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WO1993017089A1 - Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds - Google Patents

Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds Download PDF

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Publication number
WO1993017089A1
WO1993017089A1 PCT/EP1993/000335 EP9300335W WO9317089A1 WO 1993017089 A1 WO1993017089 A1 WO 1993017089A1 EP 9300335 W EP9300335 W EP 9300335W WO 9317089 A1 WO9317089 A1 WO 9317089A1
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WO
WIPO (PCT)
Prior art keywords
weight
sodium
meth
bleach
water
Prior art date
Application number
PCT/EP1993/000335
Other languages
German (de)
English (en)
Inventor
Hans Josef Beaujean
Willi Buchmeier
Birgit Burg
Jürgen Härer
Thomas Holderbaum
Franz Hundgeburt
Jochen Jacobs
Peter Jeschke
Hans Kruse
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE19924205071 external-priority patent/DE4205071A1/de
Priority claimed from DE19924210363 external-priority patent/DE4210363A1/de
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP93903957A priority Critical patent/EP0626996A1/fr
Publication of WO1993017089A1 publication Critical patent/WO1993017089A1/fr

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Classifications

    • 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
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • 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
    • C11D3/3942—Inorganic per-compounds

Definitions

  • the invention relates to a new process for the production of machine washable dishwashing detergents free of low alkali, active chlorine, silicate and phosphate in the form of storage-stable, free-flowing, dust-free granules with high bulk densities - in particular in the range from about 750 to 1,100 g / l.
  • powdery poly (meth) acrylate with an active substance content of about 92-95% by weight and / or a granular alkali cleaning additive based on sodium salts of homopolymers or copolyers (meth ) acrylic acids used the subject of German Offenlegungsschrift 39 37469. It consists of:
  • low-alkaline active chlorine and phosphate-free machine dishwashers containing calcium-binding framework substances, soda, water glass, solid per compounds, activators and surfactants and, if appropriate, other conventional constituents of such agents are in the form of a storage-stable, free-flowing, dust-free Granules with bulk densities required for practical use above 650 g / l have been developed, which were premixed with at least a portion of the liquid components and, if desired, a portion of the finely divided solid components of the machine dishwashing detergent in a first stage and then combined with the remaining components of the machine dishwashing detergent are.
  • They have bulk densities in the range from 750 to 1,000 g / l and are the subject of the older, unpublished German patent applications P 4110510.9 and P 4137470.3.
  • the admixture of the sodium carbonate in turn prevents the granules from quickly caking in the pile. This maintains the granulate structure on the way to the swirl channel in the drying zone.
  • Dusting with sodium carbonate powder additionally increases the liter weight to 850 to 1,000 g. A further increase in the liter weight is achieved if the granulation is carried out first with the addition of liquid water glass and then water or water alone, if the sodium carbonate introduced in the granulation step is partially hydrated or if the batch size is increased.
  • the dishwashing detergents produced by this process contain silicates.
  • the object of the invention was, inter alia, the production of silicate-free formulations.
  • the granules thus obtained optionally adjusted to a uniform grain distribution in a second granulation stage, it under Movement in a warm air stream dries, fine and coarse fractions are sieved off and then mixed with the bleaching agent and, if appropriate, a bleach activator, a bleach stabilizer, fragrance, enzymes, nonionic surfactants, further builders and / or dyes
  • the drying must be carried out in such a way that the bicarbonate decomposition of the sodium bicarbonate to sodium carbonate is as low as possible (or at least as constant as possible). An additional portion of sodium carbonate resulting from the drying would have to be taken into account in the formulation of the granule formulation.
  • Low drying temperatures not only counteract sodium bicarbonate decay, but also increase the solubility of the granulated detergent during use. It is therefore advantageous for drying to have a supply air temperature which, on the one hand, should be as low as possible to avoid bicarbonate decomposition and, on the other hand, must be as high as necessary in order to obtain a product with good storage properties.
  • a supply air temperature of approximately 80 ° C.
  • the granules themselves should not be heated to temperatures above about 60 ° C.
  • the disintegration of the sodium bicarbonate is definitely desirable for later use in the cleaning process in the dishwasher, since this increases the alkalinity of the liquor and thus its cleaning performance.
  • the in situ formation of sodium carbonate (irritating to the eyes and skin) from sodium bicarbonate (non-irritating) mitigates dangers for the consumer, e.g. in the event of improper use by children.
  • Sodium citrate is particularly suitable as a further structural substance. It can already be added in the granulation, but can also be added to the granulate after the drying and subsequent sieving stage, just like the other constituents of dishwashing detergents. These include bleaches, optionally bleach activators, bleach stabilizers, enzymes, dyes and fragrances.
  • Setting the pH values to about 9.0 - 10.0 via the alkali carbonate / bicarbonate buffer system is important for preventing limescale deposits on the interior of the machine or on the wash ware in areas with particularly high water hardness or in softening systems that are not used properly Dishwashers.
  • the poly (meth) acrylates can be used as powder, but preferably in granulated form.
  • the usable polyacrylates include Alcosperse (Alco: AlcosperseQv 102, 104, 106, 404, 406); Acrylsole® from Norsohaas: Acrysole® A IN, LMW 45 N, LMW 10 N, LMW 20 N, SP 02N, Norasole® WL1, WL2, WL3, WL4, Degapas® from Degussa; Good-RiteCüv'K-XP 18 from Goodrich.
  • Alcosperse AlcosperseQv 102, 104, 106, 404, 406
  • Acrylsole® from Norsohaas: Acrysole® A IN, LMW 45 N, LMW 10 N, LMW 20 N, SP 02N, Norasole® WL1, WL2, WL3, WL4, Degapas® from Degussa; Good-RiteCüv
  • Copolymers of polyacrylic acid and maleic acid can also be used, for example SokalaneQy from BASF: SokalanQ / CP 5, CP 7; AcrysoleQ from Norsohaas: Acrysol QR 1014, Alcosperse (5) from Alco: Alcosperse® 175; granular alkaline cleaning additive according to DE 3937469.
  • Anhydrous trisodium citrate or trisodium citrate dihydrate are suitable as sodium citrate. Trisodium citrate dihydrate can be used as a powder. It then has an average grain size of about 0.2 now. However, higher bulk densities are achieved with crystalline citrate.
  • Anhydrous sodium carbonate of any quality is expediently used as the alkali carbonate, e.g. calcined soda or compacted soda.
  • Compacted soda is granular calcined sodium carbonate which is commercially available (e.g. V-soda from Matthes & Weber).
  • the alkali bicarbonate is preferably sodium bicarbonate.
  • the sodium bicarbonate should preferably be used in coarse compact form with a grain size in the main fraction between 0.4 and 1.0 mm.
  • active oxygen carriers have been the preferred bleaching agent components of detergents for household dishwashing machines (HGSM). These primarily include sodium perborate mono- and tetrahydrate as well as sodium percarbonate. Compacted sodium perborate monohydrate is preferred because of the increase in bulk density. Since active oxygen only develops its full effect on its own at elevated temperatures, so-called bleach activators are used to activate it at about 60 ° C., the temperatures of the cleaning process in the HGSM.
  • Preferred bleach activators are TAED (tetraacetylenediamine), PAG (pentaacetylglucose), DADHT (1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine) and ISA (isatoic anhydride).
  • TAED tetraacetylenediamine
  • PAG penentaacetylglucose
  • DADHT 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine
  • ISA isatoic anhydride
  • small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates may also be useful.
  • Extremely low-foaming compounds are usually used as nonionic surfactants, which serve to better detach fatty food residues and as granulation aids. These preferably include C12-C18 "alkylpolyethylene glycol polypropylene glycol ethers, each with up to 8 moles of ethylene oxide and propylene oxide units in the molecule.
  • non-foaming surfactants known as low-foaming, such as, for example, Ci2-Ci8-alkylpolyethylene glycol polybutylene glycol ethers, each with up to to 8 moles of ethylene oxide and butylene oxide units in the molecule, as well as the foaming but ecologically attractive C 1 -C 4 -alkyl polyglucosides and / or - C 1 -C 4 -alkyl polyethylene glycols with 3-8 ethylene oxide units in the molecule with a degree of polymerization of about 1-4, these then together with about 0.2 to 4, preferably 0 , 2 to 2% by weight, based on the finished cleaning agent, of defoaming agents such as silicone oils, mixtures of silicone oil and hydrophobized silica, paraffin oil / Guerbet alcohols and hydrophobized silica.
  • defoaming agents such as silicone oils, mixtures of silicone oil and hydrophobized silica, paraffin oil / Guerbe
  • C ⁇ -Cio-alkyl polyglucosides with a degree of polymerization of about 1-4 can be used.
  • they In order to ensure a uniform distribution of the alkyl polyglucosides, they have to be diluted to about 35% active substance in order to lower their viscosity.
  • a bleached quality should be used, otherwise a brown granulate will result.
  • protein or starch-containing food residues can be used as other common components of such agents.
  • enzymes such as proteases, amylases and lipases can also be used, for example proteases such as BLAP®140 from Henkel; Opitmase® -M-440, Optimase® -M-330, Opticlean® -M-375, Opticleanv!
  • Y -M-250 from Solvay Enzymes; Maxacal®.CX 450,000, Maxapem® from Ibis, Savinase®4.0 T 6.0 T 8.0 T from Novo or Experase® T from Ibis and amylases such as Termamyl® 60 T, 90 T from Novo; Amylase-LT® from Solvay Enzymes or Maxamyl® P 5000, CXT 5000 or CXT 2900 from Ibis, lipases such as Lipolase®30 T from NOVO.
  • Plurafac® LF 403 alkyl (Ci2-Ci8) -polyethylene glycol ( ⁇ 8 E0) -polypropylene-glycol - ( ⁇ 8 P0) -ether (BASF)
  • APG 225 Cs-Cio fatty alcohol polyglucoside with a degree of polymerization of
  • Sokalan®CP 5 poly (meth) acrylate (BASF)
  • Norasol WL 4 polyacrylate / soda granulate (Norsohaas)
  • a trisodium citrate dihydrad quality with a bulk density of approx. 810 g / 1 was used in the preparation.
  • the bulk density of the finished product was 920 g / l.
  • the bulk density of the finished product was 894 g / 1.
  • the granular cleaning additive was partially in the granulation
  • Sodium citrate which can be either fine-grained or roughly crystalline, was not mixed in during the preparation, but was already used in the granulation:
  • the bulk density after processing was 920 g / 1:
  • the non-ionic surfactant Plurafac® was used as the granulating liquid:
  • Granular cleaning additive 29.1 (as in Example 1)
  • the bulk weight of the finished product was 900 g / 1.
  • Sokalan®CP5 granulate from BASF was used in the granulation:
  • Sokalan®CP5 granules 17.5% sodium bicarbonate, compressed 60.0% soda, compressed 18.1%
  • the bulk density of the finished product was 890 g / 1.
  • Example 1 After the addition of water, the wet granules were mixed with 0.5-2% fine-grained soda and then processed further in accordance with Example 1.
  • the preparation was also carried out as in Example 1.
  • the bulk density of the finished product was 940 g / 1.
  • Recipe I was a commercially available, highly alkaline formulation with metasilicate and phosphate.
  • the pH of a 1% solution was 12.5.
  • Recipe II was a low alkaline formulation according to DE 41 37 470. A 1% solution of this cleaner had a pH of 10.5. Cleaner II contained the weaker alkaline carbonate and disilicate instead of metasilicate.
  • Recipe III was a weakly alkaline formulation according to the present invention with a pH of 9.5 (1% by weight aqueous solution). Compared to the prior art, it contained large amounts of sodium bicarbonate.
  • Recipe IV was an even weaker alkaline formulation according to the present invention with a pH of 9.2 (1% by weight aqueous solution).
  • Table I lists the recipes for the four cleaners, which differ significantly in their alkalinity.
  • Table II shows a comparison of the cleaning results of the four formulations. This list shows that, surprisingly, the weakly alkaline cleaner also delivers a well-tolerable dishwashing result. The slight underperformance is largely compensated for by the high ecological value of the formulation.
  • Table III shows a comparison of the precipitation formation of the four cleaning agents with different pH values in hard water.
  • Dishes (glasses, porcelain, stainless steel cutlery) are washed 10 times in the dishwasher.
  • 50 g of mixed soiling starch, protein
  • Rinsing is carried out in a 65 ° C program under hard water conditions (16 ° d).
  • 20 g of detergent are dosed from the storage container in the main wash cycle per wash cycle.
  • the dishes are assessed in the "black box".
  • the scale ranges from 0 to 10. 0 means that no deposits were found on the dishes.
  • the rubbers up to grade 5 are only visible in the "black box”. Rubbers from grade 6 are also outside, i.e. also visible to the consumer.
  • the interior of the machine is assessed according to the same grading scheme as the dishes, so that two values are obtained.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

Procédé de fabrication de produits de rinçage pour lave-vaisselle, exempts de phosphates et renfermant des adjuvants, des agents de blanchiment, de l'eau, éventuellement des agents tensioactifs non ioniques, ainsi que d'autres constituants courants, dans lequel on utilise comme adjuvants, des sels de sodium pulvérulents ou liquides, de monomères ou de copolymères d'acides acrylique et méthacrylique, lesquels sont préalablement mélangés avec du carbonate de sodium et du bicarbonate de sodium, de préférence sous forme compressée, puis sont agglomérés et granulés avec addition de produits liquides. Le granulé obtenu est amené, lors d'un second stade de granulation, à une granulométrie uniforme, séché par agitation dans un courant d'air chaud, tamisé, puis mélangé avec l'agent de blanchiment et, éventuellement avec un activateur de blanchiment, un stabilisant de blanchiment, un parfum, des enzymes, des agents tensioactifs non ioniques et d'autres adjuvants.
PCT/EP1993/000335 1992-02-20 1993-02-11 Procede de fabrication de produits de rinçage pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds WO1993017089A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP93903957A EP0626996A1 (fr) 1992-02-20 1993-02-11 Procede de fabrication de produits de rin age pour lave-vaisselle faiblement alcalins, exempts de chlore actif, de silicate et de phosphates, sous forme de granules lourds

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4205071.5 1992-02-20
DE19924205071 DE4205071A1 (de) 1992-02-20 1992-02-20 Verfahren zur herstellung niederalkalischer, aktivchlor-, silikat- und phosphatfreier maschinengeschirrspuelmittel in form von schwergranulaten
DEP4210363.0 1992-03-30
DE19924210363 DE4210363A1 (de) 1992-03-30 1992-03-30 Verfahren zur Herstellung niederalkalischer, aktivchlor-, silikat- und phosphatfreier Maschinengeschirrspülmittel in Form von Schwergranulaten

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WO1993017089A1 true WO1993017089A1 (fr) 1993-09-02

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EP (1) EP0626996A1 (fr)
WO (1) WO1993017089A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4232170A1 (de) * 1992-09-25 1994-03-31 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
WO1996012783A1 (fr) * 1994-10-20 1996-05-02 Henkel Kommanditgesellschaft Auf Aktien Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine
WO1997009411A1 (fr) * 1995-09-01 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation de produits granules precurseurs de detergents de faible alcalinite
FR2791581A1 (fr) * 1999-04-02 2000-10-06 Rhodia Chimie Sa Composition a base d'un sel mineral substantiellement ou totalement hydrosoluble, formulation la comprenant, et leurs preparations
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3937469A1 (de) * 1989-11-10 1991-05-16 Henkel Kgaa Granulares, alkalisches, phosphatfreies reinigungsadditiv

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3937469A1 (de) * 1989-11-10 1991-05-16 Henkel Kgaa Granulares, alkalisches, phosphatfreies reinigungsadditiv

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4232170A1 (de) * 1992-09-25 1994-03-31 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
WO1994007981A1 (fr) 1992-09-25 1994-04-14 Henkel Kommanditgesellschaft Auf Aktien Detergent faiblement alcalin pour lave-vaisselle
DE4232170C2 (de) * 1992-09-25 1999-09-16 Henkel Kgaa Schwachalkalische Geschirreinigungsmittel
WO1996012783A1 (fr) * 1994-10-20 1996-05-02 Henkel Kommanditgesellschaft Auf Aktien Silicates stratifies cristallins utilises comme agents de rinçage pour le lavage de vaisselle a la machine
WO1997009411A1 (fr) * 1995-09-01 1997-03-13 Henkel Kommanditgesellschaft Auf Aktien Procede de preparation de produits granules precurseurs de detergents de faible alcalinite
WO2000059628A1 (fr) * 1999-04-02 2000-10-12 Rhodia Chimie Composition a base d'un sel mineral substantiellement ou totalement hydrosoluble, formulation la comprenant, et leurs preparations
FR2791581A1 (fr) * 1999-04-02 2000-10-06 Rhodia Chimie Sa Composition a base d'un sel mineral substantiellement ou totalement hydrosoluble, formulation la comprenant, et leurs preparations
EP2428572A2 (fr) 2007-03-09 2012-03-14 Danisco US, Inc., Genencor Division Variants de l'alpha-amylase d'une espèce de Bacillus alcaliphile, compositions comprenant des variants de l'alpha-amylase, et procédés d'utilisation
US8323945B2 (en) 2008-06-06 2012-12-04 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US8975056B2 (en) 2008-06-06 2015-03-10 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of uses, thereof
US9040279B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Saccharification enzyme composition and method of saccharification thereof
US9040278B2 (en) 2008-06-06 2015-05-26 Danisco Us Inc. Production of glucose from starch using alpha-amylases from Bacillus subtilis
US9090887B2 (en) 2008-06-06 2015-07-28 Danisco Us Inc. Variant alpha-amylases from Bacillus subtilis and methods of use, thereof
WO2011049945A2 (fr) 2009-10-23 2011-04-28 Danisco Us Inc. Procédés destinés à réduire le saccharide donnant une couleur bleue

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