EP0025608A2 - Catalyseur de décomposition contrôlée de composés peroxydes, sa préparation et son utilisation; produit de lavage ou de blanchiment et procédé de préparation d'un produit de lavage ou de blanchiment contenant un peroxyde - Google Patents

Catalyseur de décomposition contrôlée de composés peroxydes, sa préparation et son utilisation; produit de lavage ou de blanchiment et procédé de préparation d'un produit de lavage ou de blanchiment contenant un peroxyde Download PDF

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Publication number
EP0025608A2
EP0025608A2 EP80105554A EP80105554A EP0025608A2 EP 0025608 A2 EP0025608 A2 EP 0025608A2 EP 80105554 A EP80105554 A EP 80105554A EP 80105554 A EP80105554 A EP 80105554A EP 0025608 A2 EP0025608 A2 EP 0025608A2
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EP
European Patent Office
Prior art keywords
catalyst
heavy metal
catalyst according
silicates
detergent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP80105554A
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German (de)
English (en)
Inventor
Carl-Ernst Dr. Dipl.-Chem. Hofstadt
Rudolf Dr. Dipl.-Chem. Fahn
Klaus Dr. Dipl.-Chem. Fenderl
Jost Dr. rer. nat. Dipl.-Chem. Heimann-Trosien
Wolfgang Dipl.-Chem. Reuter
Franz Baumann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalli-Werke Maurer and Wirtz
Sued Chemie AG
Original Assignee
Dalli-Werke Maurer and Wirtz
Sued Chemie AG
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Filing date
Publication date
Application filed by Dalli-Werke Maurer and Wirtz, Sued Chemie AG filed Critical Dalli-Werke Maurer and Wirtz
Publication of EP0025608A2 publication Critical patent/EP0025608A2/fr
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes

Definitions

  • peroxo compounds are compounds in which the grouping -0- is replaced by the grouping -0-0-.
  • the simplest representative of this group is hydrogen peroxide.
  • peroxohydrates i.e. the hydrogen peroxide addition compounds on borates, carbonates, urea and phosphates, e.g. Sodium borate peroxohydrate (also known as sodium perborate), sodium carbonate peroxohydrate (also known as sodium percarbonate), urea peroxohydrate and phosphate peroxohydrate
  • Peroxyacids e.g. Peroxophosphoric acid and peroxosulfuric acid.
  • peroxo compounds is also intended to cover organic peracids, such as peracetic acid or perpropionic acid, which are usually referred to as peroxy compounds.
  • peroxo compounds are catalytically decomposed by heavy metal ions to form molecular oxygen. This decomposition must be avoided in most applications of the peroxo compounds, especially in the bleaching process, since molecular oxygen has no bleaching effect.
  • the catalytic decomposition of peroxo compounds can also generate oxygen radicals, which can have a detrimental effect on the substrates to be treated.
  • the invention has for its object to subject peroxo compounds to controlled decomposition so that the oxygen is released in such a form that on the one hand the substrate to be treated is not damaged and on the other hand the loss of active oxygen caused by the formation of molecular oxygen and thus the bleaching effect is reduced as much as possible.
  • the invention thus relates to a catalyst for the continuous decomposition of peroxo compounds, which is characterized in that it contains zeolites or silicates with layer anions or products obtained therefrom by acid treatment, their exchangeable alkali metal or alkaline earth metal cations in whole or in part by cations of one or more heavy metals from the Groups Ib, Va, Vb, VIIa and / or VIII of the periodic table are replaced, contains or consists of.
  • the catalyst according to the invention surprisingly brings about a controlled decomposition of the peroxo compounds, even though it releases some of its heavy metal cations into the solution. This effect is surprising insofar as it was previously believed that heavy metal ions should be excluded as far as possible when working with peroxo compounds.
  • the oxygen release generally begins at about 30 to 35 ° C. and increases steadily as the temperature increases further.
  • the heavy metal cations are essentially internally crystalline embedded in the zeolites or silicates with layer anions or in the products obtained therefrom by acid treatment.
  • the heavy metal cations are likely to be found inside the cage structure.
  • the heavy metal cations are located between the layers.
  • the attapulgites sinulite and palygorskite
  • the anion layers of these silicates are rolled up in a tube shape and form cylindrical cavities. The attapulgites are thus between the zeolites and the actual silicates with layer anions. This includes the clays or clay minerals.
  • Clay minerals of the kaolinite structure type include the kaolin minerals kaolinite, nacrite, dickite, anauxite and halloysite, the serpentine minerals chrysotile, serpentine, antigorite, amesite.
  • Montmorillonite-Beidellite range These include montmorillonite, which is the main mineral of bentonite, as well as hectorite, beidellite, saponite and nontronite.
  • Vermiculite series silicates include dioctahedral and trioctahedral vermiculite.
  • Illite series silicates These include the fine crystalline mica, the dioctahedral and the trioctahedral illite and the glauconite.
  • Mica minerals include in particular the muscovite and the biotite.
  • Minerals from the chlorite group are derived from the mica-like layered silicates in that a hydroxide layer Me (OH) 2 or Me (OH) 3 is introduced between the silicate layers instead of the intermediate layer cations.
  • Clay minerals with species disorder are built up alternately from layers of different clay minerals.
  • the minerals from the montmorillonite-beidellite range are particularly suitable, e.g. occur in natural bentonites.
  • Both the zeolites and the silicates with layered anions can be subjected to an acid treatment, the monovalent and divalent cations being generally dissolved out to a greater or lesser extent while maintaining the anion lattice. With intensive acid treatment, the aluminum is also partially removed.
  • the acid-treated silicates the products obtained from clays of the montmorillonite-beidellite series are preferably used according to the invention.
  • the acid-treated products obtained from natural bentonites are generally known as bleaching earths.
  • the acid treatment is generally carried out by heating the clays in aqueous mineral acids such as sulfuric or hydrochloric acid, after which the acid solution is extracted and washed out together with the dissolved cations.
  • the heavy metal cations which after the storage instead of the exchangeable alkali or alkaline earth cations sit in the cavities of the silicate lattice or between the silicate layers, catalyze the decomposition of the peroxo compounds dissolved in an aqueous solution in a controlled manner, probably by the fact that the molecules or anions of the peroxy compounds must diffuse into the cavities or into the interlayer spaces to the bound heavy metal ions. This diffusion is obviously the rate-determining process. However, the exact mechanism of the reaction is not yet known.
  • the catalyst according to the invention is preferably loaded with cations of one or more of the metals nickel, antimony, copper, vanadium, manganese, silver, cobalt or iron. Iron, copper and / or manganese are particularly preferably used.
  • the heavy metal cations are preferably in divalent or trivalent form.
  • the catalyst according to the invention preferably contains about 3 to 300 meq heavy metal cations per 100 g zeolites or silicates with layer anions. The maximum amount absorbed depends primarily on the ion exchange capacity of the silicate.
  • the catalyst according to the invention can also be a mechanical mixture of catalysts which are each loaded with different heavy metal cations.
  • the individual catalysts have different activities, and the rate of decomposition can be modified in the desired manner by a suitable selection of the catalysts.
  • the invention further relates to a process for the preparation of the catalysts described above.
  • This process is characterized in that one or more water-soluble salts of one or more heavy metals are applied to an aqueous suspension of the zeolites or silicate with layer anions or the products obtained therefrom by acid treatment the groups Ib, Va, Vb, VIIa and / or VIII of the Periodic Table, which removes the heavy metal cations not in solution by the silicates and which is in solution, washes the solid residue until practically no heavy metal ions can be detected in the washing liquid, and the washed solid residue dries.
  • the catalysts are preferably prepared in such a way that an approximately 0.5 to 3 normal, preferably 1 normal, heavy metal salt solution is allowed to act on the silicate suspension.
  • the invention further relates to the use of the catalysts described above as a component in detergents or bleaches containing peroxo compounds, in particular in detergents or bleaches to which sodium perborate has been added.
  • the peroxo compounds contained in the washing or bleaching agents usually only take effect at higher temperatures, in particular at or near the boiling point of the washing liquor.
  • the disintegration occurs more or less uncontrolled, so that a uniform bleaching effect is only achieved if relatively high proportions of peroxo compounds available.
  • These are then broken down only to a relatively small extent, for example 15 to 20%, which makes the overall effort uneconomical and ecologically questionable.
  • the proportion of the peroxo compound decomposed during the washing process is greatly increased by adding a catalyst according to the invention, so that 50 and more percent of the peroxo compound present are evaluated for the bleaching or oxidation process.
  • the amount of heavy metal cations contained in the catalyst is expediently at most equal to the amount of sodium perborate contained in the detergent or bleach.
  • the detergent or bleach contains, per 100 parts by weight, preferably at least 0.1 part by weight of the catalyst according to the invention, the amount of which may be up to about 30% by weight of the total weight of the detergent or bleach. Amounts of catalyst between about 0.5 and 10% by weight are preferred.
  • the invention further relates to detergents or bleaches containing peroxo compounds which are characterized by a content of the catalysts described above.
  • These washing or bleaching agents preferably contain about 0.1 to 30% by weight of catalyst and about 5 to 99% by weight of sodium perborate, the remainder consisting of the usual washing or bleaching agent additives.
  • the detergents or bleaches according to the invention can be prepared by spray-drying a free-flowing powder from detergent-active and complex-forming substances, builders, fillers and the catalyst according to the invention and this powder, if appropriate, still warm with a peroxo compound, preferably sodium perborate , mixed in the desired amount.
  • a peroxo compound preferably sodium perborate
  • At least part of the catalyst in powder form can be blown into the space or part of the spray drying system during the spray drying of an aqueous batch of the peroxide-free other constituents, in which the atomized particles of the aqueous batch are dried are, whereupon the peroxy compound is mixed into the powder thus obtained.
  • the detergents and bleaches produced in this way can, in addition to the constituents mentioned above, also other components in the production of detergents and bleaches Common additives, such as enzymes, brighteners, dirt carriers, phosphate substitutes, etc. contain.
  • EDTA ethylenediaminetetraacetic acid
  • the EDTA reacts with the heavy metal ions in solution to form a complex in which the heavy metal ions are no longer able to catalyze the decomposition of peroxo compounds.
  • the catalytic activity of the catalysts according to the invention is largely retained even in the presence of EDTA.
  • the course of the decomposition curves of the peroxo compounds depends on various factors, for example on the concentration of the catalyst, on the concentration and type of heavy metal cations in the catalyst and on the mixing ratio of the catalyst components loaded with different heavy metal cations. If a mixture is used, the most favorable conditions between the individual catalysts can easily be determined on the basis of simple experiments.
  • the decomposition curves for the individual catalysts are determined at the desired temperature and time parameters. If, for example, the slope of the decomposition curve obtained with a catalyst is too large, it will become Catalyst mixed with another catalyst in which the decomposition curve shows a flatter slope. Too steep a decomposition curve can also be optimized by adding a silicate to the catalyst containing the heavy metal cations that has not been loaded with heavy metal ions.
  • the time course of the release of oxygen during the decomposition of the peroxo compounds as a function of temperature can expediently be measured using the apparatus described below:
  • the gas development vessel is a narrow-necked Erlenmeyer flask (100 ml), which is equipped with a rubber stopper through which an internal thermometer and a glass tube bent at right angles are passed.
  • the other end of the glass tube is connected via a short rubber hose connection to a U-shaped glass tube, which is used as an inlet tube in a 200 ml measuring cylinder.
  • the measuring cylinder is in a drip pan.
  • the Erlenmeyer flask is in a water bath that is heated by a hotplate with a magnetic stirrer. There is a contact thermometer and a magnetic rod in the water bath. Another magnetic rod is in the Erlenmeyer flask.
  • the apparatus is now heated using the rate of heating described below.
  • the air displacement of the apparatus (volume expansion of the air in the flask) is determined as a zero value with a weight of 50 ml of distilled water while heating from 20 to 60 ° C, for example.
  • the values from the zero value curve are subtracted from the values of the individual decomposition curves at the respective temperatures.
  • the zero value after 15 minutes, i.e. after reaching a temperature of 60 ° C, is about 18.3 ml. In the drawing only the net decomposition curves, i.e. after deduction of the respective zero value.
  • the theoretical decomposition value of 1 g sodium perborate (MW 153.84, purity> 98%, 6.5 mmol) is 72.8 ml 0 2 (3.25 mmol).
  • the practical decomposition value of 1 g sodium perborate was found to be 79.5 ml. That this value is higher than the theoretical decomposition value is due to the fact that the gas volume saturated with water vapor in the measuring cylinder at room temperature.
  • the practical decomposition value was not converted to normal conditions, since all curve values were obtained under the same conditions. The practical decomposition value could therefore be set as 100%.
  • decomposition curves are shown in the drawing. 1.0 g of peroxo compound in 50 ml of distilled water were each decomposed using the catalysts according to Examples 1 to 7. The numbering of the curves corresponds to the numbering of the examples. 1 and 2 show the decomposition of perborate solutions. 3 shows the decomposition of H 2 0 2 solutions, in each case when heating up to 60 ° C.
  • amer Bentonite and Moosburger bentonite specifically coated with copper ions.
  • 5% aqueous bentonite suspensions were mixed with dilute Cu-SO 4 solutions, the following proportions being used:
  • H-bentonite an acid-activated bentonite (hereinafter referred to as H-bentonite) thus obtained were each mixed with 1 liter of a 1N solution of (a) MnCl 2 , (b) CuSO 4 and (c) NiCl 2 and after a stirring time of 16 hours filtered off. After washing until substantially free of ions, the products at 120 ° C were dried and milled (finer than 63 / u). In all cases, 200 mVal heavy metal ions were used for 100 g of silicate.
  • Example 1 (b) In the manner described in Example 1 (b), a slurry of 100 g of Moosburger clay in 3 liters of distilled water was mixed with 100 mmol VOSO 4 . 5H 2 0 and stirred for 16 hours. The reaction product was then filtered off, washed largely free of ions and dried. The bentonite had 8.7 mmol vanadium per 100 g as exchangeable ions (determined after NH 4 Cl exchange).
  • iron bentonite was prepared by treating 100 g of Moosburger clay in 2 liters of distilled water with 100 mVal Fe 3+ (from FeCl 3 .6H 2 O). The bentonite had 29.4 meq of exchangeable iron ions per 100 g (determined by extraction with 0.1 N hydrochloric acid).
  • the amounts of the heavy metal cations bound to the individual silicates were first determined, since the bound fraction is generally lower than the fraction used. Since there are certain relationships to the ion exchange capacity (IUF) of the silicate, these values are also mentioned for some examples.
  • IUF ion exchange capacity
  • the decomposition values are given in Table III below and shown in FIGS. 1 and 2. From the values it can be seen that the greater the amount of copper on offer, the faster the copper bentonites decompose the perborate.
  • Copper zeolite and copper attapulgite behave similarly to copper bentonite.
  • the catalysts with the lower activity can be mixed with the catalysts with the higher activity so that a medium activity can be obtained.
  • the decomposition was carried out (A) without the addition of a catalyst according to the invention, (B + C) after the addition of Cu bentonite according to Example 1 and (D) after the addition of Cu sulfate, in the cases (B + C) and (D ) the amounts given in Table V were used.
  • the experiment was started by turning on the heating.
  • the heating power was set so that the test temperature of 95 ° C was reached after 45 minutes and then held for 20 minutes.
  • the perborate content in a first sample of 50 ml was determined titrimetrically with potassium permanganate and set at 100% as a starting value.
  • the perborate content of the solution was determined in the same way from 50 ° C. every 10 ° C. and after reaching the test temperature every 5 minutes.
  • the data refer to% reflectance difference ( ⁇ R) between unwashed and washed fabric, the values given in Table V being average values.
EP80105554A 1979-09-18 1980-09-16 Catalyseur de décomposition contrôlée de composés peroxydes, sa préparation et son utilisation; produit de lavage ou de blanchiment et procédé de préparation d'un produit de lavage ou de blanchiment contenant un peroxyde Withdrawn EP0025608A2 (fr)

Applications Claiming Priority (2)

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DE2937739 1979-09-18
DE2937739 1979-09-18

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EP0025608A2 true EP0025608A2 (fr) 1981-03-25

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Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072166A1 (fr) * 1981-08-08 1983-02-16 THE PROCTER & GAMBLE COMPANY Compositions de catalyseur de blanchiment, leur utilisation dans les compositions détergentes de blanchiment et de lavage et procédé de blanchiment les utilisant
US4478733A (en) * 1982-12-17 1984-10-23 Lever Brothers Company Detergent compositions
US4481129A (en) * 1981-12-23 1984-11-06 Lever Brothers Company Bleach compositions
EP0143491A2 (fr) * 1983-11-23 1985-06-05 Unilever N.V. Composition détergente
US4536183A (en) * 1984-04-09 1985-08-20 Lever Brothers Company Manganese bleach activators
US4568477A (en) * 1983-12-06 1986-02-04 Lever Brothers Company Detergent bleach compositions
US4601845A (en) * 1985-04-02 1986-07-22 Lever Brothers Company Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials
US4623357A (en) * 1985-04-02 1986-11-18 Lever Brothers Company Bleach compositions
US4626373A (en) * 1983-11-08 1986-12-02 Lever Brothers Company Manganese adjuncts, their preparation and use
US4626374A (en) * 1983-11-08 1986-12-02 Lever Brothers Company Heavy metal adjuncts, their preparation and use
US4655782A (en) * 1985-12-06 1987-04-07 Lever Brothers Company Bleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween
US4655953A (en) * 1983-12-06 1987-04-07 Lever Brothers Company Detergent bleach compositions
US4711748A (en) * 1985-12-06 1987-12-08 Lever Brothers Company Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation
US4731196A (en) * 1986-10-28 1988-03-15 Ethyl Corporation Process for making bleach activator
EP0832969A2 (fr) * 1996-09-26 1998-04-01 Henkel Kommanditgesellschaft auf Aktien Composé catalytique actif pour améliorer l'efficacité de blanchiment
WO2011131422A1 (fr) * 2010-04-20 2011-10-27 Closed Stock Company "Institute Of Applied Nanotechnology" Savon de toilette possédant des propriétés antimicrobiennes

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0072166A1 (fr) * 1981-08-08 1983-02-16 THE PROCTER & GAMBLE COMPANY Compositions de catalyseur de blanchiment, leur utilisation dans les compositions détergentes de blanchiment et de lavage et procédé de blanchiment les utilisant
US4481129A (en) * 1981-12-23 1984-11-06 Lever Brothers Company Bleach compositions
US4478733A (en) * 1982-12-17 1984-10-23 Lever Brothers Company Detergent compositions
US4626373A (en) * 1983-11-08 1986-12-02 Lever Brothers Company Manganese adjuncts, their preparation and use
US4626374A (en) * 1983-11-08 1986-12-02 Lever Brothers Company Heavy metal adjuncts, their preparation and use
EP0143491A2 (fr) * 1983-11-23 1985-06-05 Unilever N.V. Composition détergente
EP0143491B1 (fr) * 1983-11-23 1989-03-22 Unilever N.V. Composition détergente
US4568477A (en) * 1983-12-06 1986-02-04 Lever Brothers Company Detergent bleach compositions
US4655953A (en) * 1983-12-06 1987-04-07 Lever Brothers Company Detergent bleach compositions
US4536183A (en) * 1984-04-09 1985-08-20 Lever Brothers Company Manganese bleach activators
EP0170346A1 (fr) * 1984-04-09 1986-02-05 Unilever Plc Activateurs de blanchiment de manganèse
JPS61259757A (ja) * 1984-04-09 1986-11-18 ユニリ−バ−・ナ−ムロ−ゼ・ベンノ−トシヤ−プ マンガン漂白活性化剤
US4601845A (en) * 1985-04-02 1986-07-22 Lever Brothers Company Bleaching compositions containing mixed metal cations adsorbed onto aluminosilicate support materials
US4623357A (en) * 1985-04-02 1986-11-18 Lever Brothers Company Bleach compositions
EP0201943B1 (fr) * 1985-04-02 1989-03-15 Unilever N.V. Compositions de blanchiment
US4655782A (en) * 1985-12-06 1987-04-07 Lever Brothers Company Bleach composition of detergent base powder and agglomerated manganese-alluminosilicate catalyst having phosphate salt distributed therebetween
US4711748A (en) * 1985-12-06 1987-12-08 Lever Brothers Company Preparation of bleach catalyst aggregates of manganese cation impregnated aluminosilicates by high velocity granulation
US4731196A (en) * 1986-10-28 1988-03-15 Ethyl Corporation Process for making bleach activator
EP0832969A2 (fr) * 1996-09-26 1998-04-01 Henkel Kommanditgesellschaft auf Aktien Composé catalytique actif pour améliorer l'efficacité de blanchiment
EP0832969A3 (fr) * 1996-09-26 1998-09-02 Henkel Kommanditgesellschaft auf Aktien Composé catalytique actif pour améliorer l'efficacité de blanchiment
WO2011131422A1 (fr) * 2010-04-20 2011-10-27 Closed Stock Company "Institute Of Applied Nanotechnology" Savon de toilette possédant des propriétés antimicrobiennes

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Inventor name: FAHN, RUDOLF, DR. DIPL.-CHEM.

Inventor name: HOFSTADT, CARL-ERNST, DR. DIPL.-CHEM.

Inventor name: FENDERL, KLAUS, DR. DIPL.-CHEM.

Inventor name: BAUMANN, FRANZ