EP0015478B1 - Chrome tanning agents resisting ageing - Google Patents

Chrome tanning agents resisting ageing 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
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Prior art keywords
mol
tanning agents
formic acid
content
chrome tanning
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German (de)
French (fr)
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EP0015478B2 (en
EP0015478A1 (en
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Herbert Dr. Knopf
Heinrich Dr. Spahrkäs
Wolfhard Dr. Luck
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Bayer AG
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Bayer AG
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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
    • 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.

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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)

Description

Die vorliegende Erfindung betrifft besonders alterungsbeständige Chromgerbstoffe, deren Löslichkeit in Wasser auch über längere Zeit erhalten bleibt.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.

Es ist bekannt, pulverförmige Chromgerbstoffe mit einem Formiatgehalt von etwa 2 Mol/Mol Cr203 und einer Basizität von etwa 50% zum Gerben von tierischen Häuten und Fellen zu verwenden (vgl. z.B. H. Erdmann, «Das Leder», 16, (1965), Seite 262). Gerbstoffe dieser Art zeichnen sich durch eine milde Gerbwirkung und eine gute Färbbarkeit der damit hergestellten Leder aus. Sie sind in Wasser leicht löslich, verlieren aber diese Eigenschaft, bei längerem Lagern. Dies ist für die praktische Anwendung von Nachteil, da Chromgerbstoffe in der Regel ohne vorangehendes Lösen in Pulverform in die Gerbfässer gegeben werden. Längere Zeit gelagerte Gerbstoffe der genannten Art lösen sich dann vielfach in der für die Gerbung zur Verfügung stehenden Zeit zu langsam oder nur unvollständig auf. Dadurch kann es zu verzögerten Gerbungen oder zu Fleckenbildungen durch ungelöst gebliebene Gerbstoffteilchen auf den gegerbten Ledern kommen, und der Handelswert der Leder wird dadurch herabgesetzt. Es wurde nun gefunden, dass pulverförmige Chromgerbstoffe mit einem Formiatgehalt von 1,8-2,6 Mol/Mol Cr203 und einer Basizität von wenigstens 42%, vorzugsweise etwa 50%, die vor dem Trocknen auf einen Sulfatgehalt von wenigstens 1,8 Mol SO3/Cr2O3 eingestellt und dann sprühgetrocknet worden sind, ihre Löslichkeit auch bei längerer Lagerdauer beibehalten.It is known to use powdered chrome tanning agents with a formate content of about 2 mol / mol Cr 2 0 3 and a basicity of about 50% for tanning animal hides and skins (cf., for example, H. Erdmann, "Das Leder", 16, (1965), page 262). 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. This can lead to delayed tanning or to the formation of spots due to undissolved tannin particles on the tanned leather, and the commercial value of the leather is thereby reduced. It has now been found that 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.

Gegenstand der vorliegenden Erfindung sind daher alterungsbeständige sprühgetrocknete Chromgerbstoffe mit einem Formiatgehalt von etwa 1,8-2,6 Mol/Mol Cr203 und einer Basizität von mindestens 42%, welche dadurch gekennzeichnet sind, dass sie einen Sulfatgehalt von mindestens 1,8 Mol SO3/Mol Cr203 aufweisen.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 .

Die eingangs genannten bekannten pulverförmigen Chromgerbstoffe mit einem Formiatgehalt von etwa 2 Mol/Mol Cr203 und einer Basizität von etwa 50% weisen nur einen Sulfatgehalt von etwa 1,6 Mol SO3/Mol Cr203 auf.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 .

Überraschenderweise hat es sich gezeigt, dass durch die Erhöhung des Sulfatgehaltes vor dem Sprühtrocknen die Löslichkeit dieser Produkte auch bei längerer Lagerung erhalten bleibt.Surprisingly, it has been shown that by increasing the sulfate content before spray drying, the solubility of these products is retained even after prolonged storage.

Die Herstellung der anspruchsgemässen Produkte erfolgt nach an sich bekannten Verfahren (vgl. z.B. Ullmann, Enz. der Techn. Chemie, 4. Aufl. 1975, Bd. 9, S. 614-615). So kann man die bekannten Chromgerbstoffe mit einem Formiatgehalt von etwa 2 Mol Formiat/Mol Cr203 mit einem Sulfatgehalt von etwa 1,6 Mol S03/Mol Cr203 vor dem Sprühtrocknen auf einen Sulfatgehalt von wenigstens 1,8 Mol S03/Mol Cr203 einstellen und dann sprühtrocknen. Man kann aber auch direkt von Chromsulfatgerbstoffen ausgehen und einen Formiatgehalt von 1,8-2,6 Mol Formiat/Mol Cr203 und einen Sulfatgehalt von wenigstens 1,8 Mol S03/Mol Cr203 mit z.B. Ameisensäure, Natriumformiat oder Calciumformiat unter entsprechender Einstellung der Basizität auf den üblichen Wegen herstellen.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. However, one can also start directly from chromium sulfate tanning agents and 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.

Die gerberischen Eigenschaften der erfindungsgemässen Gerbstoffe unterscheiden sich nicht von denen, der bekannten Formiat-maskierten Gerbstoffe mit einem niedrigeren Sulfatgehalt. Dementsprechend kann die Anwendung dererfindungsgemässen Gerbstoffe in üblicher Weise erfolgen. Die erfindungsgemässen Gerbstoffe können als solche verwendet werden, oder aber auch in Mischung mit Basifizierungsmitteln, wie Magnesiumoxid, Natriumhydrogencarbonat oder Dolomit oder/und mit anderen Maskierungsmitteln, wie z.B. Salzen von Dicarbonsäuren.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.

Besonders geeignet sind die erfindungsgemässen Chromgerbstoffe für ein Gerbverfahren bei dem durch Vorgerben der gepickelten Blössen mit Chrom(III)-Salzen und Ausgerben mit Chrom(III)-Salzen und säurebindenden Mitteln eine sehr gute Auszehrung der Chrombrühen erreicht wird. Dabei beträgt die insgesamt angebotene Chromoxid-Menge etwa 1,0 bis 1,8%, bezogen auf Blössengewicht, und die Gerbung wird bei einer Flottenlänge Z 100% (wiederum bezogen auf Blössengewicht) und bis zu einem End-pH-Wert von ≧ 3,6 durchgeführt.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.

Für die Praxis der Lederherstellung besonders wertvolle pulverförmige Chromgerbstoffe mit besonders guter Lagerbeständigkeit hinsichtlich Löslichkeit in Wasser, enthalten etwa 1,8-2,4 Mol Formiat/Mol Cr20 und 1,8-2,8 Mol SO3/Mol Cr203 bei einer Basizität von 48-52%.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%.

Anhand der folgenden Beispiele soll die vorliegende Erfindung noch näher erläutert werden. Die %-Angaben beziehen sich bei den Zusammensetzungen auf Gew.-%.The present invention will be explained in more detail with the aid of the following examples. The percentages in the compositions relate to% by weight.

Beispiel 1example 1

5000 kg Chromsulfatlauge mit einem Gehalt von 11% Cr203, 14,4% S03, 11,2% Na20 und 6,8% Ameisensäure werden in einem Sprühtrockner bei 200 °C Eintrittstemperatur und 90 °C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 21,5% Cr203, 13,3% Ameisensäure (2,0 Mol Ameisensäuren/Mol Cr203) und 2,5 Mol S03/Mol Cr203 bei einer Basizität von 50%. Der ungelöste Rückstand beträgt bei sofortiger Prüfung 0% und nach 30 Tagen Schnellalterung 0,1%.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.

Im Vergleich hierzu liegt bei einem Produkt mit 30% Cr2O3, 20% Ameisensäure (2,2 Mol Ameisensäure/Mol Cr203 ), 1,57 Mol SO3/Mol Cr203 und einer Basizität von 50% unter gleichen Bedingungen wie oben getrocknet der ungelöste Rückstand bei sofortiger Prüfung bei 1 % und nach 30 Tagen Schnellalterung bei 24%.In comparison, a product with 30% Cr 2 O 3 , 20% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ), 1.57 mol SO 3 / mol Cr 2 0 3 and a basicity of 50% Under the same conditions as above, the undissolved residue dried at 1% with immediate inspection and at 24% after 30 days of rapid aging.

Die Schnellalterung und die Prüfung der Löslichkeit werden wie folgt beschrieben durchgeführt. Das getrocknete Produkt wird unter Verschluss in einem Trockenschrank bei 50 °C über einen Zeitraum von 30 Tagen gelagert. Zur Prüfung der Löslichkeit werden 20 g des frischen bzw. des so gealterten Produktes mit 200 ml Wasser versetzt und während 1 Stunde bei Raumtemperatur unter Schütteln gelöst. Danach wird der Rückstand durch Filtrieren über eine Filternutsche gewichtsmässig bestimmt.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. To test To increase solubility, 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.

Beispiel 2Example 2

2,2 kg Chromsulfatlauge mit einem Gehalt von 13% Cr2O3, 12,6% S03, 6,4% Na20 und 8,7% Ameisensäure werden in einem Sprühtrockner bei 190 °C Eintrittstemperatur und 120 °C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 28% Cr203, 18,7% Ameisensäure (2,2 Mol Ameisensäure/Mol Cr203) und 1,85 Mol SO3/Mol Cr203 bei einer Basizität von 50%. Der ungelöste Rückstand beträgt bei sofortiger Prüfung 0% und nach 30 Tagen Schnellalterung 2%.2.2 kg of 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.

Die Schnellalterung und die Prüfung der Löslichkeit werden wie in Beispiel 1 beschrieben durchgeführt.The rapid aging and the solubility test are carried out as described in Example 1.

Beispiel 3Example 3

2,2 kg Chromsulfatlauge mit einem Gehalt von 12% Cr 2 0 3, 13,3% S03, 7,2% Na20 und 7,9% Ameisensäure werden in einem Sprühtrockner bei 190°C Eintritts- und 110°C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 26,4% Cr2O3, 17,4% Ameisensäure (2,2 Mol Ameisensäure/Mol Cr203) und 2,1 Mol S03/Mol Cr203 bei einer Basizität von 50%. Der ungelöste Rückstand beträgt bei sofortiger Prüfung 0%, nach 30 Tagen Schnellalterung 0,2%.2.2 kg of 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.

Die Schnellalterung und die Prüfung der Löslichkeit wird wie in Beispiel 1 beschrieben durchgeführt.The rapid aging and the solubility test are carried out as described in Example 1.

Beispiel 4Example 4

2,2 kg Chromsulfatlauge mit einem Gehalt von 11,1% Cr2031 12,2% SO3, 8,2% Na2O und 7,3% Ameisensäure werden in einem Sprühtrockner bei 190°C Eintritts- und 110°C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 24,4% Cr203, 16% Ameisensäure (2,2 Mol Ameisensäure/Mol Cr203) und 2,4 Mol SO3/Mol Cr203 bei einer Basizität von 50%. Der ungelöste Rückstand beträgt bei sofortiger Prüfung 0% und nach 30 Tagen Schnellalterung 0,3%.2.2 kg of 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.

Die Schnellalterung und die Prüfung der Löslichkeit wird wie in Beispiel 1 beschrieben durchgeführt.The rapid aging and the solubility test are carried out as described in Example 1.

Beispiel 5Example 5

2,5 kg Chromsulfatlauge mit einem Gehalt von 8,1% Cr203, 12,3% S03, 11,4% Na20 und 4,4% Ameisensäure werden in einem Sprühtrockner bei 190°C Eintritts- und 120°C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 20,5% Cr2O3, 11,2% Ameisensäure (1,8 Mol Ameisensäure/Mol Cr203) und 2,9 Mol S03/Mol Cr203 bei einer Basizität von 50%. Der ungelöste Rückstand beträgt bei sofortiger Prüfung 0% und nach 30 Tagen Schnellalterung 0,1%.2.5 kg of chromium sulfate liquor with a content of 8.1% Cr 2 0 3 , 12.3% S0 3 , 11.4% Na 2 0 and 4.4% formic acid are in a spray dryer at 190 ° C inlet and 120 ° C outlet temperature dried. The dried product contains 20.5% Cr 2 O 3 , 11.2% formic acid (1.8 mol formic acid / mol Cr 2 0 3 ) and 2.9 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.

Die Schnellalterung und die Prüfung der Löslichkeit wird wie in Beispiel 1 beschrieben durchgeführt.The rapid aging and the solubility test are carried out as described in Example 1.

Beispiel 6Example 6

2,5 kg Chromsulfatlauge mit einem Gehalt von 7,8% Cr203, 11,9% S03, 11,9% Na20 und 4,7% Ameisensäure werden in einem Sprühtrockner bei 190 °C Eintritts- und 120 °C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 20% Cr203, 12% Ameisensäure (2,0 Mol Ameisensäure/Mol Cr203) und 2,9 Mol SO3/Mol Cr203 bei einer Basizität von 54%. Der ungelöste Rückstand beträgt bei sofortiger Prüfung 0% und nach 30 Tagen Schnellalterung 0,1%.2.5 kg of chromium sulfate liquor with a content of 7.8% Cr 2 0 3 , 11.9% S0 3 , 11.9% Na 2 0 and 4.7% formic acid are in a spray dryer at 190 ° C inlet and 120 ° C outlet temperature dried. The dried product contains 20% Cr 2 0 3 , 12% formic acid (2.0 mol formic acid / mol Cr 2 0 3 ) and 2.9 mol SO 3 / mol Cr 2 0 3 with a basicity of 54%. The undissolved residue is 0% when tested immediately and 0.1% after 30 days of rapid aging.

Die Schnellalterung und die Prüfung der Löslichkeit wird wie in Beispiel 1 beschrieben durchgeführt.The rapid aging and the solubility test are carried out as described in Example 1.

Claims (3)

1. Pulverulent spray dried chrome tanning agents having a formate content of from ca. 1.8 to 2.6 mol formate/mol Cr2O3 and a basicity of at least 42%, characterised in that they have a sulphate content of at least 1.8 mol S03/mol Cr203. 2 Chrome tanning agents according to Claim 1, characterised in that the basicity thereof is ca. 50%.
3. Chrome tanning agents according to one of the Claims 1 or 2, characterised in that they have a sulphate content of from 1.8 to 2.8 mol S03/mol Cr203.
EP80100936A 1979-03-07 1980-02-26 Chrome tanning agents resisting ageing Expired EP0015478B2 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2908967 1979-03-07
DE19792908967 DE2908967A1 (en) 1979-03-07 1979-03-07 AGING RESISTANT CHROME TANKS

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EP0015478A1 EP0015478A1 (en) 1980-09-17
EP0015478B1 true EP0015478B1 (en) 1981-09-16
EP0015478B2 EP0015478B2 (en) 1985-07-31

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JP (1) JPS6017400B2 (en)
AR (1) AR219218A1 (en)
BR (1) BR8001342A (en)
CA (1) CA1131409A (en)
DE (2) DE2908967A1 (en)
ES (1) ES489246A1 (en)
MX (1) MX155156A (en)
NZ (1) NZ193032A (en)
YU (1) YU65180A (en)
ZA (1) ZA801325B (en)

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JPS57100200A (en) * 1980-12-15 1982-06-22 Nippon Chemical Ind Manufacture of chromium tanning agent
DE3306374A1 (en) * 1983-02-24 1984-08-30 Basf Ag, 6700 Ludwigshafen METHOD FOR TANNING SKIN WITH A HIGH BASIC CHROME TANNER
FR2721619B1 (en) * 1994-06-22 1996-08-23 Toulouse Inst Nat Polytech Masking product for metallic salts with tanning properties such as chromium salts, and process for tanning skins in an aqueous medium.
KR970010423B1 (en) * 1995-09-19 1997-06-26 엘지전자 주식회사 Method and processing for disposal garbage of a dishwasher

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Publication number Priority date Publication date Assignee Title
DE1230170B (en) * 1960-10-28 1966-12-08 Bayer Ag Tanning process
FR1304531A (en) * 1961-10-26 1962-09-21 Bayer Ag Leather manufacturing process

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

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