DK154415B - PROCEDURE FOR THE PREPARATION OF A CRYSTALLINIC SILICO ALUMINATE AND USE OF THIS - Google Patents
PROCEDURE FOR THE PREPARATION OF A CRYSTALLINIC SILICO ALUMINATE AND USE OF THIS Download PDFInfo
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- DK154415B DK154415B DK583877AA DK583877A DK154415B DK 154415 B DK154415 B DK 154415B DK 583877A A DK583877A A DK 583877AA DK 583877 A DK583877 A DK 583877A DK 154415 B DK154415 B DK 154415B
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- aluminate
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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
- C11D3/02—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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
- C01B33/28—Base exchange silicates, e.g. zeolites
- C01B33/2807—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures
- C01B33/2815—Zeolitic silicoaluminates with a tridimensional crystalline structure possessing molecular sieve properties; Isomorphous compounds wherein a part of the aluminium ore of the silicon present may be replaced by other elements such as gallium, germanium, phosphorus; Preparation of zeolitic molecular sieves from molecular sieves of another type or from preformed reacting mixtures of type A (UNION CARBIDE trade name; corresponds to GRACE's types Z-12 or Z-12L)
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Detergent Compositions (AREA)
Description
1 DK 154415 B1 DK 154415 B
Fremgangsmåde til fremstilling af et krystallinsk silico-aluminat samt anvendelse af dette._Process for preparing and using a crystalline silico aluminate.
Den foreliggende opfindelse angår en fremgangsmåde til fremstilling af et hidtil ukendt syntetisk, krystallinsk silico-aluminat i finfordelt form og produktets anvendelse i blanding med detergenter.The present invention relates to a process for preparing a novel synthetic crystalline silico aluminate in finely divided form and the use of the product in admixture with detergents.
Den almindelige metode til fremstilling af syntetiske zeoliter har længe været kendt (Kurnakow. Journal de l'Académie des Sciences d'URSS, 1381 (1937)). Ifølge denne fremstillingsmetode bringer man en opløsning af et silicat og en opløsning af et aluminat i kontakt, hvorved der dannes en gel, som underkastes krystallisation.The common method of producing synthetic zeolites has long been known (Kurnakow. Journal de l'Académie des Sciences d'URSS, 1381 (1937)). According to this method of preparation, a solution of a silicate and a solution of an aluminate are contacted to form a gel which is subjected to crystallization.
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Dannelsen af disse silicoaluminater er afhængig af et stort antal faktorer såsom reaktanternes koncentration, temperaturen ved sammenblandingen, temperaturen under modningsfasen, modningstiden og miljøets homogenitet.The formation of these silica aluminates is dependent on a large number of factors such as the concentration of the reactants, the temperature of the admixture, the temperature during the maturation phase, the maturation time and the homogeneity of the environment.
5 I GB patentskrift nr. 1223 592 beskrives fremstilling af zeo lit X ved dispergering af en vandig natriumaluminatopløsning i en vandig natriumsilicatopløsning med påfølgende hydroter-mal behandling i flere timer, fortrinsvis efter ældning af dispersionen i typisk 16 timer ved stuetemperatur.GB Patent No. 1223,592 describes the preparation of zeolite X by dispersing an aqueous sodium aluminate solution in an aqueous sodium silicate solution with subsequent hydrothermal treatment for several hours, preferably after aging the dispersion for typically 16 hours at room temperature.
10 I DE patentskrift nr. 12 18 417 beskrives en fremgangsmåde til fremstilling af en krystallinsk, zeolitisk molekylsigte af typen 3 A ved hydrotermal behandling af en natrium-, kalium-, aluminat- og silicatholdig reaktionsblanding i fortrinsvis 7-20 timer.DE patent specification No. 12,184,177 discloses a process for preparing a crystalline zeolite molecular sieve of type 3A by hydrothermal treatment of a sodium, potassium, aluminate and silicate-containing reaction mixture for preferably 7-20 hours.
15 Man har ligeledes anvendt metoder såsom tilblanding af krystal- kim for at opnå silicoaluminater med velfastlagte karakteristika, f. eks. stoffet faujasit i et miljø, som allerede indeholder en zeolit af typen 4A som anført i fransk patentansøgning nr. 2281315.Methods such as admixture of crystal germ have also been used to obtain silica aluminates having well-established characteristics, for example the substance faujasite in an environment which already contains a type 4A zeolite as disclosed in French Patent Application No. 2281315.
20 Virkningen af visse faktorer og særligt af tilstedeværelsen af natrium samt af miljøets alkalinitet er allerede blevet fremhævet af Kurnakow.20 The effect of certain factors, and in particular of the presence of sodium and of the alkalinity of the environment, has already been emphasized by Kurnakow.
I fransk patentskrift nr. 1 404 467 anføres det, at natrium-koncentrationen i den væskefase, hvori silicoaluminatbundfal- 25 det opstår, har en bestemmende indflydelse på den derved dan nede zeolit 4A's ensartethed og krystallinske renhed, og at jo mere denne koncentration blev holdt konstant, desto større blev zeolitens renhed og homogenitet.French Patent Specification No. 1,404,467 states that the sodium concentration in the liquid phase in which the silicoaluminate precipitate occurs has a determining influence on the uniformity and crystalline purity of the zeolite 4A formed and that the more this concentration was maintained constant, the greater the purity and homogeneity of the zeolite.
I DD patentskrift nr. 113 202 anføres det, at en række kat- 30 ioner udøver en skadelig virkning ved hydrotermal zeolit fremstilling, og det foreslås at man arbejder med teknisk re- 3DD Patent No. 113,202 states that a number of cations exert a deleterious effect on hydrothermal zeolite production and it is proposed to work with technical refraction.
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ne opløsninger af udgangsmaterialerne.ne solutions of the starting materials.
Indtil fornylig varde foreslåede fremgangsmåder af den dis-kontinuerte type. Man har forklaret denne situation under hensyntagen til krystallernes komplekse struktur, som normalt 5 ville kræve en relativt lang tid til at dannes ud fra forbin delser, der var irregulært og uberegneligt fordelt mellem flydende og faste faser i reaktionsblandingen.Until recently, proposed methods of the discontinuous type lasted. This situation has been explained, taking into account the complex structure of the crystals, which would normally require a relatively long time to form from compounds that were irregularly and erraticly distributed between liquid and solid phases in the reaction mixture.
Man har derfor i US patentskrift nr. 3 071 434 foreslået at forbedre kinetikken vedrørende dannelsen af zeoliter af 10 typen 4A ved at pode blandingen med en moderlud, som blev tilbageført fra et punkt anbragt efter omsætningszonen.Therefore, it has been proposed in US Patent No. 3 071 434 to improve the kinetics of the formation of zeolites of type 4A by grafting the mixture with a mother liquor which was returned from a point placed after the reaction zone.
Denne metode er imidlertid blevet kritiseret i US patentskrift nr. 3 425 800 på grund af vanskeligheden ved at praktisere den. I dette patentskrift foreslås det at anvende en 15 3-trins krystallisatør, således at den i kulden udfældede gel-suspension blev opvarmet til 100 °C og derpå indført i en krystallisatør, hvor dannelsen af det krystallinske sili-coaluminat fandt sted. Ifølge denne fremgangsmåde blev det krystallinske silicoaluminat isoleret ved dekantering.However, this method has been criticized in U.S. Patent No. 3,425,800 for the difficulty of practicing it. In this patent, it is proposed to use a 3-stage crystallizer so that the gel-precipitated gel suspension is heated to 100 ° C and then introduced into a crystallizer where the formation of the crystalline silica-coaluminate took place. According to this process, the crystalline silicoaluminate was isolated by decantation.
20 I DE offentliggørelsesskrift nr. 23 33 068 beskrives en frem gangsmåde til fremstilling af fine pulverformige zeolitiske molekylsigter ved hydrotermal krystallisation, ved hvilken den vandige reaktionsblanding før og/eller under krystallisationen påvirkes med stærke forskydningskræfter.DE-A-23 33 068 discloses a process for producing fine powdery zeolite molecular sieves by hydrothermal crystallization, in which the aqueous reaction mixture before and / or during crystallization is affected by strong shear forces.
25 I US patentskrift nr. 3 310 373 beskrives fremstilling af et krystallinsk aluminiumsilicat, ved hvilken de dannede krystaller findeles ved mekanisk påvirkning under krystallisationen.25 US Patent No. 3,310,373 discloses the preparation of a crystalline aluminum silicate in which the crystals formed are comminuted by mechanical action during crystallization.
I DE patentskrift nr. 10 38 017 beskrives en fremgangsmåde til fremstilling af krystallinske zeolitiske molekylsigter 30 af typen zeolit A, der imidlertid udviser et særdeles bredt partikelstørrelsesspektrum fra 0,01 til lOO^um.DE Patent Specification No. 10 38 017 discloses a process for producing crystalline zeolite molecular sieves 30 of type zeolite A, which, however, exhibit a very wide particle size spectrum from 0.01 to 100 µm.
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4 I fransk patentskrift nr. 2 096 360 foreslår man at undgå anvendelse af en flertrinsfremgangsmåde ved at forvarme den vandige opløsning af natriumsilikat omtrent til udfældnings-temperaturen og tilsætte den i varm tilstand til aluminatop-5 løsningen, der ligeledes blev holdt ved udfældningstemperatu ren .4 In French Patent Specification No. 2 096 360, it is proposed to avoid the use of a multistage process by preheating the aqueous solution of sodium silicate approximately to the precipitation temperature and adding it in hot state to the aluminate solution, which was also kept at the precipitation temperature.
De således fremstillede produkter er for det meste blevet værdsat på grund af deres høje absorptionsevne, som virker selektivt på molekyler afhængigt af disses dimensioner og 10 former, hvilket har ført til, at de er blevet betegnet popu lært som "molekylsigter".The products thus produced have mostly been appreciated because of their high absorbency, which acts selectively on molecules depending on their dimensions and shapes, which has led to their being called "molecular sieves".
Men man har ligeledes ønsket at anvende denne type produkter på grund af andre egenskaber, især som kationbytter. En af de mest almindelige anvendelser inden for dette område angår 15 anvendelsen af sådanne forbindelser i detergent- og rense middelblandinger.However, it has also been desired to use this type of product due to other properties, especially as cation exchange. One of the most common uses in this field relates to the use of such compounds in detergent and purifying agents.
Inkorporering af forbindelser med basis i silico-aluminater i rensemidler har faktisk været kendt lige fra bibelsk historisk tid. Men denne mulighed har været genstand for en høj 20 grad af fornyet interesse - dels efter at natriumtripolyphosphat som detergent-hjælpestof har måttet se sin dominans rystet på grund af dets forureningsvirkning - dels efter at man har gjort fremskridt i fabrikationsteknikken for silicoaluminat i retning af pålidelighed og reproducerbarhed.Indeed, the incorporation of compounds based on silico aluminates into cleansers has been known from biblical historical times. But this possibility has been the subject of a high 20 degree of renewed interest - partly after sodium tripolyphosphate as a detergent auxiliary had to shake its dominance due to its contaminant effect - and partly after advances in the silicon aluminate fabrication technique towards reliability and reproducibility.
25 Detergenthjælpestoffer som natriumtripolyphosphat virker på forskellige måder og især som kation-byttere. Silico-alumi-naterne udviser denne egenskab, og det er derfor naturligt at gøre brug heraf, så meget mere som der ikke var nogen grund til at betragte dem som tvivlsomme ud fra et økologisk syns-30 punkt.25 Detergent adjuvants such as sodium tripolyphosphate act in various ways and especially as cation exchangers. The silico alumni exhibit this characteristic and it is therefore natural to use it, so much more than there was no reason to regard them as questionable from an ecological point of view.
Man har således fornylig set foreslået forskellige typer af silicoaluminater, i almindelighed krystallinske, som udmærke 5Thus, various types of silicoaluminates, generally crystalline, have been proposed recently, which are excellent.
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de sig ved en høj evne til kation-bytning og/eller en stor udbytningshastighed.they exhibit a high capability of cation exchange and / or a high rate of exchange.
Beklageligvis frembyder disse silicoaluminater en dobbelt ulempe. Først og fremmest er de ikke i stand til fuldstæn-5 digt at erstatte natriumtripolyphosphat, for de synes kun at fungere i et detergentmiljø som kation-byttere, medens natriumtripolyphosphats virkning er mere varieret og i særlig grad dispergerende og kompleksdannende. Derudover er disse silico-aluminater opløselige, hvilket fører til et fænomen 10 kaldet inkrustering eller "mineralisering", og som fører til udfældning af partikler af de nævnte silicoaluminater på tekstiler, særligt på bomuld.Unfortunately, these silica aluminates present a double disadvantage. First of all, they are unable to completely replace sodium tripolyphosphate because they appear to function only in a detergent environment as cation exchangers, while the effect of sodium tripolyphosphate is more varied and particularly dispersive and complexing. In addition, these silico aluminates are soluble, which leads to a phenomenon 10 called encrustation or "mineralization" and which leads to the precipitation of particles of said silica aluminates on fabrics, especially on cotton.
Man har forestillet sig, at inkrusterings-fænomenet kunne formindskes ved anvendelsen af meget finkornede produkter.It has been imagined that the incremental phenomenon could be mitigated by the use of very fine-grained products.
15 Men for nærværende er kornstørrelsesfordelingens indvirkning på vaskeevnen og særligt på inkrusteringsfænomenet lidet kendt.15 However, at present, the effect of the grain size distribution on the washing ability and especially on the encroachment phenomenon is little known.
Man har imidlertid konstateret, at partiklerne bør være godt adskilt i enkeltbestanddele. Hvad. angår erstatning af natriumtripolyphosphat med et alkali-silico-aluminat har man konsta-20 teret, at fremstillingsbetingelserne er jo mere kritiske, de sto mere den relative mængde af tripolyphosphat formindskes i forhold til mængden af silicoaluminat.However, it has been found that the particles should be well separated into single constituents. What. As regards the replacement of sodium tripolyphosphate with an alkali-silico-aluminate, it has been found that the manufacturing conditions are the more critical, the more the relative amount of tripolyphosphate is reduced relative to the amount of silicoaluminate.
Man har imidlertid nu fundet en hidtil ukendt fremgangsmåde af den i hovedkravets indledning angivne art, ved hvilken 25 der kan fremstilles et hidtil ukendt natrium-silico-aluminat af typen krystallinsk, meget finkornet og i høj grad disper-gerbart. Denne fremgangsmåde er ejendommelig ved, at man blander en natriumaluminatopløsning, der er afkølet til mellem . -10 °C og +10 °C, og en natriumsilicatopløsning ved omgivel-30 sestemperatur og lader den homogene blanding undergå en gel dannelse ved en temperatur mellem 60 °C og 100 °C, idet de to reaktanters koncentration i opløsningerne er af en sådan størrelse, at den flydende fase ved procesforløbets afslutningHowever, there has now been found a novel process of the kind set forth in the preamble of the main claim in which a novel sodium silico aluminate of the crystalline type, very fine-grained and highly dispersible, can be produced. This process is characterized by mixing a sodium aluminate solution which has cooled to medium. -10 ° C and +10 ° C, and a sodium silicate solution at ambient temperature and allowing the homogeneous mixture to undergo a gel formation at a temperature between 60 ° C and 100 ° C, the concentration of the two reactants in the solutions being such size that the liquid phase at the end of the process
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6 indeholder mindst 70 g/1 Na£0 og 10 g/1 A^O^ i ligevægt med mindst 200 g/1 molekylsigte.6 contains at least 70 g / l Na 2 O and 10 g / l A 2 O 2 in equilibrium with at least 200 g / l molecular sieve.
Produktet, som er af typen 4A, svarer til den generelle formel : 5 x SiOgj y ’AlgOjf z N&^O, vr H^O, hvori y = 1, x = 1,5 til 6, 'z = 1, w = 0 til 5, fortrinsvis til formlen x = 1,85, y = 1, w = 4 til 5, z = 1#The product of type 4A corresponds to the general formula: 5 x SiO 2 y y 'AlgOjf z N & O, vr H ^ O, where y = 1, x = 1.5 to 6,' z = 1, w = 0 to 5, preferably to the formula x = 1.85, y = 1, w = 4 to 5, z = 1 #
Mikroskopisk undersøgelse afslører tilstedeværelsen af små, 10 enkeltstående terninger med en grundstørrelse hovedsageligt på mellem 0,2 og 8 ^um, med meget høj specifik overflade (BET) mellem 0,5 og 10 m^/g.Microscopic examination reveals the presence of small, 10 single cubes with a base size mainly between 0.2 and 8 µm, with very high specific surface area (BET) between 0.5 and 10 m 2 / g.
Dette silicoaluminat udviser en meget specifik kornstørrelsesfordeling inden for et stort område af kornstørrelsesmiddel-15 værdier, hvilket muliggør anvendelse inden for så forskelli ge områder som f. eks. detergenter, udtørring ved forbindelse med et bindemiddel og adskillelsesfunktioner.This silicoaluminate exhibits a very specific grain size distribution within a wide range of grain size agent values, which allows for use in such diverse areas as, for example, detergents, drying out with a binder, and separation functions.
Hvad angår anvendelse i detergenter iagttager man, at det er fordelagtigt at anvende et ved den her omhandlede fremgangs-20 måde fremstillet silicoaluminat med meget lille kornstørrel se specielt fra 0,2 til 3 /um med stor specifik overflade mel-2 lem 1 og 10 m /g og med høj kation-udbytningsevne og udbytningshastighed.With regard to use in detergents, it is considered advantageous to use a very small grain size silica aluminate made in this process, especially from 0.2 to 3 µm with a large specific surface between 2 and 10. m / g and with high cation exchange capacity and rate of exchange.
Et sådant silicoaluminat er særligt velegnet til anvendelse i 25 detergentblandinger, hvor det udviser egenskaber, som tåler sammenligning med de bedste, kendte silicoaluminater, men hvor det samtidigt udviser en særdeles lav inkrustationsgrad.Such a silicoaluminate is particularly well suited for use in 25 detergent mixtures where it exhibits properties which are comparable to the best known silicoaluminates but at the same time exhibit a very low degree of encrustation.
Den foreliggende opfindelse angår også anvendelse af det ved den her omhandlede fremgangsmåde fremstillede silicoaluminat 7The present invention also relates to the use of the silicoaluminate 7 produced by the process of the present invention
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som rensehjælpemiddel i rensemidler.as a cleaning aid in detergents.
Det hidtil ukendte silicoaluminat ifølge opfindelsen kan fremstilles efter en diskontinuert fremgangsmåde, men i praksis betjener man sig fortrinsvis af en kontinuert fremgangs-5 måde.The novel silicoaluminate of the invention can be prepared by a discontinuous process, but in practice it is preferably operated by a continuous process.
Fremgangsmåden ifølge opfindelsen er generelt set kendetegnet ved, at gel-dannelsestrinnet finder sted i et koncentreret og homogent miljø.The process of the invention is generally characterized in that the gel formation step takes place in a concentrated and homogeneous environment.
Ifølge den foreliggende opfindelse går man fortrinsvis så- 10 ledes frem: - man fremstiller først en natriumaluminatopløsning, - man nedkøler derpå denne opløsning til en temperatur, der er lavere en stuetemperatur, - man tilsætter under omrøring, således at man vedligeholder 15 et homogent miljø, en opløsning af natriumsilicat, - man bringer omsætningsmiljøet op til en temperatur, der befinder sig mellem 60 og 100 °C, hvilket tillader gel-dannelsen, og - man vedligeholder denne temperatur i en tidsperiode, der 20 befinder sig mellem 0,2 og 5 timer, indtil total redisper- gering af det dannede silico-aluminat i suspension.The present invention preferably proceeds as follows: - First, a sodium aluminate solution is prepared, - then this solution is cooled to a temperature lower than room temperature, - added under stirring to maintain a homogeneous environment. , a solution of sodium silicate, - the reaction environment is brought up to a temperature between 60 and 100 ° C, which permits the formation of gel, and - this temperature is maintained for a period of time which is between 0.2 and 5 hours until total redispersion of the silica aluminate formed in suspension.
Man udfører blandingen under omrøring med et hvilket som helst passende omrøringsorgan, som kan homogenisere reaktionsvæsken, i en tidsperiode, der er kortere end gel-dannel-25 sestiden for væsken ved blandingens ligevægtstemperatur. Denne tidsperiode er fortrinsvis kortere end 15 minutter.The mixture is carried out with stirring with any suitable stirring means capable of homogenizing the reaction liquid for a period of time shorter than the gel formation time of the liquid at the equilibrium temperature of the mixture. This time period is preferably shorter than 15 minutes.
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De to reaktanters koncentrationer vælges som nævnt således, at man ved omsætningens afslutning opnår en væskefase, som indeholder mindst 70 g/1 af Na^O og 10 g/1 af A^O^ i ligevægt med mindst 200 g/1 molekylsigte.The concentrations of the two reactants are selected as mentioned so that at the end of the reaction, a liquid phase containing at least 70 g / l of Na 2 O and 10 g / l of A 2 O 2 in equilibrium with at least 200 g / l molecular sieve is obtained.
5 Når man ønsker at fremstille et produkt med en meget lav korn- størrelse på fra 0,2 til 3 yum, vælges reaktanternes koncentrationer således, at der efter færdig omsætning fås en væskefase-indeholdende mindst 100 g/1 Na£0 og 30 g/1 A^O-j i ligevægt med mindst 200 g/1 molekylsigte, medens man ved frem-10 stilling af et produkt med en noget større kornstørrelse for trinsvis ville vælge en væskefase indeholdende mindre end 100 g/1.fortrinsvis fra 70 til 100 g/1 Na£0 og mindre end 30 g/1,fortrinsvis fra 10 til 30 g/1 Al^O^.When desiring to prepare a product with a very low grain size of from 0.2 to 3 µm, the concentrations of the reactants are chosen so that upon completion of the reaction a liquid phase containing at least 100 g / l Na 2 O and 30 g is obtained. Equilibrium with at least 200 g / l molecular sieve, while preparing a product with a somewhat larger grain size would preferably select a liquid phase containing less than 100 g / 1. preferably from 70 to 100 g And less than 30 g / l, preferably from 10 to 30 g / l Al 2 O 2.
Det er klart, at fremgangsmåden ifølge opfindelsen kan ud-15 ' føres på diskontinuert måde, men den frembyder fordelen ved muligheden for en kontinuert iværksættelse.It is to be understood that the process of the invention can be carried out in a discontinuous manner, but it offers the advantage of the possibility of a continuous implementation.
I praksis går man frem på følgende måde: - man fremstiller først blandingen af en natriumaluminatop-løsning nedkølet til det ovenfor anførte temperaturinterval 20 og af en natriumsilicatopløsning, som befinder sig ved en temperatur i nærheden af stuetemperaturen, - før geldannelsen findeler man denne blanding i en første zone, som har en vægtfylde lavere end den vandige blandings vægtfylde, og som er opvarmet til en sådan temperatur, at den 25 vandige blanding efter sammenblanding bringes til den valgte omsætningstemperatur, idet den omtalte første zone består af et varmeoverførelsesmedium ., der ikke er blandbart med vand, såsom et oliebad eller et petroleumsbad, - man vedligeholder denne temperatur i badet i en anden zone 30 længere fremme lige indtil omdannelsen til krystallinsk fase er tilendebragt, idet man stadig sikrer sig en ensartet, stem 9In practice, the procedure is as follows: - First, the mixture is prepared from a sodium aluminate solution cooled to the above-mentioned temperature range 20 and of a sodium silicate solution which is at a temperature near room temperature, a first zone having a density lower than the density of the aqueous mixture and heated to such a temperature that after mixing, the aqueous mixture is brought to the selected reaction temperature, said first zone consisting of a heat transfer medium which is not is miscible with water, such as an oil bath or a petroleum bath, - maintaining this temperature in the bath in another zone 30 further ahead until the crystalline phase conversion is complete, ensuring a uniform voice 9
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pelagtig fremadskriden i denne anden zone, hvorefter - man opsamler reaktionsmediet, som indeholder de små sili-coaluminatkrystaller i suspenderet tilstand, hvorpå - man fraskiller suspensionens krystaller på vilkårlig måde, 5 f. eks. ved filtrering eller centrifugering og derpå vasker og isolerer disse.pelagic progress in this second zone, after which - the reaction medium containing the suspended silicon-carbonuminate crystals is collected, and - the crystals of the suspension are arbitrarily separated, for example by filtration or centrifugation, and then washed and isolated.
Den første zone er fortrinsvis en gennemløbszone, hvor reaktionsvæsken udsættes for en omrøring under en meget kort opholdstid på fra 1 til 2 sekunder, medens den anden zone 10 omfatter en ensartet, stempelagtig fremadskriden og svarer til en meget længere opholdstid.Preferably, the first zone is a flow zone where the reaction fluid is subjected to a stir for a very short residence time of 1 to 2 seconds, while the second zone 10 comprises a uniform, piston-like progress and corresponds to a much longer residence time.
Som tidligere nævnt er produkterne ifølge opfindelsen særligt velegnede til anvendelse i detergentblandinger, skønt denne anvendelse på ingen måde er begrænsende.As previously mentioned, the products of the invention are particularly suitable for use in detergent mixtures, although this use is by no means limiting.
15 I det følgende forklares opfindelsen nærmere ved en række eksempler, og under henvisning til tegningen, hvor fig. 1, 3 og 5 viser elektromikroskopiske optagne billeder af produkter fremstillet ved den her omhandlede fremgangsmåde, fig.In the following, the invention is explained in more detail by a number of examples, and with reference to the drawing, in which fig. Figures 1, 3 and 5 show electromicroscopically recorded images of products made by the method of the present invention;
2 tilsvarende billeder af et produkt fremstillet under anven-20 delse af kendt teknik, medens fig. 4 skematisk viser et an læg til anvendelse ved kontinuerlig gennemførelse af den her omhandlede fremgangsmåde i industriel målestok.2 shows similar images of a product made using prior art, while FIG. Figure 4 shows schematically a plant for use in continuous implementation of the process of the present invention on an industrial scale.
For bedre at kunne belyse de egenskaber, der knytter sig til de her omhandlede produkter, har man også gennemført sammen-25 lignende forsøg med kendte produkter og gennemført følgende afprøvninger:In order to better elucidate the properties associated with the products in question, similar tests have been carried out with known products and the following tests have been carried out:
Kornstørrelses fordeling;Grain size distribution;
Denne er gennemført ved hjælp af en Coulter-tæller, idet man som elektrolyt har valgt følgende opløsning angivet i vægt-%:This was carried out by means of a Coulter counter, having chosen as the electrolyte the following solution, expressed in% by weight:
10 DK 154415BDK 154415B
vand.................... 78% glycerol ............... 20%water .................... 78% glycerol ............... 20%
NaCl ................... .1% natriumhexametaphosphat . 0,5% formaldehyd ............ 0,5%NaCl ................... .1% sodium hexametaphosphate. 0.5% formaldehyde ............ 0.5%
Dispersion 2 minutter (Ultralyd) - 40000 herz r 100 watt. Detergentvirkning:Dispersion 2 minutes (Ultrasound) - 40000 heart rate 100 watts. detergent:
Detergeritvirkningen er blevet påvist ved vaskeforsøg ved 90°C på bomulds-prøvelapper, tilsmudset med et standardsmuds fremstillet af W&schereiforschungsinstituttet i Krefeld.The detergerite effect has been demonstrated by washing tests at 90 ° C on cotton swab, soiled with a standard mud manufactured by the W & schereiforschungs Institute in Krefeld.
Forsøgene er blevet gennemført ved hjælp af et såkaldt Linitest apparat, fabrikat:11 Original Honau'J I hver beholder anbringes to tilsmudsede prøvelapper (4,2 g) og to bomulds-prøvelapper, der ikke er tilsmudset (4,2 g) såvel som 100 ml detergentopløsning, hvis sammensætning er angivet nedenunder. Vasken efterfølges af 4 på hinanden følgende renseskyl af 30 sekunders varighed.The tests have been carried out using a so-called Linitest apparatus, make: 11 Original Honau'J Each container contains two soiled sample sheets (4.2 g) and two non-soiled cotton sample sheets (4.2 g) as well as 100 ml of detergent solution, the composition of which is given below. The wash is followed by 4 consecutive cleaning rinses for 30 seconds.
Man anvender vand med 28,5° hårdhed efter fransk målesystem. Detergentblandingen anvendt i koncentrationen 9 g/l er følgende: LAB (alkylb enz ensulf onat) ................ 5,3%Water with 28.5 ° hardness is used according to French measurement system. The detergent mixture used at the concentration of 9 g / l is as follows: LAB (alkylbenzene sulfonate) ................ 5.3%
Ikke-ionogen (C 1β/ΐ4 OE) ................ 2 %Nonionic (C1β / ΐ4 OE) ................ 2%
Natriumstearat ........................... 2,8%Sodium stearate ........................... 2.8%
Natriumtripolyphosphat........ 4,2%Sodium tripolyphosphate ........ 4.2%
Natriumsilico-aluminat...................45 %Sodium silico aluminate ................... 45%
Perborat...................... 22,1%Perborate ...................... 22.1%
Natriumsilikat .......................... 2,5%Sodium silicate .......................... 2.5%
Carboxymethylcellulose .................. 1,2%Carboxymethyl cellulose .................. 1.2%
Magnesiumsilikat ........................ 1,7%Magnesium silicate ........................ 1.7%
Natriumsulfat ........................... 2,1% h2o .....................................100%Sodium Sulfate ........................... 2.1% H2 O ................. .................... 100%
Prøvelappernes reflektion måles før og efter vasken ved hjælp af et fotoelektrisk fotometer af typen "Elrépo" fra firmaet ZEISS under anvendelse af filter nr. 6.The reflection of the sample labels is measured before and after the wash using a "Elrépo" photoelectric photometer from the company ZEISS using filter # 6.
11 DK 154415 B11 DK 154415 B
Inkrustations-virkningInkrustations-effect
Man anvender en formulering af følgende sammensætning:A formulation of the following composition is used:
Silico-aluminat.................... 2,4 g/lSilico-aluminate .................... 2.4 g / l
Natriumtripolyphosphat ............. 1,6 g/l LAB (alkyl Lenzensulfonat).......... 0,8 g/lSodium tripolyphosphate ............. 1.6 g / L LAB (alkyl Lene sulfonate) ......... 0.8 g / l
Ethoxyleret alkohol (cémulsol DB25/17)0,4 g/lEthoxylated alcohol (cemulsol DB25 / 17) 0.4 g / l
Natriumstearat ..................... 0,4 g/lSodium stearate ..................... 0.4 g / l
Natriumsulfat ...................... 0,8 g/lSodium sulphate ...................... 0.8 g / l
Man gennemfører vasken i et apparat LINITEST. Bomulds-prøvelap-per (det anvendte bomuld er fremstillet af Test Fabrics Inc., reference Bleached Cotton Sheeting, Style 405) af størrelsen 10 x 12 cm modtog hver 450 cm^ af den ovenfor angivne opløsning. Vandets hårdhed var 30° fransk måleenhed (NFT 90 003).The washing is carried out in a LINITEST appliance. Cotton sample labels (the cotton used are manufactured by Test Fabrics Inc., reference Bleached Cotton Sheeting, Style 405) of size 10 x 12 cm each received 450 cm 2 of the above solution. Water hardness was 30 ° French unit of measurement (NFT 90 003).
Den egentlige vask fandt sted ved 60°C i 35 minutter (25 minutter til at nå op på temperatur + 10 minutter ved 60°C).The actual washing took place at 60 ° C for 35 minutes (25 minutes to reach temperature + 10 minutes at 60 ° C).
Man gennemførte derpå to renseskyl, den ene hurtigt på ca. 1 minut 7 3 med 350 cm-3, den anden langsomt på 5 minutter med 450 cm ledningsvand (30° fransk hårdhed).Two cleaning rinses were then carried out, one quickly at approx. 1 minute 7 3 with 350 cm-3, the other slowly in 5 minutes with 450 cm tap water (30 ° French hardness).
Man lader afdryppe, og man tørrer.You let drip and you dry.
Derpå forasker man bomulds-prøvestykkerne ved 900°C i to timer. Asken opsamles og vejes.The cotton specimens were then preheated at 900 ° C for two hours. The ash is collected and weighed.
Til disse afprøvninger er det nyttigt at tilføje afprøvninger, der direkte angår selve produktet; - specifik overflade BET, - ionbytningshastighed.To these tests, it is useful to add tests that directly relate to the product itself; - specific surface BET, - ion exchange rate.
EKSEMPEL 1EXAMPLE 1
En liter natriumaluminatopløsning, der indeholder 200 g/l regnetOne liter of sodium aluminate solution containing 200 g / l calculated
12 DK 154415 B12 DK 154415 B
som Na20 samt 200 g/l regnet som Al^O^ nedkøles til 4°C i en rund-bundet kolbe.as Na 2 O and 200 g / l, calculated as Al 2 O 2, are cooled to 4 ° C in a round bottom flask.
Hertil tilsættes under kraftig omrøring således, at reaktionsblandingen stedse holdes homogen, 0,4 1 natriumsilicatopløsning med en temperatur på 20°C indeholdende 25,4% Si02 og 7,42% Na^O regnet efter vægt. Efter afslutningen af denne tilsætning bringes temperaturen atter mod 15°C, idet væsken stadig er meget let flydende. Man standser omrøringen, og lader temperaturen stige til i nærheden af stuetemperatur, hvilket fremkalder en geldannelse i væsken. Kolben holdes nu i et vandbad termostatreguleret til 85°C i to timer; på dette tidspunkt er den oprindelige stive gel-masse omdannet til en mikrokrystallinsk suspension, som afvandes og kontinuert vaskes over en filtermembran med gennemsnitsåbning på 1 mikron. Den mikrokrystallinske suspensionskoncentration af krystallinsk silico-aluminat er ca. 320 g/l. Den vaskede kage tørres til konstant vægt i 100°C varm ovn forud for analyse.To this is added with vigorous stirring so that the reaction mixture is kept homogeneous, 0.4 liters of sodium silicate solution at a temperature of 20 ° C containing 25.4% SiO 2 and 7.42% Na 2 O by weight. Upon completion of this addition, the temperature is brought back to 15 ° C, with the liquid still very lightly flowing. Stirring is stopped and the temperature is raised to near room temperature, which produces a gelling in the liquid. The flask is now kept in a water bath thermostatically controlled to 85 ° C for two hours; at this point, the initial rigid gel mass is converted into a microcrystalline suspension which is dewatered and continuously washed over a 1 micron average opening membrane. The microcrystalline suspension concentration of crystalline silica aluminate is approx. 320 g / l. The washed cake is dried to constant weight in 100 ° C hot oven prior to analysis.
Den tørrede og analyserede zeolit svarer stort set til formlen: 1,85 Si02, 1 A1205, 1 Na£0, 3 H£0.The dried and analyzed zeolite broadly corresponds to the formula: 1.85 SiO 2, 1 Al 2 O 5, 1 Na 2 O, 3 H 2 O.
Undersøgt med røngtendiffraktion udviser den samme struktur som molekylærsigte type 4 A.Investigated with x-ray diffraction exhibit the same structure as type 4 A molecular sieve.
Ved elektronmikroskopisk undersøgelse ser man meget fritliggende terninger med ensartet komstørrelsesfordeling mindre end eller i størrelsesorden 1 micron og godt fordelt, som vist i fig. 1 med en forstørrelsesfaktor på 4500.By electron microscopic examination, very exposed cubes with uniform grain size distribution are seen less than or of the order of 1 micron and well distributed, as shown in FIG. 1 with a magnification factor of 4500.
nn
Den specifikke overflade BET er lig med 7 m /g.The specific surface BET is equal to 7 m / g.
Til sammenligning gennemfører man følgende forsøg nr. 2: 1 liter natriumaluminatopløsning indeholdende 74 g/l regnet som AI2O3 og 127 g/l regnet som Na20 bringes op på 83°C i en kolbe under god omrøring.In comparison, the following experiment # 2 is carried out: 1 liter of sodium aluminate solution containing 74 g / l calculated as Al 2 O 3 and 127 g / l calculated as Na 2 O are brought to 83 ° C in a flask under good stirring.
13 DK 15 4 415 B13 DK 15 4 415 B
Derpå indhældes hurtigt 0,271 1 silicatopløsning fremstillet ved at fortynde 50 ml af en kommerciel natriumsilicatopløsning indeholdende 477 g/l regnet som Si02 og 239 g/l regnet som Na20. Efter at temperaturen igen er bragt op på 80°C vedligeholdes den konstant i to timer under stadig omrøring. Krystal-suspensionen afvandes derpå og vaskes på filteret uden særlige forholdsregler. Den vaskede filterkage tørres derpå og analyseres som i forudgående eksempel.Then 0.271 L of silicate solution prepared by diluting 50 ml of a commercial sodium silicate solution containing 477 g / L as SiO 2 and 239 g / L as Na 2 O is quickly added. After bringing the temperature back to 80 ° C, it is constantly maintained for two hours while still stirring. The crystal suspension is then dewatered and washed on the filter without special precautions. The washed filter cake is then dried and analyzed as in the previous example.
Den tørrede zeolit svarer til formlen: 1,85 Si02, 1 A1£03, 1 Na20, 3,8 H20.The dried zeolite corresponds to the formula: 1.85 SiO 2, 1 Al 2 O 3, 1 Na 2 O, 3.8 H 2 O.
Ved røngtendiffraktionsanalyse frembyder den strukturen svarende til sigte 4 A, og den har et udseende som vist på fig. 2 (forstørrelsesfaktor 4500).In X-ray diffraction analysis, it presents the structure similar to screen 4A, and it has an appearance as shown in FIG. 2 (magnification factor 4500).
Ved elektronmikr'.oskopering ser man mikro-terninger ganske godt adskilte og med en udstrakt komstørrelsefordeling (l til 5 micron).By electron microscopy, micro cubes are seen quite well separated and with an extended grain size distribution (1 to 5 microns).
pp
Den sepcifikke overflade BET er lig med 1,2 m /g.The specific surface BET is equal to 1.2 m / g.
Man udfører med de ved forsøgene 1 og 2 fremstillede pulvere en afprøvning af ionbytnings-hastigheden Nai^Ca på følgende måde: 1 g pulver, som er tørret ved 100°C og hvis glødningstab ved 1000°C er ca. 19%, fordeles i 1 liter opløsning indeholdende 594 mg af Cl2Ca i løbet af 1 minut ved hjælp af en ultraturax-maskine med 9000 omdr. pr. min. og forsynet med et hoved af typen T 45 K. Efter dispergeringen holdes suspensionen på en mag-netomrører i 1 min., 4 min. og 14 min., før man hurtigt fraskiller (20 sek.) ved vacuumfiltrering på en milliporefilter af typen RAWP 047 et rumfang klar væske tilstrækkeligt til at bestemme mængden af Ca++-ioner, som er forblevet i opløsningen.A test of the ion exchange rate of Na 2 Ca is carried out with the powders prepared in experiments 1 and 2 as follows: 1 g powder dried at 100 ° C and whose annealing loss at 1000 ° C is approx. 19%, is distributed in 1 liter of solution containing 594 mg of Cl2Ca over 1 minute by means of a 9000 rpm ultraturax machine. mine. and provided with a T 45 K. head. After dispersion, the suspension is held on a magnetic stirrer for 1 min., 4 min. and 14 minutes, before quickly separating (20 sec) by vacuum filtration on a RAWP 047 millipore filter, a volume of clear liquid sufficient to determine the amount of Ca ++ ions remaining in the solution.
Man opnår følgende resultater, som viser en klar forskel med hensyn til ionbytnings-kinetik for det meget fintkomede silico-aluminat fremstillet ifølge opfindelsen: μ DK 154415 Β Mækv./g Mængde Ca++ ionbyttet i mækv/g tør molekylærsigteThe following results are obtained which show a clear difference in ion exchange kinetics for the very fine silica aluminate produced according to the invention: μ DK 154415 Β Meq / g Amount of Ca ++ ion exchange in Meq / g dry molecular sieve
Efter 2 min. Efter 5 min. Efter 15 min.After 2 min. After 5 min. After 15 min.
Forsøg 1 4,9 5,12 5,5Experiment 1 4.9 5.12 5.5
Forsøg 2 2,1 3,2 4Experiment 2 2.1 3.2 4
Teoretisk kapacitet 5,8.Theoretical capacity 5.8.
Detergentvirkningdetergency
Reflektion Reflektion før vask efter vaskReflection Reflection before washing after washing
Silico-aluminat ifølge opfindelsen 39,4 59,1Silico-aluminate according to the invention 39.4 59.1
Kontrol 39,3 60,7Control 39.3 60.7
Man ser, at detergentvirkningen er stort set den samme.It is seen that the detergent effect is essentially the same.
InkrusteringsvirkningInkrusteringsvirkning
Resultater i vægt% af tekstilvægten:Results by weight% of textile weight:
Ifølge opfindelsen 0,35$According to the invention, $ 0.35
Kontrol 0,9 $Check $ 0.9
Her ser man fremkomsten af en meget tydelig forskel.Here one sees the emergence of a very clear difference.
EKSEMPEL 2EXAMPLE 2
Man fremstiller et silico-aluminat af typen 4 A.med egenskaber identiske med dem, der er beskrevet i eks. 1, idet man anvender en kontinuert fremgangsmåde, som tillader den industrielle ud-A 4 A. silico aluminate is produced having properties identical to those described in Example 1 using a continuous process which allows the industrial
15 DK 154415 BDK 154415 B
nyttelse af opfindelsen (se fig. 4).use of the invention (see Fig. 4).
En natriumaluminatopløsning indeholdende 200 g/l regnet som Na20 og 200 g/l regnet som A120^ nedkøles til -4°C i en rør-varmeveks-ler (l) med en hastighed på 10 l/time. Den nedkølede strøm blandes kontinuert med en strøm (3) på 4 l/time af en natriumsilicat-opløsning holdt ved 20°C og .indeholdende 25,4% Si02 og 7,42% Na20 efter vægt, i en under omrøring værende reaktionsbeholder (2).A sodium aluminate solution containing 200 g / L calculated as Na 2 O and 200 g / L calculated as Al 2 O 3 is cooled to -4 ° C in a tube heat exchanger (1) at a rate of 10 L / h. The cooled stream is continuously mixed with a stream (3) of 4 l / h of a sodium silicate solution maintained at 20 ° C and containing 25.4% SiO 2 and 7.42% Na 2 O by weight, in a stirred reaction vessel ( 2).
Den homogene blanding, hvis temperatur lægger sig på ca. 15°C, fødes ved hjælp af en peristaltikpumpe (4), til en indsprøjtningsdyse (5) med åbninger på 0,5 mm i diameter, hvorved der konstant dannes dråber, som falder ned i den øverste del af en reaktionsbeholder (6) fyldt med petroleum, der holdes på 85°C ved cirkulation (7) af opvarmet saltvand.The homogeneous mixture whose temperature is approx. 15 ° C, is fed by means of a peristaltic pump (4) to an injection nozzle (5) with openings of 0.5 mm in diameter, thereby constantly producing droplets falling into the upper part of a reaction vessel (6) filled with petroleum kept at 85 ° C by circulating (7) heated salt water.
Badets vægtfylde justeres således, at middelfaldtiden for de dråber, der vandes af indsprøjtningsdysen, er på 3 sek. Efter denne tid, er de runde partikler omdannet til gel og samler sig ovenpå et netværk (8) anbragt i reaktionsbeholderens bund, hvorefter de lidt efter lidt omdannes til en flydende suspension af silico-alu-minat, der samler sig i reaktionsbeholderens (6) koniske del (9). Man fjerner kontinuert denne suspension ved hjælp af et afsug-· ningsrør (10) med hastigheden 14 l/time, efter en times kontinuert tilførsel af reaktanter med det formål at fastlægge en middelopholdstid for reaktanter i reaktionsbeholderen på 1 time.The density of the bath is adjusted so that the mean drop time of the drops irrigated by the injection nozzle is 3 sec. After this time, the round particles are converted to gel and accumulate on top of a network (8) disposed in the bottom of the reaction vessel, after which they are gradually converted into a liquid suspension of silico-aluminate which accumulates in the reaction vessel (6). tapered portion (9). This suspension is continuously removed by means of a suction tube (10) at the rate of 14 l / hour, after one hour of continuous supply of reactants for the purpose of determining a mean residence time of reactants in the reaction vessel of 1 hour.
Den afsugede suspension afvandes derpå og vaskes med et hvilket som helst kendt udstyr.The aspirated suspension is then dewatered and washed with any known equipment.
EKSEMPEL 5EXAMPLE 5
Man går frem analogt med eks. 1 med undtagelse af, at man tilsætter 0,6 1 silicatopløsning i stedet for 0,4 1.You proceed by analogy with Example 1 except that 0.6 L of silicate solution is added instead of 0.4 L.
Man opnår således et silico-aluminatsuspensionskoncentration på ca. 450 g/l.Thus, a silico-aluminate suspension concentration of approx. 450 g / l.
16 DK 154415 B16 DK 154415 B
Man iagttager, at silico-aluminatets gennemsnitlige kornstørrelsesfordeling er større, således som det fremgår af fig. 3, hvis forstørrelsesfaktor er 4500.It is observed that the average grain size distribution of the silico aluminate is larger, as shown in FIG. 3, whose magnification factor is 4500.
EKSEMPEL 4EXAMPLE 4
Man fremstiller et silico-aluminat af typen 4 A ifølge opfindelsen, idet man anvender en kontinuert fremgangsmåde som angivet i fig. 4, hvilket tillader den industrielle anvendelse af opfindelsen.A silica aluminate of type 4A according to the invention is prepared using a continuous process as indicated in FIG. 4, which allows the industrial application of the invention.
En natriumaluminatopløsning indeholdende 110 g/l regnet som Na^O og 150 g/l regnet som A120^ nedkøles til 0°C i en rør-varmeveksler (l) med en hastighed af 10 l/time. Den nedkølede strøm "blandes kontinuert med en strøm (3) på 4 l/time af en natriumsilicatopløsning, der holdes ved 20°C, og som indeholder 25% SiOr, og 11,6% Na£0 på vægtbasis, i en under omrøring værende reaktionsbeholder (2).A sodium aluminate solution containing 110 g / L calculated as Na 2 O and 150 g / L counted as Al 2 O 3 is cooled to 0 ° C in a tube heat exchanger (1) at a rate of 10 L / h. The cooled stream is continuously mixed with a stream (3) of 4 l / h of a sodium silicate solution maintained at 20 ° C containing 25% SiOr and 11.6% Na 2 O by weight in a stirred mixture. being a reaction vessel (2).
Den homogene blanding, hvis temperatur indstiller sig i nærheden af 12°C, føder ved hjælp af en peristaltikpumpe (4) en indsprøjtningsdyse (5) med åbninger på 0,5 mm i diameter, hvorved der kontinuert dannes dråber, som falder ned i den øvre del af en reaktionsbeholder (6) fyldt med petroleum, der hpldes ved 85°C ved cirkulation (7) af opvarmet saltvand.The homogeneous mixture, whose temperature settles in the vicinity of 12 ° C, feeds by means of a peristaltic pump (4) an injection nozzle (5) with openings of 0.5 mm in diameter, thereby continuously producing droplets falling into it. upper portion of a reaction vessel (6) filled with petroleum which is heated at 85 ° C by circulation (7) of heated brine.
Badets vægtfylde justeres således, at middelfaldtiden for de dråber, der er dannet af indsprøjtningsdysen, er ca. 3 sek. Efter denne tid, er de runde partikler omdannet til gel, og de samler sig ovenpå et netværk (8) anbragt nederst i reaktionsbeholderen, og de omdanner sig lidt efter lidt til en flydende suspension af silicoaluminat, der samler sig i reaktionsbeholderens (6) koniske del (9)· Man fjerner kontinuert denne suspension gennem et afsugningsrør (10) med hastigheden 14 l/time, efter to timers kontinuert tilsætning.af reaktanter, således at man fastlægger middelopholdstid for reaktanter i reaktionsbeholderen på to timer.The density of the bath is adjusted so that the mean drop time of the droplets formed by the injection nozzle is approx. 3 sec. After this time, the round particles are converted to gel and they accumulate on top of a network (8) located at the bottom of the reaction vessel and gradually convert to a liquid suspension of silica aluminate which accumulates in the conical of the reaction vessel (6). part (9) · This suspension is continuously removed through a suction tube (10) at the rate of 14 l / h, after two hours of continuous addition of reactants, to determine the mean residence time of reactants in the reaction vessel for two hours.
I dette eksempel er den mikrokrystallinske suspensionskoncentration af krystallinsk natriumsilico-aluminat ca. 340 g/l, den van-In this example, the microcrystalline suspension concentration of crystalline sodium silicon aluminate is approx. 340 g / l,
17 DK 154415 B17 DK 154415 B
dige fase, som er praktisk talt fri for Si02, indeholder 76 g/l Na20 og 12 g/l A120^. Den dannede mikrokrystallinske suspension afvandes og vaskes på en filtermembran med gennemsnitsåbning på 1 yum. Den vaskede kage tørres derpå til konstant vægt i 100°C varm ovn før analyse.This phase, which is practically free of SiO 2, contains 76 g / l Na 2 O and 12 g / l Al 2 O 2. The resulting microcrystalline suspension is dewatered and washed on a 1 µm average orifice filter membrane. The washed cake is then dried to constant weight in 100 ° C hot oven before analysis.
Det dannede produkt, som er af typen 4A, frembyder en homogen korn-størrelsesfordeling med middelværdi på 3 til 4 /um godt fordelt som vist på fig. 5 (forstørrelsesfaktor 4500).The formed product, which is of type 4A, presents a homogeneous grain size distribution with an average value of 3 to 4 µm well distributed as shown in FIG. 5 (magnification factor 4500).
Produktet udviser en specifik overflade BET på 1 m /g.The product exhibits a specific surface BET of 1 m / g.
Ionbytningskapacitet Mængde Ca++ ionbyttet i mækv/g tør molekylærsigteIon exchange capacity Amount of Ca ++ ion exchange in meq / g dry molecular sieve
Efter 2 minutter Efter 5 minutter Efter 15 minutter 4,2 4,7 5,3After 2 minutes After 5 minutes After 15 minutes 4.2 4.7 5.3
Den efterfølgende tabel viser Coulter-kornstørrelsesfordelingen efter tørring for kontrolprøven, produktet fremstillet analogt med eks. 2 og produktet fremstillet analogt med eks. 4.The following table shows the Coulter grain size distribution after drying for the control sample, the product prepared analogously to Example 2, and the product prepared analogously to Example 4.
Kontrol Eks. 2 Eks. 4 % partikler mindre end 1 /um 0 20 2 2 yum 12 68 20 5 Vum 87 95 92 10 y-um 95 98 98Control Ex. 2 Ex. 4% particles less than 1 µm 0 20 2 2 yum 12 68 20 5 From 87 95 92 10 y-um 95 98 98
Partiklernes middeldiameter i yum 3 1,5 3 “ DK 154415 ΒThe mean diameter of the particles in yum 3 1.5 3 ”DK 154415 Β
Man bemærker, at man på den ene side kan opnå et mere finkornet produkt, og på den anden side, at man med en identisk middel-kom-størrelse opnår forskellige komstørrelses-profiler.It is noted that on the one hand, a finer-grained product can be obtained, and on the other hand that with an identical medium-grain size different grain profiles are obtained.
Inkrusterings- eller mineralisationsgraden er anført i følgende tabel:The degree of encrustation or mineralization is given in the following table:
Kontrol Eks. 2 Eks. 4 1 vask 0,3 0,15 0,25 10 vaskninger 1,0 0,45 0,9Control Ex. 2 Ex. 4 1 wash 0.3 0.15 0.25 10 wash 1.0 0.45 0.9
Claims (2)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7639527 | 1976-12-30 | ||
| FR7639527A FR2376074A1 (en) | 1976-12-30 | 1976-12-30 | Silico-aluminate(s) esp. for use in washing powders - with higher cation exchange power and less incrustation |
| FR7708932 | 1977-03-25 | ||
| FR7708932A FR2384716A2 (en) | 1977-03-25 | 1977-03-25 | Silico-aluminate(s) esp. for use in washing powders - with higher cation exchange power and less incrustation |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK583877A DK583877A (en) | 1978-07-01 |
| DK154415B true DK154415B (en) | 1988-11-14 |
| DK154415C DK154415C (en) | 1989-04-17 |
Family
ID=26219771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK583877A DK154415C (en) | 1976-12-30 | 1977-12-29 | PROCEDURE FOR THE PREPARATION OF A CRYSTALLINIC SILICO ALUMINATE AND USE OF THIS |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5857367B2 (en) |
| BR (1) | BR7708747A (en) |
| CA (1) | CA1132526A (en) |
| CH (1) | CH628004A5 (en) |
| DE (1) | DE2759110B2 (en) |
| DK (1) | DK154415C (en) |
| ES (1) | ES465558A1 (en) |
| FI (1) | FI66130C (en) |
| GB (1) | GB1563467A (en) |
| IE (1) | IE46054B1 (en) |
| IT (1) | IT1090149B (en) |
| LU (1) | LU78780A1 (en) |
| NL (1) | NL188402C (en) |
| NO (1) | NO152746C (en) |
| PT (1) | PT67480B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2528722A1 (en) * | 1982-06-18 | 1983-12-23 | Rhone Poulenc Chim Base | ZEOLITE AS AUXILIARY OF DETERGENCE |
| US5572812A (en) * | 1993-06-25 | 1996-11-12 | World Auto Plate Ltd. | Number plate including luminous characters |
| US5935891A (en) * | 1995-05-26 | 1999-08-10 | W. R. Grace & Co.-Conn. | High-loading adsorbent/organic matrix composites |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1038017B (en) * | 1953-12-24 | 1958-09-04 | Union Carbide Corp | Process for making crystalline zeolitic molecular sieves |
| DE1218417B (en) * | 1963-11-19 | 1966-06-08 | Wolfen Filmfab Veb | Process for the production of crystalline zeolitic molecular sieves |
| US3310373A (en) * | 1963-04-03 | 1967-03-21 | Mobil Oil Corp | Method for producing crystalline aluminosilicates |
| GB1223592A (en) * | 1967-03-22 | 1971-02-24 | Grace W R & Co | Process for the preparation of aluminosilicate ion exchange materials |
| DE2333068A1 (en) * | 1973-06-29 | 1975-03-20 | Degussa | METHOD OF MANUFACTURING NEW POWDERED ZEOLITHIC MOLECULAR SCREENS AND USE |
| DD113202A1 (en) * | 1974-07-08 | 1975-05-20 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1949360A (en) * | 1928-12-29 | 1934-02-27 | Burgess Lab Inc C F | Method for making artificial zeolites |
| BE440125A (en) * | 1939-12-26 | |||
| DE1138383B (en) * | 1961-03-23 | 1962-10-25 | Union Carbide Corp | Method of making zeolite X. |
| DE1667620C3 (en) * | 1967-08-09 | 1980-04-03 | Deutsche Gold- Und Silber-Scheideanstalt Vormals Roessler, 6000 Frankfurt | Process for the controlled production of sodium aluminum silicates with predetermined chemical and / or physical properties |
| US3425800A (en) * | 1967-10-05 | 1969-02-04 | Aluminum Co Of America | Production of crystalline zeolites |
| US3619134A (en) * | 1970-03-16 | 1971-11-09 | Gwen J Burke | Method of producing small particle size z{14 14 zeolite |
| NO148854C (en) * | 1973-04-13 | 1985-05-29 | Henkel Kgaa | POWDER FORM FOR CORN WASHING OR BLEACHING MIXTURE, WITHOUT OR WITH REDUCED PHOSPHATE CONTENT |
| US4605509A (en) * | 1973-05-11 | 1986-08-12 | The Procter & Gamble Company | Detergent compositions containing sodium aluminosilicate builders |
-
1977
- 1977-12-28 NO NO774491A patent/NO152746C/en unknown
- 1977-12-28 LU LU78780A patent/LU78780A1/xx unknown
- 1977-12-28 FI FI773942A patent/FI66130C/en not_active IP Right Cessation
- 1977-12-29 GB GB54158/77A patent/GB1563467A/en not_active Expired
- 1977-12-29 JP JP52158700A patent/JPS5857367B2/en not_active Expired
- 1977-12-29 DK DK583877A patent/DK154415C/en not_active IP Right Cessation
- 1977-12-29 CA CA294,125A patent/CA1132526A/en not_active Expired
- 1977-12-29 BR BR7708747A patent/BR7708747A/en unknown
- 1977-12-29 NL NLAANVRAGE7714535,A patent/NL188402C/en not_active IP Right Cessation
- 1977-12-29 PT PT67480A patent/PT67480B/en unknown
- 1977-12-29 IE IE2643/77A patent/IE46054B1/en not_active IP Right Cessation
- 1977-12-29 CH CH1619777A patent/CH628004A5/en not_active IP Right Cessation
- 1977-12-29 ES ES465558A patent/ES465558A1/en not_active Expired
- 1977-12-30 DE DE2759110A patent/DE2759110B2/en active Granted
- 1977-12-30 IT IT31465/77A patent/IT1090149B/en active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1038017B (en) * | 1953-12-24 | 1958-09-04 | Union Carbide Corp | Process for making crystalline zeolitic molecular sieves |
| US3310373A (en) * | 1963-04-03 | 1967-03-21 | Mobil Oil Corp | Method for producing crystalline aluminosilicates |
| DE1218417B (en) * | 1963-11-19 | 1966-06-08 | Wolfen Filmfab Veb | Process for the production of crystalline zeolitic molecular sieves |
| GB1223592A (en) * | 1967-03-22 | 1971-02-24 | Grace W R & Co | Process for the preparation of aluminosilicate ion exchange materials |
| DE2333068A1 (en) * | 1973-06-29 | 1975-03-20 | Degussa | METHOD OF MANUFACTURING NEW POWDERED ZEOLITHIC MOLECULAR SCREENS AND USE |
| DD113202A1 (en) * | 1974-07-08 | 1975-05-20 |
Also Published As
| Publication number | Publication date |
|---|---|
| FI773942A (en) | 1978-07-01 |
| CH628004A5 (en) | 1982-02-15 |
| NL188402C (en) | 1992-06-16 |
| NO152746C (en) | 1985-11-13 |
| NO774491L (en) | 1978-07-03 |
| BR7708747A (en) | 1978-08-08 |
| LU78780A1 (en) | 1978-07-11 |
| DK154415C (en) | 1989-04-17 |
| JPS53102299A (en) | 1978-09-06 |
| DE2759110C3 (en) | 1987-01-22 |
| DE2759110A1 (en) | 1978-07-06 |
| IT1090149B (en) | 1985-06-18 |
| JPS5857367B2 (en) | 1983-12-20 |
| DK583877A (en) | 1978-07-01 |
| PT67480B (en) | 1979-05-30 |
| DE2759110B2 (en) | 1979-11-22 |
| FI66130B (en) | 1984-05-31 |
| FI66130C (en) | 1984-09-10 |
| GB1563467A (en) | 1980-03-26 |
| CA1132526A (en) | 1982-09-28 |
| NO152746B (en) | 1985-08-05 |
| PT67480A (en) | 1978-01-01 |
| NL188402B (en) | 1992-01-16 |
| IE46054L (en) | 1978-06-30 |
| NL7714535A (en) | 1978-07-04 |
| ES465558A1 (en) | 1979-01-01 |
| IE46054B1 (en) | 1983-02-09 |
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| PBP | Patent lapsed |