DK160885B - Free-flowing spray-dried particulate detergent - Google Patents
Free-flowing spray-dried particulate detergent Download PDFInfo
- Publication number
- DK160885B DK160885B DK083382A DK83382A DK160885B DK 160885 B DK160885 B DK 160885B DK 083382 A DK083382 A DK 083382A DK 83382 A DK83382 A DK 83382A DK 160885 B DK160885 B DK 160885B
- Authority
- DK
- Denmark
- Prior art keywords
- zeolite
- water
- detergent
- beads
- sodium
- Prior art date
Links
- 239000003599 detergent Substances 0.000 title claims description 83
- 239000010457 zeolite Substances 0.000 claims description 91
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 75
- 229910021536 Zeolite Inorganic materials 0.000 claims description 72
- 239000011324 bead Substances 0.000 claims description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000000440 bentonite Substances 0.000 claims description 35
- 229910000278 bentonite Inorganic materials 0.000 claims description 35
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 29
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 18
- 239000011734 sodium Substances 0.000 claims description 18
- 230000036571 hydration Effects 0.000 claims description 16
- 238000006703 hydration reaction Methods 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 9
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 9
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 7
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- 238000001556 precipitation Methods 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229940024999 proteolytic enzymes for treatment of wounds and ulcers Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910000031 sodium sesquicarbonate Inorganic materials 0.000 description 1
- 235000018341 sodium sesquicarbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 1
- WCTAGTRAWPDFQO-UHFFFAOYSA-K trisodium;hydrogen carbonate;carbonate Chemical compound [Na+].[Na+].[Na+].OC([O-])=O.[O-]C([O-])=O WCTAGTRAWPDFQO-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0084—Antioxidants; Free-radical scavengers
-
- 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
- C11D11/02—Preparation in the form of powder by spray drying
-
- 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
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
- C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
Landscapes
- 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)
- Biochemistry (AREA)
- Detergent Compositions (AREA)
Description
iin
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Den foreliggende opfindelse angår et fritstrømmende sprøjtetørret partikelformet rensemiddel, der omfatter sprøjtetørrede grundperler.The present invention relates to a free flowing spray dried particulate cleaner comprising spray dried base beads.
Syntetiske organiske rensemidler indeholdende vandblødgørende aluminiumsilikater såsom zeolitter er blevet opfundet og bragt på markedet i de senere år. I sådanne midler, der også indeholder en syntetisk organisk detergent eller overfladeaktiv komponent, virker zeolitten som kompleksbindingsmiddel for calcium og som builder for den organiske detergent og forbedrer dens rensevirkninger, især i hårdt vand. I sådanne midler er natriumsilikat også blevet anvendt som builder og som korrosionsforhindrende additiv for at beskytte alumi= niumdele i vaskeanlæg, som de vandige opløsninger af rensemidlet kommer i berøring med under vask. Silikaterne kan også være nyttige til at modvirke skadelige virkninger, som magniumioner i vaskevandet kunne have på vaskeaktiviteten af rensemidlet. Desuden menes det, at silikatet hjælper til at fremstille mere stabile rensemiddelperler, især når disse fremstilles ved sprøjtetørring af en blanding af rensemiddelkomponenter. Det er imidlertid kendt, at zeolitter ofte er tilbøjelige til at aflejre sig som en tydelig rest på vasketøj vasket i vandige rensemedier, der indeholder dem, og forskellige forskere har nævnt, at tilstedeværelsen af et silikat i et sådant medium med zeolit forøger mængden af aflejret rest.Synthetic organic cleansers containing water softening aluminum silicates such as zeolites have been invented and marketed in recent years. In such agents, which also contain a synthetic organic detergent or surfactant component, the zeolite acts as a complexing agent for calcium and as a builder for the organic detergent and improves its purification effects, especially in hard water. In such agents, sodium silicate has also been used as a builder and as an anticorrosive additive to protect aluminum parts in washing systems with which the aqueous solutions of the detergent come into contact with under washing. The silicates can also be useful in counteracting the detrimental effects that magnesium ions in the wash water could have on the washing activity of the detergent. Furthermore, it is believed that the silicate helps to produce more stable detergent beads, especially when prepared by spray-drying a mixture of detergent components. However, it is known that zeolites are often prone to deposit as a clear residue on laundry washed in aqueous cleaning media containing them, and various researchers have mentioned that the presence of a silicate in such a medium with zeolite increases the amount of deposited residue.
Bentonit, som er en kvældende lerart med forholdsvis mindre ionbytningskapacitet for hårdhedsdannende ioner, har været foreslået til brug i forskellige rensemiddelprodukter såsom sæbestykker og tøjvaskemidler, hvori det ofte hovedsagelig har tjent som fyldstof. Det hævdes dog, at det i nogle tilfælde udfører andre funktioner. Por eksempel angives det i amerikansk patent nr. 4.166.039, at det bidrager til fremstilling af homogene rensemiddelopslæmninger, når sådanne opslæmninger indeholder phosphater. Normalt undgåsBentonite, an asphyxiating clay with relatively less ion exchange capacity for hardness-forming ions, has been proposed for use in various detergent products such as soaps and laundry detergents, in which it has often served mainly as a filler. However, it is claimed that in some cases it performs other functions. For example, U.S. Patent No. 4,166,039 states that it contributes to the preparation of homogeneous cleanser slurries when such slurries contain phosphates. Usually avoided
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2 inkorporering af lerarter i rensemidler dog, fordi de er uopløselige og kan forventes at aflejre sig på materialer, der vaskes. Fjernelse af lersnavs er faktisk en af de prøver, der anvendes til at bedømme rensemiddelvirkningsgraden.2 incorporation of clays into detergents, however, because they are insoluble and can be expected to deposit on materials being washed. In fact, removing clay dirt is one of the tests used to evaluate the cleaning efficiency.
5 Til trods for, at det kunne forventes, at tilsætningen af bentonit kun ville forværre de restproblemer, der forekommer, når tøj vaskes med vandige medier indeholdende rensemidler, som omfatter zeolit og silikat, har det overraskende vist sig, at restaflejringen formindskes. Desuden forøges den ^0 grad, hvori calciumioner bindes.5 Although it was expected that the addition of bentonite would only aggravate the residual problems encountered when washing clothes with aqueous media containing detergents including zeolite and silicate, it has surprisingly been found to reduce residual deposition. In addition, the ^ 0 degree to which calcium ions are increased increases.
Fra patent nr. 154.346 kendes et rensemiddel, der kan indeholde natriumcarbonat, natriumbicarbonat, ionbyttende zeolit, bentonit og natriumsilikat, idet formålet med silikatet her er at erstatte de uønskede phosphater.Patent No. 154,346 discloses a cleaning agent which may contain sodium carbonate, sodium bicarbonate, ion-exchange zeolite, bentonite and sodium silicate, the purpose of the silicate being here to replace the undesirable phosphates.
Formålet med den foreliggende opfindelse er at fremstille et rensemiddel, der er fast og fritstrømmende, og som ikke giver et klæbrigt bundfald, som er tilbøjeligt til at klæbe til vasketøjet, og dette formål opnås ved at erstatte opløselige silikater med bentonit.The object of the present invention is to produce a solid and free flowing cleanser which does not provide a tacky precipitate which is prone to adhering to the laundry, and this object is achieved by replacing soluble silicates with bentonite.
Rensemidlet ifølge opfindelsen er ejendommeligt ved, at grundperlerne efter vægt indeholder 15-30% natriumcarbonat, 10-22% natriumbicarbonat, 10-50% ionbyttende zeolit, 5-20% 2 5 bentonit og 1-15% vand eksklusiv zeolittens eventuelle hydra-tiseringsvand sammen med 8-30% beregnet på rensemidlet af en ikke-ionisk detergent, som er kondensationsproduktet af en højere fedtalkohol med 12-16 carbonatomer med 6-12 mol ethylenoxid per mol alkohol, absorberet i grundperlerne. .The detergent according to the invention is characterized in that the base beads by weight contain 15-30% sodium carbonate, 10-22% sodium bicarbonate, 10-50% ion-exchanging zeolite, 5-20% 25 bentonite and 1-15% water excluding the possible hydration water of the zeolite together with 8-30% calculated on the detergent of a nonionic detergent, which is the condensation product of a higher fatty alcohol of 12-16 carbon atoms with 6-12 moles of ethylene oxide per mole of alcohol, absorbed in the base beads. .
De forskellige komponenter af grundperleme i rensemidlet ifølge opfindelsen, undtagen vand, er normalt i flydende tilstand, selv om nogle, når de sættes til b1åndeapparatet, kan være i form af hydrater eller kan være opløst eller dispergeret i et van- 3 5 digt medium såsom vand. Natriumbicarbonatet er vandfrit, og natriumcarbonat anvendes i almindelighed som vandfrit natrium= carbonat. Alligevel kan carbonathydraterne såsom monohydratetThe various components of the basic beads of the detergent of this invention, except water, are usually in liquid state, although some when added to the mixing apparatus may be in the form of hydrates or may be dissolved or dispersed in an aqueous medium such as water. The sodium bicarbonate is anhydrous and sodium carbonate is generally used as anhydrous sodium = carbonate. Nevertheless, the carbonate hydrates such as the monohydrate
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3 anvendes, hvis det ønskes, og i nogle tilfælde kan det være muligt at anvende andre carbonater og bicarbonater såsom andre alkalimetalsalte, f.eks. kaliumsalte, til erstatning af i det mindste noget af natriumsaltet, selv om natriumsal-5 tene meget foretrækkes.3 is used if desired and in some cases it may be possible to use other carbonates and bicarbonates such as other alkali metal salts, e.g. potassium salts, to replace at least some of the sodium salt, although the sodium salts are much preferred.
De anvendte zeolitter indbefatter krystallinske, amorfe og blandet krystallinsk-amorfe zeolitter af både naturlig og syntetisk oprindelse, som har tilfredsstillende hurtig og 10 tilstrækkeligt effektiv aktivitet til at modvirke calcium hårdhedsioner i vaskevand. Fortrinsvis er sådanne materialer i stand til at reagere tilstrækkeligt hurtigt med calciumionerne , s åledes at de alene eller sammen med andre vandblødgøren-de forbindelser i rensemidlet blødgør vaskevandet, før der 15 sker skadelige reaktioner af disse ioner med andre komponen ter af det syntetiske organiske rensemiddel. De anvendte zeolitter kan karakteriseres som havende en høj ionbytningskapacitet for calciumion, der normalt er fra ca. 200 til 400 eller flere milligram ækvivalenter calciumcarbonathårdhed pr.The zeolites used include crystalline, amorphous and mixed crystalline-amorphous zeolites of both natural and synthetic origin, which have satisfactory rapid and sufficiently effective activity to counteract calcium hardness ions in wash water. Preferably, such materials are capable of reacting sufficiently rapidly with the calcium ions so that they alone or together with other water-softened compounds in the detergent soften the wash water before adverse reactions of these ions with other components of the synthetic organic detergent occur. . The zeolites used can be characterized as having a high ion exchange capacity for calcium ion, which is usually from ca. 200 to 400 or more milligrams equivalents of calcium carbonate hardness per
20 gram aluminiumsilikat, fortrinsvis fra 250 til 350 mg ækvi valenter pr.gram og fortrinsvis reduceret i hårdheden til en resthårdhed på 0,02 - 0,05 mg CaCC>3 pr. liter på 1 minut, fortrinsvis 0,02 - 0,03 mg pr. liter og mindre end 0,01 mg pr. liter på 10 minutter, alle beregnet på basis af vandfri 25 zeolit.20 grams of aluminum silicate, preferably from 250 to 350 mg of equivalents per gram and preferably reduced in hardness to a residual hardness of 0.02 - 0.05 mg CaCC> 3 per gram. 1 liter, preferably 0.02 - 0.03 mg per liter. liter and less than 0.01 mg per liter. liter of 10 minutes, all calculated on the basis of anhydrous 25 zeolite.
Selv om andre ionbyttende zeolitter også kan anvendes, vil de findelte syntetiske zeolitbuilderpartikler, der normalt anvendes ifølge opfindelsen, være af formlen 30 (Na20) X - <M2°3 > y' (Si021 z'wH2°' hvor x er 1, y er fra 0,8 til 1,2, fortrinsvis ca. 1, z er fra 1,5 til 3,5, fortrinsvis 2-3 eller ca. 2, og w er fra 0 til 9, fortrinsvis 2,5 - 6.Although other ion-exchanging zeolites may also be used, the finely divided synthetic zeolite builder particles normally used in accordance with the invention will be of formula 30 (Na 2 O) X - <M 2 ° 3> y '(SiO 21 is from 0.8 to 1.2, preferably about 1, z is from 1.5 to 3.5, preferably 2-3 or about 2, and w is from 0 to 9, preferably 2.5 - 6.
Zeolitten skal være en monovalent kationbyttende- zeolit, d.v.s. den skal være et aluminiumsilikat af en monovalent kation såsom natrium, kalium, lithium (hvor dette er prak- 35The zeolite must be a monovalent cation exchange zeolite, i.e. it must be an aluminum silicate of a monovalent cation such as sodium, potassium, lithium (where this is practicable).
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4 tisk) eller andet alkalimetal, ammonium eller hydrogen (sommetider) . Fortrinsvis er den monovalente kation i den anvendte zeolit en alkalimetalkation, især natrium eller kalium og fortrinsvis natrium.4 t) or other alkali metal, ammonium or hydrogen (sometimes). Preferably, the monovalent cation in the zeolite used is an alkali metal cation, especially sodium or potassium and preferably sodium.
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Krystallinske typer zeolitter, der kan anvendes som gode ionbyttere ifølge opfindelsen,i det mindste delvis, indbefatter zeolitter af følgende krystalstrukturgrupper: A, X, Y, L, mordenit og erionit, af hvilke typerne A, X og Y foretrækkes. Blandinger af disse molekularsigtezeolitter kan også være nyttige, især når zeolit af type A er til stede.Crystalline types of zeolites which can be used as good ion exchangers according to the invention, at least in part, include zeolites of the following crystal structure groups: A, X, Y, L, mordenite and erionite, of which types A, X and Y are preferred. Mixtures of these molecular sieve zeolites may also be useful, especially when type A zeolite is present.
Disse krystallinske typer zeolitter er velkendt og er nærmere beskrevet i Zeolite Molecular Sieves af Donald W.Breck, udgivet i 1974 af John Wiley & Sons. Typiske industrielt tilgængelige zeolitter af dé førnævnte strukturtyper er anført 15 i tabel 9.6 på side 747 - 749 i ovennævnte tekst af Breck.These crystalline types of zeolites are well known and are described in greater detail in Zeolite Molecular Sieves by Donald W.Breck, published in 1974 by John Wiley & Sons. Typical industrially available zeolites of the aforementioned structural types are listed 15 in Table 9.6 on pages 747 - 749 of the above text by Breck.
Disse zeolitter er velkendte. Nogle og andre egnede zeo= litter er blevet beskrevet i mange patenter i de senere år til brug som buildere i rensemidler.These zeolites are well known. Some and other suitable zeolites have been described in many patents in recent years for use as builders in detergents.
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Zeolitten, der anvendes i opfindelsen, er i reglen syntetisk og er ofte karakteristisk ved at have et netværk af porer af i hovedsagen ensartet størrelse i intervallet fra ca. 3 tilThe zeolite used in the invention is usually synthetic and is often characterized by having a network of pores of substantially uniform size in the range of from 3 to
10 Ångstrøm og er ofte ca. 4 Å (normal), hvilken størrelse I10 Angstroms and is often approx. 4 Å (normal), what size I
bestemmes alene af enhedsstrukturen af zeolitkrystallen.is determined solely by the unitary structure of the zeolite crystal.
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Fortrinsvis er den af type A eller lignende struktur, der især | er beskrevet på side 133 i førnævnte tekst. Gode resultater er opnået, når der anvendes en type 4A molekularsigtezeolit, \ hvori den monovalente kation af zeolitten er natrium, og porestørrelsen af zeolitten er ca. 4 Å. Disse zeolitmolekular-sigter er beskrevet i amerikansk patent nr. 2.882.243, der omtaler dem som Zeolit A.Preferably, it is of type A or similar structure, in particular | are described on page 133 of the aforementioned text. Good results are obtained when using a type 4A molecular sieve zeolite, wherein the monovalent cation of the zeolite is sodium and the pore size of the zeolite is approx. 4 Å. These zeolite molecular sieves are described in U.S. Patent No. 2,882,243 which describes them as Zeolite A.
Molekularsigtezeolitter kan fremstilles i enten en dehydrati- seret eller calcineret form, der indeholder fra ca. 0 eller 35 ca. 1,5% til ca. 3% fugtighed,eller i en hydratiseret eller vandladet form, der indeholder yderligere bundet vand i en mængde fra ca. 4% og op til ca. 36% af zeolittens samlede 5Molecular sieve zeolites can be prepared in either a dehydrated or calcined form containing from ca. 0 or 35 approx. 1.5% to approx. 3% moisture, or in a hydrated or urinated form containing additional bonded water in an amount of from approx. 4% and up to approx. 36% of the total zeolite 5
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vægt, afhængende af den anvendte type zeolit. Den vandholdige hydratiserede form af molekularsigtezeolitten (fortrinsvis ca. 15 - 70% hydratiseret) foretrækkes til udførelse af den foreliggende opfindelse, når der anvendes et sådant kry-5 stallinsk produkt. Fremstilling af disse krystaller er vel kendt. Ved fremstilling af ovennævnte Zeolit A bliver de hydratiserede zeolitkrystaller, som dannes i krystallisationsmediet (såsom en vandholdig amorf natriumaluminiumsilikatgel) f.eks. anvendt uden højtemperaturdehydratisering (calcinering til 3% eller mindre vandindhold), som normalt praktiseres ved fremstilling af sådanne krystaller til brug som katalysatorer, f.eks. krakningskatalysatorer. Den krystallinske zeolit, enten i fuldstændigt hydratiseret eller delvis hydratiseret form, kan udvindes ved at frafiltrere krystallerne fra krystallisa-1® tionsmediet og tørre dem i luft ved omgivelsernes temperatur, således at deres vandindhold er i intervallet fra 5 til 30% fugtighed, fortrinsvis ca. 10 - 25%, såsom 17 - 22%. Fugtig-hedsindholdet af den molekularsigtezeolit, der anvendes, kan dog være meget lavere, hvilket tidligere har været beskrevet, 20 i hvilket tilfælde zeolitten i reglen bliver hydratiseret un der blanding i blandeapparat eller ved anden forarbejdning.weight, depending on the type of zeolite used. The aqueous hydrated form of the molecular sieve zeolite (preferably about 15-70% hydrated) is preferred for carrying out the present invention when using such a crystalline product. The preparation of these crystals is well known. In the preparation of the above Zeolite A, the hydrated zeolite crystals formed in the crystallization medium (such as an aqueous amorphous sodium aluminum silicate gel) are used without high temperature dehydration (calcination to 3% or less water content), which is usually practiced in the preparation of such crystals for use as catalysts, e.g. cracking catalysts. The crystalline zeolite, either in fully hydrated or partially hydrated form, can be recovered by filtering the crystals from the crystallization medium and drying them in air at ambient temperature so that their water content is in the range of 5 to 30% humidity, preferably approx. . 10 to 25%, such as 17 to 22%. However, the moisture content of the molecular sieve zeolite used may be much lower, as previously described, in which case the zeolite is usually hydrated during mixing in the mixer or other processing.
Fortrinsvis skal zeolitten være i findelt tilstand, hvor den endelige partikeldiameter er op til 20 mikron, f.eks. 0,005 2 5 eller 0,01 - 20 mikron, og er fortrinsvis fra 0,01 til 15 mikron og især fra 0,01 til 8 mikron i gennemsnitspartikelstørrelse, f.eks. 3-7 eller 12 mikron, hvis den er krystallinsk, og 0,01 - 0,1 mikron, f.eks. 0,01 - 0,05 mikron, hvis den er amorf. Selv om de endelige partikelstør- 3 0 reiser er meget mindre, vil zeolitpartiklerne i reglen have størrelser i intervallet fra 100 til 400 mesh, fortrinsvis 140 - 325 mesh. Zeolitter med mindre størrelser vil ofte blive for støvede, og de med større størrelser kan muligvis ikke på tilfredsstillende måde dække de grundpartikelkerner 3 5 a af carbonat-bicarbonat, hvorpå de aflejres under sprøjtetørring af en blanding fra et blandeapparat til dannelse af grundperlerne.Preferably, the zeolite should be in a finely divided state where the final particle diameter is up to 20 microns, e.g. 0.005 or 0.01 - 20 microns, and is preferably from 0.01 to 15 microns and especially from 0.01 to 8 microns in average particle size, e.g. 3-7 or 12 microns, if crystalline, and 0.01 - 0.1 microns, e.g. 0.01 - 0.05 micron if amorphous. Although the final particle sizes are much smaller, the zeolite particles will generally have sizes in the range of 100 to 400 mesh, preferably 140 to 325 mesh. Smaller sizes of zeolites will often become too dusty, and those of larger sizes may not adequately cover the carbonate-bicarbonate base particle cores upon which they are deposited during spray drying a mixture from a mixer to form the base beads.
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Den anvendte bentonit er en kolloid lerart (aluminiumsilikat) indeholdende montmorillonit. Montmorillonit er et hydrati-seret aluminiumsilikat, hvori ca. 1/6 af aluminiumatomerne kan erstattes med magniumatomer, og hvori varierende mængder 5 hydrogen, natrium, kalium, calcium, magnium og andre metaller kan være løst bundne. Den type bentonit, der specielt beskrives i den foreliggende beskrivelse til fremstilling af de opfundne grundperler, er den, der er kendt som natrium= bentonit(eller Wyoming-bentonit eller western-bentonit), der 10 normalt er et lyst til flødefarvet uhåndterligt pulver, som i vand danner en kolloid suspension med stærkt tiksotrope egenskaber. I vand vil kvældningskapaciteten af leret i reglen være i intervallet 3 - 15 ml pr. gram, fortrinsvis 7 -15 ml pr. gram, og viskositeten i en koncentration på 6% i vand 15 vil i reglen være i intervallet fra 3 til 30 centipoise, for trinsvis 8 - 30 centipoise. Foretrukne kvældende bentonitter af denne type er de, der har været forhandlet under varemærket THIXO-JEL som industrielle bentonitter af Benton Clay Company, et datterselskab af Georgia Kaolin Co. Disse materia-20 ler er selektivt udvundne og koncentrerede bentonitter, og de, der anses for at være de mest nyttige, er dem, der er bleves identificeret som THIXO-JEL's nr. 1, 2, 3 og 4. Disse materialer har en pH-værdi (6% koncentration i vand) i intervallet fra 8 til 9,4,et maksimalt frit fugtighedsindhold på 25 ca. 8% og vægtfylder på ca. 2,6, og for de pulveriserede iThe bentonite used is a colloidal clay (aluminum silicate) containing montmorillonite. Montmorillonite is a hydrated aluminum silicate in which ca. 1/6 of the aluminum atoms can be replaced by magnesium atoms, wherein varying amounts of hydrogen, sodium, potassium, calcium, magnium and other metals can be loosely bonded. The type of bentonite specifically described in the present specification for the preparation of the inventive base beads is that known as sodium = bentonite (or Wyoming bentonite or western bentonite), which is usually a light to cream colored intractable powder. which in water forms a colloidal suspension with highly thixotropic properties. In water, the swelling capacity of the clay will usually be in the range of 3 - 15 ml. grams, preferably 7-15 ml per gram. and the viscosity at a concentration of 6% in water 15 will generally be in the range of 3 to 30 centipoise, preferably 8 to 30 centipoise. Preferred asphyxiating bentonites of this type are those that have been traded under the trademark THIXO-JEL as industrial bentonites by Benton Clay Company, a subsidiary of Georgia Kaolin Co. These materials are selectively recovered and concentrated bentonites and those considered to be the most useful are those identified as THIXO-JEL Nos. 1, 2, 3 and 4. These materials have a pH value (6% concentration in water) in the range of 8 to 9.4, a maximum free moisture content of about 25%. 8% and a density of approx. 2.6, and for the powdered i
kvaliteters vedkommende passerer ca. 85¾ gennem en 200 mesh US-sigte. Disse materialer udviser en ombyttelig calcium- Iin terms of quality, approx. 85¾ through a 200 mesh US sieve. These materials exhibit an interchangeable calcium I
oxidprocent i intervallet fra ca. 1 til 1,8, og med hensyn ! til magniumoxid er denne procent normalt i intervallet fra 1 30 0,04 til 0,41. Typiske kemiske analyser af disse materia ler er fra 64,8 til 73,0% SiC>2, 1,4 - 1,8% A1203, 1,6 -2,7% MgO, 1,3 - 3,1% CaO, 2,3 - 3,4%· Pe Oj, 0,8 - 2,8% Na20 og 0,4 - 7,0% K20. Selv om disse bentonitter foretrækkes, kan der i stedet anvendes ækvivalente materialer fra andre 35 kilder.oxide percent in the range of approx. 1 to 1.8, and with regard to! for magnesium oxide, this percentage is usually in the range of 1 0.04 to 0.41. Typical chemical analyzes of these materials are from 64.8 to 73.0% SiC> 2, 1.4 - 1.8% Al 2 O 3, 1.6 -2.7% MgO, 1.3 - 3.1% CaO , 2.3 - 3.4% · Pe Oj, 0.8 - 2.8% Na 2 O and 0.4 - 7.0% K 2 O. Although these bentonites are preferred, equivalent materials from other sources may be used instead.
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Det eneste andet materiale, der er nødvendigt til fremstilling af de foreliggende perler, er vand, og under tørring af perlerne kan deres vandindhold formindskes, således at produktet er næsten vandfrit. Det foretrækkes at anvende afioniseret 5 vand, således at indholdet af hårdhedsioner deraf kan være meget lavt, og således at metalioner, der kan fremme dekompo-nering af eventuelle organiske materialer, som kan være til stede i de endelige perler og rensemiddel, formindskes, men normalt byvand eller postevand kan anvendes i stedet. Normalt 10 vil hårdhedsindholdet af vand være mindre end 150 ppm somThe only other material needed to make the present beads is water, and during drying the beads their water content can be reduced so that the product is almost anhydrous. It is preferred to use deionized water so that the content of hardness ions thereof can be very low and so that metal ions which can promote decomposition of any organic materials which may be present in the final beads and detergent are reduced, but usually urban or tap water can be used instead. Usually, the hardness of water will be less than 150 ppm as
CaCO^, og fortrinsvis vil hårdhedsindholdet være mindre end 100 ppm og bedst mindre end 50 ppm.And preferably the hardness content will be less than 100 ppm and preferably less than 50 ppm.
Da ret koncentrerede vandige blandinger i blandeapparatet af 15 carbonat, bicarbonat, zeolit og bentonit kan "fryse" i blandeapparatet på grund af reaktioner af komponenterne, hvis de holdes ud over en tilladelig tid, er der fortrinsvis forarbejdshjælpemidler til stede i blandeapparatet, og derfor i 20 de færdige grundperler og rensemidlet, for at forhindre for tidlig størkning eller gelering af blandingen. Mest hensigtsmæssigt indeholder de citronsyre og magniumsulfat. I stedet for citronsyre kan anvendes opløselige citrater såsom natrium= citrat, og det foretrækkes at anvende vandfrit magniumsulfat, 25 men forskellige hydrater deraf såsom epsomsalt kan anven des. Magniumcitrat kan også anvendes i stedet. I Stedet for det foretrukne antigeleringssystem kan der anvendes andre midler og egnede systemer til at opretholde blandingen flydende i blandeapparatet, f.eks. natriumsesquicarbonat anvendt til 3ø erstatning af noget af natriumcarbonatet og natriumbicarbona= tet.Since fairly concentrated aqueous mixtures in the mixer of carbonate, bicarbonate, zeolite and bentonite can "freeze" in the mixer due to reactions of the components if kept for a permissible time, processing aids are preferably present in the mixer, and therefore in 20 to prevent the premature solidification or gelling of the mixture. Most suitably, they contain citric acid and magnesium sulfate. Instead of citric acid, soluble citrates such as sodium citrate may be used, and it is preferred to use anhydrous magnesium sulfate, but various hydrates thereof such as epsome salt may be used. Magnesium citrate can also be used instead. In place of the preferred anti-gelling system, other means and suitable systems can be used to maintain the mixture liquid in the mixer, e.g. sodium sesquicarbonate used to replace some of the sodium carbonate and sodium bicarbonate.
Forskellige tilsætninger såsom parfumer, enzymer, farvende stoffer, blegemidler og strømningsfremmende midler kan ofte 35 sprøjtes på eller på anden måde blandes med grundperlerne efter deres fremstilling sammen med den ikke-ioniske detergent eller adskilt fra denne, således at de ikke påvirkes skadeligt af sprøjtetørringsoperationen, og også således at deresVarious additives such as perfumes, enzymes, dyes, bleaches and flow promoters can often be sprayed or otherwise mixed with the base beads after their preparation with the non-ionic detergent or separated therefrom so as not to be adversely affected by the spray drying operation. and also so that theirs
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8 tilstedeværelse i de sprøjtetørrede perler ikke hindrer absorption af ikke-ionisk detergent. Por stabile og normalt faste tilsætninger er iblanding sammen med de uorganiske salte i opslæmning i blandeapparatet også mulig. Det er således tan-5 kenr at farvende midler og fluorescerende klaringsmidler nor malt vil være til stede i blandingen i blandeapparatet, hvorfra de foreliggende grundperler sprøjtes. Det foretrukne farvende middel er ultramarinblåt, men andre stabile pigmenter og farvestoffer kan anvendes sammen med det eller til erstatning 10 af det. Blandt de fluorescerende klaringsmidler er det mest foretrukne TINOPAL 5BM. Forskellige andre bomuldsklaringsmidler såsom de, der sommetider omtales som CC/DAS-klarings-midler, og som er afledt af reaktionsproduktet af cyanur= syrechlorid, og dinatriumsaltet af diaminostilbendisulfon-15 syre kan dog også anvendes, herunder variationer deraf8 presence in the spray dried beads does not prevent the absorption of nonionic detergent. For stable and normally solid additions, admixture with the inorganic salts in slurry in the mixer is also possible. Thus, it is conceivable that staining agents and fluorescent clearing agents will normally be present in the mixer in the mixer from which the present beads are sprayed. The preferred coloring agent is ultramarine blue, but other stable pigments and dyes can be used with it or to replace it. Among the fluorescent detergents, the most preferred is TINOPAL 5BM. Various other cotton clearing agents, such as those sometimes referred to as CC / DAS clearing agents, which are derived from the reaction product of cyanuric acid chloride, and the disodium salt of diaminostilbendisulfonic acid may also be used, including variations thereof.
med hensyn til substituenterne på triazinringen og aromatiske ringe. Denne klasse klaringsmidler er kendt inden for rensemiddelindustrien og vil ofte blive anvendt, når der ikke er blegekomponenter til stede i slutproduktet. I sådan-20 ne tilfælde kan blegestabile klaringsmidler anvendes. Blandt Iwith respect to the substituents on the triazine ring and aromatic rings. This class of detergents is known in the cleaning industry and will often be used when there are no bleaching components present in the final product. In such cases, bleach-stable clarifiers can be used. Among I
disse kan nævnes benzidinsulfondisulfonsyrer, naphthotriazolyl= stilbensulfonsyrer og benzimidazolylderivater. Polyamid- ; klaringsmidler, der også kan være til stede, indbefatter amino= j coumarin eller diphenylpyrazolinderivater og polyesterklarings-25 midler, der også kan anvendes, indbefatter naphthotriazolyl- ; stilbener. Alle disse klaringsmidler anvendes normalt som ' deres opløselige salte, men de kan også tilsættes som de til- j svarende syrer. Bomuldsklaringsmidlerne vil i reglen udgøre størstedelen af klaringssystemerne.these may be mentioned benzidine sulfone disulfonic acids, naphthotriazolyl = stilbenzulfonic acids and benzimidazolyl derivatives. Polyamide; clarifiers which may also be present include amino acid coumarin or diphenylpyrazoline derivatives and polyester clarifiers which may also be used include naphthotriazolyl; stilbene. All of these clarifiers are usually used as their soluble salts, but they can also be added as the corresponding acids. The cotton clearing agents will usually constitute the majority of the clearance systems.
30 I30 I
Blandt de materialer, der kan tilsættes bagefter til de sprøjte-tørrede grundperler, er det vigtigste naturligvis den ikke-ioniske detergent, som er et kondensationsprodukt af ethylen-oxid og højere fedtalkohol. I disse produkter har den højere 35 fedtalkohol 12 - 16 kulstofatomer, og den ikke-ioniske deter gent indeholder fra 6 til 12 ethylenoxidgrupper per mol. Sådanne detergenter fremstilles af Shell Chemical Company og kan fås under handelsnavnene NEODOL 23-6.5 og 23-7.Of course, among the materials that can be added afterwards to the spray-dried primer beads, the most important is of course the nonionic detergent, which is a condensation product of ethylene oxide and higher fatty alcohol. In these products the higher 35 fatty alcohol has 12 to 16 carbon atoms and the nonionic detergent contains from 6 to 12 ethylene oxide groups per mole. Such detergents are manufactured by Shell Chemical Company and are available under the trade names NEODOL 23-6.5 and 23-7.
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Enzympræparaterne, der normalt sættes til perlerne bagefter, kan være ethvert af forskellige industrielt tilgængelige produkter, blandt hvilke er ALCALASE, fremstillet af Novo Industri A/S, og MAXATASE, der begge er alkaliske proteaser 5 (subtilisin). Selv om alkaliske proteaser foretrækkes, kan amylolytiske enzymer såsom a-amylase samt proteolytiske en= zymer anvendes. De nævnte midler indeholder i reglen aktive enzymer i kombination med en indifferent pulverformet bærer såsom natrium- eller calciumsulfat, og mængden af aktivt enzym 10 kan variere meget og er i reglen fra 2 til 80% af det industrielle præparat. De anvendte parfumer, som i reglen er varme-følsomme og kan indeholde noget flygtigt opløsningsmiddel såsom alkohol, er normalt syntetiske parfumerimaterialer, sommetider blandet med naturlige komponenter, og indeholder i 15 almindelighed alkoholer, aldehyder, terpener, fiksativer og andre normale parfumekomponenter. Strømningsfremmende midler såsom specielle lerarter, der sommetider sættes til rense-middelprodukterne, er ofte nyttige til at forbedre strømmeevnen og til at formindske klæbrigheden af forskellige midler, 20 men er unødvendige i de foreliggende tilfælde, muligvis delvis som følge af tilstedeværelsen af bentonitten. De kan dog tilsættes, hvis det ønskes, for yderligere at fremme strømmeevnen.The enzyme preparations normally added to the beads afterwards can be any of various industrially available products, among which are ALCALASE, manufactured by Novo Industri A / S, and MAXATASE, both of which are alkaline proteases 5 (subtilisin). Although alkaline proteases are preferred, amylolytic enzymes such as α-amylase as well as proteolytic enzymes can be used. Said agents generally contain active enzymes in combination with an inert powdered carrier such as sodium or calcium sulfate, and the amount of active enzyme 10 can vary widely and is generally from 2 to 80% of the industrial composition. The perfumes used, which are generally heat sensitive and may contain some volatile solvent such as alcohol, are usually synthetic perfume materials, sometimes mixed with natural components, and generally contain alcohols, aldehydes, terpenes, fixatives and other normal perfume components. Flow enhancers such as special clays, sometimes added to the detergent products, are often useful for improving the flowability and for reducing the tackiness of various agents, but are unnecessary in the present case, possibly partly due to the presence of the bentonite. However, they may be added, if desired, to further promote flowability.
Mængdeforholdene mellem de forskellige komponenter i grundper-25 lerne er således, at de resulterer i, at de er fritstrømmende og tilstrækkeligt absorberende for en ikke-ionisk detergent, som påføres derpå i flydende tilstand, således at rensemidlet fremstillet af dem ved inkorporering af denne detergent også vil være tilfredsstillende fritstrømmende. Rensemidlet frem-30 stillet af grundperlerne skal naturligvis også være et effektivt rensemiddel, hvor de tilstedeværende buildere virker til at understøtte den organiske detergent i vandige opløsninger af midlet, og det er vigtigt, at det fremkomne produkt er et produkt, som ikke forårsager skadelig aflejring af zeo= 35 litpartikler på vaskede materialer. Det har vist sig, at ret ίοThe proportions of the various components of the base beads are such that they result in being free flowing and sufficiently absorbent to a nonionic detergent which is then applied in liquid state so that the detergent produced by them by incorporating this detergent will also be satisfactory free-flowing. Of course, the detergent produced from the primer beads must also be an effective detergent in which the present builders act to support the organic detergent in aqueous solutions of the agent, and it is important that the resulting product is a product which does not cause harmful deposition. of zeo = 35 liters of particles on washed materials. It has turned out to be right
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tilfredsstillende grundperler for at tilfredsstille dette formål, kan omfatte efter vægt fra 15 til 30% natriumcar-bonat, 10 - 22% natriumbicarbonat, 20 - 40% vandblødgørende aluminiumsilikat (zeolit), og 5 - 15% bentonit som de ak-5 tive komponenter og 1 - 15% vand. I disse perler er alumi niumsilikatet fortrinsvis en natriumzeolit indeholdende fra 15 til 25 vægt% hydratiseringsvand, og fortrinsvis er zeolitten en Zeolit A. Det foretrukne vægtforhold natrium-carbonat:natriumbicarbonat i produktet er i intervallet fra ca. 1 til 3, og de fremstillede perler har en masserumvægt . . 3 i intervallet fra 0,6 til 0,9 g pr. cm , fortrinsvis 0,7 - 3 . .satisfactory base beads to fulfill this purpose may include by weight from 15 to 30% sodium carbonate, 10 to 22% sodium bicarbonate, 20 to 40% water softening aluminum silicate (zeolite), and 5 to 15% bentonite as the active components and 1 - 15% water. In these beads, the aluminum silicate is preferably a sodium zeolite containing from 15 to 25% by weight of hydration water, and preferably the zeolite is a zeolite A. The preferred weight ratio of sodium carbonate: sodium bicarbonate in the product is in the range of from about 1 to 3, and the beads produced have a bulk space weight. . 3 in the range of 0.6 to 0.9 g per cm, preferably 0.7-3. .
0,8 g pr. cm , og perlens partikelstørrelse er i intervallet fra nr. 10 til nr. 100 (gennem nr. 10 og fastholdt på nr. 100), US sigte-standard, fortrinsvis 10 - 60, US sigte-standard.0.8 g per and the particle size of the bead is in the range of # 10 to # 100 (through # 10 and maintained at # 100), US sieve standard, preferably 10 to 60, US sieve standard.
Når perlerne, der skal fremstilles, skal have intet eller kun lidt vandopløseligt silikat til stede som tidligere nævnt, vil mængdeforholdene mellem de forskellige komponenter i 20 grundperlerne være således, at de resulterer i, at de er fritstrømmende og tilstrækkeligt absorberende for en ikke- ! ionisk detergent, som påføres derpå i flydende tilstand, således at rensemidlet fremstillet af dem ved inkorporering j af en sådan detergent også vil være tilfredsstillende frit-2 5 strømmende. Det er også vigtigt, at det fremkomne produkt j er et, der ikke forårsager skadelig aflejring af zeolitpartikler (eventuelt sammen med andre stoffer) på vaskede materia- i ler. Det er også ønskeligt, at de fremstillede grundpérler har en passende masserumvægt og farve. Det har vist sig, at 30 for at opnå disse formål omfatter tilfredsstillende grund- perler efter vægt fra 15 til 30% natriumcarbonat, 10 - 22% natriumbicarbonat, 10 - 50% vandblødgørende aluminiumsilikat (zeolit),0-3% natriumsilikat og 5 - 20% bentonit som de aktive komponenter og 1 - 15% vand. Den anførte procentmængde 35 vand er frit vand og indbefatter ikke zeolittens hydratiseringsvand. Tilsvarende inkluderer procentmængden af zeolit hydratiseringsvand. I nogle tilfælde kan produktet væreWhen the beads to be manufactured should have no or little water-soluble silicate present, as previously mentioned, the proportions of the various components of the basic beads will be such that they are free flowing and sufficiently absorbent for a non-liquid bead. ionic detergent which is then applied in a liquid state so that the detergent prepared by them upon incorporation of such detergent will also be satisfactorily free flowing. It is also important that the resulting product j is one that does not cause harmful deposition of zeolite particles (possibly together with other substances) on washed materials. It is also desirable for the prepared beads to have a suitable bulk space weight and color. It has been found that to achieve these purposes, satisfactory base beads by weight range from 15 to 30% sodium carbonate, 10 to 22% sodium bicarbonate, 10 to 50% water softening aluminum silicate (zeolite), 0 to 3% sodium silicate and 20% bentonite as the active components and 1 - 15% water. The indicated percentage of water is free water and does not include the hydration water of the zeolite. Similarly, the percentage of zeolite includes hydration water. In some cases, the product may be
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11 vandfrit, forsåvidt angår indhold af fri fugtighed, men disse tilfælde er sjældne, og det er normalt ønskeligt, at der i det mindste er en lille mængde vand i grundperlerne for at forhindre uønsket pulverisering deraf, hvilket sommetider el-5 lers kunne ske med partikelformede vandfrie præparater. Det foretrukne vægtforhold natriumcarbonatrnatriumbicarbonat i produktet er i intervallet fra ca. 1 til 3, og de fremstillede perler har en masserumvægt i intervallet fra 0,6 til 0,9 g 3 3 pr. cm , fortrinsvis 0,6 eller 0,7 - 0,8 g pr. cm , og perler- 10 ues partikelstørrelse er i intervallet fra nr. 10 til nr. 100 (gennem nr. 10 og fastholdt på nr. 100), US sigte-standard, fortrinsvis 10 - 60, US sigte standard. Andre foretrukne mængdeforhold mellem komponenterne er fra 20 til 27% natrium= carbonat, 14 - 21% natriumbicarbonat, 20 - 50% hydratiseret 15 zeolit, 0% natriumsilikat, 5 - 20% bentonit og 1 - 5% vand eksklusive zeolittens hydratiseringsvand. I sådanne mere foretrukne produkter er vægtforholdet natriumcarbonat:na= triumbicarbonat i intervallet 1 til 2. Når der er silikat i sådanne grundperler, foretrækkes det at begrænse dets ind-20 hold til 2%, især fra 0,5 til 1%. Andre foretrukne inter valler for mængder af vigtige komponenter ifølge opfindelsen er 35 - 45% hydratiseret zeolit og 5 - 15%, specielt 10 - 15%, bentonit.11 anhydrous, as far as free moisture content is concerned, but these cases are rare and it is usually desirable that there is at least a small amount of water in the base beads to prevent unwanted pulverization thereof, which could sometimes occur with particulate anhydrous preparations. The preferred weight ratio of sodium carbonate sodium bicarbonate in the product is in the range of about 1 to 3, and the beads produced have a mass compartment weight in the range of 0.6 to 0.9 g 3 cm, preferably 0.6 or 0.7 - 0.8 g / cm and the bead 10-hour particle size is in the range of # 10 to # 100 (through # 10 and maintained at # 100), US sieve standard, preferably 10 to 60, US sieve standard. Other preferred proportions of the components are from 20 to 27% sodium = carbonate, 14 to 21% sodium bicarbonate, 20 to 50% hydrated zeolite, 0% sodium silicate, 5 to 20% bentonite and 1 to 5% water, excluding the zeolite hydration water. In such more preferred products, the weight ratio is sodium carbonate: sodium bicarbonate in the range of 1 to 2. When there is silicate in such base beads, it is preferred to limit its content to 2%, especially 0.5 to 1%. Other preferred ranges for amounts of important components of the invention are 35 - 45% hydrated zeolite and 5 - 15%, especially 10 - 15%, bentonite.
25 Det har vist sig, at rensemidlet ifølge opfindelsen ikke kræver tilstedeværelse af noget antikorrosions-additiv for at erstatte silikatet, men det ligger inden for opfindelsens rammer at anvende sådanne egnede materialer, og det foretrækkes at anvende dem, der er stabile under blandings- og 30 sprøjtetørringsbetingelser, og som ikke har nogen skadelig virk ning på disse operationer. Disse antikorrosionsadditiver eller antioxidanter kan være organiske eller uorganiske, idet uorganiske materialer normalt foretrækkes, og de vil normalt blive valgt for egnethed til at hindre korrosion af aluminiumdele i 35 vaskemaskiner. Hvis det ønskes at fortsætte med at anvende et silikat til dette formål eller at anvende et silikat for dets virkning til behandling af magniumionhårdhed, vil et pulveriseret silikat normalt blive foretrukket, såsom vandigt 12It has been found that the detergent according to the invention does not require the presence of any anti-corrosion additive to replace the silicate, but it is within the scope of the invention to use such suitable materials, and it is preferred to use those which are stable during mixing and mixing. 30 spray drying conditions and which have no detrimental effect on these operations. These anti-corrosion additives or antioxidants may be organic or inorganic, with inorganic materials usually being preferred, and they will usually be selected for suitability to prevent corrosion of aluminum parts in 35 washing machines. If it is desired to continue to use a silicate for this purpose or to use a silicate for its effect in treating magnesium ion hardness, a powdered silicate will usually be preferred, such as aqueous
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natriumsilikat, der kan fås i handelen under navnet BRITESIL, fremstillet af Philadelphia Quartz Co, (Na20iSi02 = 1:2,4) , og dette vil blive tilsat bagefter. Andre normale faste opløselige silikater, fortrinsvis alkalimetaller, kan dog også til-5 sættes bagefter til perlerne r hvori ikke-ionisk detergent forud er blevæc absorberet.commercially available sodium silicate under the name BRITESIL, manufactured by Philadelphia Quartz Co, (Na 2 O 2 SiO 2 = 1: 2.4), and this will be added afterwards. However, other normal solid soluble silicates, preferably alkali metals, may also be added afterwards to the beads r in which nonionic detergent has been pre-absorbed.
Når det ønskes, at det fremstillede produkt har tekstil-blødgørende egenskaber, kan blødgørende materialer, for-10 trinsvis i tør pulverform, også tilsættes bagefter til grund- perlerne på passende måde. Denne klasse materialer er velkendt, og i almindelighed er sådanne blødgøringsmidler kat-ioniske forbindelser, især kvaternære ammoniumforbindelser såsom kvaternære ammoniumhalogenider. Særligt foretrukne 15 er de højere alkyl-, alkylaryl- og arylalkyl-lavere alkyl kvaternære ammoniumchlorider og bromider såsom distearyl= dimethylammoniumchlorid. Blandt industrielle blødgørende mate- , rialer er det, der foretrækkes mest, det, der forhandles un- i der handelsnavnet AROSURF TA-100, der fremstilles af Sherex 20 Chemical Company, Inc. Sådanne forbindelser har også antistatiske og antibakterielle egenskaber, men hvis det ønskes, i kan andre bakterielle tilsætninger også anvendes, og de inkorporeres fortrinsvis i produktet ved tilsætning bagefter. j 25 Det er et vigtigt træk ved den foreliggende opfindelse, at et effektivt opbygget rensemiddel baseret på ikke-ionisk rensemiddel alene kan fremstilles ved en industriel velegnet proces, men sommetider kan det være ønskeligt også at have et anionisk overfladeaktivt middel eller detergentkomponent ! 30 til stede i slutproduktet, i reglen fordi det bidrager til. j produktet med skummeegenskaber og supplerende rensevirkninger. j Normalt vil det blive foretrukket ikke at inkorporere sådanne anioniske detergentmaterialer i blandingen i blandeapparatet, J så hvis sådanne skal anvendes, vil de fortrinsvis blive til-35 sat bagefter til de sprøjtetørrede grundperler, og normalt vil en sådan tilsætning bagefter finde sted, efter at perler- iWhen it is desired that the manufactured product has textile-softening properties, softening materials, preferably in dry powder form, can also be added afterwards to the base beads appropriately. This class of materials is well known and in general, such plasticizers are cationic compounds, especially quaternary ammonium compounds such as quaternary ammonium halides. Particularly preferred are the higher alkyl, alkylaryl and arylalkyl lower alkyl quaternary ammonium chlorides and bromides such as distearyl = dimethylammonium chloride. Among industrial softening materials, what is most preferred is that traded under the trade name AROSURF TA-100, manufactured by Sherex 20 Chemical Company, Inc. Such compounds also have antistatic and antibacterial properties, but if desired, other bacterial additives may also be used, and are preferably incorporated into the product upon addition afterwards. It is an important feature of the present invention that an efficiently constructed non-ionic detergent-based cleaner can only be produced by an industrially suitable process, but sometimes it may also be desirable to have an anionic surfactant or detergent component! 30 present in the final product, usually because it contributes. j the product with foam properties and additional cleaning effects. Normally, it would be preferable not to incorporate such anionic detergent materials into the mixture in the mixer, so that, if used, they will preferably be added afterwards to the spray dried base beads, and usually such addition will occur afterwards. pearls- i
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13 ne har absorberet den flydende ikke-ioniske detergent. Der kan anvendes forskellige typer anioniske detergenter, fortrinsvis fuldstændigt i pulverform og/eller sommetider blandet med buildermateriale, men de, der foretrækkes, er lineære højere g alkylbenzensulfonater, højere fedtalkoholsulfater og poly= ethoxylerede højere fedtalkoholsulfater. I sådanne produkter vil de højere alkyl- og højere alkoholdele normalt have 8-20, fortrinsvis 12 - 16 kulstofatomer/ og detergenterne vil være til stede som deres vandopløselige alkalimetalsalte, jq fortrinsvis som natriumsalte. Det ethoxylerede alkoholsulfat vil normalt indeholde fra 3 til 20 mol ethylenoxid pr. mol fedtalkohol.13 ne has absorbed the liquid nonionic detergent. Various types of anionic detergents may be used, preferably completely in powder form and / or sometimes mixed with builder material, but those preferred are linear higher g alkylbenzenesulfonates, higher fatty alcohol sulfates and polyethoxylated higher fatty alcohol sulfates. In such products, the higher alkyl and higher alcohol moieties will normally have from 8 to 20, preferably 12 to 16 carbon atoms, and the detergents will be present as their water-soluble alkali metal salts, and preferably as sodium salts. The ethoxylated alcohol sulfate will normally contain from 3 to 20 moles of ethylene oxide per liter. moles of fatty alcohol.
Intervallerne for mængderne af de forskellige perlekomponen-j5 ter i det færdige rensemiddel kan let beregnes af dem, der anført for grundperlerne, formindsket med mængderne af detergent eller andre materialer, der bagefter sættes til perlerne. Hvis det endelige rensemiddel således kun har fået tilsat ikke-ionisk detergent, således at slutproduktet indeholder 20 20% ikke-ionisk detergent, kan der af de forskellige interval ler anført for komponenterne i grundperlerne beregnes intervaller for mængder deraf ved at multiplicere med 0,8, d.v.s.The ranges of the amounts of the various bead components in the finished cleaner can easily be calculated by those listed for the base beads, reduced by the amounts of detergent or other materials added to the beads. Thus, if the final detergent has only added non-ionic detergent, so that the final product contains 20% non-ionic detergent, the various beads listed for the components in the base beads can be calculated intervals for amounts thereof by multiplying by 0.8 , ie
(100 - 20)/100. Når mængden af ikke-ionisk detergent (i sammensætninger, hvori det er det eneste additiv til perlerne) 25 kan ligge fra 8 til 25% af rensemidlet, vil faktorerne til svarende være fra 0,75 til 0,92. I reglen vil den endelige procentmængde af ikke-ionisk detergent i produktet være i intervallet 8 - 25% og er fortrinsvis 15 - 22% og især ca.(100-20) / 100. When the amount of nonionic detergent (in compositions in which it is the only additive to the beads) 25 can range from 8 to 25% of the detergent, the corresponding factors will be from 0.75 to 0.92. As a rule, the final percentage amount of non-ionic detergent in the product will be in the range of 8 - 25% and is preferably 15 - 22%, and most preferably about
20%,men i nogle situationer for visse typer produkter kan fore-gø trækkes mængder i intervallet 8 - 13%. Normalt vil procenten af parfume i slutproduktet være i intervallet 0,1 - 1%, fortrinsvis 0,2 - 0,4%, procenten af enzymet vil være fra 0,5 til 3%, fortrinsvis 1 eller 1,5 - 2,5%, og procenten af strømnings-forbedrende middel, der kan tilsættes bagefter, vil være min-dre end 2%, fortrinsvis mindre end 1%. For at beregne intervallerne af perlekomponenter i det endelige middel må beregningerne af procenterne af andre tilsatte additiver naturlig-20%, but in some situations for certain types of products, quantities can be preferred in the range of 8 - 13%. Usually, the percentage of perfume in the final product will be in the range of 0.1 - 1%, preferably 0.2 - 0.4%, the percentage of the enzyme will be from 0.5 to 3%, preferably 1 or 1.5 - 2.5. %, and the percent of flow enhancer which may be added afterwards will be less than 2%, preferably less than 1%. To calculate the intervals of bead components in the final agent, the calculations of the percentages of other added additives must be natural.
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14 vis også tages i betragtning foruden procenten af ikke-ionisk detergent i slutproduktet (tilsat bagefter) . Hvis nogle tilsætninger foretaget bagefter sker ved hjælp af vandige opløsninger af additiverne/ vil dette også påvirke fugtighedsindholdet, 5 hvilket ofte holdes i intervallet 1 - 12%, men sommetider kan det udvides til 15%.14 are also considered in addition to the percentage of non-ionic detergent in the final product (added afterwards). Afterwards, if some additions are made using aqueous solutions of the additives / this will also affect the moisture content, which is often kept in the range 1 - 12%, but sometimes it can be extended to 15%.
Intervallerne og mængderne af de forskellige perlekomponenter i den sprøjtetørrede del af det endelige rensemiddel, når der jq ikke er noget silikat eller kun lidt silikat til stede, kan beregnes på den tidligere beskrevne måde. Hvad angår bagefter tilsatte komponenter, vil procenten af : ikke-ionisk detergent være den samme som tidligere anført, procenten af parfume i slutproduktet vil være i intervallet 0,1 - 1%, fortrinsvis 0,2 - 0,4%, procenten af enzym vil være fra 0,5 til 3%, fortrinsvis 1 - 2%, og hvis et vandigt silikat tilsættes bagefter, vil mængden deraf normalt være fra 2 til 10%, fortrinsvis 3 - 8%, f.eks, ca. 5%. Når en blødgørende : forbindelse er til stede i slutproduktet, vil mængden deraf i 20 normalt være i intervallet 3 - 12%, fortrinsvis 5 - 10%, og når der anvendes anioniske detergenter, vil mængden deraf i være begrænset til ikke mere end mængden af ikke-ionisk de- i tergent, og den samlede vægt af anionisk og ikke-ionisk de- ; tergent i slutproduktet vil være i intervallet, der tidli- ! i 25 gere er anført for ikke-ionisk detergent alene. Hvis der j anvendes anionisk detergent, vil den tilstedeværende mængde ] deraf normalt være i intervallet 0,2 - 0,8 gange vægten af ] ikke-ionisk detergent. For at beregne intervallerne for per- j lekomponenter i det endelige middel må disse beregninger na- | 30 turligvis, foruden at være baseret på procenten af ikke-ionisk i detergent i slutproduktet (tilsat bagefter), baseres på pro- centerne af andre bagefter tilsatte stoffer. Hvis nogle til- : sætninger bagefter foretages ved hjælp af vandige opløsninger af additiverne, vil dette også påvirke fugtighedsindholdet, 35 men dette vil i reglen holdes i intervallet 1 - 12% for slut produktet, der sommetider kan udvides til 15%.The intervals and amounts of the various bead components in the spray-dried portion of the final cleaner when no silicate or little silicate is present can be calculated in the manner previously described. In the case of subsequently added components, the percentage of: nonionic detergent will be the same as previously stated, the percentage of perfume in the final product will be in the range 0.1 - 1%, preferably 0.2 - 0.4%, the percentage of enzyme will be from 0.5 to 3%, preferably 1-2%, and if an aqueous silicate is added afterwards, the amount thereof will normally be from 2 to 10%, preferably 3 - 8%, e.g. 5%. When an emollient: compound is present in the final product, the amount thereof for 20 will normally be in the range of 3 - 12%, preferably 5 - 10%, and when anionic detergents are used, the amount thereof will be limited to no more than the amount of non-ionic de- tergent, and the total weight of anionic and non-ionic de-; tergent in the final product will be in the range of time! 25 are listed for non-ionic detergent alone. If an anionic detergent is used, the amount present] will normally be in the range of 0.2 - 0.8 times the weight of] nonionic detergent. In order to calculate the intervals for per- form components in the final mean, these calculations must be calculated | 30, in addition to being based on the percentage of non-ionic detergent in the final product (added afterwards), is based on the percentages of other subsequently added substances. Afterwards, if some additions are made using aqueous solutions of the additives, this will also affect the moisture content, but this will generally be kept in the range 1 - 12% for the end product, which can sometimes be extended to 15%.
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1515
Grundperlerne i rensemidlet ifølge opfindelsen sprøjtetørres af en vandig blanding fra et blandeapparat, der normalt vil indeholde fra ca. 40 til ca. 70 eller 75% fast stof, fortrinsvis 50 - 65% deraf, idet resten er vand, fortrinsvis afioniseret vand 5 som tidligere beskrevet, men postevand kan også anvendes.The basic beads of the cleaner according to the invention are spray dried by an aqueous mixture from a mixer which will normally contain from approx. 40 to approx. 70 or 75% solids, preferably 50-65% thereof, the remainder being water, preferably deionized water 5 as previously described, but tap water can also be used.
Sammensætningerne af blandingen i blandeapparatet kan beregnes af de ønskede sammensætninger af grundperlerne på grundlag af fugtighedsindholdet af perlerne og blandingen. I en blanding i blandeapparatet, der skal indeholde 50% fugtighed, 10 og hvoraf der skal fremstilles en blanding af grundperler indeholdende 5% fugtighed (idet der ses bort fra zeolittens hydratiseringsvand), skal procenterne af komponenterne i grundperlen multipliceres med 10/19, hvilket er (100/2(100-5]). De ovenstående beregninger er tilfredsstillende for komponenter, 15 som ikke dekomponerer ved sprøjtetørringen, men det er kendt, at en del af bicarbonatet ændres til carbonat, når det tørres ved forhøjet temperatur i et sprøjtetårn. Når man derfor kender egenskaberne af tårnet og tørrebetingelserne, således at omfanget af bicarbonatdekomponeringen kan forudsiges, 20 kan man beregne den mængde carbonat og bicarbonat, man skal have i blandingen i blandeapparatet. Når man f.eks. ønsker at fremstille et produkt, der indeholder ca. 22% natrium= carbonat og ca. 16% natriumbicarbonat, kan man i de tilfælde, hvor ca. 1/3 af bicarbonatet dekomponerer til carbonat i 25 sprøjtetårnet (hvor 2 dele carbonat fremkommer af 3 dele de- komponeret bicarbonat), indføre 24% bicarbonat og 17% car= bonat i blandeapparatet (beregnet på tørstof).The compositions of the mixture in the mixer can be calculated from the desired compositions of the base beads on the basis of the moisture content of the beads and the mixture. In a mixture in the mixer to contain 50% moisture, 10 and from which a mixture of basic beads containing 5% moisture (excluding the hydration water of the zeolite) must be prepared, the percentages of the components in the basic bead must be multiplied by 10/19, The above calculations are satisfactory for components which do not decompose by spray drying, but it is known that part of the bicarbonate is changed to carbonate when dried at elevated temperature in a spray tower. Therefore, knowing the properties of the tower and the drying conditions so that the extent of the bicarbonate deposition can be predicted, 20 one can calculate the amount of carbonate and bicarbonate to be contained in the mixture in the mixer. contains about 22% sodium = carbonate and about 16% sodium bicarbonate, in cases where about 1/3 of the bicarbonate decomposes to carbonate in 25 brittle The tower (where 2 parts of carbonate is formed from 3 parts of decomposed bicarbonate), introduce 24% bicarbonate and 17% carbonate into the mixer (based on dry matter).
Med hensyn til de forskellige sammensætninger og beregninger 30 vil det ses, at zeolitten i blandingen i blandeapparatet og i de sprøjtetørrede grundperler og rensemidlet er hydratise-ret i et omfang af ca. 20% hydratiseringsvand, men hydrati-seringsgraden kan variere. Af hensyn til konsekvente resultater og med henblik på disse beregninger vil en sådan kon-35 stant hydratiseringsgrad dog blive antaget.With regard to the various compositions and calculations 30, it will be seen that the zeolite in the mixture in the mixer and in the spray-dried primer beads and the cleaner is hydrated to an extent of approx. 20% hydration water, but the degree of hydration may vary. However, for consistent results and for the purposes of these calculations, such a constant degree of hydration will be assumed.
Blandingen i blandeapparatet, hvoraf grundperlerne fortrinsvis fremstilles ved sprøjtetørring, er en, 16The mixture in the mixer, the base beads being preferably prepared by spray drying, is one, 16
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der hovedsagelig er uorganisk, og indholdet af organisk materiale er i reglen begrænset til 10%, fortrinsvis til 7% og især til 4%, beregnet på fast stof. Blandt de organiske ma-. terialer, som kan være til stede, er citronsyrematerialer 5 (citronsyre og opløselige citrater), fluorescerende klarings- midler, farvestoffer og pigmenter. Andre orga niske materialer kan også være til stede, herunder hydrotrope salte,chelateringsmidler og polyelektrolytter, men det er klart, at blandingen i blandeapparatet vil forblive over-0 vejende af uorganiske materialer og vand.which is mainly inorganic and the content of organic matter is usually limited to 10%, preferably to 7% and especially to 4%, based on solid. Among the organic ma-. Materials that may be present are citric acid materials 5 (citric acid and soluble citrates), fluorescent brighteners, dyes and pigments. Other organic materials may also be present, including hydrotropic salts, chelating agents and polyelectrolytes, but it is clear that the mixture in the mixer will remain predominantly of inorganic materials and water.
Blandingen i blandeapparatet fremstilles fortrinsvis ved tilsætning i rækkefølge af forskellige komponenter på en måde, som resulterer i den mest muligt blandbare, let pumpelige 15 og ikke udfældende opslæmning til sprøjtetørring. Rækkeføl- ; gen af tilsætning af de forskellige komponenter kan varieres, afhængende af omstændighederne, men det er meget ønskeligt at tilsætte den eventuelle silikatopløsning sidst, og hvis det ikke er .til sidst, så i det mindste efter tilsætningen af 2q en eventuel gelhindrende eller størkningshindrende kombina tion af materialer eller forarbejdningshjælpemidler. Normalt j foretrækkes det, at alt eller næsten alt vandet sættes til 1 i blandeapparatet først, fortrinsvis ved ca. forarbejdningstemperaturen, hvorefter forarbejdningshjælpemidlerne (hvis 2g sådanne anvendes) og andre mindre komponenter, herunder pig menter og fluorescerende klaringsmidler tilsættes, efterfulgt j af bentonit,' zeolit, bicarbonat, carbonat. og silikat (hvis j dette anvendes). Under sådanne tilsætninger vil hver kompo- | nent i reglen blive- blandet grundigt før tilsætning af næste S 30 komponent, men tilsætningsmåder kan varieres, afhængende af j omstændighederne, således at samtidige tilsætninger kan til- j lades, når dette er muligt. Sommetider kan tilsætninger af . en komponent såsom silikattilsætninger ske i to eller flere dele. Forskellige komponenter kan forblandes før tilsætnin- ; 35 gen for at fremskynde blandingsprocessen. Normalt vil blan dingshastighed og blandekraft blive forøget, efterhånden somThe mixing in the mixer is preferably prepared by adding in order of various components in a manner which results in the most miscible, easily pumpable and non-precipitating slurry for spray drying. Sequence; gene of addition of the various components may be varied, depending on the circumstances, but it is highly desirable to add the possible silicate solution last, and if it is not eventually, then at least after the addition of 2q, any gel antifouling or antifouling combination may be added. of materials or processing aids. Normally, it is preferred that all or nearly all of the water be added to 1 in the mixer first, preferably at approx. the processing temperature, after which the processing aids (if 2g used) and other minor components, including pigments and fluorescent clarifiers, are added, followed by j of bentonite, zeolite, bicarbonate, carbonate. and silicate (if used). During such additions, each compo- | Generally, mix thoroughly before adding the next S 30 component, but modes can be varied, depending on the circumstances, so that concurrent additions can be allowed when possible. Sometimes additions of. a component such as silicate additives occurs in two or more parts. Various components may be premixed before addition; 35 gene to speed up the mixing process. Normally, the mixing speed and mixing force will be increased as
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17 materialerne tilsættes. For eksempel kan lave hastigheder anvendes indtil efter iblanding af den sidste af bentonit eller zeolit, hvorefter hastigheden kan forøges til middelhastighed og derefter til høj hastighed før, under eller ef-5 ter tilsætning af eventuel silikatopløsning.17 materials are added. For example, low rates may be used until after the last of the bentonite or zeolite is admixed, after which the rate may be increased to medium speed and then to high speed before, during, or after addition of any silicate solution.
Temperaturen af det vandige medium i blandeapparatet vil i reglen være omkring stuetemperatur eller højere temperatur og er normalt i intervallet 20 - 80°C, fortrinsvis 30 - 75°C og især 40 - 70°C. Opvarmning af mediet i blandeapparatet 10 kan fremme opløsning af de vandopløselige salte i blandingen og derved forøge blandbarheden, men opvarmning, når den foretages i blandeapparatet, kan nedsætte produktionshastigheden og kan fremme udfældning af blandingen. En fordel ved at have forarbejdningshjælpemidler i blandingen er derfor, 15 at de sikrer, at de ønskelige ikke-gelerende opslæmninger fremkommer ved både lavere og højere temperaturer. Temperaturer højere end 80°C (og sommetider 70°C) undgås i reglen på grund af muligheden af dekomponering af en eller flere komponenter i blandingen, f.eks. natriumbicarbonat. I nogle 20 tilfælde forøger lavere temperaturer i blandeapparatet også de øvre grænser for faststofindholdet i blandeapparatet, sandsynligvis på grund af uopløseliggøreIse af normalt gelerende eller størknende komponenter.The temperature of the aqueous medium in the mixer will generally be around room temperature or higher temperature and is usually in the range of 20 - 80 ° C, preferably 30 - 75 ° C and especially 40 - 70 ° C. Heating the medium in the mixer 10 can promote dissolution of the water-soluble salts in the mixture, thereby increasing the miscibility, but heating when done in the mixer can slow down the production rate and promote precipitation of the mixture. An advantage of having processing aids in the mixture is therefore that they ensure that the desirable non-gelling slurries appear at both lower and higher temperatures. Temperatures higher than 80 ° C (and sometimes 70 ° C) are usually avoided due to the possibility of decomposition of one or more components of the mixture, e.g. sodium bicarbonate. In some 20 cases, lower temperatures in the mixer also increase the upper limit of the solids content of the mixer, probably due to insolubilization of normally gelling or solidifying components.
Blandetider for at opnå gode opslæmninger kan variere meget, 25 fra så lidt som 5 minutter i små blandeapparater og for opslæmninger med højere fugtighedsindhold til så meget som 4 timer i nogle tilfælde. De blandetider, der er nødvendige for at føre alle komponenterne i blandingen i hovedsagen homogent sammen i ét medium, kan være så lidt som 10 minutter, 30 men kan i nogle tilfælde vare op til 1 time, selv om 30 minutter fortrinsvis er den øvre grænse. Under medregning af sådanne indledende blandetider vil normale perioder i blandeapparatet være fra 15 minutter til 2 timer, f.eks. 20 minutter til 1 time, men blandingen i blandeapparatet skal være således, 18Mixing times to obtain good slurries can vary greatly, from 25 as little as 5 minutes in small mixers and for slurries with higher moisture content to as much as 4 hours in some cases. The mixing times required to bring all the components of the mixture substantially homogeneously together in one medium may be as little as 10 minutes, 30 but in some cases may last up to 1 hour, although 30 minutes is preferably the upper limit. . Taking such initial mixing times into account, normal periods in the mixer will be from 15 minutes to 2 hours, e.g. 20 minutes to 1 hour, but the mixture in the mixer should be thus, 18
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at den er bevægelig/ ikke geleret eller størknet i mindst én time, fortrinsvis i 2 timer og bedst i 4 timer eller mere, efter fuldendelse af fremstillingen af blandingen, og kan endog være bevægelig i så meget som 10 - 30 timer før udpump-5 ning til sprøjtetårnet i situationer, hvor andre fremstillingsproblemer kan indtræffe.it is movable / non-gelled or solidified for at least one hour, preferably for 2 hours and best for 4 hours or more, after completion of the preparation of the mixture, and may even be movable for as much as 10-30 hours before pump-out to the spray tower in situations where other manufacturing problems may occur.
Den blandede opslæmning med de forskellige salte og andre komponenter, der er opløst eller i partikelform, ensartet fordelt deri, overføres på sædvanlig måde til et sprøjte-10 tørringstårn, der normalt er beliggende nær ved blandeappa-ratet. Opslæmningen falder fra bunden af blandeapparatet til en positiv fortrængningspumpe, som tvinger den ved højt tryk gennem sprøjtedyser i toppen af et sædvanligt sprøjtetårn (medstrøm eller modstrøm), hvori de små dråber af opslæm-15 ning falder gennem en varm tørregas, i reglen forbrændingsprodukterne af brændselsolie eller naturgas, hvori dråberne i tørres til den ønskede absorberende perleform. Under tørrin- j gen kan en del af bicarbonatet (ofte fra 1/4 til 1/2, f.eks.The mixed slurry with the various salts and other components dissolved or in particulate form, uniformly distributed therein, is transferred in the usual manner to a spray-drying tower which is normally located near the mixing apparatus. The slurry falls from the bottom of the mixer to a positive displacement pump which forces it at high pressure through spray nozzles at the top of a conventional spray tower (co-current or countercurrent), wherein the small droplets of slurry fall through a hot drying gas, usually the combustion products of fuel oil or natural gas in which the droplets are dried to the desired absorbent bead form. During drying, a portion of the bicarbonate (often from 1/4 to 1/2, e.g.
1/3) blive omdannet til carbonat med frigørelse af kuldioxid, j 20 der sammen med indholdet af polyacrylat, som kan være til i stede i blandingen, der sprøjtetørres, kan forbedre de fysi- j ske egenskaber af de fremstillede perler, således at de bli- j ver mere absorberende for væsker såsom flydende ikke-ionisk j detergent, der bagefter kan sprøjtes på dem. Zeolit- og ben-25 tonitkomponenter i de fremstillede perler synes også at fremme J absorption af væske.1/3) be converted to carbonate with carbon dioxide release, 20 which, together with the content of polyacrylate which may be present in the mixture which is spray dried, can improve the physical properties of the beads made so that become more absorbent of liquids such as liquid non-ionic detergent, which can subsequently be sprayed onto them. Zeolite and bone-25 tonite components in the beads made also appear to promote J absorption of liquid.
Efter tørring sigtes produktet til den ønskede størrelse, 1 f.eks. 10 - 60 eller 100 US standard-sigte, og er parat til ’ 30 påføring af ikke-ionisk detergent sprøjtet derpå, idet perlerne enten er i varm eller afkølet (til stuetemperatur) tilstand. Den ikke-ioniske detergent vil dog i reglen være ved en forhøjet temperatur såsom 30 - 60°C, f.eks. 50°C, for at sikre, at den er flydende. Dog vil den efter afkøling tilAfter drying, the product is sieved to the desired size, e.g. 10 - 60 or 100 US standard sieve, and is ready for 30 non-ionic detergent application sprayed thereon, the beads being either in hot or cooled (to room temperature) state. However, the nonionic detergent will generally be at an elevated temperature such as 30 - 60 ° C, e.g. 50 ° C to ensure that it is liquid. However, after cooling it will
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19 stuetemperatur hensigtsmæssigt være et fast stof, der ofte ligner et voksagtigt fast stof. Selv om den ikke-ioniske detergent ved stuetemperatur er noget klæbrig, gør denne egenskab ikke slutproduktet dårligt strømmende, fordi deter-5 genten trænger ned under (eller ind i) perleoverfladen.19 room temperature may conveniently be a solid often resembling a waxy solid. Although the nonionic detergent at room temperature is somewhat sticky, this property does not make the final product poorly flowing because the detergent penetrates below (or into) the bead surface.
Den ikke-ioniske detergent påført på perler, der er i bevægelse eller omvæltes på kendt måde, som en udsprøjtet væske eller som små dråber, er fortrinsvis et kondensationsprodukt af ethylenoxid og højere fedtalkohol, som tidligere 10 beskrevet, men andre ikke-ioniske stoffer kan også anvendes. Enzympræparatet (i det foreliggende omtalt som enzym, selv om det erkendes, at det også indeholder et bæremateriale), vandholdigt silikat og eventuelle andre pulveriserede tilsætninger, der skal tilsættes bagefter, må støves på detergent-15 partiklerne, og parfume og eventuelle andre væsker kan sprøjtes på på et egnet punkt før eller efter tilsætning af pulver.The nonionic detergent applied to beads which are moving or reversed in known manner, as an sprayed liquid or as small droplets, is preferably a condensation product of ethylene oxide and higher fatty alcohol, as previously described, but other nonionic substances may also used. The enzyme preparation (hereinafter referred to as enzyme, although recognized to contain a carrier material), aqueous silicate and any other powdered additives to be added afterwards, must be dusted on the detergent particles and perfume and any other liquids may sprayed on at a suitable point before or after the addition of powder.
De sprøjtetørrede grundperler og rensemidlerne fremstillet deraf kan indeholde intet eller kun en lille mængde silikat fra blandingen i blandeapparatet, og i sådanne tilfælde kan 20 silikat i fast form tilsættes bagefter. Det bagefter tilsatte pulveriserede silikat, hvis et sådant anvendes, synes ikke at reagere med zeolitten ret meget, således at agglomera-ter af zeolit og silikat, der er tilbøjelige til at aflejre sig på vaskede genstande, formindskes. De foreliggende 25 rensemidler har vist sig ikke at korrodere aluminiumgenstande, selv uden silikat. Endvidere har bentonit ikke nogen skadelig virkning på stabiliteten af produktet og synes faktisk at hjælpe til at holde perlerne sammen og gøre dem modstandsdygtige mod knusning og pulverisering 30 under forsendelse og brug. Tilstedeværelse af bentonit forbedrer kendeligt egenskaberne af det endelige rensemiddel, idet bentonit frembringer højere calciumion-bindingsevne og resulterer i, at mindre zeolit aflejres på vaskede stoffer. I betragtning af, at bentonit er en 35 lerart og kunne forventes at skabe aflejrings- og gele-The spray-dried primer beads and the cleaners prepared therefrom may contain no or only a small amount of silicate from the mixture in the mixer, and in such cases 20 solid silicate may be added afterwards. The powdered silicate subsequently added, if used, does not appear to react very much with the zeolite, so that zeolite and silicate agglomerates which tend to deposit on washed articles are diminished. The present cleaning agents have been found not to corrode aluminum objects, even without silicate. Furthermore, bentonite has no detrimental effect on the stability of the product and in fact appears to help hold the beads together and make them resistant to crushing and pulverization during shipping and use. Presence of bentonite appreciably improves the properties of the final detergent as bentonite produces higher calcium ion binding capacity and results in less zeolite deposited on washed substances. Given that bentonite is a clay species and could be expected to create deposition and gelation.
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20 ringsproblemer i sig selv, er den nedsatte aflejring af zeolit og fravær af gelering overraskende og er vigtige resultater af den foreliggende opfindelse.In itself, the reduced deposition of zeolite and the absence of gelling are surprising and are important results of the present invention.
5 De følgende eksempler illustrerer- opfin delsen. Mad mindre andet er anført, er alle temperaturer i °C, og 1 alle dele er efter vægt i eksemplerne og i beskrivelsen. Når vægte og mængder af zeolit er anført, skal disse være for det normale hydrat, der anvendes, fordi det menes, at zeolit-10 tens hydratiseringsvand ikke forlader zeolitten dg ikke bli ver en del af det vandige opløsende medium ved de foreliggende blandinger, og også fordi noget af vandet, der findes i grundperlerne og rensemidlerne, er til stede som zeolittens hydratiseringsvand.The following examples illustrate the invention. Unless otherwise stated, all temperatures are in ° C and 1 all parts are by weight in the Examples and in the specification. When weights and amounts of zeolite are listed, these should be for the normal hydrate used because it is believed that the hydration water of the zeolite does not leave the zeolite and does not become part of the aqueous dissolving medium of the present mixtures, and also because some of the water found in the foundation beads and cleansers is present as the hydration water of the zeolite.
15 EKSEMPEL 1,EXAMPLE 1,
Et parti på 4.536 kg af en blanding i et blandeapparat til. sprøjtetørring til grundperler ifølge opfindelsen og omdan-20 nelse til et rensemiddel fremstilles ved til blandeapparatet at sætte 1.832 kg afioniseret vand med en temperatur på ca.A portion of 4,536 kg of a mixture in a mixer. spray drying for basic beads according to the invention and conversion to a cleaning agent is prepared by adding to the mixer 1,832 kg of deionized water at a temperature of approx.
27°C og derpå med lav blandehastighed at iblande 51,3 kg vandfrit magniumsulfat (105,5 kg epsomsalt kan anvendes i stedet, i hvilket tilfælde det oprindeligt tilsatte vand reduceres 25 til 1.777,4 kg)/ 12,7 kg citronsyre, 57,6 kg TINOPAL 5BM, eks- ; tra concentreret, Ciba-Geigy), 68 kg ultramarinblåt pulver, | 169,6 kg THIXO-JEL nr. 1 (bentonit), 914 kg Linde hydratise- 1 ret Zeolit 4A (20% krystallisationsvand), 636,9 kg natriumbi= j carbonat og 456,3 kg natriumcarbonat (vandfrit). Blanderens ! 30 hastighed forøges så til stor hastighed (i nogle tilfælde kan den forøges til middelhastighed på et tidligere tidspunkt, , hvis blandingen ikke blandes så godt som ønsket), og der iblandes 189,6 kg natriumsilikat med et Na20:Si02-forhold på 1:2,4 (som 399,2 kg af en 47,5% vandig opløsning). Blan-35 ding af hele partiet fortsætter i ca. 1 time (i nogle tilfæl de kan bruges så meget som 4 timers blanding), hvorunder ca.27 ° C and then mixing at a low mixing rate 51.3 kg of anhydrous magnesium sulfate (105.5 kg of Epsom salt can be used instead, in which case the initially added water is reduced 25 to 1,777.4 kg) / 12.7 kg of citric acid, 57 , 6 kg TINOPAL 5BM, ex-; tra concentrated, Ciba-Geigy), 68 kg ultramarine blue powder, | 169.6 kg of THIXO-JEL No. 1 (bentonite), 914 kg of Linde hydrated Zeolite 4A (20% crystallization water), 636.9 kg of sodium bis = 1 carbonate and 456.3 kg of sodium carbonate (anhydrous). Mixer! 30 speed is then increased to high speed (in some cases it can be increased to medium speed at an earlier stage if the mixture is not mixed as well as desired) and 189.6 kg of sodium silicate with a Na 2 O: SiO 2 ratio of 1: 2.4 (as 399.2 kg of a 47.5% aqueous solution). Mixing of the whole batch continues for approx. 1 hour (in some cases they can be used as much as 4 hours of mixing), during which approx.
90,7 - 272,2 kg vand kan gå tabt ved fordampning, hvilket90.7 - 272.2 kg of water can be lost by evaporation, which
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21 vand kan erstattes, hvis det ønskes. Under blandingen er opslæmningen i blandeapparatet kontinuerligt bevægelig og gelerer ikke, størkner ikke og bager ikke sammen. Fordi bi= carbonat delvis dekomponerer til carbonat under sprøjtetør-5 ringen, kan mængderne deraf varieres, afhængende af sprøjte tårnets egenskaber.21 water can be replaced if desired. During the mixing, the slurry in the mixer is continuously movable and does not gel, solidify or bake together. Because bi = carbonate partially decomposes to carbonate during the spray drying, the amounts thereof can be varied depending on the characteristics of the spray tower.
Begyndende ca. 5 minutter efter, at alle komponenterne i blandingen er til stede, lader man blandingen falde fra blan-10 deapparatet til en pumpe, som pumper den med et tryk på ca.Starting approx. Five minutes after all the components of the mixture are present, the mixture is dropped from the mixing apparatus to a pump which pumps it at a pressure of approx.
21 kg pr. cm ind foroven i et modstrømssprøjtetårn, hvor begyndelsestemperaturen er ca. 430°C og sluttemperaturen ca. 105°C. De i det væsentlige uorganiske grundperler, der fremkommer, har en masserumvægt på ca. 0,6 - 0,7 g pr. ml, en be-15 gyndelsesklæbning, der nærmer sig 40%, et partikelstørrelses interval i det væsentlige mellem 10 og 100 mesh, US standardsigte (de sigtes til dette interval) og har en andel fint materiale på ca. 15% (gennem US sigte nr. 50). Perlernes fug-tighedsindhold er ca. 7%. Grundperlerne viser sig at være 20 fritstrømmende, ikke-klæbrige, tilfredsstillende porøse, men alligevel faste på overfladerne og er i stand til let at absorbere betydelige mængder flydende ikke-ionisk detergent uden at blive for klæbrige.21 kg per cm into the top of a countercurrent spray tower, where the initial temperature is approx. 430 ° C and the final temperature approx. 105 ° C. The essentially inorganic base beads that appear have a mass compartment weight of approx. 0.6 - 0.7 g per a starting adhesive approaching 40%, a particle size range substantially between 10 and 100 mesh, US standard sieve (sieved to this range), and having a proportion of fine material of approx. 15% (through US Sieve No. 50). The moisture content of the beads is approx. 7%. The primer beads are found to be 20 free-flowing, non-sticky, satisfactorily porous, yet solid on the surfaces and capable of easily absorbing significant amounts of liquid non-ionic detergent without becoming too sticky.
25 Rensemiddelprodukter fremstilles af de sprøjtetørrede perler ved på overfladerne af de omvæltende perler at sprøjte en normalt voksagtig ikke-ionisk detergent, enten NEODOL 23-6.5 eller NEODOL 23-7, i opvarmet flydende tilstand i en sådan mængde, at der fås et slutprodukt indeholdende 20% ikke-30 ionisk detergent, og proteolytisk enzym (ALCALASE) påføres i pulverform, således at der fås en koncentration på 1,99% i produktet. Parfume sprøjtes på produktet, således at der fås en koncentration på 0,25% deri. De fremkomne rense-middelprodukter har en rumvægt på ca. 0,7 eller 0,8 g pr.Detergent products are prepared from the spray-dried beads by spraying a normally waxy non-ionic detergent, either NEODOL 23-6.5 or NEODOL 23-7, in the heated liquid state in an amount to provide an end product containing 20% non-ionic detergent and proteolytic enzyme (ALCALASE) are applied in powder form to obtain a concentration of 1.99% in the product. Perfume is sprayed onto the product to give a concentration of 0.25% therein. The resulting detergent products have a room weight of approx. 0.7 or 0.8 g per
35 ml og indeholder 27,3% zeolit (hydratiseret), 20,1% ikke- ionisk detergent, 17,8% natriumcarbonat (hvoraf noget produceres ved dekomponering af natriumbicarbonat), 12,7% na= triumbicarbonat, 5,6% natriumsilikat, 5,45% vand, 2,0% enzym, 2235 ml and contains 27.3% zeolite (hydrated), 20.1% nonionic detergent, 17.8% sodium carbonate (some of which is produced by decomposition of sodium bicarbonate), 12.7% Na = tri-bicarbonate, 5.6% sodium silicate , 5.45% water, 2.0% enzyme, 22
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1,7% fluorescerende klaringsmiddel, 1,5% magniumsulfat, 0,4% citronsyre (i form af citrat), 0,25% parfume, 0,2% ultramarinblåt, 5,0% bentonit (THIXO-JEL). Det fremstillede rensemiddel af den ovennævnte sammensætning er et udmærket kraftigt 5 virkende tøjvaskemiddel og er særligt nyttigt til vask af husholdningsvask i automatiske vaskemaskiner. Det er fysisk og æstetisk fordelagtigt og tiltalende, fordi det ikke støver og er meget fritstrømmende, således at det kan pakkes i glas-og plasticflasker med snæver hals, hvorfra det strømmer let 10 ved udtømning. Rensemidlerne ifølge opfindelsen indeholdende bentonit som beskrevet viser sig at have betydeligt forbedret calciumionbindeevne, men vigtigere er det, at de efterlader mindre rest på tøj, som er vasket dermed (i en automatisk vaskemaskine med sædvanlige koncentrationer for et sådant pro-15 dukt og ved normale vasketemperaturer) end lignende midler, der ikke indeholder bentonit,gør. Denne forskel fremhæves, når vaskevandet har høj hårdhed, f.eks. 200 ppm som calcium= carbonat, vaskevandet er koldt, og der anvendes mild omrøring.1.7% fluorescent brightening agent, 1.5% magnesium sulfate, 0.4% citric acid (in the form of citrate), 0.25% perfume, 0.2% ultramarine blue, 5.0% bentonite (THIXO-JEL). The fabricated cleaner of the above composition is an excellent powerful laundry detergent and is particularly useful for washing household laundry in automatic washing machines. It is physically and aesthetically advantageous and appealing because it does not dust and is very free-flowing so that it can be packed in glass and plastic bottles with narrow necks, from which it flows easily 10 upon discharge. The cleaning agents of the invention containing bentonite as described are found to have significantly improved calcium ion binding capacity, but more importantly they leave less residue on clothes which are washed therewith (in an automatic washing machine with usual concentrations for such a product and at normal washing temperatures) than similar agents that do not contain bentonite do. This difference is highlighted when the wash water has a high hardness, e.g. 200 ppm as calcium = carbonate, the wash water is cold and gentle stirring is used.
20 Ved et kontrolforsøg fremstilles grundperler, hvori bentonitten | er udeladt fra blandingen i blandeapparatet, og erstattes med lige så store vægtmængder natriumcarbonat og natriumbicarbo= i nat, idet den samlede mængde tilsatte materialer er lig med i vægten af den erstattede bentonit. Blandingen fra blandeappa- ; 25 ratet sprøjtetørres og omdannes til et rensemiddel på samme i måde som anvendt til fremstilling af rensemidlet ifølge op- j findelsen. Dette kontrolprodukt, der ganske vist er nyttigt j20 In a control experiment, ground beads are prepared in which the bentonite | is omitted from the mixture in the mixer, and is replaced by equal weight amounts of sodium carbonate and sodium bicarbonate = night, the total amount of added materials being equal to the weight of the bentonite replaced. The mixture from the mixing apparatus; The rat is spray dried and converted to a detergent in the same manner as used to prepare the detergent according to the invention. This control product which is admittedly useful j
som rensemiddel, resulterer i, at mere rest aflejres på va- Ias a cleanser, more residue is deposited on the va- I
sket tøj end med forsøgsproduktet ifølge opfindelsen, og det j 30 har mindre calciumbindeevne. Når på lignende måde indholdet i i af silikat i kontrolperlerne forøges til 10,7%, idet koncen- i trationerne af natriumcarbonat og natriumbicarbonat nedsæt- j sættes for at kompensere for den forøgede mængde silikat, er aflejringen af rest endnu værre end med kontrollen.made clothes than with the test product of the invention and it has less calcium binding capacity. Similarly, when the content of silicate in the control beads is increased to 10.7%, when the concentrations of sodium carbonate and sodium bicarbonate are reduced to compensate for the increased amount of silicate, the deposition of residue is even worse than with the control.
Ved at følge normal fremgangsmåde fremstilles blandinger i blandeapparatet hurtigt og kan udtømmes fra blandeapparatet 35 23Following the normal procedure, mixtures in the mixer are prepared quickly and can be discharged from the mixer 35 23
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lige så hurtigt og kan sommetider fremstilles i en periode så kort som 5 minutter og pumpes ud af blandeapparatet på så kort tid som 10 minutter. Alligevel er det ofte vigtigt, at de foreliggende blandinger kan modstå mindst 1 time i 5 blandeapparatet uden at gelere eller størkne, fordi der somme tider forekommer opholdstider af denne størrelsesorden i industriel produktion. Den beskrevne blanding i blandeapparatet kan holdes så længe som 4 timer og ofte betydeligt længere uden at gelere eller størkne, hvilket tilskrives, i det 10 mindste delvis, indholdet af magniumsulfat og citronsyre som forarbejdningshjælpemidler. I stedet for kan der dog anvendes andre forarbejdningshjælpemidler, beregnet til at forhindre gelering og størkning af blandingerne i blandeapparatet, og under nogle omstændigheder kan mængderne deraf nedsættes, 15 og den ene eller begge kan udelades. På lignende måde kan andre mindre komponenter af blandingen i blandeapparatet såsom det fluorescerende klaringsmiddel og pigment udelades, og enzym og parfume kan udelades af slutproduktet, omend det meget foretrækkes, at alle disse materialer er til stede.just as fast and can sometimes be produced for a period as short as 5 minutes and pumped out of the mixer in as short a time as 10 minutes. Still, it is often important that the present compositions be able to withstand at least 1 hour in the mixer without gelling or solidifying, because sometimes residence times of this magnitude occur in industrial production. The mixture described in the mixer can be kept for as long as 4 hours and often considerably longer without gelling or solidifying, which is attributed, at least in part, to the content of magnesium sulfate and citric acid as processing aids. However, other processing aids may be used instead to prevent gelling and solidification of the blends in the mixer, and in some circumstances the amounts thereof may be reduced, and one or both may be omitted. Similarly, other minor components of the blend in the blender such as the fluorescent clarifier and pigment may be omitted and enzyme and perfume may be omitted from the final product, although it is highly preferred that all of these materials be present.
20 Temperaturen af blandingen i blandeapparatet kan modificeres, f.eks. ved forhøjelse til 52°C, og mængderne af de forskellige 4· “f* 4* komponenter kan varieres -10%, -20% og -30% og alligevel holdes inden for de foran anførte intervaller, og der kan fås bearbejdelige blandinger, som resulterer i de ønskede perler og 25 rensemidler.The temperature of the mixture in the mixer can be modified, e.g. at elevation to 52 ° C, and the amounts of the various 4 · “f * 4 * components can be varied -10%, -20% and -30% and yet kept within the ranges specified above and machinable mixtures available, which results in the desired beads and cleansers.
I stedet for at anvende vandfrit magniumsulfat kan der benyttes en ækvivalent mængde epsomsalt, og forskellige andre komponenter kan tilsættes som vandige opløsninger, forudsat at 30 de mængder fugtighed, som tilsættes sammen med dem, trækkes fra den, der sættes til blandeapparatet. Andre rækkefølger af tilsætningen kan anvendes, men normalt er det ønskeligt, at forarbejdningshjælpemidlerne tilsættes tidligt under fremstillingen, og at silikatet tilsættes sidst eller nær slutnin-35 gen. I stedet for at anvende Zeolit 4A kan der anvendes Zeo lit X og Y og andre typer Zeolit A. Det foretrækkes at anvende hydratiseret Zeolit 4A som i dette eksempel, men for-Instead of using anhydrous magnesium sulfate, an equivalent amount of epsome salt can be used, and various other components can be added as aqueous solutions, provided that the amounts of moisture added thereto are subtracted from that added to the mixer. Other sequences of the additive may be used, but usually it is desirable that the processing aids are added early in the preparation and that the silicate is added at or near the end. Instead of using Zeolite 4A, Zeolite X and Y and other types of Zeolite A. can be used. It is preferred to use hydrated Zeolite 4A as in this example, but preferred.
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24 skellige grader af hydratisering af zeolitten er acceptable, og i nogle tilfælde kan anvendes næsten vandfri krystallinske zeolitter eller amorfe zeolitter. Variering af mængden af bentonit inden for det anførte interval til f.eks. 3% og 5 10% resulterer stadig i nyttige produkter, men de, der inde holder større mængder bentonit, vil i reglen være mere effektive til at forhindre zeolitaflejring på vasketøj. Den industrielt anvendte mængde vil dog afhænge af forskellige faktorer og vil normalt repræsentere en balance mellem den ønskede 10 formindskelse af zeolitresten og den ønskede opbygning og andre funktionelle virkninger af andre komponenter af rensemidlet.Twenty-four degrees of hydration of the zeolite are acceptable, and in some cases almost anhydrous crystalline zeolites or amorphous zeolites can be used. Variation of the amount of bentonite within the indicated range to e.g. 3% and 5 10% still result in useful products, but those containing larger amounts of bentonite will generally be more effective in preventing zeolite deposition on laundry. However, the amount of industry used will depend on various factors and will usually represent a balance between the desired reduction of the zeolite residue and the desired structure and other functional effects of other components of the detergent.
Fremstillingsmetoder med variationer som befekrevet i eksempel 1 kan følges, og visse tilsætninger kan udelades som 15 beskrevet deri. Mængder af de forskellige komponenter kan + + 4* varieres -10%, -20% og -30% og stadig være inden for de anførte intervaller, og der vil fås bearbejdelige blandinger i blandeapparatet, som resulterer i de ønskede perler og rensemidler. Indholdet af fast stof i blandingen i blandeappara-20 tet kan varieres inden for det nævnte interval, f.eks. til 45% og 65%, og der kan fås god blanding og sprøjtetørring.Preparation methods with variations as described in Example 1 may be followed and certain additions may be omitted as described therein. Amounts of the various components may be + + 4 * varied -10%, -20% and -30% and still be within the indicated ranges, and machinable mixtures will be obtained in the mixer resulting in the desired beads and cleaners. The solids content of the mixture in the mixing apparatus may be varied within said range, e.g. to 45% and 65%, and good mixing and spray drying is available.
I stedet for Zeolit 4A kan der anvendes Zeolit X og Y og an-dre typer Zeolit A. Det foretrækkes at anvende den hydrati-serede Zeolit 4A, men forskellige hydratise- 25 ringsgrader af zeolitten er acceptable, og i nogle tilfælde ' kan anvendes næsten vandfrie krystallinske zeolitter eller amorfe zeolitter. Variering af mængden af bentonit i det an- ] førte interval til 10 og 17% f.eks. resulterer stadig i nyt- j tige produkter, men de, der indeholder de større mængder ben= 30 tonit, vil i reglen være mere effektive til at hjælpe til at forhindre zeolitaflejring på vasketøj.Instead of Zeolite 4A, Zeolite X and Y and other types of Zeolite A. may be used. It is preferred to use the hydrated Zeolite 4A, but different degrees of hydration of the zeolite are acceptable and in some cases can be used almost anhydrous crystalline zeolites or amorphous zeolites. Variation of the amount of bentonite in the range indicated to 10 and 17% e.g. still results in useful products, but those containing the larger amounts of bone = 30 tonite will generally be more effective in helping prevent zeolite deposition on laundry.
Den iagttagne forbedring af rensemidlerne ifølge opfindelsen med lavt indhold af opløseligt silikat eller uden silikat, der 35 består i aflejring af mindre rest på vasket tøj, bekræftes ved afprøvning af det beskrevne produkt sammenlignet med et kontrolprodukt af i hovedsagen samme sammensætning, men uden bentonit 25The observed improvement of the low-solubility soluble or silicate solvents of the invention consisting of depositing less residue on washed clothing is confirmed by testing the product described as compared to a control product of substantially the same composition but without bentonite.
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og indeholdende ca. 8% natriumsilikat. Ved denne bedømmelse anvendes en Whirlpool vaskemaskine/ hvor vaskeperioderne er 8 minutter i et mildt vaskeprogram. Rensemiddelkoncentrationen er 0/06%, vaskevandet har en blandet calcium- og magnium-5 hårdhed med en total hårdhed på 200 ppm, som calciumcarbonat, og vandets temperatur er 24°C. De vaskede dele er: 100% bom uld, 100% polyester, 85% acetat og 15% nylon samt 65% polyester og 35% bomuld. Vasken iagttages våd og efter tørring på snor. Der iagttages ingen rest i nogen af tilfældene. Når kontrol-10 vaskemidlet afprøves, iagttages moderat rest på alle forsøgs stykkerne.and containing ca. 8% sodium silicate. This rating uses a Whirlpool washing machine / where the washing periods are 8 minutes in a mild washing program. The detergent concentration is 0/06%, the wash water has a mixed calcium and magnesium hardness with a total hardness of 200 ppm, such as calcium carbonate, and the temperature of the water is 24 ° C. The washed parts are: 100% cotton wool, 100% polyester, 85% acetate and 15% nylon as well as 65% polyester and 35% cotton. The wash is observed wet and after drying on a leash. No residue is observed in any of the cases. When the control detergent is tested, moderate residue is observed on all the test pieces.
Resultaterne af de praktiske prøver med aflejrede rester, der er beskrevet ovenfor, bekræftes ved at veje aflejrede rester på et denim-forsøgsmateriale. Ved denne prøve filtreres et rensemiddel ifølge opfindelsen gennem en prøve af denimmateriale, idet rensemidlet er i en opløsningsuspension med en koncentration på 0,12% i vand med en hårdhed på 200 ppm (som CaCOg) ved 24°C. Vægten af resten på stoffet noteres og sammenlignes med den i et kontrolforsøg.The results of the practical residue samples described above are confirmed by weighing deposited residues on a denim test material. In this test, a detergent according to the invention is filtered through a sample of denim material, the detergent being in a solution suspension with a concentration of 0.12% in water with a hardness of 200 ppm (as CaCOg) at 24 ° C. The weight of the remainder on the substance is noted and compared with that in a control experiment.
2020
Ved denne afprøvning er procenten af rest sammenlignet med kontrollen ca. 75%, hvilket anses for en betydelig forbedring.In this test, the percentage of residue compared to the control is approx. 75%, which is considered a significant improvement.
Klæbeprøven, der tidligere er omtalt, som omtaler klæbrighe-2 5 , den af rensemiddelprodukter, er en prøve, ved hvilken 10 g grundperler (eller rensemiddel i nogle tilfælde) anbringes jævnt mellem to urglas, der begge har en diameter på ca.The adhesive test previously mentioned, which refers to tackiness, that of detergent products, is a test in which 10 g of primer beads (or detergent in some cases) are evenly placed between two watches, both of diameter approx.
23 cm, idet der er en vægt på 500 g oven på det øvre urglas (begge urglas har den konkave side opad). Efter henstand i 30 ca. 5 minutter fjernes vægten og det øverste urglas, og det nederste urglas vendes om, hvorefter produktet, der forbliver klæbet til urglasset, vejes. Den procentiske klæbning er antallet af gram produkt, som bliver tilbage på urglasset, divideret med 10 og multipliceret med 100.23 cm, with a weight of 500 g on top of the upper watch glass (both watch glasses have the concave side facing up). After standing for 30 approx. 5 minutes, the weight and upper watch glass are removed and the lower watch glass is inverted and the product remaining adhered to the watch glass is weighed. The percent adhesion is the number of grams of product left on the watch glass, divided by 10 and multiplied by 100.
Strømningsindekset er det, der fremkommer ved en strømningsprøve, ved hvilken de volumetriske strømningshastigheder af grundperler (og i nogle tilfælde slutprodukt) og standardise- 35The flow index is that which results from a flow test at which the volumetric flow rates of basic beads (and in some cases the final product) and standard
Claims (3)
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US23862081A | 1981-02-26 | 1981-02-26 | |
US23861981A | 1981-02-26 | 1981-02-26 | |
US23862081 | 1981-02-26 | ||
US23861981 | 1981-02-26 | ||
US27955081A | 1981-07-01 | 1981-07-01 | |
US27955081 | 1981-07-01 |
Publications (3)
Publication Number | Publication Date |
---|---|
DK83382A DK83382A (en) | 1982-08-27 |
DK160885B true DK160885B (en) | 1991-04-29 |
DK160885C DK160885C (en) | 1991-10-21 |
Family
ID=27399126
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DK083382A DK160885C (en) | 1981-02-26 | 1982-02-25 | Free-flowing spray-dried particulate detergent |
Country Status (22)
Country | Link |
---|---|
AT (1) | AT388172B (en) |
AU (1) | AU549000B2 (en) |
BR (1) | BR8200996A (en) |
CA (1) | CA1188953A (en) |
CH (1) | CH652416A5 (en) |
DE (1) | DE3206265A1 (en) |
DK (1) | DK160885C (en) |
DO (1) | DOP1982003096A (en) |
ES (1) | ES509904A0 (en) |
FR (1) | FR2500475B1 (en) |
GB (1) | GB2097419B (en) |
GR (1) | GR76028B (en) |
HK (1) | HK36190A (en) |
IE (1) | IE52739B1 (en) |
IT (1) | IT1147643B (en) |
MX (1) | MX158565A (en) |
NL (1) | NL8200804A (en) |
NO (1) | NO153736C (en) |
NZ (1) | NZ199773A (en) |
PT (1) | PT74486B (en) |
SE (2) | SE452773B (en) |
ZW (2) | ZW3282A1 (en) |
Families Citing this family (47)
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AU549122B2 (en) * | 1981-02-26 | 1986-01-16 | Colgate-Palmolive Pty. Ltd. | Spray dried base beads and detergent compositions |
ATE20476T1 (en) * | 1983-04-08 | 1986-07-15 | Procter & Gamble | GRANULATED DETERGENT COMPOSITIONS CONTAINING A MIXED POLYMER ADDITIVE SYSTEM. |
US4490271A (en) * | 1983-06-30 | 1984-12-25 | The Procter & Gamble Company | Detergent compositions containing polyethylene glycol and polyacrylate |
US4510066A (en) * | 1983-07-06 | 1985-04-09 | Colgate-Palmolive Company | Retarding setting of crutcher slurry for manufacturing base beads for detergent compositions |
FR2568790B1 (en) * | 1984-08-10 | 1990-01-12 | Rhone Poulenc Chim Base | PROCESS FOR OBTAINING A STABLE AND PUMPABLE AQUEOUS SUSPENSION OF ZEOLITE AND SUSPENSION THUS OBTAINED |
DE3444960A1 (en) * | 1984-12-10 | 1986-06-12 | Henkel KGaA, 4000 Düsseldorf | GRAINY ADSORPTION |
IN165509B (en) * | 1984-12-24 | 1989-11-04 | Colgate Palmolive Co | |
CA1297376C (en) * | 1985-11-01 | 1992-03-17 | David Philip Jones | Detergent compositions, components therefor, and processes for theirpreparation |
GB8526999D0 (en) * | 1985-11-01 | 1985-12-04 | Unilever Plc | Detergent compositions |
DE3545947A1 (en) * | 1985-12-23 | 1987-07-02 | Henkel Kgaa | PHOSPHATE-FREE, GRANULAR DETERGENT |
GB8607388D0 (en) * | 1986-03-25 | 1986-04-30 | Unilever Plc | Activator compositions |
CA1286563C (en) * | 1986-04-04 | 1991-07-23 | Jan Hendrik Eertink | Detergent powders and processes for preparing them |
GB8609044D0 (en) * | 1986-04-14 | 1986-05-21 | Unilever Plc | Detergent powders |
DE3641314A1 (en) * | 1986-12-03 | 1988-06-09 | Henkel Kgaa | LAUNDRY TREATMENT AGENT BASED ON LAYERED SILICATE |
GB8709057D0 (en) * | 1987-04-15 | 1987-05-20 | Unilever Plc | Composition for softening fabrics |
DE3715052A1 (en) * | 1987-05-06 | 1988-11-17 | Degussa | GRAINY ADSORPTION |
DE3717227A1 (en) * | 1987-05-21 | 1988-12-01 | Henkel Kgaa | PHOSPHATE-FREE DETERGENT WITH REDUCED INCRUSTING TENDENCY |
DE3818660A1 (en) * | 1987-06-05 | 1988-12-15 | Colgate Palmolive Co | FREE-FLOWING, POWDERY DISHWASHING DETERGENT AND METHOD FOR PRODUCING THE SAME |
GB2194793A (en) * | 1987-10-15 | 1988-03-16 | Unilever Plc | Mottled liquid detergents |
GB8823008D0 (en) * | 1988-09-30 | 1988-11-09 | Unilever Plc | Composition for softening fabrics |
DE3835918A1 (en) * | 1988-10-21 | 1990-04-26 | Henkel Kgaa | METHOD FOR PRODUCING TENSIDE CONTAINING GRANULES |
GB8918984D0 (en) * | 1989-08-21 | 1989-10-04 | Unilever Plc | Detergent compositions |
DE3943019A1 (en) * | 1989-12-27 | 1991-07-04 | Henkel Kgaa | GRANULAR, AVIVATING ACTIVITY OF DETERGENT ADDITIVE AND METHOD FOR THE PRODUCTION THEREOF |
GB9008462D0 (en) * | 1990-04-12 | 1990-06-13 | Ecc Int Ltd | Granules for detergent compositions |
EP0477974B1 (en) * | 1990-09-28 | 1995-09-13 | Kao Corporation | Nonionic powdery detergent composition |
AU649504B2 (en) * | 1991-07-03 | 1994-05-26 | Kao Corporation | Nonionic powder detergent composition |
AU3524093A (en) * | 1992-03-27 | 1993-09-30 | Kao Corporation | Nonionic powdery detergent composition and process for producing the same |
AU4324693A (en) * | 1992-06-18 | 1994-01-04 | Unilever Plc | Machine dishwashing composition |
AU660101B2 (en) * | 1992-08-07 | 1995-06-08 | Colgate-Palmolive Company, The | Heavy duty laundry detergent compositions of reduced dye transfer properties |
TR27896A (en) * | 1993-08-05 | 1995-10-11 | Colgate Palmolive Co | Heavy duty laundry detergent compositions with reduced dye transfer properties. |
DE19538028A1 (en) * | 1995-10-12 | 1997-04-17 | Sued Chemie Ag | detergent additive |
DE19538029A1 (en) * | 1995-10-12 | 1997-04-17 | Sued Chemie Ag | detergent additive |
US5962389A (en) * | 1995-11-17 | 1999-10-05 | The Dial Corporation | Detergent having improved color retention properties |
US5726142A (en) * | 1995-11-17 | 1998-03-10 | The Dial Corp | Detergent having improved properties and method of preparing the detergent |
DE19858888A1 (en) * | 1998-12-19 | 2000-06-21 | Henkel Kgaa | Use of low molecular weight homopolymeric polyacrylates in water softeners and in preventing deposits on heating rods during machine washing of textiles |
JP3912985B2 (en) * | 1998-12-28 | 2007-05-09 | 花王株式会社 | Method for producing surfactant-supporting granules |
GB2348435A (en) * | 1999-04-01 | 2000-10-04 | Procter & Gamble | Softening compositions |
GB2348434A (en) * | 1999-04-01 | 2000-10-04 | Procter & Gamble | Detergent compositions |
KR100434923B1 (en) * | 1999-06-14 | 2004-06-09 | 카오카부시키가이샤 | Granules for carrying surfactant and method for producing the same |
WO2000077158A1 (en) * | 1999-06-14 | 2000-12-21 | Kao Corporation | Granular base and particulate detergent |
US6333005B1 (en) * | 1999-06-16 | 2001-12-25 | Hercules Incorporated | Methods of preventing scaling involving inorganic compositions in combination with copolymers of maleic anhydride and isobutylene, and compositions therefor |
WO2000077159A1 (en) * | 1999-06-16 | 2000-12-21 | Kao Corporation | Particles for detergent addition |
DE19938640A1 (en) * | 1999-08-14 | 2001-02-15 | Henkel Kgaa | Prevention of deposits |
DE10032127A1 (en) * | 2000-07-05 | 2002-01-24 | Henkel Kgaa | Mechanically stable soda particles |
DE10040631A1 (en) * | 2000-08-16 | 2002-03-07 | Wolfram Koch | Yellowing inhibitor for blue denim textiles |
DE602007002796D1 (en) * | 2006-02-24 | 2009-11-26 | Unilever Nv | FAST DELIVERY GRANULAT |
WO2009063725A1 (en) * | 2007-11-16 | 2009-05-22 | Kao Corporation | Detergent builder granule |
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4166039A (en) * | 1973-10-15 | 1979-08-28 | The Proctor & Gamble Company | Detergent composition and process |
DE2547389A1 (en) * | 1975-10-23 | 1977-05-05 | Henkel & Cie Gmbh | Phosphate-free detergent - contg. nonionic surfactant having different degrees of ethoxylation and sodium aluminium silicate builder |
NZ188469A (en) * | 1977-10-06 | 1980-12-19 | Colgate Palmolive Co | Detergent composition comprising a univalent cation-exchanging zeolite a nonionic detergent and builder salts |
US4303556A (en) * | 1977-11-02 | 1981-12-01 | The Procter & Gamble Company | Spray-dried detergent compositions |
GB2063289B (en) * | 1979-11-13 | 1984-02-22 | Unilever Ltd | Low phosphate spray-dried powders |
-
1982
- 1982-02-09 AU AU80283/82A patent/AU549000B2/en not_active Ceased
- 1982-02-10 DO DO1982003096A patent/DOP1982003096A/en unknown
- 1982-02-17 GR GR67338A patent/GR76028B/el unknown
- 1982-02-18 NZ NZ199773A patent/NZ199773A/en unknown
- 1982-02-20 DE DE19823206265 patent/DE3206265A1/en active Granted
- 1982-02-23 ZW ZW32/82A patent/ZW3282A1/en unknown
- 1982-02-23 ZW ZW33/82A patent/ZW3382A1/en unknown
- 1982-02-24 CH CH1136/82A patent/CH652416A5/en unknown
- 1982-02-24 AT AT0069082A patent/AT388172B/en not_active IP Right Cessation
- 1982-02-25 SE SE8201170A patent/SE452773B/en not_active IP Right Cessation
- 1982-02-25 NO NO820589A patent/NO153736C/en unknown
- 1982-02-25 ES ES509904A patent/ES509904A0/en active Granted
- 1982-02-25 DK DK083382A patent/DK160885C/en active
- 1982-02-25 IT IT47865/82A patent/IT1147643B/en active
- 1982-02-25 BR BR8200996A patent/BR8200996A/en not_active IP Right Cessation
- 1982-02-25 FR FR8203113A patent/FR2500475B1/en not_active Expired
- 1982-02-25 CA CA000397017A patent/CA1188953A/en not_active Expired
- 1982-02-25 PT PT74486A patent/PT74486B/en not_active IP Right Cessation
- 1982-02-26 MX MX191612A patent/MX158565A/en unknown
- 1982-02-26 NL NL8200804A patent/NL8200804A/en active Search and Examination
- 1982-02-26 IE IE433/82A patent/IE52739B1/en not_active IP Right Cessation
- 1982-02-26 GB GB8205685A patent/GB2097419B/en not_active Expired
-
1987
- 1987-09-08 SE SE8703474A patent/SE502089C2/en not_active IP Right Cessation
-
1990
- 1990-05-10 HK HK361/90A patent/HK36190A/en unknown
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