WO1997043482A1 - Enzyme granulate for washing and cleaning - Google Patents
Enzyme granulate for washing and cleaning Download PDFInfo
- Publication number
- WO1997043482A1 WO1997043482A1 PCT/US1997/007982 US9707982W WO9743482A1 WO 1997043482 A1 WO1997043482 A1 WO 1997043482A1 US 9707982 W US9707982 W US 9707982W WO 9743482 A1 WO9743482 A1 WO 9743482A1
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- Prior art keywords
- enzyme
- granulate
- fact
- weight
- flour
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Classifications
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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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/386—Preparations containing enzymes, e.g. protease or amylase
- C11D3/38672—Granulated or coated enzymes
-
- 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
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
- C11D3/3776—Heterocyclic compounds, e.g. lactam
-
- 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
- C11D3/16—Organic compounds
- C11D3/38—Products with no well-defined composition, e.g. natural products
- C11D3/382—Vegetable products, e.g. soya meal, wood flour, sawdust
-
- 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
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/40—Products in which the composition is not well defined
- C11D7/44—Vegetable products
Definitions
- the invention concerns the preparation of an activity-stable and low-dust enzyme granulate for washing and cleaning applications, i.e. , for use in granular washing and cleaning agent compositions. Additionally the invention concerns the activity-stable and low-dust enzyme granulate obtained by the method of preparation as well as their use. In a special additional aspect the enzyme concerns the use of specially selected flours entirely generally as auxiliary materials (e.g. , as vehicles or fillers) for preparation of enzyme granulates for various application. In numerous washing and cleaning agent compositions, e.g. , for cleaning textiles or utensils, enzymes are used to improve the washing or cleaning efficiency.
- Proteases, Upases, amylases or cellulases are customarily used as enzymes; the enzymes can be used as individual enzymes or as enzyme mixtures.
- the enzymes are added to powdered or granular washing and cleaning agent formulations in the form of the so-called enyzme granulates, which contain the relevant enzyme or enzyme mixture together with a filler, binder and optionally other granulation auxiliary agents and formulation agents.
- Enzyme granulates of this kind are customarily obtained by processing an enzyme granulate with a filler and binder as well as optionally with additional granulation auxiliary agents and formulation agents into a mixture and granulating it.
- the resulting wet granulate particles are optionally additionally rounded and then dried.
- the dried granulate particles are additionally coated with a protective coating and they can then be used in powdered or granular washing and cleaning agent formulations.
- DE 27 30 481 a method for preparation of enzyme granulates using a granulation apparatus (mixer) is proposed, in which, however, a relatively large amount (up to 40 wt%) of cellulose fiber powder without binding capacity must be added to the remaining constituents in order to avoid layers of wet granulate mass that adhere to the walls in the drum granulator and that are difficult to remove and in part are quite thick. Only by the addition of said cellulose powder does one succeed, in accordance with DE 27 30 481, in carrying out the granulation, which is hard to control.
- a method for preparation of an activity-stable and low-dust enzyme granulate for washing and cleaning applications is made available through the invention, where the method in accordance with the invention is characterized by the fact that one first prepares a moist granulate, 0.1 to 25 parts by weight enzyme or enzyme mixture (calculated as dry substance content of the enzyme preparation that is used), 75 to 99.9 parts by weight (including moisture content) of an organic flour type with a degree of grinding of 30 to 100%, where the flour type was obtained by grinding of a flour source that had been treated with dry superheated steam that was optionally washed and/or purified beforehand, and where the parts by weight of the enzyme or enzyme mixture and of the flour type add up to 100 parts by weight, optionally up to a total maximum of 20 parts by weight customary granulation and/or formulation auxiliary agents (calculated as water-free auxiliary agents), using a calculated amount of water, which is sufficient to produce a moisture content of 15 to 50 wt% in the moist granulate (with respect to the method in
- this method is characterized by the fact that 2 to 25 parts by weight of enzyme or enzyme mixture, 75 to 98 parts by weight flour type, optionally up to a maximum total of 15 parts by weight granulation and formation auxiliary agents and a calculated amount of water, which is sufficient to produce a moisture content of 15 to 40 wt%, are used for preparation of the moist granulate.
- organic flours (thus flours of organic starting materials) of certain types are used.
- organic flour here encompasses, within the scope of the invention, all more or less size-reduced, powdered to fine grained products, which have been obtained by size reduction
- the flour source is especially wheat or rye, but barley, oats, rice and maize, as well as sorghum and other types of millet can also be used.
- buckwheat itself is not a cereal (it is a knot grass), its beechnut-like flour-yielding parts can likewise be used as flour source within the source the scope of the invention.
- legumes serve as a flour source.
- Legumes here are understood to mean vegetable foodstuffs (legumes) belonging to the fruits and vegetables.
- the fruits of leguminous species such as Pisum (pea), Cajamus (pigeon pea), Cicer (chick pea); Lens (lentils); Phaseolus (kidney bean), Vigna (cow pea); Dolchius (lablab bean); Cassavalia (sword bean), Vicia (horse-bean or vetch); Peluschken [maple pea]; Arachis (peanut); lupins; lucerne; soybeans as well as lima beans and, if applicable, other legumes and other Malvaceae fruits (e.g., of the genus Gossipium, cotton) may be considered as flour sources within the scope of the invention.
- leguminous flours or flours from fruits of the Malvaceae family are entirely generally especially advantageously suitable as auxiliary materials for the preparation of enzyme granulates, since when they are used as vehicles or fillers or also when they are used as additional formulation constituents in addition to other customary vehicles and fillers, they have a positive effect on the enzyme stability both of the individual enzymes and enzyme mixtures as well as the dust properties of the enzyme granulates thus produced; in addition, these flours allow a preparation of enzyme granulates that is simpler, more enzyme-sparing and more economical compared to other customary vehicles or fillers, not only for washing and cleaning applications, but also for many other industrial fields of use.
- the invention thus also quite generally concerns the use of leguminous flours or flours of fruits of the Malvaceae family for preparation of enzyme granulates for any applications, especially here, however, for preparation of enzyme granulates for washing and cleaning applications in household use, in commercial and/or industrial use.
- oil-containing fruits [beans] of these examples both defatted and partially defatted as well as oil-containing fruits can be used to make the flour that is used in accordance with the invention; for these purposes partially to completely defatted fruits are preferred, especially partially to completely defatted legumes, e.g., to a large extent defatted soybeans.
- the defatting can here take place in substantially known ways.
- the flours used within the scope of the invention are, in each case according to the grinding methods that are used and the degree of grinding that is attained in each case, fine powders of yellowish- white to dark gray color (light or dark flours) or optionally more or less granular (whole meal, semolina, fine semolina) or white-yellowish brown mixed products.
- the organic flour types usually exhibit a moisture content up to about 15 wt% (e.g., moisture content of 7 to 15 wt%), which should be taken into consideration in calculating the percentage moisture content of the moist granulate prepared in accordance with the invention in a high-speed mixer.
- those cereal flours are used in the invention that have a moisture content of about 10 to 15 wt%, especially 13 to 15 wt%. In the case of the preferred leguminous or also Malvaceae flours, these have a moisture content of about 7 to 11 wt%.
- Other important criteria for characterization of the flour type used in accordance with the invention are the degree of grinding and the so-called flour type; these criteria correlate with each other so much that the index of the flour type also increases with an increasing degree of grinding (i.e., the degree of size reduction or the fineness of the flour).
- the degree of grinding corresponds to the amount by weight of flour obtained with respect to 100 parts by weight of the flour material that is used (within the scope of the invention, therefore the cereal or the legumes or Malvaceae fruit that is used); it is therefore a percent flour yield.
- very fine flour accumulates at first, e.g., from the heart of the cereal grain, and with further grinding, therefore, e.g., with increasing degree of grinding, the proportion of crude fiber and hull in the flour increases; the starch content then will be lower.
- the degree of grinding is also reflected in the so-called “flour type, " which is used as a numerical value for classification of flours, especially cereal flours, and which is based on the ash content of the flour (the so-called ash scale).
- the flour type or the type number in this connection gives the amount of ash (mineral materials) in mg that remain behind when 100 g dry flour substance is burned.
- the type number can be illustrated as follows: the higher the type number, the darker the flour will be and the higher the degree of grinding will be, since the kernel of the cereal grain contains only about 0.4 wt% ash while the hull contains something around 5 wt% ash.
- a white flour of type 405 thus contains, e.g., an average of 0.405 wt% ash.
- the cereal flour in contrast consists predominantly of the size-reduced flour particles, i.e., the starch constituent of the cereal grains; at a higher degree of grinding the cereal flours also contain the size-reduced, protein-containing aleuronic layer of the cereal grains, in the case of whole flour it also contains the constituents of the protein- and fat-containing germ, as well as the crude fiber- and ash-containing seed hulls.
- the degree of grinding of the flour used in the course of the invention is
- a degree of grinding of 30% corresponds to a very fine flour, while a degree of grinding of 100% corresponds to a whole grain flour.
- the invention is distinguished by the fact that the degree of grinding of the flour type amounts to 50 to 100%, preferably 70 to 100%.
- leguminous fine flour e.g., pea or especially soy fine flour, is preferably used.
- the flour used in the method in accordance with the invention is distinguished by the fact that it was obtained from a flour source which before grinding was subjected to a treatment with dry superheated steam with a temperature of especially 100 to about 110°C at nearly normal pressure to low overpressure (e.g., 0.8 to 1.2 bar overpressure) and a treatment time (residence time in the superheated steam treatment apparatus described below) of up to about 1 hour.
- Dry superheated steam is a superheated and unsaturated steam, which can be obtained in the conventional way by superheating and removal of possible water condensate or by expansion of steam from high pressure.
- the superheated steam treatment of the flour source can, e.g.
- the hopper can intermittently or continuously be supplied with the flour source, e.g., through screw conveyors and evacuated through heated screw conveyors.
- the superheated steam-treated flour source will then, e.g., in a connected fluidized bed dryer, be conditioned to a constant water content of a maximum of 15 wt% and cooled in an additional fluidized bed dryer for the subsequent grinding.
- the treated and cooled flour source is then continuously fed to a grinding machine and ground to a particle size distribution with the primary proportion of particle sizes in the range of 500 to 5 ⁇ m; preferably the proportion of particles with a particle size of 300 to
- 500 ⁇ m does not exceed 10 wt%.
- Nonsticking moist granulate is obtained, in which water is dispensed, optionally via an enzyme solution or with a possibly added granulation or formulation or auxiliary element, continuously in dependence on the feed of the solid primary constituents so that the moisture content in the moist granulate (thus before drying) at the mixer outlet is in general 15 to 50 wt%, preferably 15 to 40 wt%, and especially 15 to 30 wt%.
- the solid constituents for the granulate composition can if desired be premixed in the mixer up to about 5 to 10 minutes before the aqueous granulation liquid (e.g., water, enzyme solution or aqeuous solution of constituents for the granulate) is mixed in and granulated; at the end of the granulation time the cutter head of the mixing apparatus is switched on for a few more minutes.
- a moist granulate with a particle size range of 200 to 2000 ⁇ m, preferably 200 to 1000 ⁇ m will thus be obtained.
- the mixing time in the high-speed mixer or in the continuous method the average residence time will be in the method in accordance with the invention as a rule up to a maximum of about 30 minutes; here the specialist can adjust the mixing time or the residence time, which includes the necessary time for the introduction of the granulation liquid and the mixing and the cutter head treatment, to the desired properties of the moist granulate (e.g., freedom from stickiness, particles sizes) or to the mixer.
- Time periods up to about 25 minutes, especially from 3 to 8 minutes, are sufficient as expedient mixing or residence times, especially in batchwise processing; in continuous processing shorter average residence times in the mixer can be sufficient according to the type of high-speed mixer. If desired, to improve the granulate size they can be postmixed additionally up to several minutes using the cutter head.
- the moist granulate can be formed in a rounding apparatus, preferably in a rotary table apparatus or a so-called Marumerizer * by'postrolling for a time of 0.5 to 10 minutes, preferably 0.5 to 5 minutes.
- a conventional, enzyme-sparing drying e.g., in a fluidized bed [Fliessbett] or a fluidized bed [Wirbel harsh] and dried to a granulate with a desired moisture content, especially a moisture content of 3 to 12 wt%, preferably 8 to 10 wt%.
- the dried granulate can, if desired be separated from oversize and undersize particles by screening, and the particles separated from the acceptable particle fraction can be ground and recycled to the granulation method. Fine dust portions that may arise can here by removed by screening, e.g., on an air jet classifier; the screening optionally can take place only after coating of the granulate particles with a protective coating or, if desired, can be repeated.
- the powdered, optionally premixed constituents for the enzyme granulate can be fed batchwise or continuously to the high-speed mixer and then likewise partially or continuously a suitable amount of water for adjustment of the moisture content or a suitable amount of an aqueous solution, optionally with the granulation and/or formulation auxiliary agents dissolved therein or the enzyme or enzyme mixture dissolved therein, can be dispensed to the mixer and after the given residence time the moist enzyme granulate is removed or continuously withdrawn from the high-speed mixer.
- An expedient mode of action in this variation of the method is distinguished, e.g., by the fact that of the constituents for the enzyme granulate only the flour type in powdered form is fed batchwise or continuously to the high-speed mixer and then likewise batchwise or continuously an aqueous enzyme solution with a content of enzyme or enzyme mixture determined according to the amount of flour and an amount of water suitable for adjustment of the moisture content are dispensed to the mixer.
- the enzyme granulate can additionally be coated in a customary way with a varnish or film or other protective coating.
- the coating or varnish can contain an additional enzyme or, alternatively can serve to color the granulate or for protection of the enzyme, or also can cause retardation of the release of the enzyme or enzyme mixture.
- the varnish or the coating can be applied both continuously or batchwise to the enzyme granulate.
- the amount of protective layer constituents can as a rule amount to 5 to 26 wt% with respect to the particles of the uncoated enzyme granulate.
- the customary varnishes or coatings for enzyme granulates can be applied as the protective layer, i.e., the customary organic polymers, with or without additional pigments.
- An expedient protective layer or coating is distinguished, e.g., by the fact that 100 parts by weight of the protective layer are made up of the constituents 40 to 60 parts by weight, preferably 45 to 55 parts by weight pigments, especially white pigments titanium dioxide and/or calcium carbonate, and 60 to 40 parts by weight, preferably 55 to 45 parts by weight varnish binder selected from water soluble polymers, especially polyethylene glycol with molecular weights in the range of 1500 to 10,000, from polyvinyl alcohols or polyvinyl alcohol copolymers with molecular weight characteristics in the range of K 70 to K 110, polyacrylic acids, polymethacrylic acids and/or cellulose ethers.
- substantially all enzymes can be used that are common for washing and cleaning agent compositions.
- the enzyme can in this case be an isolated, pure enzyme (i.e., without side activities) or a mixture of enzymes.
- An enzyme mixture can be composed of pure enzymes without side activities or can be obtained in a simple way equally in the form of a process-dependent enzyme mixture obtained in the production of enzymes from microorganisms; such process-dependent enzyme mixtures obtained in dependence on microorganism include as a rule, besides a main enzyme, various accompanying enzymes (the so-called side activities), which optionally display a favorable synergistic side effect.
- the enzyme or enzyme mixture can thus in general be a hydrolase, oxidase or reductase or a mixture thereof.
- Preferred hydrolases are carbohydrases, proteases, lipases, esterases.
- the carbohydrases for the method in accordance with the invention are, e.g., selected from cellulases, xylanases, pentosanases and amylases. If oxidases are used, they can be glucose oxidases or peroxidases; other very practical enzymes within the scope of the invention are catalase (desizing of textiles), lysozyme, muramidase.
- enzymes can also optionally be used, e.g., /3-glucanases, pectinases, arabanases, hemicellulases, galactomannanases, polygalacturonases, glucoamyases, ⁇ -galactosidases, pullulanases, Driselase ® and others.
- the proportion (the amount) of enzyme that is used in this connection is dependent on the individual specific enzyme activity and the desired activity in the prepared enzyme granulate.
- pentosanase has as a rule a high specific activity and can, in amounts up to 0.1 parts by weight, assure a sufficient enzyme activity in the prepared enzyme granulate.
- bacteria especially from the genus Pseudomonas or Bacillus (e.g. , B. subtilis, B. licheniformis, B. alkalophilus, B. lentus, B. amyloliquefaciens and others) or fungi, especially from the genus Aspergillus, Trichoderma, Rhizopus, Penicillium, Irpex can be used for preparation of the enzyme or enzyme mixtures; other sources for appropriate enzymes within the scope of this invention are, e.g., Ascomycetes, Streptomycetes, Humicola, Micrococcus and, e.g., bromelias and papaya plants for enzymes of plant and pancreas for enzymes of animal origin should be named.
- Bacillus e.g. , B. subtilis, B. licheniformis, B. alkalophilus, B. lentus, B. amyloliquefaciens and others
- fungi especially from the genus As
- the enzyme or enzyme mixture used in the method in accordance with the invention can be used in the form of a powder or an aqueous solution of the enzyme or enzyme mixture.
- Practical enzymes or enzyme mixtures are in this connection enzyme preparations such as customarily arise in industrial preparation methods.
- Such enzyme preparations contain as a rule not only a single enzyme or a mixture of enzymes, but also subordinate amounts of other accompanying substances that are dependent on the preparation method.
- accompanying substances are, e.g., salts, which are added for precipitation or crystallization of the enzyme from an enzyme concentrate, such as is obtained after separation of the biomass from a fermentation broth, or accompanying substances that are already contained in the enzyme concentrates such as proteins, peptides, amino acids, and, e.g., monomeric, dimeric, trimeric, oligo- and polymeric saccharides; the accompanying substances that are added or that are already in the enzyme concentrate could be enclosed in the precipitation or crystallization partially by the enzyme precipitate.
- the enzymes or enzyme mixtures could contain additionally customary enzyme stabilizers and customary suspension agents or preservatives as additional accompanying substances.
- aqueous solutions of the enzyme or enzyme mixture can be prepared by subsequent dissolving of the enzyme or enzyme mixture-powder; or in another variation the enzyme concentrates such as are obtained after separation of the biomass from the fermentation solution, optionally after being concentrated or diluted, can be used directly.
- Such aqueous solutions of the enzymes or enzyme mixtures also contain as a rule a certain portion of preparation method-dependent accompanying substances in addition to the true enzyme activity or in addition to the actual enzyme activities in the case of enzyme mixtures.
- Enzyme mixtures can, on the one hand, be obtained, e.g., directly by fermentation, where the enzymes, which in each case are then customarily fo ⁇ ned via the microorganism that is used, must be mixed with each other in natural ratios.
- enzymes can also be prepared by simple mixing of commercially available individual enzymes. It is also possible to prepare modified or optimized enzymes by gene engineering, e.g. , by mutation, and to use them within the scope of the invention.
- the enzyme granulates in accordance with the invention contain a cellulase, lipase, catalase, oxidase, peroxidase, thermostable ⁇ -amylase or a protease, especially an alkaline and highly alkaline protease.
- protease especially an alkaline and highly alkaline protease.
- Proteases that have improved qualities such as elevated washing performance or improved stability because of chemical and/or gene engineered modifications can in particular be incorporated advantageously.
- subtilisins are especially advantageous as alkali and highly alkaline proteases.
- Subtilisins are proteases with a pH optimum in the alkaline pH range and an essential serine residue in the active center.
- subtilisins that are obtained from bacillus strains are preferred in this case, for example subtilisins such as subtilisin BPN', subtilisin Carlsberg and subtilisins that can be isolated from Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus lentus, Bacillus mesentericus or Bacillus alcalophilus.
- subtilisins such as subtilisin BPN', subtilisin Carlsberg and subtilisins that can be isolated from Bacillus subtilis, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus lentus, Bacillus mesentericus or Bacillus alcalophilus.
- subtilisins that have a pH optimum in the range of 7 to 13 and that are commercially available, e.g., as Savinase ® , Maxacal ® , Durazym ® , Maxapem ® or Opticlean ® .
- the enzymes that are suitable for the enzyme granulates in accordance with the invention can be obtained in substantially known ways by fermentation processes from suitable microorganisms, especially from bacteria or fungi.
- the fermenter broths obtained in fermentation are separated from insoluble accompanying substances, e.g. , by filtration or microfiltration and then concentrated in substantially known ways, e.g. , by a membrane filtration method or ultrafiltration with optionally subsequent dialysis and/or by removal of the water by evaporation.
- enzyme concentrates which customarily contain the enzyme or enzyme mixture in an amount of 2 to 50 wt%, with respect to dry substance, in addition to possibly other unseparated accompanying substances. If desired these liquid enzyme concentrates can still additionally be converted to dry enzyme concentrates, for example, by spray drying and/or freeze drying.
- an enzyme granulate can preferably be prepared whose granulate cores essentially consist only of the described organic flour type as vehicle and the enzyme or enzyme mixture as active component.
- Granulation and formulation auxiliary agents are not necessary here for carrying out the method in accordance with the invention.
- those granulation and auxiliary materials can if desired be added in an amount up to maximum of 20 wt%, expediently to a maximum of 15 wt%, with respect to the prepared moist granulate.
- Granulation and formulation auxiliary agents are preferably used only in an amount from 0 to 5 wt% .
- customary enzyme, compatible binders, fillers, suspension agents, crosslinking agents, mediators (to improve bleaching action) and/or organic solvents as well as optionally enzyme stabilizers and/or reversible enzyme inhibitors can be used as granulation and formulation auxiliary agents.
- customary water-insoluble fillers are in particular cellulose, laminar silicates, such as e.g., kaolin and bentonite, and/or starches.
- Customary water-soluble fillers are, for example, alkali chloride, alkali acetate, alkali sulfate, calcium carbonate, calcium sulfate, magnesium sulfate, sugar such as e.g., sucrose, lactose, maltose and other disaccharides, trisaccharides or polysaccharides such as dextrins.
- binders or binder mixtures are binders or binder mixtures.
- Expedient binders are in particular degraded soluble starch and/or wheat gluten.
- Other expedient binders are polyethylene glycol with molecular weights in the range of 200 to 10,000, polyvinylpyrrolidone with molecular weights in the range from 12,000 to 3 million, preferably from 1 ,300,000 to 2,800,000; polyvinyl alcohol or copolymers, e.g., polyvinyl alcohol copolymers with molecular weight indices in the range from K 70 to K 110.
- These binders can be provided both individually and in combination with one another.
- the enzyme granulate prepared in accordance with the invention can optionally also contain a crosslinking agent as an additional granulation and formulation auxiliary agent.
- a crosslinking agent e.g., ethoxylated alcohols, especially ones with 10 to 80 ethoxy groups.
- Enzyme stabilizers are, e.g., borates, borax, formates, di- and tricarboxylic acids.
- Reversible enzyme inhibitors are, e.g., organic compounds with sulfhydryl groups or alkylated or arylated boric acids.
- the substantially customary granulation and formulation auxiliary agents of the type listed above can be used.
- a preferred embodiment of the invention is, however, distinguished by the fact that granulation auxiliary agents such as binders, fillers, suspension agents, crosslinking agents or organic solvents are not used.
- the moist granulate is formed only from an enzyme or enzyme mixture, the flour type and, optionally as formulation axuiliary agents, enzyme stabilizers and/or reversible enzyme inhibitors while using the calculated amount of water to adjust the moisture content without using additional granulation auxiliary agents.
- the invention also concerns the enzyme granulates prepared by the method in accordance with the invention, which are specially suited for use in washing and cleaning applications.
- Such enzyme granulates in accordance with with the invention are especially further characterized by the fact that they consist of a granulate core with the composition 0.08 to 26.4 wt% (dry substance) enzyme or enzyme mixture, 96.92 to 43.8 wt% (dry substance without moisture) of a flour type with a degree of grinding of 30 to 100%, where the flour type was obtained by grinding of a flour source that was optionally washed and/or purified beforehand, and that was treated with dry superheated steam, optionally up to a total maximum of 17.8 wt% customary granulation or formulation agents (calculated as water-free substance), and 3 to 12 wt% moisture, where the sum of the constituents of the granulate core (thus the enzyme or enzyme mixture, flour - dry substance, water and optionally granulation and formulation auxiliary agents) amounts to 100 wt%, and optionally from one or more protective layers encasing the granulate core.
- a granulate core with the composition 0.08 to 26.4 wt%
- Expedient enzyme granulates in accordance with the invention consist of a granulate core without other granulation and formulation auxiliary agents with the composition 0.09 to 26 wt% (dry substance) enzyme or enzyme mixture, 96.91 to
- a flour type with a degree of grinding of 30 to 100%, where the flour type was obtained by grinding of a flour source that had been treated with dry superheated steam, 3 to 12 wt%, preferably 8 to 10 wt%, moisture, where the sum of the constituents of the granulate core is 100 wt%, and optionally of one or more protective layers encasing the granulate core.
- the amount of the protective layer constituent is 5 to 26 wt% with respect to the uncoated granulate core.
- the substantially customary varnishes or coatings for enzyme granulates can be applied as protective layer, e.g., the customary organic polymers, with or also without additional pigments.
- An expedient protective layer (100 parts by weight) is, e.g., composed of the constituents 40 to 60 parts by weight, preferably 45 to 55 parts by weight pigment, especially white pigment titanium dioxide and/or calcium carbonate, 60 to 40 parts by weight, preferably 55 to 45 parts by weight of a binder selected from water-soluble polymers, especially polyethylene glycol with molecular weights in the range of 1500 to 10,000, polyvinyl alcohols or polyvinyl alcohol copolymers with molecular weight indices in the range from K 70 to K 110, from polyacrylic acids, polymethacrylic acid and/or cellulose ethers.
- a binder selected from water-soluble polymers, especially polyethylene glycol with molecular weights in the range of 1500 to 10,000, polyvinyl alcohols or polyvinyl alcohol copolymers with molecular weight indices in the range from K 70 to K 110, from polyacrylic acids, polymethacrylic acid and/or cellulose ethers.
- the invention additionally concerns the use of the enzyme granulates in accordance with the invention, e.g., in powdered or granular washing and cleaning agent compositions or in general the use of these granulates in washing and cleaning applications in the household and in industry or commerce.
- the enzyme granulates thus can be used in powdered or granular household washing or household cleaning agent compositions of diverse kind or, e.g., especially in dishwashing compositions.
- the enzyme granulates for industrial or commercial washing or cleaning applications such as, especially for decoating or for preparation of textiles or fabrics for subsequent processing, dyeing or other treatments are within the scope of the processing of textiles or fabrics.
- the method in accordance with the invention is an extremely economical method of preparation for high value enzyme granulates.
- premixtures for the preparation can be formulated extremely simply, and the method is then, e.g. , equally insensitive to variations of the amount, the dry substance composition and the quality of the enzyme preparation or concentrate.
- the method in accordance with the invention it is possible to use a high proportion of natural products, e.g., flours of the type given as the granulate basis, which are ecologically more advantageous than synthetic materials.
- the enzyme can thus optionally be also incorporated into the particles of a washing and cleaning agent granulate within the scope of the customary compaction methods without considerable losses of activity that occur because of pressure and friction loads in the preparation of pressed particles.
- the enzymes are thus placed in a form for disposal that ensures that the enzymes withstand the high load that may arise in a compaction operation.
- the enzyme granulate in accordance with the invention has a number of other favorable properties.
- the enzyme granulate in accordance with the invention shows good storage stability and exhibits an especially and at most negligible extraordinarily low bacterial load.
- the excellent storage stability appears, e.g. , in the fact that the half-life in customary test methods is slightly more than twice that of the products on the market; for example, the half-life of the enzyme granulates on the market in customary washing agent basis is 1.3 to 1.8 days in a quick test, while the values for the granulates in accordance with the invention are increased to about 4 to 5 days.
- the enzyme granulates in accordance with the invention also show outstanding washing power after storage in washing and cleaning agent formulations.
- the enzyme therefore is favorably stabilized in the granulate in accordance with the invention, so that it does not have a tendency to react with accompanying constituents from the enzyme concentrate used for preparation or constituents of the recipe.
- the enzyme granulate in accordance with the invention additionally has an advantageous particle size setting to which especially a favorable ability to be mixed and incorported in the constituents of washing and cleaning agent granulates is ensured; the enzyme granulate particles in accordance with the invention do not have any tendency toward demixing, and for this reason can readily be mixed with other washing and cleaning agent constituents and incorporated (dispersed) in washing and cleaning agent granulates. They are free-flowing, and for this reason have good bulk flow properties and dispensability. On top of that they do not show any tendency to cake according to the customary test methods in the washing agent industry.
- the superheated steam treatment of the flour sources takes place in a sterilization plant with the following structure: - steam heated preheater screw, conveyor temperature about 40 to 50°C;
- the cereal or leguminous or Malvaceae grains (optionally after first being partially or completely defatted) were continuously transported to the conical steamer with the aid of the steam heated preheating screw conveyor. There, via the three ring nozzles and three steam lances, treatment with dry superheated steam (overpressure reduced from 8 bar to 0.8 bar), took place.
- the material temperature in the steamer was about 100°C, and the residence was a time of about 40 minutes.
- the flours treated with superheated steam in accordance with the invention thus exhibited an outstanding microbiological purity. This high microbiological purity was obtained also at high degrees of grinding (higher share of hull in flour).
- the flours treated in accordance with the invention were outstandingly suitable for the subsequent granulation of washing agent enzymes under mild conditions.
- enzyme preparation for preparation of enzyme granulates in accordance with the invention for washing agent granulates enzyme preparation and cereal and/or leguminous or
- Malvaceae flours obtained in accordance with Example 1 were prepared by agglomeration of a powdered starting mixture with the addition of granulation liquid.
- the powdered starting mixture of cereal or leguminous or Malvaceae flour was vigorously mixed in a batchwise operating plowshare mixer/agglomerator (Lodige mixer with cutter head) while spraying in an enzyme-containing aqueous granulation liquid, and the resulting granulate was then dried in a batch operating fluidized bed dryer. Undersize grain ( ⁇ 200 ⁇ m) and oversize grain (especially > 1000 ⁇ m) were screened out and ground. The off sized grain was completely recycled to the granulation method.
- the aqueous liquid that was used - the enzyme concentrate - was put together as follows from the listed constituents: a) Enzyme concentrate of a highly alkaline protease of subtilisin type 309:
- pea fine flour 64 wt% ⁇ 36 ⁇ m
- soy fine flour 49 wt% ⁇ 36 ⁇ m
- the soy flour was completely defatted; the flours had a moisture content of 9.4 wt%.
- the powdered starting mixture of flour used in the granulation method was granulated with an aqueous spray solution of enzyme concentrate containing a highly alkaline protease of Subtilisin 309 type or a thermostable ⁇ -amylase.
- a 5-L Lodige mixer with cutter head, a peristaltic pump (without nozzles) and a fluidized bed dryer were used as equipment.
- a standard varnish of the following composition was applied to the granulate particles in an amount of 23 wt% with respect to the uncoated granulate (spraying in a fluidized bed):
- titanium dioxide 50 wt% titanium dioxide, 25 wt% calcium carbonate, 22.5 wt% polyethylene glycol 4000; 2.5 wt% polyethylene glycol 200.
- the solubility is sharply improved compared to the commercially available standard goods (95% in 8 minutes and 95% in 5 minutes), with 100% after 5 minutes.
- the washing power does not fall off in a load test at elevated temperature and elevated air humidity after 7 days. In comparison one sees a significant decrease for the base granulate of 12%.
- the enzyme granulate with the standard varnish showed a half-life time of 4.2 days. Comparable commercially available granulates in contrast showed half-life times of 1.3 to 1.8 days.
- the Heubach dust values of the granulate with standard coatings are very good.
- the solubility is outstanding compared to the commercially available standard goods (95% in 8 minutes and 95% in 5 minutes) with 100% after 5 minutes.
- the washing power does not decrease significantly after 7 days in a load test at elevated temperature and elevated air humidity; in comparison a significant decrease of 12% is seen for the base granulate.
- the granulate in accordance with the invention with standard varnish shows a half-life of 4.4 days. Comparable commercially available granulates showed, in contrast, only half-life of 1.3 to 1.8 days.
- the particle size distribution of the product is influenced very little by the Marumerization (rounding) and thus corresponds essentially to that of the moist granulate.
- Heubach enzyme dust The Heubach dust measurement is used to determine abrasion dust.
- the dust is generated from the sample by the mechanical action of steel balls in a dust pot. Particles smaller than 50 ⁇ m are removed through a controlled dry stream of air and collected on a filter and weighed.
- the enzyme activity collected from the filter can be measured in the customary way and be given in the corresponding enzyme unit with respect to the amount of sample that was used.
- E test elutriation test.
- a bed of granulate is blown for a set time with a controlled air velocity and the removed dust collected in a wash bottle.
- the content of dissolved enzyme is then measured with the determination method for the enzyme activity to be investigated and given in the corresponding enzyme unit with respect to the test amount of granulate in g.
- DU The activity of the protease incorporated into the enzyme granulate was determined in Delft units (DU). 1000 DU corresponds to the proteolytic activity that yields an extinction difference (1 cm light path; 275 nm; determination against a blind test sample) of 0.400 for a volume of 1 mL of a 2% enzyme solution (w/w) after decomposition of casein.
- MWU Modified Wohlgemuth unit; the amount of enzyme that decomposes 1 mg soluble starch in 30 minutes to a dextrin of defined size is measured.
- the solubility was determined as follows:
- the storage stability of the enzyme granulates in the presence of washing agent ingredients was determined as follows:
- enzyme granulate was mixed in in an amount of 1.0 wt% with respect to the washing agent base formulation.
- diis mixture was poured into Schott flasks with a broad neck and stored uncovered in a climate chamber at 45 °C and 80% relative air humidity. At the end of the storage time samples were taken, dissolved in sodium sulfate solution (10 g/L, pH 8.5) and the enzyme activity was determined with this solution in a substantially known way.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9709892A BR9709892A (en) | 1996-05-13 | 1997-05-13 | Process for preparing an enzyme granule stable in activity and with low powder content for washing and cleaning applications the respective granulate and uses of granules and flours of legumes or fruit flours |
US09/180,181 US6248706B1 (en) | 1996-05-13 | 1997-05-13 | Enzyme granulate for washing and cleaning |
AU31223/97A AU3122397A (en) | 1996-05-13 | 1997-05-13 | Enzyme granulate for washing and cleaning |
CA002254985A CA2254985C (en) | 1996-05-13 | 1997-05-13 | Enzyme granulate for washing and cleaning |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19619221.8 | 1996-05-13 | ||
DE1996119221 DE19619221A1 (en) | 1996-05-13 | 1996-05-13 | Enzyme granules for washing and cleaning applications |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997043482A1 true WO1997043482A1 (en) | 1997-11-20 |
Family
ID=7794167
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1997/007982 WO1997043482A1 (en) | 1996-05-13 | 1997-05-13 | Enzyme granulate for washing and cleaning |
Country Status (5)
Country | Link |
---|---|
AU (1) | AU3122397A (en) |
BR (1) | BR9709892A (en) |
CA (1) | CA2254985C (en) |
DE (1) | DE19619221A1 (en) |
WO (1) | WO1997043482A1 (en) |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6221406B1 (en) * | 1996-05-13 | 2001-04-24 | Beate Meschonat | Enzyme pre-granules for granular fodder |
JP2002534076A (en) * | 1999-01-08 | 2002-10-15 | ジェネンコア インターナショナル インコーポレーテッド | Low density composition and fine particles including the same |
JP2007503500A (en) * | 2003-08-26 | 2007-02-22 | ロケット・フルーレ | Powdered or granular compositions based on legume starch and their use in non-food and non-pharmaceutical applications |
WO2019206994A1 (en) | 2018-04-26 | 2019-10-31 | Basf Se | Lipase enzymes |
WO2019211143A1 (en) | 2018-05-03 | 2019-11-07 | Basf Se | Amylase enzymes |
WO2020169563A1 (en) | 2019-02-20 | 2020-08-27 | Basf Se | Industrial fermentation process for bacillus using defined medium and magnesium feed |
WO2020169564A1 (en) | 2019-02-20 | 2020-08-27 | Basf Se | Industrial fermentation process for bacillus using defined medium and trace element feed |
WO2020193532A1 (en) | 2019-03-25 | 2020-10-01 | Basf Se | Cleaning composition having amylase enzymes |
WO2020193534A2 (en) | 2019-03-25 | 2020-10-01 | Basf Se | Amylase enzymes |
WO2020193535A2 (en) | 2019-03-25 | 2020-10-01 | Basf Se | Amylase enzymes |
EP3353274B1 (en) | 2015-09-17 | 2020-11-04 | Henkel AG & Co. KGaA | Use of high-concentration enzyme granules for increasing the storage stability of enzymes |
WO2020249546A1 (en) | 2019-06-13 | 2020-12-17 | Basf Se | Method of recovering a protein from fermentation broth using a divalent cation |
WO2021001297A1 (en) | 2019-07-02 | 2021-01-07 | Basf Se | Method for preparing a fermentation medium |
WO2021004830A1 (en) | 2019-07-05 | 2021-01-14 | Basf Se | Industrial fermentation process for microbial cells using a fed-batch pre-culture |
WO2021032881A1 (en) | 2019-08-22 | 2021-02-25 | Basf Se | Amylase variants |
WO2022049228A1 (en) | 2020-09-04 | 2022-03-10 | Basf Se | Method for removing antifoaming agents from a fermentation broth |
WO2022063770A1 (en) | 2020-09-22 | 2022-03-31 | Basf Se | Method for recovering a protein from a fermentation broth comprising a high degree of lysed cells |
EP4047088A1 (en) | 2021-02-22 | 2022-08-24 | Basf Se | Amylase variants |
WO2022175435A1 (en) | 2021-02-22 | 2022-08-25 | Basf Se | Amylase variants |
WO2024028340A1 (en) | 2022-08-02 | 2024-02-08 | Basf Se | Stabilized protein production process using bacillus host cells with salt feed |
WO2024033135A2 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Amylase variants |
WO2024033134A1 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Enzyme compositions comprising protease, mannanase, and/or cellulase |
WO2024033133A2 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Enzyme compositions comprising an amylase |
WO2024033136A1 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Amylase variants |
WO2024094733A1 (en) | 2022-11-04 | 2024-05-10 | Basf Se | Polypeptides having protease activity for use in detergent compositions |
WO2024094735A1 (en) | 2022-11-04 | 2024-05-10 | Basf Se | Polypeptides having protease activity for use in detergent compositions |
WO2024094732A1 (en) | 2022-11-04 | 2024-05-10 | Basf Se | Polypeptides having protease activity for use in detergent compositions |
EP4389864A1 (en) | 2022-12-20 | 2024-06-26 | Basf Se | Cutinases |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
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DE19732750A1 (en) | 1997-07-30 | 1999-02-04 | Henkel Kgaa | Cleaning agent containing glucanase for hard surfaces |
DE19732751A1 (en) | 1997-07-30 | 1999-02-04 | Henkel Kgaa | New Bacillus beta glucanase |
DE19732749A1 (en) * | 1997-07-30 | 1999-02-04 | Henkel Kgaa | Detergent containing glucanase |
CA2348896A1 (en) * | 1998-11-13 | 2000-05-25 | Douglas A. Dale | Fluidized bed low density granule |
DE102006018780A1 (en) * | 2006-04-20 | 2007-10-25 | Henkel Kgaa | Granules of a sensitive detergent or cleaning agent ingredient |
DE102007056166A1 (en) * | 2007-11-21 | 2009-05-28 | Henkel Ag & Co. Kgaa | Granules of a sensitive detergent or cleaning agent ingredient |
Citations (5)
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US4106991A (en) * | 1976-07-07 | 1978-08-15 | Novo Industri A/S | Enzyme granulate composition and process for forming enzyme granulates |
US4418147A (en) * | 1978-11-20 | 1983-11-29 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Ten Behoeve Van Nijverheid, Handel En Verkeer | Enzyme immobilization in a starch gel |
US4689297A (en) * | 1985-03-05 | 1987-08-25 | Miles Laboratories, Inc. | Dust free particulate enzyme formulation |
US5318733A (en) * | 1989-08-09 | 1994-06-07 | Henkel Kommanditgesellschaft Auf Aktien | Production of compacted granules for detergents |
US5324649A (en) * | 1991-10-07 | 1994-06-28 | Genencor International, Inc. | Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof |
-
1996
- 1996-05-13 DE DE1996119221 patent/DE19619221A1/en not_active Withdrawn
-
1997
- 1997-05-13 AU AU31223/97A patent/AU3122397A/en not_active Abandoned
- 1997-05-13 CA CA002254985A patent/CA2254985C/en not_active Expired - Fee Related
- 1997-05-13 BR BR9709892A patent/BR9709892A/en not_active Application Discontinuation
- 1997-05-13 WO PCT/US1997/007982 patent/WO1997043482A1/en active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4106991A (en) * | 1976-07-07 | 1978-08-15 | Novo Industri A/S | Enzyme granulate composition and process for forming enzyme granulates |
US4418147A (en) * | 1978-11-20 | 1983-11-29 | Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Ten Behoeve Van Nijverheid, Handel En Verkeer | Enzyme immobilization in a starch gel |
US4689297A (en) * | 1985-03-05 | 1987-08-25 | Miles Laboratories, Inc. | Dust free particulate enzyme formulation |
US5318733A (en) * | 1989-08-09 | 1994-06-07 | Henkel Kommanditgesellschaft Auf Aktien | Production of compacted granules for detergents |
US5324649A (en) * | 1991-10-07 | 1994-06-28 | Genencor International, Inc. | Enzyme-containing granules coated with hydrolyzed polyvinyl alcohol or copolymer thereof |
Cited By (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6221406B1 (en) * | 1996-05-13 | 2001-04-24 | Beate Meschonat | Enzyme pre-granules for granular fodder |
JP2002534076A (en) * | 1999-01-08 | 2002-10-15 | ジェネンコア インターナショナル インコーポレーテッド | Low density composition and fine particles including the same |
JP2007503500A (en) * | 2003-08-26 | 2007-02-22 | ロケット・フルーレ | Powdered or granular compositions based on legume starch and their use in non-food and non-pharmaceutical applications |
EP3353274B1 (en) | 2015-09-17 | 2020-11-04 | Henkel AG & Co. KGaA | Use of high-concentration enzyme granules for increasing the storage stability of enzymes |
WO2019206994A1 (en) | 2018-04-26 | 2019-10-31 | Basf Se | Lipase enzymes |
WO2019211143A1 (en) | 2018-05-03 | 2019-11-07 | Basf Se | Amylase enzymes |
WO2020169564A1 (en) | 2019-02-20 | 2020-08-27 | Basf Se | Industrial fermentation process for bacillus using defined medium and trace element feed |
WO2020169563A1 (en) | 2019-02-20 | 2020-08-27 | Basf Se | Industrial fermentation process for bacillus using defined medium and magnesium feed |
WO2020193532A1 (en) | 2019-03-25 | 2020-10-01 | Basf Se | Cleaning composition having amylase enzymes |
WO2020193534A2 (en) | 2019-03-25 | 2020-10-01 | Basf Se | Amylase enzymes |
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WO2021004830A1 (en) | 2019-07-05 | 2021-01-14 | Basf Se | Industrial fermentation process for microbial cells using a fed-batch pre-culture |
WO2021032881A1 (en) | 2019-08-22 | 2021-02-25 | Basf Se | Amylase variants |
WO2022049228A1 (en) | 2020-09-04 | 2022-03-10 | Basf Se | Method for removing antifoaming agents from a fermentation broth |
WO2022063770A1 (en) | 2020-09-22 | 2022-03-31 | Basf Se | Method for recovering a protein from a fermentation broth comprising a high degree of lysed cells |
EP4047088A1 (en) | 2021-02-22 | 2022-08-24 | Basf Se | Amylase variants |
WO2022175435A1 (en) | 2021-02-22 | 2022-08-25 | Basf Se | Amylase variants |
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WO2024028338A1 (en) | 2022-08-02 | 2024-02-08 | Basf Se | Stabilized protein production process using bacillus host cells |
WO2024033135A2 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Amylase variants |
WO2024033134A1 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Enzyme compositions comprising protease, mannanase, and/or cellulase |
WO2024033133A2 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Enzyme compositions comprising an amylase |
WO2024033136A1 (en) | 2022-08-11 | 2024-02-15 | Basf Se | Amylase variants |
WO2024094733A1 (en) | 2022-11-04 | 2024-05-10 | Basf Se | Polypeptides having protease activity for use in detergent compositions |
WO2024094735A1 (en) | 2022-11-04 | 2024-05-10 | Basf Se | Polypeptides having protease activity for use in detergent compositions |
WO2024094732A1 (en) | 2022-11-04 | 2024-05-10 | Basf Se | Polypeptides having protease activity for use in detergent compositions |
EP4389864A1 (en) | 2022-12-20 | 2024-06-26 | Basf Se | Cutinases |
Also Published As
Publication number | Publication date |
---|---|
DE19619221A1 (en) | 1997-11-20 |
BR9709892A (en) | 1999-08-10 |
CA2254985A1 (en) | 1997-11-20 |
AU3122397A (en) | 1997-12-05 |
CA2254985C (en) | 2008-10-21 |
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