  • the known powdery chrome tanning agents mentioned at the outset with a formate content of about 2 mol / mol Cr 2 0 3 and a basicity of about 50% have only a sulfate content of about 1.6 mol SO 3 / mol Cr 2 0 3 .
  • the products according to the claims are produced by processes known per se (cf., for example, Ullmann, Enz. Der Techn. Chemie, 4th edition 1975, vol. 9, pp. 614-615).
  • the known chrome tanning agents with a formate content of about 2 mol formate / mol Cr 2 0 3 with a sulfate content of about 1.6 mol S0 3 / mol Cr 2 0 3 can be spray dried to a sulfate content of at least 1.8 mol S0 Adjust 3 / mol Cr 2 0 3 and then spray dry.
  • chromium sulfate tanning agents have a formate content of 1.8-2.6 mol formate / mol Cr 2 0 3 and a sulfate content of at least 1.8 mol SO 3 / mol Cr 2 0 3 with, for example, formic acid, sodium formate or Prepare calcium formate by adjusting the basicity in the usual way.
  • the tanning properties of the tanning agents according to the invention do not differ from those of the known formate-masked tanning agents with a lower sulfate content. Accordingly, the tanning agents according to the invention can be used in a customary manner.
  • the tannins according to the invention can be used as such, or else in a mixture with base agents, such as magnesium oxide, sodium hydrogen carbonate or dolomite or / and with other masking agents, e.g. Salts of dicarboxylic acids.
  • the chrome tanning agents according to the invention are particularly suitable for a tanning process in which very good exhaustion of the chrome broths is achieved by pre-tanning the pickled pelts with chrome (III) salts and tanning with chrome (III) salts and acid-binding agents.
  • the total amount of chromium oxide offered is about 1.0 to 1.8%, based on the pelvis weight, and the tanning becomes 100% (again based on the pelvis weight) with a liquor length Z and up to a final pH of ⁇ 3 , 6 performed.
  • Powdery chrome tanning agents which are particularly valuable in the practice of leather production and have particularly good storage stability with regard to solubility in water contain about 1.8-2.4 mol of formate / mol of Cr 2 0 and 1.8-2.8 mol of SO 3 / mol of Cr 2 0 3 with a basicity of 48-52%.
  • 5000 kg of chromium sulfate liquor containing 11% Cr 2 0 3 , 14.4% S0 3 , 11.2% Na 2 0 and 6.8% formic acid are dried in a spray dryer at an inlet temperature of 200 ° C. and an outlet temperature of 90 ° C.
  • the dried product contains 21.5% Cr 2 0 3 , 13.3% formic acid (2.0 mol formic acids / mol Cr 2 0 3 ) and 2.5 mol S0 3 / mol Cr 2 0 3 with a basicity of 50% .
  • the undissolved residue is 0% when tested immediately and 0.1% after 30 days of rapid aging.
  • the rapid aging and the solubility test are carried out as described below.
  • the dried product is stored under lock and key in a drying cabinet at 50 ° C for a period of 30 days.
  • 20 g of the fresh or of the product so aged are mixed with 200 ml of water and dissolved for 1 hour at room temperature with shaking. The residue is then determined by weight by filtering through a suction filter.
  • chromium sulfate liquor with a content of 13% Cr 2 O 3 , 12.6% S0 3 , 6.4% Na 2 0 and 8.7% formic acid are in a spray dryer at 190 ° C inlet temperature and 120 ° C outlet temperature dried.
  • the dried product contains 28% Cr 2 0 3 , 18.7% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 1.85 mol SO 3 / mol Cr 2 0 3 with a basicity of 50%.
  • the undissolved residue is 0% when checked immediately and 2% after 30 days of rapid aging.
  • chromium sulfate liquor with a content of 12 % Cr 2 0 3 , 13.3% S0 3 , 7.2% Na 2 0 and 7.9% formic acid are in a spray dryer at 190 ° C inlet and 110 ° C. Outlet temperature dried.
  • the dried product contains 26.4% Cr 2 O 3 , 17.4% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 2.1 mol SO 3 / mol Cr 2 0 3 with a basicity of 50% .
  • the undissolved residue is 0% when checked immediately, and 0.2% after 30 days of rapid aging.
  • chromium sulfate liquor with a content of 11.1% Cr 2 0 31 12.2% SO 3 , 8.2% Na 2 O and 7.3% formic acid are in a spray dryer at 190 ° C inlet and 110 ° C outlet temperature dried.
  • the dried product contains 24.4% Cr 2 0 3 , 16% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 2.4 mol SO 3 / mol Cr 2 0 3 with a basicity of 50%.
  • the undissolved residue is 0% when tested immediately and 0.3% after 30 days of rapid aging.

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)

Claims (3)

1. Substances de tannage au chrome en poudre, séchées par pulvérisation, ayant une teneur en formiate d'environ 1,8-2,6 moles de formiate/ mole de Cr2O3 et une basicité d'au moins 42%, caractérisées en ce qu'elles présentent une teneur en sulfate d'au moins 1,8 mole de SO3/mole de Cr203.
2. Substances de tannage au chrome suivant la revendication 1, caractérisées en ce que leur basicité s'élève à environ 50%.
3. Substances de tannage au chrome suivant la revendication 1 ou 2, caractérisées en ce qu'elles présentent une teneur en sulfate de 1,8 à 2,8 moles de S03/mole de Cr2O3.
EP80100936A 1979-03-07 1980-02-26 Tannins au chrome stables au vieillissement Expired EP0015478B2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19792908967 DE2908967A1 (de) 1979-03-07 1979-03-07 Alterungsbestaendige chromgerbstoffe
DE2908967 1979-03-07

Publications (3)

Publication Number Publication Date
EP0015478A1 EP0015478A1 (fr) 1980-09-17
EP0015478B1 true EP0015478B1 (fr) 1981-09-16
EP0015478B2 EP0015478B2 (fr) 1985-07-31

Family

ID=6064761

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80100936A Expired EP0015478B2 (fr) 1979-03-07 1980-02-26 Tannins au chrome stables au vieillissement

Country Status (12)

Country Link
US (1) US4298344A (fr)
EP (1) EP0015478B2 (fr)
JP (1) JPS6017400B2 (fr)
AR (1) AR219218A1 (fr)
BR (1) BR8001342A (fr)
CA (1) CA1131409A (fr)
DE (2) DE2908967A1 (fr)
ES (1) ES489246A1 (fr)
MX (1) MX155156A (fr)
NZ (1) NZ193032A (fr)
YU (1) YU65180A (fr)
ZA (1) ZA801325B (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57100200A (en) * 1980-12-15 1982-06-22 Nippon Chemical Ind Manufacture of chromium tanning agent
DE3306374A1 (de) * 1983-02-24 1984-08-30 Basf Ag, 6700 Ludwigshafen Verfahren zum gerben von haeuten mit einem hochbasischen chromgerbstoff
FR2721619B1 (fr) * 1994-06-22 1996-08-23 Toulouse Inst Nat Polytech Produit de masquage pour sels métalliques à propriétés tannantes tels que sels de chrome, et procédé de tannage de peaux en milieu aqueux.
KR970010423B1 (ko) * 1995-09-19 1997-06-26 엘지전자 주식회사 식기세척기의 오물 처리방법 및 그 장치

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1230170B (de) * 1960-10-28 1966-12-08 Bayer Ag Gerbverfahren
FR1304531A (fr) * 1961-10-26 1962-09-21 Bayer Ag Procédé de fabrication de cuir

Also Published As

Publication number Publication date
MX155156A (es) 1988-02-01
EP0015478B2 (fr) 1985-07-31
AR219218A1 (es) 1980-07-31
DE2908967A1 (de) 1980-09-18
JPS6017400B2 (ja) 1985-05-02
NZ193032A (en) 1982-03-16
YU65180A (en) 1983-01-21
BR8001342A (pt) 1980-11-04
ES489246A1 (es) 1980-08-16
JPS55120699A (en) 1980-09-17
CA1131409A (fr) 1982-09-14
DE3060022D1 (en) 1981-12-03
EP0015478A1 (fr) 1980-09-17
US4298344A (en) 1981-11-03
ZA801325B (en) 1981-04-29

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