EP0085107B1 - Tanning agent for skins and method of obtaining it - Google Patents

Tanning agent for skins and method of obtaining it Download PDF

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Publication number
EP0085107B1
EP0085107B1 EP81903143A EP81903143A EP0085107B1 EP 0085107 B1 EP0085107 B1 EP 0085107B1 EP 81903143 A EP81903143 A EP 81903143A EP 81903143 A EP81903143 A EP 81903143A EP 0085107 B1 EP0085107 B1 EP 0085107B1
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Prior art keywords
ammonium
sulphate
titanium
solution
zirconium
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EP81903143A
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German (de)
French (fr)
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EP0085107A4 (en
EP0085107A1 (en
Inventor
David Lazarevich Motov
Ljudmila Petrovna Tjurkina
Maria Moiseevna Godneva
Alexandr Ivanovich Metelkin
Nina Ivanovna Kolesnikova
Galina Grigorievna Yakusheva
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INSTITUT KHIMII I TEKHNOLOGII REDKIKH ELEMENTOV I MINERALNOGO SYRYA KOLSKOGO FILIALA AKADEMII NAUK SSSR
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INSTITUT KHIMII I TEKHNOLOGII REDKIKH ELEMENTOV I MINERALNOGO SYRYA KOLSKOGO FILIALA AKADEMII NAUK SSSR
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Priority to AT81903143T priority Critical patent/ATE21935T1/en
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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

Definitions

  • the tanning agents used in the leather industry include chrome tanning agents and vegetable tanning agents such as oak, spruce bark, chestnut, quebracho, mimosa extracts, etc.
  • chrome tanning agents and vegetable tanning agents such as oak, spruce bark, chestnut, quebracho, mimosa extracts, etc.
  • chromium is harmful to the operator, leads to environmental pollution
  • vegetable Tanning agents require a large consumption of vegetable raw materials, which also damages the environment.
  • a titanium tanning agent for leather which contains a double sulfate of titanyl and ammonium in the monohydrate form (NH 4 ) 2 TiO (SO 4 ) 2 .
  • H 2 represents 0 (SU-PS 234598, published 1969).
  • the use of the titanium tanning agent eliminates the need to use vegetable tanning agents and reduces the consumption of chrome tanning agents.
  • the titanium tanning agent enables the tanning of the leather to be carried out effectively, the leather showing improved characteristic values, but the shrinking temperature of the tanned skin bare has not yet reached the desired value.
  • a zirconium tanning agent for leather which, compared to the titanium tanning agent, increases the shrinking temperature of the tanned skin (AIMetelkin, NIKolesnikova.EV Kurmina "Zirconium tanning” published in 1972, publisher “Logkaya industrial, Moscow, p.220").
  • the zirconium tanning agent is more expensive than the titanium tanning agent.
  • a tanning agent containing titanium and zirconium is known, the use of which improves the quality of the leather (SU-PS 340 702, 1972).
  • the process for preparing this tanning agent is to mix two solutions, a solution containing titanium salt and a solution containing a zirconium salt, after which the solutions are evaporated to dryness. This process requires high energy consumption.
  • a tanning agent which contains 20 to 32% ammonium sulfato zirconate, 0.1 to 19.0% ammonium sulfato aluminate and 39 to 78.9% ammonium sulfate titanate. It is obtained by simply mixing the solid components. The leather tanned with this agent is not very elastic and has a contraction of the scars.
  • the object of the present invention was to develop a tanning agent for leather which, in terms of its tanning properties, surpasses the known tanning agents, namely a titanium tanning agent which can be obtained by simple technology using accessible reaction agents and accessible starting raw materials.
  • the above-mentioned tanning agent is obtained by a process which is characterized in accordance with the invention in that a titanium-containing solution which contains 80-200 g / l of titanium, converted to its dioxide, is taken, and this with a solution of aluminum sulfate, the 80-130 g / I aluminum, converted to its oxide, contains and / or with a solution of zirconium sulfate containing 50-200 g / I zirconium, converted to its dioxide, in the presence of sulfuric acid and ammonium sulfate.
  • the process according to the invention for the production of tanning agents has the advantage that it can be easily implemented under industrial conditions, since the process is carried out under normal conditions, at room temperature and under normal pressure, using readily available and inexpensive reactants and readily available mineral raw materials .
  • composition of the sulfate tanning agent is proposed, depending on the combination of the sulfates taken, namely a tanning agent consisting of two or three components.
  • This tanning agent makes it possible to increase the shrinking temperature of the skin pelt tanned with it by 4-6 ° C. compared to the known titanium tanning agent.
  • This tanning agent makes it possible to increase the shrinking temperature of the skin pelt tanned with it by 10-12 ° C. compared to the known titanium tanning agent.
  • the titanium-aluminum tanning agent can contain 1 to 10% by weight of silica, which serves as a filler for leather and makes it possible to increase its mass and thickness yield during tanning by 0.8-1.0% compared to the known one To increase titanium tanning agents.
  • the limits of the content of the said sulfates in the tanning agent are due to the fact that activation of the tanning effect of the ammonium titanyl sulfate does not appear if the ammonium aluminum sulfate content is less than 3% by weight.
  • An increase in the content of ammonium aluminum sulfate to more than 20% by weight leads to a reduction in the content of basic tanning component in ammonium titanyl sulfate - which in turn leads to a deterioration in the tanning properties.
  • the tanning agent content of basic ammonium zirconium sulfate is less than 20% by weight, the tanning effect becomes weaker, and if this component contains more than 50% by weight, the tanning effect of titanium is suppressed by zirconium. This also increases the cost of the tanning agent.
  • the limit of the content of the additives Ti0 2 , Zr0 2 and Al 2 O 3 , which are chemically bound in the sulfates, is due to the fact that, at a content below 0.001% by weight, their effect as activators in the tanning with sulfates is not is detected and the upper limit is determined by the conditions for carrying out the process for producing the tanning agents.
  • tanning agent namely titanium-aluminum tanning agent, or titanium-zirconium tanning agent, or titanium-zirconium-aluminum tanning agent.
  • the titanium-aluminum tanning agent is obtained according to the invention by a process which consists in taking a solution of the ammonium titanyl sulfate containing 80-140 g / l titanium, converted to its dioxide, and ammonium sulfate and sulfuric acid to this solution until Beginning of the crystallization of the ammonium titanyl sulfate is added, after which a solution of aluminum sulfate and additionally sulfuric acid and ammonium sulfate is obtained within 1 to 5 hours until a total content of free sulfuric acid and free aluminum sulfate of 400 to 600 g / l and a molar ratio are achieved in the reaction solution from aluminum to titanium from 0.03: 1 to 0.24: 1.
  • the titanium-aluminum tanning agent can also be obtained from a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300 -520 g / l sulfuric acid, which is obtained from the digestion of raw materials containing titanium.
  • a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300 -520 g / l sulfuric acid, which is obtained from the digestion of raw materials containing titanium.
  • ammonium sulfate is introduced into this solution until the crystallization of the ammonium titanyl sulfate formed, after which a solution of aluminum sulfate and additional ammonium sulfate is obtained until the free ammonium sulfate content in the reaction solution is from 210 to 350 g / l and one Molar ratio of aluminum to titanium from 0.03: 1 to 0.24: 1 added.
  • the production process is carried out with the addition of silica in an amount of 1 to 10% by weight or of its sodium salt.
  • the silica contained in the tanning agent serves as a filler and increases the yield of leather by mass and thickness.
  • the process for the preparation of titanium-zirconium tanning agent according to the invention consists in taking a solution containing zirconium and adding ammonium sulfate and sulfuric acid until crystallization of the ammonium-zirconium sulfate which forms, after which a solution of the ammonium is added within 1 to 5 hours Titanium sulfates, the 80 to 140 g / I titanium, converted to its dioxide, and additionally ammonium sulfate and sulfuric acid until a total content of free ammonium sulfate and free sulfuric acid in the reaction solution of 770 to 1000 g / I and a molar ratio of zirconium to titanium from 0.10: 1 to 0.65: 1.
  • the titanium-zirconium tanning agent can also be obtained according to a variant which consists in that a solution containing zirconium is added within 6 to 10 hours with a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300- Contains 520 g / l of sulfuric acid, which is obtained from the digestion of a titanium-containing raw material, and at the same time ammonium sulfate until a content of free ammonium sulfate in the reaction solution of 400 to 580 g / l and a molar ratio of zirconium to titanium of 0.10: 1 is achieved up to 0.65: 1.
  • a variant of the process consists in taking a solution containing zirconium and adding this ammonium sulfate and sulfuric acid until the crystallization of the ammonium zirconium sulfate which forms, after which a solution of the ammonium titanyl sulfate is added to this solution within 1 to 5 hours 80 to 140 g / l titanium, converted to its dioxide content, a solution of aluminum sulfate and additionally ammonium sulfate and sulfuric acid until a total content of free ammonium sulfate and free sulfuric acid in the reaction solution of 770 to 1000 g / l and a molar ratio of aluminum are obtained Titanium from 0.03: 1 to 0.24: 1 and from zirconium to titanium from 0.10: 1 to 0.65: 1.
  • Another variant of the process for the preparation of titanium-zirconium-aluminum tanning agents is that a solution containing zirconium is mixed with a sulfuric acid solution, the 100 to 200 g / l titanium, converted to its dioxide, and 300 to within 6 to 10 hours Contains 520 g / l sulfuric acid, which is obtained from the digestion of a titanium-containing raw material, a solution of aluminum sulfate and ammonium sulfate until a free ammonium sulfate content in the reaction solution of 400 to 580 g / l and a molar ratio of aluminum and titanium of 0.03: 1 to 0.24: 1 and from zirconium to titanium from 0.10: 1 to 0.65: 1.
  • ammonium-titanyl sulfate is used, which is obtained by digesting a raw material containing titanium, or this raw material immediately after its treatment with sulfuric acid.
  • Ilmenite, Sphen, Leukoxen concentrate and other concentrates of titanium minerals can be considered as raw materials.
  • Zirconium sulfate is used to prepare a zirconium-containing solution, obtained when a zirconium-containing raw material, for example zirconium concentrate, is digested.
  • Ammonium sulfate and sulfuric acid are introduced into the resulting solution until the crystallization of the ammonium titanyl sulfate begins, after which 0.04 liter of aluminum sulfate, which contains 113 g / l of aluminum, converted to its oxide, and aluminum sulfate are added over the course of 2 hours and sulfuric acid until a total content of free sulfuric acid and free ammonium sulfate in the reaction solution of 550 g / I and a molar ratio of aluminum sum titanium of 0.05: 1 is achieved.
  • the precipitate formed is separated from the solution by filtration.
  • the weight ratio of silica to titanium dioxide in the end product is 0.05: 1.
  • zirconium sulfate solution containing 180 g / l of zirconium, converted to the amount of dioxide, is used.
  • 1 liter of sulfuric acid solution is passed into the solution over the course of 8 hours, obtained when processing a titanium-containing raw material which contains 160 g / l titanium, converted to its dioxide, and 400 g / l sulfuric acid, and ammonium sulfate until a content is achieved the solution of free ammonium sulfate of 500 g / I and a molar ratio of zirconium to titanium of 0.35: 1.
  • the suspension is kept for 35 hours.
  • the precipitate is separated off by filtration.
  • the basic ammonium zirconium sulfate which forms is crystallized from the solution.
  • 1.5 liters of a solution of ammonium titanyl sulfate containing 100 g / l titanium, converted to its dioxide, and 0.05 liter of a solution of aluminum sulfate, the 113 g / l aluminum, are converted into the reaction solution
  • Its oxide contains and additionally sulfuric acid and ammonium sulfate until a total content of free sulfuric acid and free ammonium sulfate of 820 g / l and a molar ratio of aluminum to titanium of 0.05: 1 of zirconium to titanium of 0.40: 1 is achieved.
  • the suspension is held for 20 hours.
  • the precipitate is separated off by filtration.
  • the tanning properties of the products are given in accordance with the shrinkage temperature of the skin exposed with them (see table). From the experimental data for the shrinkage temperature of the tanned skin, it follows that the tanning agent according to the invention, which is obtained according to Examples 1 to 7, increases the quality of the leather compared to the known titanium tanning agent.
  • the improved tanning properties of the tanning agent are achieved in comparison to the known tanning agents by using a combination of sulfates which contain the additives Ti0 2 , Zr0 2 and Al 2 O 3 in the composition.
  • the present invention can be used in the leather industry in leather manufacture.

Abstract

PCT No. PCT/SU81/00043 Sec. 371 Date Jan. 18, 1983 Sec. 102(e) Date Jan. 18, 1983 PCT Filed May 19, 1981 PCT Pub. No. WO82/04071 PCT Pub. Date Nov. 25, 1982.A leather tanning agent characterized in that it contains the following components, percent by weight: -sulphate of aluminum and ammonium 3 to 20 -containing 0.001 to 1.0% of TiO2 or -TiO2 and ZrO2 -and/or sulphate of zirconium and ammonium 20 to 50 -containing 0.001 to 0.5% of TiO2 -or TiO2 and Al2O3 -and sulphate of titanyl and ammonium -containing of 0.001 to 1.0% of Al2O3 -and/or ZrO2 the balance. - The above-mentioned additives of TiO2, ZrO2 and Al2O3 incorporated in the sulphates are present therein in a chemically combined state. In the process for producing the leather tanning agent a titanium-containing solution with a concentration of titanium of from 80 to 200 g/l as calculated for titanium dioxide is reacted with a solution of aluminum sulphate containing 80 to 130 g/l of aluminum as calculated for alumina, and/or a solution of zirconium sulphate containing 50 to 200 g/l of zirconium as calculated for zirconium dioxide in the presence of sulphuric acid and ammonium sulphate. The sulphate tanning agent according to the present invention can be very useful in the leather industry.

Description

Zu den in der Lederindustrie verwendeten Gerbmitteln gehören Chromgerbmittel und pflanzliche Gerbmittel wie Eichenholz-, Fichtenrinden-, Kastanienholz-, Quebracho-, Mimosaextrakte u.a.m.. Die Verwendung von Chrom ist jedoch für das Bedienungspersonal schädlich, führt zur Veiunreinigung der Umwelt, während die Verwendung von pflanzlichem Gerbmittel einen großen Verbrauch an pflanzlichem Rohstoff erfordert, was auch die Umwelt schädigt.The tanning agents used in the leather industry include chrome tanning agents and vegetable tanning agents such as oak, spruce bark, chestnut, quebracho, mimosa extracts, etc. However, the use of chromium is harmful to the operator, leads to environmental pollution, while the use of vegetable Tanning agents require a large consumption of vegetable raw materials, which also damages the environment.

Bekannt ist ein Titangerbmittel für Leder, das ein Doppelsulfat von Titanyl und Ammonium in der Monohydratform (NH4)2 TiO(SO4)2. H20 darstellt (SU-PS 234598, bekanntgemacht 1969). Die Verwendung des Titangerbmittels beseitigt die Notwendigkeit, pflanzliche Gerbmittel zu benutzen und vermindert den Verbrauch an Chromgerbmitteln.A titanium tanning agent for leather is known which contains a double sulfate of titanyl and ammonium in the monohydrate form (NH 4 ) 2 TiO (SO 4 ) 2 . H 2 represents 0 (SU-PS 234598, published 1969). The use of the titanium tanning agent eliminates the need to use vegetable tanning agents and reduces the consumption of chrome tanning agents.

Das Titangerbmittell ermöglicht es, die Gerbung der Leder wirksam durchzuführen, wobei die Leder verbesserte Kennwerte zeigen, jedoch die Schrumpfungstemperatur der durchgegerbten Hautblöße den erwünschten Wert noch nicht erreicht.The titanium tanning agent enables the tanning of the leather to be carried out effectively, the leather showing improved characteristic values, but the shrinking temperature of the tanned skin bare has not yet reached the desired value.

Bekannt ist ein Zirconiumgerbmittel für Leder, das im Vergleich zu dem Titangerbmittel die Schrumpfungstemperatur der durchgegerbten Hautblöße erhöht (A.I.Metelkin, N.I.Kolesnikova.E.V. Kurmina "Zirconiumgerbung" bekanntgemacht 1972, Verlag "Logkaya industrial, Moskau, S.220). Das Zirconiumgerbmittel ist jedoch teurer als das Titangerbmittel.A zirconium tanning agent for leather is known which, compared to the titanium tanning agent, increases the shrinking temperature of the tanned skin (AIMetelkin, NIKolesnikova.EV Kurmina "Zirconium tanning" published in 1972, publisher "Logkaya industrial, Moscow, p.220"). However, the zirconium tanning agent is more expensive than the titanium tanning agent.

Bekannt ist ein Titan und Zirconium enthaltendes Gerbmittel, dessen Anwendung zur Verbesserung der Qualität der Leder führt (SU-PS 340 702, 1972).A tanning agent containing titanium and zirconium is known, the use of which improves the quality of the leather (SU-PS 340 702, 1972).

Das Verfahren zur Herstellung dieses Gerbmittels besteht darin, daß man zwei Lösungen, und zwar eine Titansalz enthaltende Lösung und eine ein Zirconiumsalz enthaltende Lösung vermischt, wonach man die Lösungen zur Trockne eindampft. Dieses Verfahren erfordert einen hohen Energieverbrauch.The process for preparing this tanning agent is to mix two solutions, a solution containing titanium salt and a solution containing a zirconium salt, after which the solutions are evaporated to dryness. This process requires high energy consumption.

Aus der SU-PS 783 342 ist schließlich ein Gerbmittel bekannt, das 20 bis 32 % Ammoniumsulfatozirconat, 0,1 bis 19,0% Ammoniumsulfatoaluminat und 39 bis 78,9% Ammoniumsulfatotitanat enthält. Es wird durch einfaches Vermischen der festen Komponenten erhalten. Das mit diesem Mittel gegerbte Leder ist wenig elastisch und weist eine Zusammenziehung der Narben auf.Finally, from SU-PS 783 342 a tanning agent is known which contains 20 to 32% ammonium sulfato zirconate, 0.1 to 19.0% ammonium sulfato aluminate and 39 to 78.9% ammonium sulfate titanate. It is obtained by simply mixing the solid components. The leather tanned with this agent is not very elastic and has a contraction of the scars.

Die Aufgabe der vorliegenden Erfindung bestand in der Entwicklung eines Gerbmittels für Leder, das seinen Gerbeigenschaften nach die bekannten Gerbmittel übertrifft, und zwar eines Titangerbmittels, das nach einer einfachen Technologie unter Ausnutzung zugänglicher Reaktionsmittel und zugänglicher Ausgangsrohstoffe erhalten werden kann.The object of the present invention was to develop a tanning agent for leather which, in terms of its tanning properties, surpasses the known tanning agents, namely a titanium tanning agent which can be obtained by simple technology using accessible reaction agents and accessible starting raw materials.

Diese Aufgabe wird ein Gerbmittel für Leder das Ammonium-aluminiumsulfat, Ammonium-zirconiumsulfat und Ammonium-titanylsulfat enthält, erfindungsgemäß dadurch erreicht, daß die genannten Komponenten Zusätze von Titan, Zirconium und Aluminium, berechnet als Oxyde, chemisch gebunden enthalten und im Gerbmittel in folgendem Mengenverhältnis (in Gew.-%) vorhanden sind:

  • 3-20 Gw.-% Ammonium-aluminiumsulfat der Formel NH4Al(SO4)2.12H2O, das 0,001 bis 1,0% Ti02, oder Ti02, und Zr02 enthält, und/oder
  • 20-50 Gw.-% basisches Ammonium-zirconiumsulfat der Formel (NH4)2Zr2(OH)5(S04)2,5.H20, das 0,001 bis 0,5 % Ti02 oder Ti02 und AI203 enthält, und
  • Rest Ammonium-titanylsulfat der Formel (NH4)2TiO(SO4)2.H2O, das
  • 0,001 bis 1,0 % AI203 und/oder Zr02 enthält.
This object is a tanning agent for leather containing ammonium aluminum sulfate, ammonium zirconium sulfate and ammonium titanyl sulfate, according to the invention achieved in that the components mentioned contain additions of titanium, zirconium and aluminum, calculated as oxides, chemically bound and in the tanning agent in the following proportions (in% by weight) are present:
  • 3-20 wt .-% ammonium aluminum sulfate of the formula NH 4 Al (SO 4 ) 2 .12H 2 O, which contains 0.001 to 1.0% Ti0 2 , or Ti0 2 , and Zr0 2 , and / or
  • 20-50 wt .-% basic ammonium zirconium sulfate of the formula (NH 4 ) 2 Zr 2 (OH) 5 (S0 4 ) 2 , 5 .H 2 0, the 0.001 to 0.5% Ti0 2 or Ti0 2 and Al 2 0 3 contains, and
  • Remainder ammonium titanyl sulfate of the formula (NH 4 ) 2 TiO (SO 4 ) 2 .H 2 O, the
  • Contains 0.001 to 1.0% Al 2 0 3 and / or Zr0 2 .

Das obengenannte Gerbmittel erhält man nach einem Verfahren, das erfindungsgemäß dadurch gekennzeichnet ist, daß man eine titanhaltige Lösung, die 80-200 g/I Titan, umgerechnet auf sein Dioxyd, enthält, nimmt und diese mit einer Lösung von Aluminiumsulfat, die 80-130 g/I Aluminium, umgerechnet auf sein Oxyd, enthält und/oder mit einer Lösung von Zirconiumsulfat, die 50-200 g/I Zirconium, umgerechnet auf sein Dioxyd, enthält, in Gegenwart von Schwefelsäure und Ammoniumsulfat umsetzt.The above-mentioned tanning agent is obtained by a process which is characterized in accordance with the invention in that a titanium-containing solution which contains 80-200 g / l of titanium, converted to its dioxide, is taken, and this with a solution of aluminum sulfate, the 80-130 g / I aluminum, converted to its oxide, contains and / or with a solution of zirconium sulfate containing 50-200 g / I zirconium, converted to its dioxide, in the presence of sulfuric acid and ammonium sulfate.

Das erfindungsgemäße Verfahren zur Herstellung von Gerbmittel verfügt über den Vorteil, daß es unter großtechnischen Bedingungen ohne weiteres verwirklicht werden kann, da man den Prozeß unter normalen Bedingungen, bei Zimmertemperatur und unter Normaldruck, unter Benutzung gut zugänglicher und billiger Reaktionsmittel und gut zugänglichen mineralischen Rohstoffes durchführt.The process according to the invention for the production of tanning agents has the advantage that it can be easily implemented under industrial conditions, since the process is carried out under normal conditions, at room temperature and under normal pressure, using readily available and inexpensive reactants and readily available mineral raw materials .

Man schlägt folgende bevorzugte Varianten der Zusammensetzung des Sulfatgerbmittels je nach der Kombination der genommenen Sulfate vor, und zwar ein Gerbmittel aus zwei oder drei Komponenten.The following preferred variants of the composition of the sulfate tanning agent are proposed, depending on the combination of the sulfates taken, namely a tanning agent consisting of two or three components.

Titan-Aluminium-Gerbmittel folgender Zusammensetzung in Gew.%:

  • Ammonium-Aluminiumsulfat, das
  • 0,001-1,0% Ti02 enthält, 3-20
  • Ammonium-titanylsulfat das
  • 0,001-1,0% AI203 enthält. Rest
Titanium-aluminum tanning agents with the following composition in% by weight:
  • Ammonium aluminum sulfate, the
  • Contains 0.001-1.0% Ti0 2 , 3-20
  • Ammonium titanyl sulfate that
  • Contains 0.001-1.0% AI 2 0 3 . rest

Dies Gerbmittel ermöglicht es, die Schrumpfungstemperatur der mit ihm durchgegerbten Hautblöße um 4-6°C im Vergleich zu dem bekannten Titangerbmittel zu steigern.This tanning agent makes it possible to increase the shrinking temperature of the skin pelt tanned with it by 4-6 ° C. compared to the known titanium tanning agent.

Titan-Zirconium-Gerbmittel folgender Zusammensetzung in Gew.%:

  • Basisches Ammonium-zirconiumsulfat, das
  • 0,001-0,1% Ti02 enthält, 20-50
  • Ammonium-titanylsulfat, das
  • 0,001-0,1% Zr02 enthält. Rest
  • Dieses Gerbmittel ermöglicht es, die Schrumpfungstemperatur der mit ihm durchgegerbten Hautblöße um 8-9°C im Vergleich zu dem bekannten Titangerbmittel zu steigern.
Titanium-zirconium tanning agent with the following composition in% by weight:
  • Basic ammonium zirconium sulfate, the
  • Contains 0.001-0.1% Ti02, 20-50
  • Ammonium titanyl sulfate, the
  • Contains 0.001-0.1% Zr0 2 . rest
  • This tanning agent makes it possible to reduce the shrinking temperature of the pale skin tanned with it by 9 ° C increase compared to the known titanium tanning agent.

Titan-Zirconium-Aluminium-Gerbmittel folgender Zusammensetzung in Gew.%:

  • Ammonium-aluminiumsulfat das
  • 0,001-1,0% Ti02 und Zr02 enthält, 3-20
  • basisches Ammonium-zirconiumsulfat, das
  • 0,001-0.5% Ti02 und AI203 enthält, 20-50
  • Ammonium-titalylsulfat, das
  • 0,001-1,0% AI203 und Zr02 enthält. Rest
Titanium-zirconium-aluminum tanning agent with the following composition in% by weight:
  • Ammonium aluminum sulfate that
  • Contains 0.001-1.0% Ti0 2 and Zr0 2 , 3-20
  • basic ammonium zirconium sulfate, the
  • Contains 0.001-0.5% Ti0 2 and AI 2 0 3 , 20-50
  • Ammonium titalyl sulfate, the
  • Contains 0.001-1.0% AI 2 0 3 and Zr0 2 . rest

Dieses Gerbmittel gestattet es, die Schrumpfungstemperatur der mit ihm durchgegerbten Hautblöße um 10-12° C im Vergleich zu dem bekannten Titangerbmittel zu steigern.This tanning agent makes it possible to increase the shrinking temperature of the skin pelt tanned with it by 10-12 ° C. compared to the known titanium tanning agent.

Das Titan-Aluminium-Gerbmittel kann erfindungsgemäß 1 bis 10 Gew.% Kieselsäure enthalten, die als Füllstoff für Leder dient und es möglich macht, ihre Massen- und Dickeausbeute bei der Gerbung um 0,8-1,0% im Vergleich zu dem bekannten Titangerbmittel zu erhöhen.According to the invention, the titanium-aluminum tanning agent can contain 1 to 10% by weight of silica, which serves as a filler for leather and makes it possible to increase its mass and thickness yield during tanning by 0.8-1.0% compared to the known one To increase titanium tanning agents.

Die Grenzen des Gehaltes des Gerbmittels an den genannten Sulfaten sind dadurch bedingt, daß bei einem Gehalt an Ammonium-aluminiumsulfat von weniger als 3 Gew.% eine Aktivierung auf die Gerbwirkung des Ammonium-titanylsulfates nicht in Erscheinung tritt. Eine Steigerung des Gehaltes an Ammonium-aluminiumsulfat auf mehr als 20 Gew.% führt zur Verminderung des Gehaltes an Grundgerbkomponente an Ammonium-titanylsulfat - was seinerseits eine Verschlechterung der Gerbeigenschaften mit sich bringt.The limits of the content of the said sulfates in the tanning agent are due to the fact that activation of the tanning effect of the ammonium titanyl sulfate does not appear if the ammonium aluminum sulfate content is less than 3% by weight. An increase in the content of ammonium aluminum sulfate to more than 20% by weight leads to a reduction in the content of basic tanning component in ammonium titanyl sulfate - which in turn leads to a deterioration in the tanning properties.

Bei einem Gehalt des Gerbmittels an basischem Ammonium-zirconiumsulfat von weniger als 20 Gew.% wird die Gerbwirkung schwächer, und bei einem Gehalt an dieser Komponente von mehr als 50 Gew.% wird die Gerbwirkung von Titan durch Zirconium unterdrückte darüber hinaus führt dies zur Verteuerung des Gerbmittels.If the tanning agent content of basic ammonium zirconium sulfate is less than 20% by weight, the tanning effect becomes weaker, and if this component contains more than 50% by weight, the tanning effect of titanium is suppressed by zirconium. This also increases the cost of the tanning agent.

Die Grenze des Gehaltes an den Zusätzen Ti02, Zr02 und Al2O3, die in den Sulfaten chemisch gebunden sind, werden dadurch bedingt, daß bei einem unterhalb 0,001 Gew.% liegenden Gehalt ihre Wirkung als Aktivatoren bei der Gerbung mit Sulfaten nicht nachgewiesen wird und die obere Grenze ist durch Bedingungen der Durchführung des Verfahrens zur Herstellung der Gerbmittel bestimmt.The limit of the content of the additives Ti0 2 , Zr0 2 and Al 2 O 3 , which are chemically bound in the sulfates, is due to the fact that, at a content below 0.001% by weight, their effect as activators in the tanning with sulfates is not is detected and the upper limit is determined by the conditions for carrying out the process for producing the tanning agents.

Es ist möglich, nachstehende Varianten des Verfahrens in Abhängigkeit von dem gewünschten Gerbmittel, und zwar Titan-Alumimium-Gerbmittel, oder Titan-Zirconium-Gerbmittel, oder Titan-Zirconium-Aluminium-Gerbmittel, zu erzielen.It is possible to achieve the following variants of the process depending on the desired tanning agent, namely titanium-aluminum tanning agent, or titanium-zirconium tanning agent, or titanium-zirconium-aluminum tanning agent.

Das Titan-Aluminium-Gerbmittel erhält man erfindungsgemäß nach einem Verfahren, das darin besteht, daß man eine Lösung des Ammonium-titanylsulfates, die 80-140 g/I Titan, umgerechnet auf sein Dioxyd enthält, nimmt und dieser Lösung Ammoniumsulfat und Schwefelsäure bis zum Beginn der Kristallisation des Ammonium-titanylsulfates zugibt, wonach man innerhalb von 1 bis 5 Stunden eine Lösung von Aluminiumsulfat und zusätzlich Schwefelsäure und Ammoniumsulfat bis zur Erzielung eines Gesamtgehaltes in der Reaktionslösung an freier Schwefelsäure und freiem Aluminiumsulfat von 400 bis 600 g/I und eines Molverhältnisses von Aluminium zu Titan von 0,03: 1 bis 0,24: 1 hinzufügt.The titanium-aluminum tanning agent is obtained according to the invention by a process which consists in taking a solution of the ammonium titanyl sulfate containing 80-140 g / l titanium, converted to its dioxide, and ammonium sulfate and sulfuric acid to this solution until Beginning of the crystallization of the ammonium titanyl sulfate is added, after which a solution of aluminum sulfate and additionally sulfuric acid and ammonium sulfate is obtained within 1 to 5 hours until a total content of free sulfuric acid and free aluminum sulfate of 400 to 600 g / l and a molar ratio are achieved in the reaction solution from aluminum to titanium from 0.03: 1 to 0.24: 1.

Das Titan-Aluminium-Gerbmittel kann man auch aus einer schwefelsauren Lösung erhalten, die 100-200 g/I Titan, umgerechnet auf sein Dioxyd und 300 -520 g/1 Schwefelsäure enthält, die bei dem Aufschluß von titanhaltigem Rohstoff gewonnen wird. Zu diesem Zweck führt man in diese Lösung Ammoniumsulfat bis zum Beginn der Kristallisation des gebildeten Ammonium-titanylsulfates ein, wonach man eine Lösung von Aluminiumsulfat und zusätzlich Ammoniumsulfat bis zur Erzielung eines Gehaltes an freiem Ammoniumsulfat in der Reaktionslösung von 210 bis 350 g/I und eines Molverhältnisses von Aluminium zu Titan von 0,03: 1 bis 0,24: 1 hinzufügt.The titanium-aluminum tanning agent can also be obtained from a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300 -520 g / l sulfuric acid, which is obtained from the digestion of raw materials containing titanium. For this purpose, ammonium sulfate is introduced into this solution until the crystallization of the ammonium titanyl sulfate formed, after which a solution of aluminum sulfate and additional ammonium sulfate is obtained until the free ammonium sulfate content in the reaction solution is from 210 to 350 g / l and one Molar ratio of aluminum to titanium from 0.03: 1 to 0.24: 1 added.

Die Verwendung der genannten schwefelsaueren Lösung weist folgende Vorteile auf:

  • 1) Man muß nicht speziell Ammonium-titanylsulfat isolieren;
  • 2) der Ausscheidungsgrad von Titan aus der schwefelsauerem Lösung ist höher als aus der Lösung des Ammonium-titanylsulfates;
  • 3) man erhält ein Produkt mit besseren Gerbeigenschaften.
The use of the sulfuric acid solution mentioned has the following advantages:
  • 1) One does not have to specifically isolate ammonium titanyl sulfate;
  • 2) the degree of excretion of titanium from the sulfuric acid solution is higher than from the solution of the ammonium titanyl sulfate;
  • 3) a product with better tanning properties is obtained.

Zur Verbesserung der Gerbeigenschaften des Titan-Aluminium-Gerbmittels führt man den Herstellungsprozeß unter Zugabe von Kieselsäure in einer Menge von 1 bis 10 Gew.% oder von dessen Natriumsalz aus. Die in dem Gerbmittel enthaltene Kieselsäure dient als Füllstoff und steigert die Ausbeute an Leder nach der Masse und Dicke.To improve the tanning properties of the titanium-aluminum tanning agent, the production process is carried out with the addition of silica in an amount of 1 to 10% by weight or of its sodium salt. The silica contained in the tanning agent serves as a filler and increases the yield of leather by mass and thickness.

Das Verfahren zur Herstellung von Titan-Zirkonium-Gerbmittel besteht erfindungsgemäß darin, daß man eine zirkoniumhaltige Lösung nimmt und dieser Ammoniumsulfat und Schwefelsäure bis zum Beginn der Kristallisation des sich bildenden Ammonium-zirconiumsulfates hinzufügt, wonach man innerhalb von 1 bis 5 Stunden eine Lösung des Ammonium-titansulfates, die 80 bis 140 g/I Titan, umgerechnet auf sein Dioxyd, und zusätzlich Ammoniumsulfat und Schwefelsäure bis zum Erzielen eines Gesamtgehaltes an freiem Ammoniumsulfat und freier Schwefelsäure in der Reaktionslösung von 770 bis 1000 g/I und eines Molverhältnisses von Zirkonium zum Titan von 0,10: 1 bis 0,65: 1 einführt.The process for the preparation of titanium-zirconium tanning agent according to the invention consists in taking a solution containing zirconium and adding ammonium sulfate and sulfuric acid until crystallization of the ammonium-zirconium sulfate which forms, after which a solution of the ammonium is added within 1 to 5 hours Titanium sulfates, the 80 to 140 g / I titanium, converted to its dioxide, and additionally ammonium sulfate and sulfuric acid until a total content of free ammonium sulfate and free sulfuric acid in the reaction solution of 770 to 1000 g / I and a molar ratio of zirconium to titanium from 0.10: 1 to 0.65: 1.

Das Titan-Zirconium-Gerbmittel kann man auch nach einer Variante erhalten, die darin besteht, daß man einer zirconiumhaltigen Lösung innerhalb von 6 bis 10 Stunden eine schwefelsaure Lösung hinzufügt, die 100-200 g/I Titan, umgerechnet auf sein Dioxyd und 300-520 g/I Schwefelsäure enthält, die beim Aufschluß eines titanhaltigen Rohstoffes gewonnen wird, und gleichzeitig Ammoniumsulfat bis zum Erzielen eines Gehaltes an freiem Ammoniumsulfat in der Reaktionslösung von 400 bis 580 g/I und eines Molverhältnisses von Zirconium zu Titan von 0,10: 1 bis 0,65: 1 zusetzt.The titanium-zirconium tanning agent can also be obtained according to a variant which consists in that a solution containing zirconium is added within 6 to 10 hours with a sulfuric acid solution containing 100-200 g / l titanium, converted to its dioxide and 300- Contains 520 g / l of sulfuric acid, which is obtained from the digestion of a titanium-containing raw material, and at the same time ammonium sulfate until a content of free ammonium sulfate in the reaction solution of 400 to 580 g / l and a molar ratio of zirconium to titanium of 0.10: 1 is achieved up to 0.65: 1.

Man sieht erfindungsgemäß zwei Varianten des Verfahrens zur Herstellung von Titan-Zirconium-Gerbmittel vor. Eine Variante des Verfahrens besteht darin, daß man eine zirconiumhaltige Lösung nimmt und dieser Ammoniumsulfat und Schwefelsäure bis zum Beginn der Kristallisation des sich bildenden Ammonium-zirconiumsulfates hinzufügt, wonach man in diese Lösung innerhalb von 1 bis 5 Stunden eine Lösung des Ammonium-titanylsulfates, die 80 bis 140 g/I Titan, umgerechnet auf sein Dioxyd anthält, eine Lösung von Aluminiumsulfat und zusätzlich Ammoniumsulfat und Schwefelsäure bis zur Erzielung eines Gesamtgehaltes an freiem Ammoniumsulfat und freier Schwefelsäure in der Reaktionslösung von 770 bis 1000 g/I und eines Molverhältnisses von Aluminium zu Titan von 0,03: 1 bis 0,24: 1 und von Zirconium zu Titan von 0,10: 1 bis 0,65: 1 einführt.According to the invention, two variants of the method for producing titanium-zirconium tanning agents are provided. A variant of the process consists in taking a solution containing zirconium and adding this ammonium sulfate and sulfuric acid until the crystallization of the ammonium zirconium sulfate which forms, after which a solution of the ammonium titanyl sulfate is added to this solution within 1 to 5 hours 80 to 140 g / l titanium, converted to its dioxide content, a solution of aluminum sulfate and additionally ammonium sulfate and sulfuric acid until a total content of free ammonium sulfate and free sulfuric acid in the reaction solution of 770 to 1000 g / l and a molar ratio of aluminum are obtained Titanium from 0.03: 1 to 0.24: 1 and from zirconium to titanium from 0.10: 1 to 0.65: 1.

Eine andere Variante des Verfahrens zur Herstellung von Titan-Zirconium-Aluminium-Gerbmittel besteht darin, daß man einer zirconiumhaltigen Lösung innerhalb von 6 bis 10 Stunden eine schwefelsaure Lösung, die 100 bis 200 g/I Titan, umgerechnet auf sein Dioxyd, und 300 bis 520 g/I Schwefelsäure enthält, die beim Aufschluß eines titanhaltigen Rohstoffes gewonnen wird, eine .Lösung von Aluminiumsulfat und Ammoniumsulfat bis zur Erzielung eines Gehaltes an freiem Ammoniumsulfat in der Reaktionslösung von 400 bis 580 g/I und eines Molverhältnisses von Aluminium und zu Titan von 0,03: 1 bis 0,24: 1 und von Zirconium zu Titan von 0.10: 1 bis 0,65: 1 zugibt.Another variant of the process for the preparation of titanium-zirconium-aluminum tanning agents is that a solution containing zirconium is mixed with a sulfuric acid solution, the 100 to 200 g / l titanium, converted to its dioxide, and 300 to within 6 to 10 hours Contains 520 g / l sulfuric acid, which is obtained from the digestion of a titanium-containing raw material, a solution of aluminum sulfate and ammonium sulfate until a free ammonium sulfate content in the reaction solution of 400 to 580 g / l and a molar ratio of aluminum and titanium of 0.03: 1 to 0.24: 1 and from zirconium to titanium from 0.10: 1 to 0.65: 1.

Alle Varianten des Verfahrens zur Herstellung von Sulfatgerbmittel werden bei Zimmertemperatur und unter Normaldruck vorgenommen. Der Ausgangsrohstoff und die Reaktionsstoffe sind gut zugänglich.All variants of the process for the production of sulfate tanning agents are carried out at room temperature and under normal pressure. The starting raw material and the reactants are easily accessible.

Zur Herstellung einer titanhaltigen Lösung verwendet man Ammonium-titanylsulfat, das beim Aufschluß eines titanhaltigen Rohstoffes erhalten wird, oder unmittelbar diesen Rohstoff nach seiner Behandlung mit Schwefelsäure. Als Rohstoff können Ilmenit-, Sphen-, Leukoxenkonzentrat sowie andere Konzentrate von Titanmineralien in Frage kommen.To prepare a titanium-containing solution, ammonium-titanyl sulfate is used, which is obtained by digesting a raw material containing titanium, or this raw material immediately after its treatment with sulfuric acid. Ilmenite, Sphen, Leukoxen concentrate and other concentrates of titanium minerals can be considered as raw materials.

Zur Herstellung einer zirconiumhaltigen Lösung verwendet man Zirconiumsulfat, erhalten beim Aufschluß eines zirconiumhaltigen Rohstoffes, beispielsweise von Zirconiumkonzentrat.Zirconium sulfate is used to prepare a zirconium-containing solution, obtained when a zirconium-containing raw material, for example zirconium concentrate, is digested.

Zum besseren Verständnis der Erfindung werden folgende Beispiele zur Herstellung von Gerbmittel angeführt.To better understand the invention, the following examples are given for the preparation of tanning agents.

Beispiel 1.Example 1.

Man nimmt 500 g Ammonium-titanylsulfat, löst dieses in 1 I Wasser und erhält eine Lösung, die 100 g/I Titan, umgerechnet auf sein Dioxyd enthält.500 g of ammonium titanyl sulfate are taken, this is dissolved in 1 l of water and a solution is obtained which contains 100 g / l of titanium, converted to its dioxide.

In die erhaltende Lösung führt man Ammoniumsulfat und Schwefelsäure bis zum Beginn der Kristallisation des Ammonium-titanylsulfates ein, wonach man im Verlaufe von 2 Stunden 0,04 Liter Aluminiumsulfat, das 113 g/I Aluminium, umgerechnet auf sein Oxyd, enthält, und zusätzlich Aluminiumsulfat und Schwefelsäure bis zur Erzielung eines Gesamtgehaltes an freier Schwefelsäure und freiem Ammoniumsulfat in der Reaktionslösung von 550 g/I und eines Molverhältnisses von Aluminium sum Titan von 0,05: 1 hinzufügt. Man trennt den gebildeten Niederschlag von der Lösung durch Filtration ab.Ammonium sulfate and sulfuric acid are introduced into the resulting solution until the crystallization of the ammonium titanyl sulfate begins, after which 0.04 liter of aluminum sulfate, which contains 113 g / l of aluminum, converted to its oxide, and aluminum sulfate are added over the course of 2 hours and sulfuric acid until a total content of free sulfuric acid and free ammonium sulfate in the reaction solution of 550 g / I and a molar ratio of aluminum sum titanium of 0.05: 1 is achieved. The precipitate formed is separated from the solution by filtration.

Die Ausbeute an Endprodukt beträgt 540 g. Das Endprodukt enthält 18,2 Gew.% Ti02 und 1,2 Gew.% AI203. Es besteht aus zwei Sulfaten in Gew.%:

  • 13 % Ammonium aluminiumsulfat, das 0,5% Ti02 enthält,
  • Rest Ammonium-titanylsulfates
  • das 0,5 % Al2O3 enthält.
The yield of the final product is 540 g. The end product contains 18.2% by weight of Ti0 2 and 1.2% by weight of Al 2 0 3 . It consists of two sulfates in% by weight:
  • 13% ammonium aluminum sulfate, which contains 0.5% Ti0 2 ,
  • Balance ammonium titanyl sulfates
  • that contains 0.5% Al 2 O 3 .

Beispiel 2.Example 2.

Man nimmt 1 Liter schwefelsaure Lösung, erhalten bei der Verarbeitung von titanhaltigem Rohstoff, die 160 g/I Titan, umgerechnet auf sein Dioxyd, und 400 g/I Schwefelsäure enthält. In die erhaltende Lösung führt man Ammoniumsulfat bis um Beginn der Kristallisation des sich bildenden Ammonium-titanylsulfates ein, wonach man im Verlaufe von 8 Stunden 0,2 Liter Aluminiumsulfatlösung, die 113 g/I Aluminium, umgerechnet auf sein Oxyd, enthält, und zusätzlich Ammoniumsulfat bis zur Erzielung eines Gehaltes der Lösung an freiem Ammoniumsulfat von 300 g/1 und eines Molverhältnisses von Aluminium zu Titan von 0,20: 1 hinzufügt. Man trennt den Niederschlag von der Lösung durch Filtration ab.One takes 1 liter of sulfuric acid solution, obtained when processing titanium-containing raw material, which contains 160 g / l titanium, converted to its dioxide, and 400 g / l sulfuric acid. Ammonium sulfate is introduced into the resulting solution until the crystallization of the ammonium titanyl sulfate which forms begins, after which 0.2 liter of aluminum sulfate solution, which contains 113 g / l of aluminum, converted to its oxide, and additionally ammonium sulfate are added over the course of 8 hours until the solution has a free ammonium sulfate content of 300 g / l and a molar ratio of aluminum to titanium of 0.20: 1. The precipitate is separated from the solution by filtration.

Die Ausbeute an Endprodukt beträgt 980 g. Das Endprodukt enthält 16,3 Gew.% Ti02 und 2,05 Gew.% AI203. Das Produkt besteht aus zwei Sulfaten in Gew.%:

  • 17,8 % Ammonium-aluminiumsulfat,
  • das 0,6 % Ti02 enthält,
  • Rest Ammonium-titanylsulfat,
  • das 0,6 % AI203 enthält.
The yield of the final product is 980 g. The end product contains 16.3% by weight Ti0 2 and 2.05% by weight Al 2 0 3 . The product consists of two sulfates in% by weight:
  • 17.8% ammonium aluminum sulfate,
  • which contains 0.6% Ti0 2 ,
  • Remainder ammonium titanyl sulfate,
  • that contains 0.6% AI 2 0 3 .

Beispiel 3.Example 3.

Man verfährt analog den Beispielen 1 und 2 mit dem Unterschied, daß man nach den Einführen der Komponenten Kieselsäure in einer Menge von 3,8 g (gemäß den Beispiel 1) und 6,0 g (gemäß den Beispiel 2) hinzufügt.The procedure of Examples 1 and 2 is repeated, with the difference that, after the components have been introduced, 3.8 g (according to Example 1) and 6.0 g (according to Example 2) are added.

Das Gewichtsverhältnis der Kieselsäure zum Titandioxid macht in den Endprodukt 0,05:1 aus.The weight ratio of silica to titanium dioxide in the end product is 0.05: 1.

Beispiel 4.Example 4.

Man nimmt 0,5 Liter Zirconiumsulfatlösung, die 180 g/I Zirconium, umgerechnet auf sein Dioxyd enthält. Man führt in die Lösung Schwefelsäure und Ammoniumsulfat bis zu einem Gesamtgehalt an freier Schwefelsäure und freiem Ammoniumsulfat von 770 g/I ein. Dabei kristallisiert aus der Lösung das sich bildende basische Ammonium-zirconiumsulfat aus. In die Reaktionslösung führt man innerhalb von 2 Stunden 1 Liter einer Lösung des Ammonium-titanylsulfates, die 117 g/I Titan, umgerechnet auf sein Dioxyd enthält, und zusätzlich Ammoniumsulfat und Schwefelsäure bis zu Erzielung eines Gesamtgehaltes an freier Schwefelsäure und freiem Ammoniumsulfat von 820 g/I und eines Molverhältnisses von Zirconium zu Titan von 0,5: 1 ein. Die Suspension wird im Verlaufe von 24 Stunden gehalten. Der Niederschlag wird abfiltriert.0.5 liter of zirconium sulfate solution containing 180 g / l of zirconium, converted to its dioxide, is taken. Sulfuric acid and ammonium sulfate are introduced into the solution up to a total content of free sulfuric acid and free ammonium sulfate of 770 g / l. The basic ammonium zirconium sulfate which forms is crystallized from the solution. 1 liter of a solution of ammonium titanyl sulfate, which contains 117 g / l titanium, converted to its dioxide, and additional ammonium sulfate and sulfuric acid are added to the reaction solution within 2 hours until a total content of free sulfuric acid and free ammonium sulfate of 820 g is achieved / I and a molar ratio of zirconium to titanium of 0.5: 1. The suspension is held for 24 hours. The precipitate is filtered off.

Die Ausbeute an Produkt beträgt 1000 g. Das Produkt enthält 11,0 Gew.% Ti02 und 8,5 Gew.% Zr02. Das Produkt besteht aus zwei Sulfaten in Gew.%:

  • 45 % basisches Ammonium-zirconiumsulfat
  • das 0,005 % Ti02 enthält,
  • Rest Ammonium-titanlysulfat
  • das 0,005 % Zr02 enthält.
The yield of the product is 1000 g. The product contains 11.0% by weight of Ti0 2 and 8.5% by weight of Zr0 2 . The product consists of two sulfates in% by weight:
  • 45% basic ammonium zirconium sulfate
  • that contains 0.005% Ti0 2 ,
  • Balance ammonium titanium lysulfate
  • that contains 0.005% Zr0 2 .

Beispiel 5.Example 5.

Man nimmt 0,5 Liter Zirkoniumsulfatlösung, die 180 g/I Zirconium, umgerechnet auf seim Dioxyd, enthält. Man führt in die Lösung im Verlaufe von 8 Stunden 1 Liter schwefelsaure Lösung, erhalten bei der Verarbeitung eines titanhaltigen Rohstoffes, die 160 g/I Titan, umgerechnet auf sein Dioxyd, und 400 g/I Schwefelsäure enthält, und Ammoniumsulfat bis zur Erzielung eines Gehaltes der Lösung an freiem Ammoniumsulfat von 500 g/I und eines Molverhältnisses von Zirconium zu Titan von 0,35 : 1 ein. Man hält die Suspension während 35 Sunden. Der Niederschlag wird durch Filtrieren abgetrennt.0.5 liter of zirconium sulfate solution containing 180 g / l of zirconium, converted to the amount of dioxide, is used. 1 liter of sulfuric acid solution is passed into the solution over the course of 8 hours, obtained when processing a titanium-containing raw material which contains 160 g / l titanium, converted to its dioxide, and 400 g / l sulfuric acid, and ammonium sulfate until a content is achieved the solution of free ammonium sulfate of 500 g / I and a molar ratio of zirconium to titanium of 0.35: 1. The suspension is kept for 35 hours. The precipitate is separated off by filtration.

Die Ausbeute an Endprodukt beträgt 1200 g. Das Produkt enthält 12,9 Gew.% Ti02 und 7,3 Gew.% ZrO2, es besteht aus zwei Sulfaten in Gew.%:

  • 35 % basisches Ammonium-zirconiumsulfat,
  • das 0,006 % Ti02 enthält,
  • Rest Ammonium-titanylsulfat
  • das 0,006 % ZrO2 enthält.
The yield of the final product is 1200 g. The product contains 12.9% by weight Ti0 2 and 7.3% by weight ZrO 2 , it consists of two sulfates in% by weight:
  • 35% basic ammonium zirconium sulfate,
  • that contains 0.006% Ti0 2 ,
  • Balance ammonium titanyl sulfate
  • that contains 0.006% ZrO 2 .

Beispiel 6.Example 6.

Man nimmt 0,5 Liter Zirconiumsulfatlösung, die 180 g/I Zirconium, umgerechnet auf sein Dioxyd, enthält. Man führt in die Lösung Schwefelsäure und Ammoniumsulfat bis zu einem Gesamtgehalt an freiem Ammoniumsulfat und freier Schwefelsäure von 770 g/I ein.0.5 liter of zirconium sulfate solution containing 180 g / l of zirconium, converted to its dioxide, is taken. Sulfuric acid and ammonium sulfate are introduced into the solution up to a total content of free ammonium sulfate and free sulfuric acid of 770 g / l.

Dabei kristallisiert aus der Lösung das sich bildende basische Ammonium-zirconiumsulfat aus. Man führt in die Reaktionslösung im Verlaufe von 1 Stunde 1,5 Liter einer Lösung des Ammonium titanylsulfates, die 100 g/I Titan, umgerechnet auf sein Dioxyd enthält, 0,05 Liter einer Lüsung von Aluminiumsulfat die 113 g/l Aluminium, umgerechnet auf sein Oxyd, enthält und zusätzlich Schwefelsäure und Ammoniumsulfat ein bis zur Erzielung eines Gesamtgehaltes an freier Schwefelsäure und freiem Ammoniumsulfat von 820 g/I und eines Molverhältnisses von Aluminium zu Titan von 0,05: 1 von Zirconium zu Titan von 0,40: 1. Die Suspension wird während 20 Stunden gehalten. Der Niederschlag wird durch Filtrieren abgetrennt.The basic ammonium zirconium sulfate which forms is crystallized from the solution. In the course of 1 hour, 1.5 liters of a solution of ammonium titanyl sulfate containing 100 g / l titanium, converted to its dioxide, and 0.05 liter of a solution of aluminum sulfate, the 113 g / l aluminum, are converted into the reaction solution Its oxide contains and additionally sulfuric acid and ammonium sulfate until a total content of free sulfuric acid and free ammonium sulfate of 820 g / l and a molar ratio of aluminum to titanium of 0.05: 1 of zirconium to titanium of 0.40: 1 is achieved. The suspension is held for 20 hours. The precipitate is separated off by filtration.

Die Ausbeute an Endprodukt beträgt 1500 g. Das Produkt enthält 9,5 Gew.% Ti02, 5,9 Gew.% Zr02 und 0,3 Gew.% Al2O3. Das Produkt besteht aus drei Sulfaten in Gew.%:

  • 3 % Ammonium-aluminiumsulfat das 0,5 % Ti02 und Zr02 enthält,
  • 45 % basisches Ammonium-zirconiumsulfat,
  • das 0,2 % Ti02 und Al2O enthält,
  • Rest Ammonium-titanylsulfat,
  • das 0,4 % A1203 und Zr02 enthält.
The yield of the final product is 1500 g. The product contains 9.5% by weight Ti0 2 , 5.9% by weight Zr0 2 and 0.3% by weight Al 2 O 3 . The product consists of three sulfates in% by weight:
  • 3% ammonium aluminum sulfate containing 0.5% Ti0 2 and Zr0 2 ,
  • 45% basic ammonium zirconium sulfate,
  • that contains 0.2% Ti0 2 and Al 2 O,
  • Remainder ammonium titanyl sulfate,
  • that contains 0.4% A1 2 0 3 and Zr0 2 .

Beispiel 7.Example 7.

Man nimmt 0,5 Liter Zirconiumsulfatlösung, die 150 g/I Zirconium, umgerechnet auf sein Dioxyd enthält. Man führt in die Lösung innerhalb von 8 Stunden 1,7 Liter schwefelsaure Lösung, erhalten bei der Verarbeitung von titanhaltigem Rohstoff, die 160 g/l Titan, umgerechnet auf sein Dioxyd, und 400 g/I Schwefelsäure enthält, 0,04 Liter Aluminiumsulfatlösung, 113 g/I Aluminium, umgerechnet auf sein Oxyd, enthält und Ammoniumsulfat bis zur Erzielung eines Gehaltes an freiem Ammoniumsulfat in der Reaktionslösung von 500 g/I und eines Molverhältnisses von Aluminium zu Titan von 0,18: 1 und von Zirconium zu Titan von 0.20: 1 ein. Nach dem Einführen der Reaktionsmittel wird die Suspension innerhalb von 40 Stunden gehalten. Der Niederschlag wird durch Filtrierem abgetrennt. Das Gewicht des Niederschlags beträgt 1885 g. Der Niederschlag enthält 14,0 Gew.% TiO2, 4,3 Gew.% ZrO2 und 2,8 Gew.% Al2O3. Der Niederschlag besteht aus drei Sulfaten in Gew%:

  • 20 % Ammonium-aluminiumsulfat,
  • das 0,5 % Ti02 und Zr02 enthält,
  • 21 % basisches Ammonium-zirconiumsulfat,
  • das 0,2 % Ti02 und AI203 enthält,
  • Rest Ammonium-titanylsulfat, das
  • 0,6 % Al2O und ZrO2 enthält.
0.5 liter of zirconium sulfate solution containing 150 g / l of zirconium, converted to its dioxide, is taken. 1.7 liters of sulfuric acid solution are introduced into the solution within 8 hours, obtained when processing titanium-containing raw material containing 160 g / l titanium, converted to its dioxide, and 400 g / l sulfuric acid, 0.04 liter aluminum sulfate solution, 113 g / l aluminum, converted to its oxide, contains and ammonium sulfate until a free ammonium sulfate content of 500 g / l is achieved in the reaction solution and a molar ratio of aluminum to titanium of 0.18: 1 and of zirconium to titanium of 0.20 : 1 a. After the reactants have been introduced, the suspension is held within 40 hours. The precipitate is separated off by filtration. The weight of the precipitation is 1885 g. The precipitate contains 14.0% by weight of TiO 2 , 4.3% by weight of ZrO 2 and 2.8% by weight of Al 2 O 3 . The precipitation consists of three sulfates in% by weight:
  • 20% ammonium aluminum sulfate,
  • that contains 0.5% Ti0 2 and Zr0 2 ,
  • 21% basic ammonium zirconium sulfate,
  • that contains 0.2% Ti0 2 and AI 2 0 3 ,
  • Remainder ammonium titanyl sulfate, the
  • Contains 0.6% Al 2 O and ZrO 2 .

Das Verfahren gemäß den Beispielen 1 bis 7 wird bei konventionellen Bedingungen und zwar bei Zimmertemperatur und Normaldruck durchgeführt.The process according to Examples 1 to 7 is carried out under conventional conditions, namely at room temperature and normal pressure.

Die Gerbeigenschaften der Produkte sind gemäß der Schrumpfungstemperatur der mit diesen bearbeiteten Hautblöße angeführt (siehe Tabelle).

Figure imgb0001
Aus den Versuchsdaten für die Schrumpfungstemperatur der durchgegerbten Hautblöße folgt, daß das erfindungsgemäße Gerbmittel, das gemäß den Beispielen 1 bis 7 erhalten wird, die Qualität der Leder im Vergleich zu dem bekannten Titangerbmittel erhöht.The tanning properties of the products are given in accordance with the shrinkage temperature of the skin exposed with them (see table).
Figure imgb0001
 From the experimental data for the shrinkage temperature of the tanned skin, it follows that the tanning agent according to the invention, which is obtained according to Examples 1 to 7, increases the quality of the leather compared to the known titanium tanning agent.

Die besten Ergebnisse nach der Schrumpfungstemperatur der durchgegerbten Blöße werden bei der Durchführung der Variante mit einem Titan-Zirconium-Aluminium-Gerbmittel erreicht, das unter Verwendung einer bei der Verarbeitung von titanhaltigem Rohstoff anfallenden schwefelsaueren Lösung (Beispiel 7) erhalten wird.The best results after the shrinkage temperature of the tanned pelts are achieved when the variant is carried out with a titanium-zirconium-aluminum tanning agent which is obtained using a sulfuric acid solution obtained in the processing of titanium-containing raw material (example 7).

Die verbesserten Gerbeigenschaften des Gerbmittels werden im Vergleich zu den bekannten Gerbmitteln dadurch erzielt, daß man eine Kombination von Sulfaten verwendet, die in der Zusammensetzung die Zusätze Ti02, Zr02 und Al2O3 enthalten.The improved tanning properties of the tanning agent are achieved in comparison to the known tanning agents by using a combination of sulfates which contain the additives Ti0 2 , Zr0 2 and Al 2 O 3 in the composition.

Gewerbliche VerwertbarkeitCommercial usability

Die vorliegende Erfindung kann in der Lederindustrie bei Lederherstellung eingesetzt werden.The present invention can be used in the leather industry in leather manufacture.

Claims (13)

1. A leather tanning agent containing sulphate of ammonium and aluminium, sulphate of ammonium and zirconium and sulphate of ammonium and titanyl characterized in that said components contain chemically bonded additions of titanium, zirconium and aluminium, calculated as oxides and that said components are present in the tanning agent in the following proportions:
3 to 20% by weight of sulphate of ammonium and aluminium of the formula NH4Al(SO4)2.12H2O, which contains 0,001 to 1,0% of Ti02 or Ti02 and ZrO2, and/or
20 to 50% by weight of basic sulphate of ammonium and zirconium of the formula (NH4)2Zr2(OH)5 (S04)2,5).H20 which contains 0,001 to 0,5% of Ti02 or Ti02 and AI203 and
balance sulphate of ammonium and titanyl of the formula (NH4)2TiO(SO4)2.H2O, which contains 0,001 to 1,0% of A1203 and/or Zr02.
2. A tanning agent according to claim 1, characterized in that it contains the following components:
3 to 20% by weight of sulphate of ammonium and aluminium, which contains 0,001 to 1,0% of TiO2,
balance sulphate of ammonium and titanyl, which contains 0,001 to 1,0% of AlzO3.
3. A tanning agent according to claim 1, characterized in that it contains the following components:
20 to 50% by weight of basic sulphate ammonium and zirconium, which contains 0,001 to 0,1% of TiO2, balance sulphate of ammonium and titanyl, which contains 0,001 to 0,1% of ZrOz.
4. A tanning agent according to claim 1, characterized in that it contains the following components:
3 to 20% by weight of sulphate of ammonium and aluminium, which contains 0,001 to 1,0% of Ti02 and Zr02
20 to 50% by weight of basic sulphate of ammonium and zirconium, which contains 0,001 to 0,5% of Ti02 and AI203
balance sulphate of ammonium and titanyl, which contains 0,001 to 1,0% of Al2O3 and ZrO2.
5. A tanning agent according to claim 1 or 2, characterized in that it contains 1 to 10% by weight of silicic acid.
6. A method of obtaining a leather tanning agent according to claims 1 to 4 characterized in that a titanium-containing solution containing 80 to 200 g/I of titanium, as calculated for its dioxide, is reacted with a solution of aluminium sulphate containing 80 to 130 g/I of aluminium, as calculated for its oxide and/or a solution of zirconium sulphate containing 50 to 200 g/I of zirconium as calculated for its dioxide, in the presence of sulphuric acid and ammonium sulphate.
7. A method according to claim 6, characterized in that as titanium-containing solution use is made of a solution of sulphate of ammonium and titanyl containing 80 to 140 g/I of titanium, as calculated for its dioxide and it is added with ammonium sulphate and sulphuric acid till the moment of the beginning of crystallization of sulphate of ammonium and titanyl, whereafter for a period of from 1 to 5 hours a solution of aluminium sulphate and, additionally, sulphuric acid and ammonium sulphate are added to obtain in the reaction solution a total content of free sulphuric acid and free ammonium sulphate of 400 to 600 g/I and a molar ratio of aluminium and titanium of from 0,03:1 to 0,24:1.
8. A method according to claim 6, characterized in that as the titanium-containing solution use is made of a sulphate solution, obtained from processing of a titanium-containing raw material, containing 100 to 200 g/I of titanium as calculated for its dioxide and 300 to 520 g/I of sulphuric acid and to this solution ammonium sulphate is added till the moment of the beginning of crystallization of the formed sulphate of ammonium and titanyl, whereafter for a period of from 6 to 10 hours a solution of aluminium sulphate is added along with an additional amount of ammonium sulphate till a content of free ammonium sulphate in the reaction solution of 210 to 350 g/I and a molar ratio of aluminium to titanium of from 0,03:1 to 0,24:1.
9. A method according to claim 7 and 8, characterized in that after the addition of all the above mentioned components silicic acid or its sodium salt is added to the reaction solution till the molar ratio of silicon to titanium amounts to from 0,07:1 to 0,70:1.
10. A method according to claim 6, characterized in that to a zirconium-containing solution there are added ammonium sulphate and sulphuric acid till the moment of the beginning of crystallization of the formed sulphate of ammonium and zirconium whereafter for a period of from 1 to 5 hours it is added with a solution of sulphate of ammonium and titanyl containing 80 to 140 g/I of titanium as calculated for its dioxide and additionally ammonium sulphate and sulphuric acid till a total content of free ammonium sulphate and free sulphuric acid in the reaction solution of from 770 to 1000 g/I and a molar ratio of zirconium to titanium of from 0,10:1 to 0,65:1.
11. A method according to claim 10, characterized in that to the reaction solution, after the beginning of crystallization of sulphate of ammonium and zirconium a solution of aluminium sulphate is added till the molar ratio of aluminium to titanium in the solution is from 0,03:1 to 0,24:1.
12. A method according to claim 6, characterized in that to the zirconium-containing solution there is added for a period of from 6 to 10 hours, a sulphate solution obtained from processing of a titanium-containing raw material containing 100 to 200 g/I of titanium as calculated for its dioxide, and 300 to 520 g/I of sulphuric acid and ammonium sulphate till a content of free ammonium sulphate in the reaction solution of from 400 to 580 g/I and a molar ratio of zirconium to titanium of from 0,10:1 to 0,65:1.
13. A method according to claim 12, characterized in that to the reaction solution a solution of aluminium sulphate is added to obtain a molar ratio of aluminium to titanium in the solution of from 0,03:1 to 0,24:1.
EP81903143A 1981-05-19 1981-05-19 Tanning agent for skins and method of obtaining it Expired EP0085107B1 (en)

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AT81903143T ATE21935T1 (en) 1981-05-19 1981-05-19 TANNING AGENTS FOR HIDES AND PROCESS FOR PRODUCTION THEREOF.

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US5306435A (en) * 1991-07-11 1994-04-26 Nihon Junyaku Co., Ltd. Treating agent composition for leather, for fibrous materials
DE19546946A1 (en) 1995-12-15 1997-06-19 Hoechst Ag Precursor for alkoxylation catalysts
DE19624821A1 (en) * 1996-06-21 1998-01-02 Bayer Ag Leather tanning process
DE19849577C2 (en) 1998-10-27 2000-12-07 Agie Sa Method and device for three-dimensional machining of a workpiece by means of electroerosive or electrochemical machining
CN104357596B (en) * 2014-11-11 2016-05-18 陕西科技大学 Green leather fatting agent and method thereof prepared by Pickering emulsion method
CN107649799A (en) * 2017-09-22 2018-02-02 攀钢集团研究院有限公司 Welding material titanium system raw material and preparation method thereof

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DE1257353B (en) * 1965-03-26 1967-12-28 Bayer Ag Method of tanning
SU783342A1 (en) * 1979-01-04 1980-11-30 Институт Химии И Технологии Редких Элементов И Минерального Сырья Ордена Ленина Кольского Филиала Им. С.М.Кирова Ан Ссср Leather tanning composition
SU859455A1 (en) * 1979-10-29 1981-08-30 Джамбульский Технологический Институт Легкой И Пищевой Промышленности Method of producing mineral tanning agent

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* Cited by examiner, † Cited by third party
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DK19083D0 (en) 1983-01-18
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