EP0015478B2 - Chrome tanning agents resisting ageing - Google Patents
Chrome tanning agents resisting ageing Download PDFInfo
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- EP0015478B2 EP0015478B2 EP80100936A EP80100936A EP0015478B2 EP 0015478 B2 EP0015478 B2 EP 0015478B2 EP 80100936 A EP80100936 A EP 80100936A EP 80100936 A EP80100936 A EP 80100936A EP 0015478 B2 EP0015478 B2 EP 0015478B2
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- Prior art keywords
- mol
- tanning agents
- formic acid
- chrome tanning
- dried
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Classifications
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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 colorability 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 result in delayed tanning or the formation of spots due to undissolved tanning agent particles on the tanned leather, and the commercial value of the leather is thereby reduced.
- powdery 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 Cr 2 0 3 and a basicity of at least 42%, which are characterized in that they are spray-dried to a sulfate content of at least 1 , 8 mol S0 3 / mol Cr 2 O 3 can be set.
- 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 SO 3 / mol Cr 2 O 3 can be spray dried to a sulfate content of at least 1.8 mol SO Adjust 3 / MolCr 2 O 3 and then spray dry.
- 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 tanning agents 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, such as, for. B. 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 pretanning the pickled pelts with chromium (III) salts and tanning with chromium (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 is at a fleet length ⁇ 100% (again based on pelvis weight) 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 a particularly long shelf life with regard to solubility in water contain about 1.8-2.4 mol of formate / mol of Cr 2 O and 1.8-2.8 mol of S0 3 / mol of Cr 2 0 3 with a basicity of 48-52%.
- the present invention is to be explained in more detail with the aid of the following examples.
- the percentages for the compositions relate to% by weight.
- 5000 kg of chromium sulfate liquor containing 11% Cr 2 O 3, 14.4% SO 3 , 11.2% NazO 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 O 3 , 13.3% formic acid (2.0 mol formic acids / mol Crz0 3 ) and 2.5 mol SO 3 / mol Cr 2 O 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 examination of the release 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 the so aged product are mixed with 200 ml of water and dissolved for 1 hour at room temperature with shaking Then the residue is determined by weight by filtering through a suction filter.
- chromium sulfate liquor containing 13% Cr 2 0 3 , 12.6% SO 3 , 6.4% NazO and 8.7% formic acid are dried in a spray dryer at an inlet temperature of 190 ° C. and an outlet temperature of 120 ° C.
- the dried product contains 28% Cr 2 O 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 11.1% Cr 2 0 3 , 12.2% S0 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 O 3 , 16% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 2.4 mol SO 3 / mol Crz0 3 with a basicity of 50%.
- the undissolved residue is 0% when tested immediately and 0.3% after 30 days of rapid aging.
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 Flekkenbildungen durch ungelöst gebliebene Gerbstoffteilchen auf den gegerbten Ledern kommen, und der Handelswert der Leder wird dadurch herabgesetzt.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, BH Erdmann, "Das Leder", 16, (1965), page 262). Tanning agents of this type are characterized by a mild tanning effect and good colorability 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 result in delayed tanning or the formation of spots due to undissolved tanning agent particles on the tanned leather, and the commercial value of the leather is thereby reduced.
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 has now been found that powdery 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 Cr203 und einer Basizität von mindestens 42%, welche dadurch gekennzeichnet sind, daß sie vor dem Sprühtrocknen auf einen Sulfatgehalt von mindestens 1,8 Mol S03/ Mol Cr2O3 eingestellt werden.The present invention therefore relates to age-resistant spray-dried chrome tanning agents with a formate content of about 1.8-2.6 mol Cr 2 0 3 and a basicity of at least 42%, which are characterized in that they are spray-dried to a sulfate content of at least 1 , 8 mol S0 3 / mol Cr 2 O 3 can be set.
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 the solubility of these products is retained even after prolonged storage by increasing the sulfate content before spray drying.
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 SO3/Mol Cr2O3 vor dem Sprühtrocknen auf einen Sulfatgehalt von wenigstens 1,8 Mol SO3/MolCr2O3 eintstellen und dann sprühtrocknen. Man kann aber auch direkt von Chromsulfatgerbstoffen ausgehen und einen Formiatgehalt von 1,8-2,6 Mol Formiat/Mol Cr2O3 und einen Sulfatgehalt von wenigstens 1,8 Mol SO3/Mol Crz03 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 SO 3 / mol Cr 2 O 3 can be spray dried to a sulfate content of at least 1.8 mol SO Adjust 3 / MolCr 2 O 3 and then spray dry. But you can also start directly from chromium sulfate tanning agents and a formate content of 1.8-2.6 mol formate / mol Cr 2 O 3 and a sulfate content of at least 1.8 mol SO 3 / mol Crz0 3 with z. B. formic acid, sodium formate or calcium formate with appropriate adjustment of the basicity in the usual ways.
Die gerberischen Eigenschaften der erfindungsgemäßen Gerbstoffe unterscheiden sich nicht von denen, der bekannten Formiat-maskierten Gerbstoffe mit einem niedrigeren Sulfatgehalt. Dementsprechend kann die Anwendung der erfindungsgemäßen 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 tanning agents 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, such as, for. B. 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 < 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 pretanning the pickled pelts with chromium (III) salts and tanning with chromium (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 is at a fleet length <100% (again based on pelvis weight) 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 Cr2O und 1,8-2,8 Mol S03/ Mol Cr203 bei einer Basizität von 48-52%.Powdery chrome tanning agents which are particularly valuable in the practice of leather production and have a particularly long shelf life with regard to solubility in water contain about 1.8-2.4 mol of formate / mol of Cr 2 O and 1.8-2.8 mol of S0 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 is to be explained in more detail with the aid of the following examples. The percentages for the compositions relate to% by weight.
5000 kg Chromsulfatlauge mit einem Gehalt von 11% Cr2O314,4% SO3, 11,2% NazO und 6,8% Ameisensäure werden in einem Sprühtrockner bei 200° C Eintrittstemperatur und 90° C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 21,5% Cr2O3, 13,3% Ameisensäure (2,0 Mol Ameisensäuren/Mol Crz03) und 2,5 Mol SO3/Mol Cr2O3 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 O 3, 14.4% SO 3 , 11.2% NazO 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 O 3 , 13.3% formic acid (2.0 mol formic acids / mol Crz0 3 ) and 2.5 mol SO 3 / mol Cr 2 O 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 CrzOs), 1,57 Mol SO3/Mol Cr2O3 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 moles formic acid / mole CrzOs), 1.57 moles SO 3 / mole Cr 2 O 3 and a basicity of 50% under the same conditions as above, the undissolved residue dried with immediate inspection at 1% and after 30 Days rapid aging at 24%.
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 examination of the release 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 the solubility, 20 g of the fresh or the so aged product are mixed with 200 ml of water and dissolved for 1 hour at room temperature with shaking Then the residue is determined by weight by filtering through a suction filter.
2,2 kg Chromsulfatlauge mit einem Gehalt von 13% Cr203, 12,6% SO3, 6,4% NazO und 8,7% Ameisensäure werden in einem Sprühtrockner bei 190°C Eintrittstemperatur und 120°C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 28% Cr2O3, 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 containing 13% Cr 2 0 3 , 12.6% SO 3 , 6.4% NazO and 8.7% formic acid are dried in a spray dryer at an inlet temperature of 190 ° C. and an outlet temperature of 120 ° C. The dried product contains 28% Cr 2 O 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.
2,2 kg Chromsulfatlauge mit einem Gehalt von 12% Cr203, 13,3% S03, 7,2% Na2O und 7,9% Ameisensäure werden in einem Sprühtrockner bei 190°C Eintritts- und 110°C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 26,4% Cr203, 17,4% Ameisensäure (2,2 Mol Ameisensäure/Mol Crz03) und 2,1 Mol SO3/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 O 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 0 3 , 17.4% formic acid (2.2 mol formic acid / mol Crz0 3 ) and 2.1 mol SO 3 / mol Cr 2 0 3 with a basicity of 50%. The undissolved residue is 0% when tested 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.
2,2 kg Chromsulfatlauge mit einem Gehalt von 11,1% Cr203, 12,2% S03,8,2% Na2O und 7,3% Ameisensäure werden in einem Sprühtrockner bei 190°C Eintritts- und 110°C Austrittstemperatur getrocknet. Das getrocknete Produkt enthält 24,4% Cr2O3, 16% Ameisensäure (2,2 Mol Ameisensäure/Mol Cr203) und 2,4 Mol SO3/Mol Crz03 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 3 , 12.2% S0 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 O 3 , 16% formic acid (2.2 mol formic acid / mol Cr 2 0 3 ) and 2.4 mol SO 3 / mol Crz0 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.
2,5 kg Chromsulfatlauge mit einem Gehalt von 8,1% Cr2O3. 12,3% S03, 11,4% Na2O 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 Cr2O3) und 2,9 Mol SO3/Mol Cr2O3 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 containing 8.1% Cr 2 O 3 . 12.3% S0 3 , 11.4% Na 2 O and 4.4% formic acid are dried in a spray dryer at an inlet temperature of 190 ° C. and an outlet temperature of 120 ° C. The dried product contains 20.5% Cr 2 O 3 , 11.2% formic acid (1.8 mol formic acid / mol Cr 2 O 3 ) and 2.9 mol SO 3 / mol Cr 2 O 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.
2,5 kg Chromsulfatlauge mit einem Gehalt von 7,8% Cr203, 11,9% S03, 11,9% Na2O 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 Cr2O3) und 2,9 Mol SO3/Mol Cr2O3 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 solution with a content of 7.8% Cr 2 0 3 , 11.9% S0 3 , 11.9% Na 2 O 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 O 3 ) and 2.9 mol SO 3 / mol Cr 2 O 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)
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 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP0015478A1 EP0015478A1 (en) | 1980-09-17 |
| EP0015478B1 EP0015478B1 (en) | 1981-09-16 |
| EP0015478B2 true EP0015478B2 (en) | 1985-07-31 |
Family
ID=6064761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP80100936A Expired EP0015478B2 (en) | 1979-03-07 | 1980-02-26 | Chrome tanning agents resisting ageing |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US4298344A (en) |
| EP (1) | EP0015478B2 (en) |
| 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) |
Families Citing this family (4)
| 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 (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 |
Family Cites Families (2)
| 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 |
-
1979
- 1979-03-07 DE DE19792908967 patent/DE2908967A1/en not_active Withdrawn
-
1980
- 1980-02-15 US US06/121,863 patent/US4298344A/en not_active Expired - Lifetime
- 1980-02-26 DE DE8080100936T patent/DE3060022D1/en not_active Expired
- 1980-02-26 EP EP80100936A patent/EP0015478B2/en not_active Expired
- 1980-03-04 NZ NZ193032A patent/NZ193032A/en unknown
- 1980-03-05 MX MX181442A patent/MX155156A/en unknown
- 1980-03-05 CA CA347,016A patent/CA1131409A/en not_active Expired
- 1980-03-05 JP JP55026813A patent/JPS6017400B2/en not_active Expired
- 1980-03-06 ZA ZA00801325A patent/ZA801325B/en unknown
- 1980-03-06 ES ES489246A patent/ES489246A1/en not_active Expired
- 1980-03-06 BR BR8001342A patent/BR8001342A/en not_active IP Right Cessation
- 1980-03-07 YU YU00651/80A patent/YU65180A/en unknown
- 1980-03-07 AR AR280216A patent/AR219218A1/en active
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| Publication number | Publication date |
|---|---|
| CA1131409A (en) | 1982-09-14 |
| DE2908967A1 (en) | 1980-09-18 |
| AR219218A1 (en) | 1980-07-31 |
| NZ193032A (en) | 1982-03-16 |
| BR8001342A (en) | 1980-11-04 |
| EP0015478A1 (en) | 1980-09-17 |
| US4298344A (en) | 1981-11-03 |
| DE3060022D1 (en) | 1981-12-03 |
| ES489246A1 (en) | 1980-08-16 |
| YU65180A (en) | 1983-01-21 |
| JPS6017400B2 (en) | 1985-05-02 |
| MX155156A (en) | 1988-02-01 |
| EP0015478B1 (en) | 1981-09-16 |
| JPS55120699A (en) | 1980-09-17 |
| ZA801325B (en) | 1981-04-29 |
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