DE2531961C3 - Process for the production of storage-stable enzyme preparations and detergents or washing auxiliaries containing them - Google Patents

Description

- Me ₂ O ₃ - (SiO ₂ ),

in which KLat is a calcium-exchangeable cation of valency α, χ a number from 0.7-1.5, Me denotes boron or aluminum and y denotes a number from 0.8-6, this compound having a calcium binding capacity of at least 50 mg CaO / g of the anhydrous active substance, adsorbed, the compound is separated from the enzyme solution and converted into a dry product, or the enzyme active substances dissolved or suspended in water are precipitated in the presence of this water-insoluble compound which binds the cakäumbinding, the solid substance is separated from the solution and put in transferred a dry product.

Z Process according to Claim 1, characterized in that y in the general formula of Claim 1 denotes a number from 13-4

3. The method according to claim 1 and 2, characterized in that the water-insoluble inorganic compound is the composition

0.7-1.1 Na ₂ O _{· Al 2} O ₃ · 13-33SiO ₂

having

4. The method according to claim 1 to 3, characterized in that in claims 1 to 3 defined inorganic compounds are crystalline in nature.

5. The method according to claim 1 to 4, characterized in that proteases are used as enzymes uses, whose isoelectric point is in the pH range of 7-12 and whose proteolytic activity 1000-5CK) 000, in particular 2000-200,000 PU / g amounts to.

6. Storage-stable enzyme preparations, characterized in that they are prepared by the method according to Claims I to 5 have been made.

7. Washing or washing auxiliaries, characterized by a content of enzyme preparations according to Claim 6.

55

It is known. Incorporate proteases into laundry detergents, soaking agents or other washing auxiliaries for textiles in order to accelerate the removal of protein-containing stains and soiling during soaking or washing. According to the teaching of DE-OS 16 17 190, these proteases, which are usually obtained as moist filter cakes during their production, are first converted into enzyme powder and these are then mixed with calcined, hydrated salts such as Na ₂ SO ^ Na ₂ CO ₃ or Na ^ PjOio, converted into dry μ granules in the presence of water, which are then mixed with the detergents and auxiliary washing agents. According to another, described in DE-OS 16 17 188 The enzyme powder is made using glue acting nonionic surfactants bound to the granulated hydratable salt. From the U.S. PS 36 50 967 are also enzyme granules with a hydrated water-soluble salt as a carrier known which also has an inorganic one. Colloid containing silica to avoid otherwise In these known granules, those used as granulation aids are hydratable and in the granules partially hydrated salts and these colloidal odor binders are usually an undesirable addition This also applies to detergent phosphates, in addition to detergent-active carriers, if to reduce them The provision of phosphate-free or low-phosphate levels of waste water / pollution from detergent phosphates Fund is sought.

The invention relates to a method for the production of storage-stable enzyme preparations, which thereby is characterized in that the enzymes present in aqueous solution or suspension to a for Binding of calcium capable of finely divided, bound water-containing water-insoluble compound of general formula

Me ₂ O ₃ - (SiO ₂ ) ,,

in which the cat is a calcium-exchangeable cation with the valency η, χ a number from OJ-IA Me boron or aluminum and y a number from 0.8-6, this compound having a calcium binding capacity of at least 50 mg CaO / g of the anhydrous active substance has adsorbed, separates the compound from the enzyme solution and converts it into a dry product, or that the enzyme active ingredients dissolved or suspended in water are precipitated in the presence of calcium-binding water-insoluble silicates, the solid substance is separated from the solution and converted into a dry product Enzyme preparations produced by the above process and detergents or washing auxiliaries containing these enzyme preparations. In particular, the enzyme preparations are products containing proteases.

The calcium binding capacity of the compounds defined above can reach values of 200 mg CaO / g ai and is preferably in the range of 100-200 mg CaO / g ai, in particular in the case of those water-insoluble compounds of the general formula given above in which y is a number of 13-4 means The compounds defined above are referred to here as "aluminosilicates" for the sake of simplicity. The cation present in the aluminosilicates to be used according to the invention is preferably sodium; but it can also be replaced by lithium, potassium, ammonium or magnesium and by the cations of water-soluble organic bases, e.g. B. by those of primary, secondary or tertiary amines or alkylolamines with a maximum of 2 carbon atoms per alkyl radical or a maximum of 3 carbon atoms per alkylolfesl.

The aluminosilicates described are synthetically manufactured products that can be found in simple way, e.g. B, by reaction of water-soluble silicates with water-soluble aluminates in In the presence of water. For this purpose, aqueous solutions of the starting materials can be mixed with one another or one in solid

Condition present component with the other than aqueous solution present component are implemented. Also by mixing both, in solid In the state of the components present, the desired aluminosilicates are obtained in the presence of water, preferably with comminution of the mixture.

The water-containing products obtained in this way are initially X-ray amorphous; they can be age of water or convert to a crystalline state by heating to temperatures of 50-200 ⁰ C in the presence of. The amorphous or crystalline aluminosilicate obtained as an aqueous suspension during production can be separated off from the remaining aqueous solution by filtration and stored at temperatures of, for. B. 50-400 ⁰ C dry. Depending on the drying conditions, the product contains more or less bound water. Anhydrous products are obtained at 800 ° C .; the AS contents of the aluminosilicates are determined by heating to 800 ° C. for one hour.

Such high drying or dewatering temperatures are not recommended for the aluminosilicates to be used according to the invention. It is a particular advantage that even at much lower temperatures of, for. B. 80-200 ⁰ C dried products are useful for the purposes of the invention. The aluminosilicates that are produced in this way and contain varying amounts of bound water are obtained as fine powders after the dried filter cake has been divided. B. up to 0.1 μ, it must be taken into account that the primary particles can be agglomerated to form larger structures. Ls is easily possible. Manufacture products with primary particle sizes in the range of 30-1μ.

It is particularly advantageous to use aluminosilicates which are at least 80% by weight of particles of a Size of 10-0.01 μ, preferably 8-0.1 μ, exist. These aluminosilicates preferably contain no primary or secondary particles above 30 μ. As far as these are crystalline products, these are referred to as "microcrystalline" for the sake of simplicity

To form small particle sizes can already contribute to the precipitation conditions, whereby the mixed together aluminate and silicate solutions - which also enter the reaction vessel at the same time can be conducted - subject to strong shear forces. If one sets the preferred according to the invention If crystallized aluminosilicates are used, this prevents the formation of large ones, possibly even oneself penetrating crystals by slowly stirring the crystallizing mass.

Nevertheless, undesired agglomeration of crystallite particles can occur during drying, so that it is advisable to use these secondary particles in a suitable manner, e.g. B. by air sifting to remove. Also in In a coarser condition, leave any aluminosilicates that have been ground to the desired grain size use yourself. For this purpose, z. B. mills and / or air separators or their combinations. the the latter are z. B. at U11 m a η η: »Encyclopedia of the technical chemistry ", Volume 1, 1951, pages 632-634, described.

It is preferred to use compounds with the following composition:

0.7-1.1 Na ₂ O • AI ₂ O) • 1.3-3.3 SiO ₂ .

This molecular formula comprises two different types of crystalline aluminosilicates or their X-ray amorphous preliminary products. These two types differ in their crystal structures (am X-ray diffraction diagram) and by their compositions. These are:

a) 0.7-1.1 Na ₂ O-Al ₂ O ₃

b) 0.7-1.1 Na ₂ O-Al ₂ O ₃

13-2.4SiO ₂ > 2.4-3.3 SiO ₂ .

The proteases present in the enzyme preparations produced according to the invention can be vegetable, be of animal or bacterial origin; Such enzymes can also be obtained from fungi or algae to win.

Ms source of bacterial proteases, which can also contain certain amounts of amylases, are suitable the following bacteria species:

Bacillus species such as B. cereus, B. licheniformis, B. mesentericus, B. brevis, lactic acid bacteria, Micrococci, Pseudomonas, Arthrobacter, Klebsiella, CoIi, Proteus and Serratia species.

As a source of fungal amylases and proteases, to serve:

Actinomycetes, streptomycetes, Alternaria, Fusaria, Sporangia, Miknospora, Penicillium, Cephalosporium, Rhizopus, Keratinomyces, Aspergillus, Mucor, Gliocladeum, Mortierella Species as well as yeasts (Candida, Saccharomyces). The following proteases can be used: Peptildyl peptide hydrolases such as Leucine aminopeptidase, aminopeptidase) !, Carboxy pep tidasen, Di- and tripeptidases, Pepsin, rennin, Trypsin, chymotrypsin, Pancreatic peptidase, enteropeptidase, Cathepsins, collagenase, Elastase, papain, Chymopapain, ficin, Subtilopeptidases, aspergillopeptidases, Streptococcal peptidases, Clostridiopeptidases, Thermolysin, Streptomyces peptidases, bromelain and Keratinase.

Examples of proteases which are useful for the purposes of the invention are aspergillopeptidase A and aspergillopeptidase B and those proteolytic enzymes isolated from streptomycosis species. The proteases used are preferably subtilisin, BPN 'and the proteases isolated from Streptomyces species. Furthermore, those according to DE-OS 20 63 988 are from

Bacillus licheniformis from the strain P 300 proteases available usable.

The proteases to be used according to the invention preferably have an isoelectric point in pH range of 7-12.0.

In the process according to the invention one expediently starts from aqueous solutions or Suspensions of the enzymes, in particular of the filtered and concentrated fermenter broths.

From these enzyme-containing liquids Prepare dry enzyme preparations according to the invention as follows:

1. The aluminosilicates are introduced into the fermenter broth and after adsorption by the enzymes filtered off and dried at temperatures not exceeding 50 ° C

2. After the aluminosilicates have been added to the fermenter broth, the enzymes are z. B. by inorganic salts or organic solvents, precipitated and those with the precipitated Enzymes-laden aluminosilicates are filtered off and dried as described under 1.

3. The aluminosilicates that are as water-free as possible loaded with such amounts of fermenter broth that they still appear dry, and then if so necessary, dried as described under 1. If you work in a fluidized bed, some of the evaporates Fennenter broth sprayed on and accordingly enzyme-rich preparations are obtained.

The enzyme preparations obtained in this way have enzyme contents of 1,000-500,000, preferably 2000-200,000 PU / g (PU = protease units).

While in the known processes the enzyme is used as a powdered precursor, and this Enzyme powder then to granulated, hydrated salts with the addition of water or with the addition of a jo adhesive surfactant is bound, for which complex mixing measures are necessary, can in the process according to the invention aqueous solutions or suspensions of the enzyme, so-called Fermenter broths can be used directly, since the active enzyme is surprisingly derived from this aqueous phase to the added aluminosilicate plant, so that the resulting enzyme preparation through easy filtering and gentle drying can be obtained as a powder If you use an aluminosilicate, which contains so much bound water that it is just powdery, or an undried, of its production still moist aluminosilicate, z. B. as a suspension or as a moist filter cake, then when mixed with the aqueous enzyme phase no heat of hydration is released, so that this too significant advantages over the known methods in which to avoid enzyme inactivation must be provided for a dissipation of the heat of hydration, result. It was further found that the calcium binding capacity of the water-insoluble silicates used as carriers through the adsorption of the Enzyme is not impaired when it is later used in the wash liquor.

When using the enzyme preparations according to the invention it has been shown that the action of the enzymes is favorably influenced by simultaneously present salts of aminocarboxylic acids. Such aminocarboxylic acids ! are for example glycine, glycylglycine, alanine, glutamic acid, etc.

The invention further relates to washing or washing auxiliaries for textiles which, in addition to the enzyme preparations described above, contain at least one further substance with a washing, cleaning or bleaching effect. These include anionic, zwitterionic and nonionic surfactants, complex-forming or non-complex-forming structural substances, aluminosilicates not loaded with enzymes, bleaching agents and other additives, which are usually present in smaller quantities. The enzyme preparations according to the invention are present in the detergents or washing auxiliaries in such quantities that their enzyme activity is in the range of 100-2000 PU / g.

The surfactants are known to contain at least one hydrophobic organic Resi u, id in the molecule a water-solubilizing anionic, zwitterionic or nonionic group. With the hydrophobic residue it is mostly an aliphatic hydrocarbon radical with 8-26, preferably 10-22 and in particular 12-18 carbon atoms or an alkyl aromatic Remainder with 6-18, preferably 8-16, aliphatic carbon atoms.

Useful anionic surfactants include those of the soap, alkylbenzenesulfonate, the mixtures of alkene, hydroxyalkane and disulfonates accessible by olefin sulfonation, furthermore Alkanesulfonates and esters of α-sulfofatty acids, such as z. B. xite a-sulfofatty acids from hydrogenated methyl or Ethyl esters of coconut, palm, or tallow fatty acids. Other suitable surfactants are sulfuric acid monoesters of primary or secondary alcohols, e.g. B. such from coconut fatty alcohols, tallow fatty alcohols, oleyl alcohol or from the secondary alcohols accessible by oxidation of paraffins and from the addition products from 1-5 mol ethylene oxide to the alcohols mentioned. The anionic surfactants can be used in Form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, e.g. the Salts of mono-, di- or triethanolamine are present.

Addition products of 4-40, preferably 4-20 mol of ethylene oxide with 1 mol of fatty alcohol, alkylphenol or fatty acid can be used as nonionic surfactants. The addition products of 1-16 mol of ethylene oxide with coconut or tallow fatty alcohols, with oleyl alcohol or with secondary alcohols with 8-18, preferably 12-18 carbon atoms, and with mono- or dialkylphenols with 6-14 carbon atoms in the are particularly important Alkyl radicals. In addition to these water-soluble nonionics, however, polyglycol ethers with 1-4 ethylene glycol ether residues in the molecule that are not or not completely water-soluble are also of interest, especially if they are not together with water-soluble ones ^; onic or anionic surfactants are used.

Nonionic surfactants of the amine oxide or sulfoxide type can also be used.

The zwitterionic surfactants include substances of the carboxy betaines or sulfobetaines.

Both compounds that are able to bind calcium in a complex manner and those that do not have this ability are suitable as structural substances. The latter include, for example, the bicarbonates, carbonates, borates or silicates of alkalis, the alkali sulfates and the alkali salts of organic, non-capillary-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 1-8 carbon atoms. Examples are the water-soluble salts of benzene, toluene or xylene sulfonic acid and the water-soluble salts of sulfoacetic acid, sifobenzoic acid or of sulfodiacid. The triphosphate and a large number of known organic complexing agents of the polycarboxylic acid type, including polymeric carboxylic acids, aminocarboxylic acids, phosphonic acids, phosphonocarboxylic acids, hydrocarboxylic acids, carboxyalkyl ethers, etc., are suitable as complex-forming structural substances.

If the detergents contain substances containing P, the total phosphorus content of the agents should be a maximum of 6%, preferably a maximum of 3%.

The composition of the detergents according to the invention is generally in the range of following recipe:

5 - 30% by weight of anionic and / or nonionic and / or zwitlerionic surfactants,

5-50% by weight with enzymes bcladcnc and optionally aluminosilicates not loaded with enzymes, the enzyme content being 100-2000 PU / g Detergent.

15-90% by weight complexing and / or non-complexing Odorous substances,

0-50% by weight of bleaching agents and others, mostly in smaller quantities, in such products

Suitable bleaching agents are compounds which release H ₂ O ₂ in aqueous solution, such as. B. perborate. Other additives, usually present in smaller quantities, are z. B. foam stabilizers or inhibitors. Fabric softeners. Stabilizers and / or activators for the bleaching agents. Corrosion inhibitors, antimicrobial substances, dirt carriers, brighteners, dyes and fragrances, etc.

Examples

The synthesis of some of the enzyme preparations according to the invention which can be used to produce the enzyme preparations according to the invention will first be synthesized synthetic aluminosilicates, for which no protection is sought here.

The with Deionized water diluted aluminate solution with vigorous stirring mixed with the silicate solution. Both Solutions were at room temperature. It formed as a primary precipitation product with an exothermic reaction X-ray amorphous sodium aluminosilicate. which was stirred vigorously for 10 minutes. For the production of crystalline The suspension of the X-ray amorphous precipitation products for the purpose of crystallization remained a few products Time at elevated temperature in a dedicated container. After sucking off the lye from the amorphous The filter residue was the precipitate or the crystals and washing with deionized water for one hour in aqueous suspension with stirring by adding acid at pH 6.5-7.5 held. The filter cake obtained after filtering off was partly as such, partly after drying Used to manufacture enzyme loaded products. The aluminosilicate contents given in these examples relate to the products that have been dried in this way and still contain bound water. The active ingredient contents (= AS) of the aluminosilicates dried in this way were obtained by heating the products to 800.degree. C. for one hour certainly.

In the production of microcrystalline aluminosilicates, marked by the suffix »m«, was marked with Deionized water diluted aluminate solution mixed with the silicate solution and with a high-speed Intensive stirrer (10,000 rpm; make »Ultraturrax« of the company Janke and Kunkel IKA-Werk, Staufen / Breisgau, Federal Republic of Germany). After 10 Minutes of vigorous stirring was the suspension of the amorphous precipitate in a crystallization vessel transferred, where the formation of large particles by stirring the suspension prevents became. After the lye was filtered off with suction from the crystal slurry and washed with deionized water, the Filter residue processed as described above The dried products were ground in a ball mill and placed in a centrifugal classifier (microplcx Wind sifter from Alpine, Augsburg, Federal Republic of Germany), separated into two fractions by which the finer one did not contain any proportions above 10 μ Sedimentation balance determined.

The degree of crystallization of an aluminosilicate läßi from the intensity of the interferences / lines a * X-ray diffraction diagrams of the respective product tes compared to the corresponding diagrammers of X-ray amorphous b / w. fully crystallized

All percentages are percentages by weight.

The calcium binding capacity of the aluminosilicates was determined in the following way:

II an aqueous. 0.594 g of CaCl ₂ (= 300 nif CaO / l = 30 ° dH) containing solution and adjusted to a pH of 10 with dilute NaOH is mixed with 1 g of aluminosilicate (based on AS) Vigorously stirred at a temperature of 22 ° C (± 2 ° C). After filtering off de; Aluminosilicates determine the residual hardness χ de; Filtrates. The calcium binding capacity in mg CaO / g AS is calculated from this using the formula: (30— x) ■ 10.

Manufacturing conditions for the aluminosilicate II

π precipitation:

2.115 kg of aluminate solution with the composition:
1 7.7% Na ₂ 0.15.8% Al ₂ Oj. 66.5% H ₂ O
0.585 kg caustic soda
9.615 kg of water

2.685 kg of a 25.8% sodium silicate solution with the composition 1 Na ₂ O 6 SiO ₂ (prepared as indicated under I)
Crystallization:

24 hours at 80 ° C
4ϊ drying:

24 hours at 100 ° C and 20 torr
Composition:

0.8Na ₂ O - 1 AI ₂ Oi · 2.655SiO ₂ · 5.2 H ₂ O
Degree of crystallization:
fully crystalline

Calcium binding capacity:
120 mg CaO / g ai

Manufacturing conditions for the aluminosilicate Um

Precipitation:

as with the aluminosilicate II
Crystallization:
12 hours at 90 ° C

Drying:

24 hours at 100 ° C and 20 torr
Composition:

0.8 Na ₂ O · 1 Al ₂ O ₃ · 2,655 SiO ₂ · 5.2 H ₂ O
tn degree of crystallization:

fully crystalline
Calcium binding capacity:

145 mg CaO / gAS

030 218/226

Herslelliingsbcd indungen for the Λlumosilik.it III

precipitation:

2.983 kg of aluminate solution with the composition:

17.7% N? /). 15.8% Al, O ,, 66.5% HjO 2,445 kg of a 25.8% solution of a sodium silicate the composition:

I Na ₂ O • 6SiOj 0.15 kg NaOII

9.420 kg H ₂ O crystallization:

not applicable
Drying:

24 hours at 23X 'and 20 lorr Composition:

0.9 Na ₂ O i AU), 2.04 SiO. 4.7IU) Degree of crystallization:

X-ray amorphous calcium binders are capable of:

160mgCaO / eAS

Production conditions for the aluminosilicate XII

Precipitation:

2.01 kg of aluininate solution with the composition:

20.0% NaA 10.2% Al ₂ O ,, 69.8% H ₂ O 1.395 kg caustic soda 9.405 kg water 2.19 kg of a 25.8% sodium silicate solution of the composition:

I Na ₂ O 6 SiO ₂ (prepared as indicated under I) Crystallization:

24 hours at 8O ⁰ C drying:

24 hours at 100 "C Composition:

0.9 Na ₂ O I AI ₂ O, 2 SiO ₂ 3 H ₂ O Degree of crystallization:

fully crystalline calcium binding capacity:

160mgCaO / gAS

Manufacturing conditions for the aluminosilicate XIIm

Precipitation:

as with aluminosilicate from crystallization:

6 hours at 90 ° C drying:

24 hours at 100 ° C Composition:

0.9 Na ₂ O ■ 1 AI ₂ O, 2SiO ₂ 3 H ₂ O Degree of crystallization:

fully crystalline calcium binding capacity:

175 mg CaO / gAS

The particle size distribution determined by sedimentation analysis of the microcrystalline products Um and XIIm described above was in the following range:

> 40μ = 0% <10μ = 85-95% <8 μ = 50-85%

Maximum of the particle size distribution curve: 3-6μ.

Manufacturing conditions for the aluminosilicate R I

Precipitation:

7.63 kg of an aluminate solution with the composition 13.2% Na ₂ O; 8.0% Al ₂ O ₃ ; 78.8% H ₂ O; 2 ^ 7 kg of a sodium silicate solution with the composition 8.0% Na ₂ O; 26.9% SiO ₂ ; 65.1% H ₂ O; Make-up ratio in moles:

J.24 Na ₂ O: 1.0 ΛΙ.Ο ,: 1.78 SiO ₂ ; 70.3 H ₂ O;
Crystallization:

6 hours at 90'C with gentle stirring:
Drying:

24 hours at 100 C;
Composition of the dried product:

0.99Na ₂ O · 1.0OAI ₂ O, ■ 1.83SiO ₂ ■ 4.0 IbO:
Degree of crystallization:

fully crystalline: the cubic crystals point strongly

rounded corners and edges;
Mean particle diameter (for the area

0-30 µ): 5.4 µ;
Maximum of the particle size distribution curve:

lies below 3 u:
Calcium binding capacity:

172 mg CaO / g ai

The crystalline aluminosilicates show the following interference lines in the X-ray diffraction diagram:

U-Wci ic, «üigcnuininci'i iViii Cü-K _χ -5ίΓίΐίϊ! ΫΠ $ · in r \

Il and lim:

14.4 H.8 4.4 (+) 3.8 (+) 2.88 (+) 2.79 (+)

2.66 (+)
XII.XIImundRI:

12.4 8.6 7.0 4.1 (+) 3.68 (+) 3.38 (+)

3.26 (+) 2.96 (+) 2.73 (+) 2.60 (+)

It is quite possible that in the X-ray diffraction diagram not all of these fringes occur.

in particular when the aluminosilicates are not full are crystallized. Therefore the most important d-values for the characterization of these types became marked with a »(+)«.

Some examples of the invention follow

π Production of the enzyme preparations using the aluminosilicates described above. The activity the proteases are given in »PE« (= protease units); it is based on one of H. G. van R a a y, H. S a r a η and H. Verbeek in the magazine "TENSI-DE". 7 (1970), pp. 125-132 certainly.

Production of the enzyme preparation E I

One from Bacillus subtilis was used as the starting material

π filtered fermenter broth obtained on a Enzyme content of 1500PE / ml. A mixture of 50 kg of this fermenter broth and one Suspension of 1 kg of the aluminosilicate XIIm in 100 kg of water was stirred for 1 hour; during this

, 0 time the pH was kept at 6.5-7.5. After the liquid was filtered off with suction from the solid residue, it fell a residue enriched with protease that can be further processed when moist (e.g.

_{by mixing the Na 2} SO ₄ ), which is finely powdered with the same amount by weight; If the residue is dried for 3 hours at 35 ° C. and 100 torr, it has an enzyme content of 41,000 PU / g.

Production of the enzyme preparation E II

bo One according to the information served as the starting material the DT-OS 20 36 988 from Bacillus ücheniformis strain P 300 obtained, as usual filtered and concentrated fermenter broth with a protease content of 25,000 PU / ml. In 100 kg of this fermenter broth were

b5 10 kg of the aluminosilicate III (based on AS) in the form of a moist product and the pH is adjusted to 5-6. After the suspension has been heated up The protease became 38 ° C. by adding 25 kg

Il

Na ₂ SO ₄ precipitated, which was deposited on the aluminosilicate. After suctioning off the alkali and drying the residue for three hours at 35 ° C. and 100 Torr, a product with 200,000 PFVg was obtained.

Production of the enzyme preparation E III

The process for the preparation of the enzyme preparation E III was modified so that as Aluminosilicate related to the product Mm and the one with the in Alumosilicate added fermenter broth was cooled to 5-10 ° C. Then the protease was precipitated Addition of 170 kg of methanol and filtered off (instead of of methanol, ethanol, isopropanol or acetone could be used with similar success). After filtering π The filter residue was dried for 3 hours at 35 ° C. and 100 torr; a product was obtained with 42,000 PU / g.

Production of the enzyme preparation EIV

The resulting as a moist filter residue aluminosilicate RI was dried in a flow drier with an inlet air temperature of 600 ⁰ C and an exhaust temperature of 180 ° C to a water content of 10%. The finely powdered product 2> was transferred into a container in which it was ventilated from below and sprayed from above with the concentrated fermenter broth used in the production of the enzyme preparation E II. The aluminosilicate was able to absorb water up to a content of 25% without losing its powder properties. However, since water was continuously evaporating as a result of the aeration, the amount of fermenter broth absorbed was somewhat larger in this process; it was 03 kg fermenter broth per kg aluminosilicate R I used. The product η obtained had an activity of 5800 PU / g.

The following examples describe some detergents, the enzyme preparations produced in the above manner contain.

Example Wl ⁴ "

Soaking agent for heavily protein-soiled laundry

5 wt% olyalcohol + 10 EO

30% by weight Na ₂ COj ₄ -,

35% by weight glutamic acid (Na salt)
30% by weight of enzyme preparation E IV

Example W 2

Anti-foam detergent designed for use in washing machines

5% by weight

2% by weight 2.8% by weight 4.2% by weight

44.5% by weight 0.8% by weight

22.1% by weight 2.5% by weight 1.2% by weight 1.7% by weight 2.1% by weight

II.I wt .-% dodecylbene / olstilfonal (technical, Na-

SaIz)

Tallow alcohol + 14 ÄO

Glutamic acid (sodium salt)

Aluminosilicate XlIm

F. enzyme preparation E Il

Sodium perborate tetrahydrate

Na ₂ O -3.3SiO ₂

CMC

MgSiO)

Na ₂ CO ₁

H ₂ O

Example W 3

Detergent suitable for removing grease and protein soiling

9.6% by weight

4.4 wt% 38.5 wt%

1.5% by weight

10.0% by weight

5.0% by weight

8.5% by weight, 9.3% by weight, 1.5% by weight Wt%

Tallow alcohol + 14 AO

Tallow alcohol + 5ÄO

Aluminosilicate R I

Enzyme preparation E I

Glycocolla (sodium salt)

Na ₂ O ■ 3,3SiO,

Na ₂ COj

Na ₂ SO ₄

CMC

H ₂ O

Example W4

Detergent intended for washing heavily soiled work clothing

18.0% by weight

8.0 wt%

5.0% by weight

20.0% by weight

25.0% by weight

9.5% by weight

5.5% by weight

l, 3% by weight

7.7 wt% octyl alcohol + 10EO

Octyl alcohol + 5 AO

Aluminosilicate R I

Enzyme preparation E IV

Na ₂ CO ₃

Alanine (Na-SaIz)

Na citrate

CMC

H ₂ O

Claims (1)

Patent claims: 1. A process for the production of storage-stable enzyme preparations, characterized in that the in aqueous solution or Suspension present enzymes to a finely divided, bound water-containing water-insoluble compound of the general formula capable of binding calcium