NO136037B

NO136037B -

Info

Publication number: NO136037B
Application number: NO74744655A
Authority: NO
Inventors: A Kamata; A Kanesaki
Original assignee: Mitsubishi Heavy Ind Ltd
Priority date: 1973-12-25
Filing date: 1974-12-23
Publication date: 1977-04-04
Also published as: NO744655L; FR2255207B1; DE2461143A1; NO136037C; DE2461143B2; NL7416885A; FR2255207A1

Description

Fremgangsmåte for fremstilling av vaskemidler. Procedure for the production of detergents.

Oppfinnelsen vedrører en fremgangsmåte for fremstilling av vaskemidler som inneholder korrosjonshindrende stoffer. The invention relates to a method for the production of detergents containing corrosion-preventing substances.

Nnoen metaller og metallegeringer, særlig sink, aluminium og galvanisert jern angripes sterkt når de kommer i berøring med vandige oppløsninger av bestemte stoffer. Denne korrosjon inntrer særlig ved oppløsninger som inneholder vannoppløse-lige kondenserte fosfater og perforbindelser, f. eks. alkaliperborat. Disse oppløsnin-ger kan dessuten inneholde syntetiske vaskeaktive stoffer og andre bestanddeler som er vanlige i vaskemidler. Korrosjonen kan også forårsakes av andre vandige vas-kemiddeloppløsninger, f. eks. sådanne som inneholder salter av organiske' sulfosyrer eller alkylsvovelsyrer med vaskevirkning, og perforbindelser, til og med når det ikke er til stede noen kondenserte fosfater. Dette er en stor ulempe, fordi slike metaller og metallegeringer ofte anvendes ved konstruksjon av vaskemaskiner og andre apparater, i hvilke de oppløsninger som kommer i betraktning, anvendes. Metall-delené i disse maskiner og apparater taper ved den normale anvendelse med oppløs-ninger, som inneholder de vanlige mengder vaskemiddel og perborat, ofte 3—10 g metall pr. m2. Some metals and metal alloys, particularly zinc, aluminum and galvanized iron, are strongly attacked when they come into contact with aqueous solutions of certain substances. This corrosion occurs in particular with solutions containing water-soluble condensed phosphates and per-compounds, e.g. alkali perborate. These solutions may also contain synthetic detergent active substances and other components that are common in detergents. The corrosion can also be caused by other aqueous detergent solutions, e.g. those containing salts of organic sulphuric acids or alkylsulphuric acids with washing action, and per compounds, even when no condensed phosphates are present. This is a major disadvantage, because such metals and metal alloys are often used in the construction of washing machines and other appliances, in which the solutions that come into consideration are used. Metal parts in these machines and devices lose during normal use with solutions containing the usual amounts of detergent and perborate, often 3-10 g of metal per m2.

Hovedpatentet, patent nr. 94 332 ved-rører rensemidler som ineholder perforbindelser d fast, pastaaktig eller flytende form, som inneholder som korrosjonsfor-hindrende stoff en vannoppløselig tinnforT bindelse, særlig en stannoforbindelse.. Det viste seg nemlig at ved denne .-.tilsetning nedsettes i vesentlig grad korrosjonsvirkr ningen. av vandige oppløsninger av, ved-kommende rensemiddel. Fortrinsvis. hianT des tinnforbindelsen med en tørr, blanding av de øvrige vaskemiddelbestanddeler.,Perforbindelsen skal herunder^ som bekjent, innforlives i et slikt trinn av fremstilings-prosessen at den videre fbrårbeidelse ut-settes den ikke for noen høye temperatu-rer. The main patent, patent no. 94 332, relates to cleaning agents that contain per compounds in solid, paste-like or liquid form, which contain as a corrosion-preventing substance a water-soluble tin compound, in particular a stannous compound. It turned out that with this .-.addition the corrosion effect is significantly reduced. of aqueous solutions of the associated cleaning agent. Preferably. while the tin compound is mixed with a dry mixture of the other detergent ingredients. The compound must, as is well known, be incorporated in such a step of the manufacturing process that it is not subjected to any high temperatures during the further processing.

Det viste seg nu at mån kan oppnå en ennå bedre korrosjonsbeskyttelse når'mån fremstiller det tørre vaskemiddel som'inneholder perforbindelsene og stanriofor-bindelsene, ved at man utsprøyter" én' vandig oppløsning av en kompleks stannoforbindelse og en grøt av de andre bestanddeler av vaskemidlet, med unntagelse' av perforbindelsen, gjennom særskilte dyser i et sprøytetårn og at det på denne'.måten erholdte tørre produkt blandes, méd. per'T forbindelsen. It now turned out that moon can achieve even better corrosion protection when moon produces the dry detergent containing the per compounds and stannous compounds, by spraying an aqueous solution of a complex stannous compound and a slurry of the other components of the detergent , with the exception of the per compound, through special nozzles in a spray tower and that the dry product obtained in this way is mixed with the per compound.

Fortririsvis utsprøytes oppløsningen av den komplekse stannoforbindelse ' i mot-strøm med grøten. På denne måten frem-stilte vaskemidler kan oppvise en forbed-ring av den korrosjbnsforhindreride effekt av 25—50 pst. like overfor dé fra patent nr. 94 332 kjehte vaskemidler av tilsvarende sammensetning... \ IZ' T, Egnete komplekse tinnforbindélser ' er de komplekse forbindelser som dannes av kondenserte fosfater, f. eks. tripolyfosfat og pyrofosfat, og av andre kompleksdannende stoffer, som f. eks. ethylendiamintetraeddiksyre og nitriltrieddiksyre med a) anorganiske stannoforbindelser, f. eks. stannohalogenider, særlig stannoklorid eller stannosulfat, og b) organiske stannoforbindelser, f. eks. stannolactat, stannotartrait, stannomalo-nat og særlige stannooxalat og stannoci-trat. Preferably, the solution of the complex stannous compound is sprayed in counter-current with the porridge. Detergents produced in this way can show an improvement in the corrosion-preventing effect of 25-50 percent compared to that from patent no. 94 332 famous detergents of a similar composition... \ IZ' T, Suitable complex tin compounds ' are the complex compounds formed by condensed phosphates, e.g. tripolyphosphate and pyrophosphate, and of other complexing substances, such as e.g. ethylenediaminetetraacetic acid and nitriletriacetic acid with a) inorganic stannous compounds, e.g. stannous halides, especially stannous chloride or stannous sulphate, and b) organic stannous compounds, e.g. stannous lactate, stannous tartrate, stannous malonate and especially stannous oxalate and stannous citrate.

Oppløsninger av de komplekse tinnfor-bindelser kan fremstilles på en hvilken som helsit egnet måte, f. eks. ved tørrblanding av et stannosalt med et kompleksdannende stoff og tilsluttende oppløsning av blan-dingen i vann. På denne måte fåes en nøy-tral oppløsning når ekvimolekylære mengder av stannoklorid og natriumtripolyfosfat blandes. Oppløsningens pH kan vari-eres ved endring av molforholdet. Solutions of the complex tin compounds can be prepared in any suitable way, e.g. by dry mixing of a stannous salt with a complexing substance and subsequent dissolution of the mixture in water. In this way, a neutral solution is obtained when equimolecular amounts of stannous chloride and sodium tripolyphosphate are mixed. The pH of the solution can be varied by changing the molar ratio.

Til de viktigste vaskemidler, som van-ligvis anvendes, hører de som inneholder vannoppløselige kondenserte fosfater. Slike kondenserte fosfater kan være til stede i blandingene i henhold til foreliggende oppfinnelse. Eksempler på kondenserte fosfater er tripolyfosfat MesPsOjo, (i hvilken formel Me betyr et alkalimetall eller am-monium), som pentanatrium-, pentaka-lium og pentaammoniumtripolyfosfat, py-rofosfatene Me4P207, som tetranatrium-, tetrakalium- og tetraammoniumpyrofosfat, og metafosfatene (MeP03)n, som natrium-, kalium- og ammoniumhexametafosfat. The most important detergents that are usually used include those that contain water-soluble condensed phosphates. Such condensed phosphates may be present in the mixtures according to the present invention. Examples of condensed phosphates are tripolyphosphate MesPsOjo, (in which formula Me means an alkali metal or ammonium), such as pentasodium, pentapotassium and pentaammonium tripolyphosphate, the pyrophosphates Me4P2O7, such as tetrasodium, tetrapotassium and tetraammonium pyrophosphate, and the metaphosphates (MePO3 )n, such as sodium, potassium and ammonium hexametaphosphate.

De midler som skal fremstilles i henhold til foreliggende oppfinnelse, kan inneholde syntetiske organiske såpefrie vaskemidler med eller uten vannoppløse-lige kondenserte fosfater. De syntetiske organiske såpefrie vaskemidler kan være anionogene vaskemidler, som f. eks. de vannoppløselige salter av organiske sulfosyrer og av alkylsvovelsyrer med vaskevirkning. Eksempler på slike anionogene vaskemidler er alkylarylsulfonatene som f. eks. dodecylbenzensulfonatene, amido-alkansulfomatene, som f. eks. natrium-palmitinsyremethyltaurid, langkjedete alifatiske sulfonater, estersalter av svovelsyre med alifatiske alkoholer med 10—18 car-bonatomer, salter av langkjedete estere og ethere av isethionsyre og salter av svovel-syreestere av fetsyremonoglycerider. Man kan også anvende ikke-ionogene vaskemidler, f. eks. k<p>ndenseringsprodukter av ethylenoxyd og propylenoxyd med alkyl-fenoler, fettalkoholer, fettsyrer eller mer-captaner, eller fettsyremono- og dialkanol-amider, samt blandinger av disse stoffer med anionogene vaskemidler. Egnete perforbindelser er f. eks. peroxyder, perbora-ter, percarbonater, persulfater, perfosfater og perpyrofosfater, særlig deres alkalisalter. The agents to be produced according to the present invention may contain synthetic organic soap-free detergents with or without water-soluble condensed phosphates. The synthetic organic soap-free detergents can be anionic detergents, such as e.g. the water-soluble salts of organic sulphonic acids and of alkylsulfuric acids with washing action. Examples of such anionic detergents are the alkylaryl sulphonates such as the dodecylbenzene sulphonates, the amido-alkane sulphonates, such as sodium palmitic acid methyl tauride, long-chain aliphatic sulphonates, ester salts of sulfuric acid with aliphatic alcohols of 10-18 carbon atoms, salts of long-chain esters and ethers of isethionic acid and salts of sulfuric acid esters of fatty acid monoglycerides. You can also use non-ionic detergents, e.g. Condensation products of ethylene oxide and propylene oxide with alkyl phenols, fatty alcohols, fatty acids or mer-captans, or fatty acid mono- and dialkanol amides, as well as mixtures of these substances with anionic detergents. Suitable per-connections are e.g. peroxides, perborates, percarbonates, persulphates, perphosphates and perpyrophosphates, especially their alkali salts.

Vaskemidler i henhold til oppfinnelsen som inneholder vannoppløselige kondenserte fosfater, syntetiske organiske såpefrie, vaskeaktive stoffer og perforbindelser, kan inneholde 5—10 vektsprosent vannoppløselig kondensert fosfat, 5—40 vektsprosent syntetisk organisk såpefritt vaskeaktivt stoff og 1—25 vektsprosent perforbindelse, mens resten består av andre Detergents according to the invention, which contain water-soluble condensed phosphates, synthetic organic soap-free, detergent-active substances and per-compounds, can contain 5-10% by weight water-soluble condensed phosphate, 5-40% by weight synthetic organic soap-free detergent-active substance and 1-25% by weight per-compound, while the rest consists of second

«byggere» («Builder») og inerte stoffer med "builders" ("Builder") and inert substances with

i det minste 1—25 vektsprosent, fortrinsvis 10—20 vektsprosent alkalisilikater. at least 1-25% by weight, preferably 10-20% by weight of alkali silicates.

Som «byggere» eller strekningsmidler (såkalte extenders) kan anvendes forbindelser som alkalisulfater, -klorider, -silika-iter, -borater, -carbonater og -orthofosfater og organiske stoffer, som stivelse, salter av carboxymethylcellulose, fluorescerende sub-stanser som bevirker hvithet og stabilisa-torer for perforbindelser, som magneslum-silikater, oxykinolin, salter av nitrileddik-syre og ethylendiamintetraeddiksyre, or-thotolylbiguanid osv. Compounds such as alkali sulphates, chlorides, silicates, borates, carbonates and orthophosphates and organic substances such as starch, salts of carboxymethylcellulose, fluorescent substances which cause whiteness can be used as "builders" or stretching agents (so-called extenders) and stabilizers for per compounds, such as magnesum silicates, oxyquinoline, salts of nitrileacetic acid and ethylenediaminetetraacetic acid, orthotolylbiguanide, etc.

Ovenanførte fremgangsmåte er særlig egnet til fremstilling av vaskemidler med 10—20. pst. kiselsyre i form av alkalisilikat. Alkalisilikat kan tilsettes i alkalisk form (forhold av MeaO : Si02 = 1:2) eller i nøytral form (forhold av Me20 : SiO = 1 : 3). Vaskemidler som inneholder nøytralt silikat, oppviser en forbedret holdbarhet sammenlignet med vaskemidler som inneholder alkalisk silikat. The above method is particularly suitable for the production of detergents with 10-20. pst silicic acid in the form of alkali silicate. Alkali silicate can be added in alkaline form (ratio of MeaO : SiO2 = 1:2) or in neutral form (ratio of Me20 : SiO = 1 : 3). Detergents containing neutral silicate show an improved durability compared to detergents containing alkaline silicate.

Etterfølgende eksempel klargjør oppfinnelsen. The following example clarifies the invention.

Eksempel. Example.

(A) En vandig oppløsning av en tinntri-polyfosfatkompleksforbindelse fremstilles (A) An aqueous solution of a tin tri-polyphosphate complex compound is prepared

ved at 11 kg stannokloriddihydrat blandes intimt med 32 kg pentanatriumtripolyfosfat og denne blanding ble oppløst i 44 liter vann ved romtemperatur under stadig om-røring. by intimately mixing 11 kg of stannous chloride dihydrate with 32 kg of pentasodium tripolyphosphate and this mixture was dissolved in 44 liters of water at room temperature with constant stirring.

En grøt av de øvrige bestanddeler av vaskemidlet fikk man ved å blande sam-men etterfølgende stoffer: A slurry of the other components of the detergent was obtained by mixing together the following substances:

490 kg natriumdodecylbenzensulfonat 83 kg laurylisopropanolamid 20 kg natriumcarboxymethylcellulose 490 kg sodium dodecylbenzenesulfonate 83 kg lauryl isopropanolamide 20 kg sodium carboxymethyl cellulose

37 kg natriumhydroxyd 37 kg of sodium hydroxide

600 kg natriumtripolyfosfat 100 kg natriumsulfat 390 kg nøytralt natriumsilikat (100 % ) 600 kg sodium tripolyphosphate 100 kg sodium sulphate 390 kg neutral sodium silicate (100%)

1250 1 vann. 1250 1 water.

Grøten ble opphetet til 75° C og tørket i et sprøytetårn av 13 m i motstrømsprosess ved utsprøytning gjennom 5 dyser ved 30 atm. Luften hadde en innløpstemperatur av 400° C og en utløpstemperatur av 115° C. På samme tid ble oppløsningen av tinnkom-pleksforbindelsen (temperatur 20° C) ut-sprøytet gjennom en særskilt dyse som var anordnet 6 m under de andre dyser og like ovenfor disse. The porridge was heated to 75° C and dried in a spray tower of 13 m in a counter-flow process by spraying through 5 nozzles at 30 atm. The air had an inlet temperature of 400° C and an outlet temperature of 115° C. At the same time, the solution of the tin complex compound (temperature 20° C) was sprayed out through a special nozzle which was arranged 6 m below the other nozzles and just above these.

Det på denne måte erholdte produkt ble blandet med 17 kg natriumperboratte-trahydrat. 4,8 g av denne blanding ble opp-løst i 1 liter ledningsvann av 14 tyske hårdhetsgrader. (B) Et andre vaskemiddelpreparat ble fremstilt av de samme utgangsmaterialer, men i dette tilfelle ble den komplekse tinn- forbindelse tilsatt grøten umiddelbart før sprøytetørkingen, mens perboratet ble tilsatt i tilslutning hertil som beskrevet. Det ble også fremstilt to oppløsninger av dette vaskemiddel av 4,8 g i 1 1 destillert vann resp. ledningsvann. Ytterligere to vaskemiddelpreparater ble fremstilt på den under (B) beskrevne måte, imidlertid ble i det ene (vaskemiddel C) mengden av natriumhydroxydet økt til 80 kg og i det annet (vaskemiddel D) ble mengden av natriumsulfat og nøytralt natriumsilikat endret til 330 kg resp. 170 kg. Det ble fremstilt -to oppløsninger av hvert av disse vaskemidler som hver inneholdt 4,8 g i 1 liter destillert vann resp, ledningsvann. I hver av de på denne måte erholdte åtte oppløsninger ble innført et flatt stykke av galvanisert jern av 9 x 10 cm med et sinksjikt av 300—700 g/m-. Oppløsningen ble opphetet i 1 time til 98—100° C, holdt i 15 minutter ved denne temperatur og derpå langsomt avkjølt i løpet av 2 timer til 45° C. Jernet ble derpå fjernet fra oppløsnin-gen, gnidd med et bløtt tøystykke for å fjerne de vedhengende korrosjonsprodukter tørket og veiet. Forsøket ble gjentatt med hver oppløsning 10 ganger og det midlere sinktap pr. forsøk beregnet i g/m<2>. Resul-tatene med de forskjellige oppløsninger er oppført i den etterfølgende tabell, i hvilken I er oppløsningen i destillert vann og II er oppløsningen i ledningsvann av 14 tyske hårdhetsgrader.. The product thus obtained was mixed with 17 kg of sodium perborate trihydrate. 4.8 g of this mixture was dissolved in 1 liter of tap water of 14 German degrees of hardness. (B) A second detergent formulation was prepared from the same starting materials, but in this case the complex tin- compound was added to the porridge immediately before the spray drying, while the perborate was added in connection with this as described. Two solutions of this detergent of 4.8 g in 1 1 distilled water or tap water. Two further detergent preparations were prepared in the manner described under (B), however, in one (detergent C) the amount of sodium hydroxide was increased to 80 kg and in the other (detergent D) the amount of sodium sulfate and neutral sodium silicate was changed to 330 kg resp. . 170 kg. Two solutions of each of these detergents were prepared, each containing 4.8 g in 1 liter of distilled water or tap water. In each of the eight solutions obtained in this way, a flat piece of galvanized iron of 9 x 10 cm with a zinc layer of 300-700 g/m- was introduced. The solution was heated for 1 hour to 98-100° C., held for 15 minutes at this temperature and then slowly cooled over 2 hours to 45° C. The iron was then removed from the solution, rubbed with a soft piece of cloth to remove the adhering corrosion products dried and weighed. The experiment was repeated with each solution 10 times and the average zinc loss per test calculated in g/m<2>. The results with the different solutions are listed in the following table, in which I is the solution in distilled water and II is the solution in tap water of 14 German degrees of hardness.

Claims

1. Process for the production of detergents containing per compounds and stannous compounds according to patent no. 94 332, characterized in that an aqueous solution of a complex stannous compound and a mash of the other components of the detergent, with the exception of the per compound. at the same time, it is sprayed through special nozzles in a spray tower and the percompound is mixed with the dry product obtained in this way.

2. Method as stated in claim 1 or 2, characterized in that the solution of the complex stannous compound is sprayed in countercurrent with the porridge.

3. Method as stated in claim 1 or 2 - characterized in that the complex stannous compound is obtained from a stannous compound bg a condensed phosphate.

4. Method as stated in claim 1 or 2, characterized in that the complex sanno compound is obtained from a stannous compound and ethylenediaminetetraacetic acid,

5. Method as stated in one of the preceding claims, characterized in that 10-20 percent by weight of a primarily neutral alkali silicate is added to the detergents. and pyrophosphate, and of other complexing substances, such as e.g. ethylenediamine triacetic acid and nitrile triacetic acid with a) inorganic stannous compounds, e.g. e.g. stannous halides, especially stannous chloride or stannous sulphate, and b) organic stannous compounds, e.g. stann lactate stann tartrate, stann malo-nate and especially stann oxalate and stann noci-trate. Solutions of the complex tin compounds can be prepared in any suitable manner, e.g. by dry mixing of a stannous salt with a complexing substance and subsequent dissolution of the mixture in water. In this way, a neutral solution is obtained when equimolecular amounts of stannous chloride and sodium tripolyphosphate are mixed. The pH of the solution can be varied by changing the molar ratio. The most important detergents that are usually used include those that contain water-soluble condensed phosphates. Such condensed phosphates may be present in the mixtures according to the present invention. Examples of condensed phosphates are the tripolyphosphate MesPaOw, (in which formula Me means an alkali metal or ammonium), such as pentasodium, pentapotassium and pentaammonium tripolyphosphate, the pyrophosphates Me^P^O?, such as tetrasodium, tetrapotassium and tetraammonium pyrophosphate , and metaphosphatehe (MePO:i)„> as sodium, potassium and ammonium hexametaphosphate. The agents to be produced according to the present invention may contain synthetic organic soap-free detergents with or without water-soluble condensed phosphates. The synthetic or ganic soap-free detergents can be anionic detergents, such as e.g. the water-soluble salts of organic sulphonic acids and of alkylsulfuric acids with washing action. Examples of such anionogens detergents are the alkylaryl sulphonates such as the dodecylbenzenesulfonates, the amido-alkanesulfonates, such as e.g. sodium palmitic acid methyl tauride, long-chain aliphatic sulphonates, ester salts of sulfuric acid with aliphatic alcohols with 10-18 carbon atoms, salts of long-chain esters and ethers of isethionic acid and salts and sulfuric acid esters of fatty acid monoglycerides. You can also use non-ionic detergents, e.g. condensation products of ethylene oxide and propylene oxide with alkyl phenols, fatty alcohols, fatty acids or mercaptans, or fatty acid mono- and dialkanol amides,, as well as. mixtures of these substances with anionic detergents. Suitable per-links are e.g. peroxides, perbora- teres, percarbonates, persulphates, perphosphates and perpyrophosphates, especially their alkali salts. Detergents according to the invention, which contain water-soluble condensed phosphates, synthetic organic soap-free, detergent-active substances and per-compounds, can contain 5-10% by weight water-soluble condensed phosphate, 5-40% by weight synthetic organic soap-free detergent-active substance and 1-25% by weight per-compound, while the rest consists of other "builders" ("Builder") and inert substances with at least 1-25% by weight, preferably 10-20% by weight of alkali silicates. Compounds such as alkali sulphates, chlorides, silicates, borates, carbonates and orthophosphates and organic substances such as starch, salts of carboxymethylcellulose, fluorescent substances which cause whiteness can be used as "builders" or stretching agents (so-called extenders) and stabilizers for per compounds, such as magnesium silicate, oxyquinoline, salts of nitrile acetic acid and ethylenediaminetetraacetic acid, orthotolyl biguanide, etc. The above method is particularly suitable for the production of detergents with 10-20 percent silicic acid in the form of alkali silicate. Alkali silicate can be added in alkaline form (ratio of Me-O : S\ Oi = 1:2) or in neutral form (ratio of Me-O : SiO = 1:3). Detergents containing neutral silicate show an improved durability compared to detergents containing alkaline silicate. The following example clarifies the invention. Example. (A) An aqueous solution of a tin tri-polyphosphate complex compound is prepared by intimately mixing 11 kg of stannous chloride dihydrate with 32 kg of pentasodium tripolyphosphate and this mixture was dissolved in 44 liters of water at room temperature with constant stirring. A slurry of the other components of the detergent was obtained by mixing together the following substances: 490 kg of sodium dodecylbenzene sulphonate 83 kg of lauryl isopropanolamide 20 kg of sodium carboxymethyl cellulose 37 kg of sodium hydroxide | 600 kg sodium tripolyphosphate .4 100 kg sodium sulfate 390 kg neutral sodium sdlicate (100% m 1250 1 water. WM The porridge was heated to 75° C and dØ^||f in a spray tower of 13 m in countercurrent process