DE1667710A1 - Process for the production of silicates - Google Patents

Description

The present invention relates to a method for producing * of silicates in active form, especially for production of crystalline synthetic zeolites.

In the earlier patent application 9 IO6 857 IVa / 12 1 was

a process for the production of silicates in active form

old of the composition (Xa ₂ O) ₁₁ SiO ₂ proposed, where η

has a value from 0.5 to 2.0. The use of such and other active silicates la the M »lekulaiwles * created« Mg 1st In the fiitisisu patent registration, S 9 / Γ 166 IVa / 12 i, j 8 103 075 m / 12 1 and 8 106 S «| 6 IVa / 12 1 beoehrleten. Of the

Advantage of the full use of active silicates in the case of preparation of 4

of molecular sieves is based on the fact that the Bsaktlon is old

higher speed and sa wider working range and in some cases, e.g. in the manufacture of Zeollth X and zeolite Y, in a more selective manner more advantageous conditions than with bargaining base materials such as water glass, colloidal silica

10982Ü / U68

- 2 - "door", silica or inactive "Xatrlusslllkat ·

It was found that the mm silicic acid and silicate of the Xusasnensetsung (Ha ₂ O) _n . SiOg.XHgO can advise »where η has a value too O bie 0.5 and X 0.1 and higher for the active rom. Since * "active ¹¹ silicate was already described in the Baralleiax report S 97 166 *, a product can be found which, when subjected to a reaction time of 5 hours, results in zeolite X. The following conditions are used!

Bel Unit eap era tug "ground 8 g Matriu-ttw nllikat pentahydrate dissolved in water at 20 ι t \ mmm 1 asysntur and in dieee solution 8t g wtturlgea latrluemlueiinat old · a Oebalt of 0.75 g of Na ₂ O and 1.0 g Al ₂ O, gifted. The water is kept under stirring at 90 to 100 ° C for 3 minutes, filtered,

iBPBBl · ^ βββτ epee ^ swi ^^ Pens ^ PejHMB ^ p ^ W ^ Mw Weßjm ^ m wk ^^^ w ^ 0 ^ J ^^ * wev ^^^^ eee «e ^^" ♦

UV · 1μκ la ejssejitlielMm raiae «Bseilttaen X bJiRtelt · IHIe

v * dekB ^ B) ie) eW ** ^ MS ^^ ei ^ ft Jt ^^ ^ y ^^ M ^ u ^^^^^^^^^ - Άβαι S ^^ M ^^ M ^ A ^ Ik ^^ ui eM ^ 4 ^

uBsl gilülBisstt Ib Asv sjsiehsn Vsisej vemssdet »

very broad range of activity according to the novel compounds in ti ¹ faseeu. Meeee mtersushymsrerern bestlssA all AktlTltltl jsiir silicic acid eggs iedhe silicates «ureh Tergleleh ■ 1t a standard sample and detects an activity level of

109828/1469 _ ^

ORIGINAL

Ofels su MbF as 10,000 unit «. The investigation for them Activity and dl · Determination of the activity values is next given below.

OemJte «inte feature of the present: <s» invention, new products of the general formula (Ka ₂ O) _n , SiO ₂ .XH ₂ O are proposed, in which X has any value from 0.1 upwards and η a value from 0 to 0 * 5 mean kran «whereby the product has the active properties»

In order to produce this novel compound, the cation is partially or completely removed from an active sodium precipitate of the formula (Ha ₂ O) ₁₁ -SiO ₂ ^ YH ₂ O, where a range is from 0.5 to 1.5 and Y is a value of 0.05 and more means »where dl · temperature is set to 60 ° C or lower. This removal of cations, for example, by Sfiuresugabe and washing xur remove soluble salts, at a temperature la Bereloh from 0 to 55 and vorsugsweis · from 80 to 4O ⁰ C take place, followed then dried or is an ion exchange carried out "while the temperature in the range of 0 to 60 and preferably 20 to 40 ° C is kept and then dried

What is essential is the distance or partial distance of the cations carried out in the specified temperature range otherwise the silicic acid or the resulting silicate in the

109828 / U69

inactive remote. Both in the Slurezugabe like you in de "Xonenaiistausohverfahren creates an uplifting Liehe wfrMMenge so dal cooling the Reaktlonsteilnehaer is an important Veil de" muddled * These compounds of Porael (Ha ₂ O) ₂ ^ SiO ₂ XH ₂ O, where η equal 0 to 0.5 and X is 0.1 or more, have active properties and are at least as effective in making crystalline synthetic zeolites as the active silicates mentioned in the copending applications cited above , X and Y is a further component of the present invention when using the new active silica and the silicates "

Furthermore, the present invention provides a method sur production of crystalline synthetic zeolite A or zeolite X with molecular sieve properties and ion exchange properties proposed, which is characterized by that nan an aqueous solution of sodium aluainate and one SlUoiuahhaltigen component Mixes with each other, so that »to Obtains solutions in which the molar ratios of the oxides In the following area are »

a)

Xa ₂ OZSiO ₂

0.06 until 4.00 0.70 until 20.00 15 * 00 until 200.00

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b) SiO ₂ ZAl ₂ O ₅ - 2.00 to 30.00

* 0.40 to 6.50 - 10.00 to 150.00

where at least a part of the catalytic converter is a connection the general fora ·! (Ka ₂ O) _n .SlO ₂ -XH ₂ O is »where X is the same 0 to 0 * 5 and X is 0.1 and more, active properties geattfi definition owns and being the proportion of active pebbles stoirekoaponente to other »KleselslhireBatorlal la area of 1.0 su 0 to I ₉ O ι 76 * 000 is "what" due to temperatures of 30 to 120 ⁰ C without aging of the reaction mixture * at feaperatures

crystallized below the crystallization temperature

The two above mentioned Berelehe a) and b) for the MoI-

The ratio of oxides refers in particular to the production of zeolite A and zeolite Xt in the outer regions the zeolites obtained optionally still crystalline or

amorphous · impurities Bcasu sequence preferably gets old

Holverhil tnlssen worked in the following areas ι _ί

Zeolite A SiO ₂ ZAl ₂ O ₃ * O ₉ 19 until 2.70 Xa ₂ OZSlO ₂ 0.85 until 9.70 R ₂ OzHa ₂ O 30.00 until 800.00 Zeollth X SiO ₂ ZAl ₂ O ₃ 2.80 until 8.00 Xa ₂ OZBiO ₂ 0 ₉ 70 until 5.00 35.00 until 120.00 109828 / U69

and waiMi the proportion of active KieseisHurekonponente ta other KleselsSurcewterlallen is in the range of 1.0 t 0 to 1.0 i7.0.

To achieve better results in the specified range • The active Kieeela whore should have an activity of at least 80 Units according to the specified method included.

Furthermore, according to the present invention, a method is used Production of the zeolite T of the utmost purity

from more than ? up to at least 6.2 suggested, in> dea Man an aqueous solution of a soluble amine solution, at least one of which is a compound of the general formula QUt ₂ O) _n . SiO ₂ -XH ₂ O, mixed, in which η 0 to 0.5 and X 0.1 or more, and which has an activity of at least 10 units and preferably more than 80 Xinhelten, so that a reaction mixture with Get ratios in the following areas

1) 0, ^ 6 - 0.30 S - 18th 80 - TO a) 0.30 - 0.31 8th - 14th 80 - 70 0.31 - 0.32 8th - 1β 80 * 90 *) 0.3 » - 0.235 8th - 80 18 * 90 5) 0.5 » - 0.4 T - 40 18 - 120 6) 0.4 • 1.0 5 - 90 18 - 120 7) 1.0 • 8.0 8th - 30th 18 - 120

109828/1469

mm. dme Reaktionsgeaisoh preferably erwtat under Bühren up ^'0 O 2 S, is filled to a crystalline product "

The proportion of active kleselsilfiir @ k3s ^ onentrm . Inactive kiesolslturokowponcttto should lie in the range from 1.0 to 1.0 to 1.0 or more, depending on the type of activity of the most in-set silicate or silicic acid. In the case of a silica or a silicate with an activity of 100 units, the working range is from 1.0 to 1.0 to 60 and preferably from 1.0 to 1.0 to 1.0.

The advantage of using active silicic acid instead of commercially available idle glass-like components is

a) a significantly increased reaction rate for any given tea temperature

b) products of greater purity}

0) longer aging pages can be omitted with the Manufacture of Zeolite Xf No aging is required in the manufacture of Zeolite T, although this according to the state of the art s »B. gealS OS patent specification 3 1 »007 was requested *

d) there are no difficulties bestiglioh the «Same and the same level of satisfaction as you for example in the geettfi britisoher process Patent specification 973 93? (Zeolite X) and U.S. Patent 3 130 007 (zeolite Y) have been described ·

109828/1469

The advantage of using active silica in one Zeolite structure can be found in Table 1. In this case The implementation underlying this table was the Molar ratio of the starting product

- 10 «0.3» 55

Trial three of fabeile 1 shows the benefits that can be achieved Use of active silica in the production of zeolite Y be achieved. Am previous aging of the reaction time is not required and the mechanical and theoretical UfcwHsung does not give rise to any difficulties. Branch is most important however, the oesastreaktlon selt when using active Silicic acid, which was less than a tenth of the time "that." was previously necessary according to the prior art using the inactive silica, as a comparison of experiments Ib and Figure 2b shows. The reactions according to experiments Ib and 2b are typical of the prior art * like them for example, in U.S. Patent 3 3-20,007 * From examples la and 2a it follows that a previous aging and not a solution in the known Methods are required »if zeolite Y is to be obtained.

109828/1469

Active silica gel or silicas can be produced «Ground» charge »«, * as mentioned above. Acid to active silicates admits and washes; the one of its experiments in Table 2 show the preparation in this way. The results show » that to maintain the maximum activity in the silica it is necessary »the temperature within narrow ranges during the manufacturing process and also during the Drying * of the hydrated silicon dioxide obtained control · Obgleioh aan active products at Raaktleaera- f Doors of below S5 ° C can achieve »If the precipitation of the Silica very slowly and to achieve optimal activity the product is preferably 1 »range from 20 to 40 ° C failed. Table 2 shows that when the precipitation temperature is increased, the activity of the silica decreases, so that sohlleBlloh obtained an inactive product at 55 to 60 ° C will.

The roeknungsteaperatur also influences the activity so that preferably the product is dried in the range of 15 to 35 ° C. Experiment 3 in table 2 shows, however, that even drying at 10O ⁰ C only partially deactivates the product.

When adding slure to active Hatrluttsillkat in firm pom or in solution enough WHrae is released "so" the activity will be completely destroyed if there is no advance payment to be hit. Hence it is in the production of

109828/1469

Active Kieeelallureverbindungen essential that the reaction "participant in the" specified temperature range "Qi to keep the temperature rise small""are used two normal sJtures" although also 0.5 normal "in each of the concentrated acids, but preferably 2 to 10 noramles Sluren used to know. But can concentrate the silicate "in solution only 0.2 mol preferably 0.5 bia S ₉ O · Get amount to achieve a sebnellen precipitation. SHure tu de «active sodium silicate is added to the silica to adjust the pH value to a value of 8 to 10, although active silica can also be retained» if the pH value generally ranges from less than 1 to about 11 in the case of strong Sturen lies, sB BOl but from 12.8 ascents at sohwaehen slur, s «B * Bsslgslure · The quenching time depends on the temperature and the pH value and takes place within a few seconds under preferred working conditions Table 2 is · Salsslftira »but any other · Siore. Since the Kieaelallure can» be used. The experiments show that the use of nitric acid and sodium chloride is also possible in Table 2. In experiments 2 and 3 according to Table 2, the acid was slowly added to a cooled aqueous solution or suspension of the active silicate. Example 7 of Table 2 shows that the use of inactive, that is, bandelsObllohesi ■ atrluaaetasllikat as starting material, gives an inactive product.

109828/1469

The active silica gel is v "s sodium salts, <g, B. Tare sodium chloride with Pil and get rid of vaseheads.Bs is essential, remove the salts formed during the reaction in order to mögiiohefc to receive active products »and roll if possible less than 2 Qe *. If catfish are present, this removal can be done by dialysis.

According to the invention, the active silica sols are produced from solutions vtn active Hatriuasilikat can be obtained «by» to this If a zone exchange hair (ζ · Β · Zeekarb 225) is brought into contact for the removal of cations »Among other things, to achieve a maximum activity of the product xu, it is again necessary to use this process watch under carefully set conditions »so dai the resulting worm is removed during the procedure. the Temperature mui in a range from 0 to 60 ° and preferably 20 to 40 ° C.

For example, the process can be performed by tubing a slurry of the ion exchange resin with a solution of active sodium silicate. Optionally, the silicate solution also by passing through a bar column. In both cases, the reaction participants must be cooled »otherwise so much warmth is developed that the whole activity of the obtained product is xeretört. Table 3 shows the results some attempts in the production of typical active silica sols according to the invention. Example 3 shows that it is necessary

109828 / H69

to use as Auagange material "an active" form of the silicate, "active" silica according to the process. In order to stabilize the active silica sol obtained after this process and to avoid filling with silica gel, it is advisable to use small amounts of alkali after the exchange step so that a SiOg / alkali ratio of 60 to 130% is obtained becomes · The product alt of the general formula (Ma ₂ O) _n -SiO ₂ -XH ₂ O then has an η value of 0.07 to 0.17.

Active silica brines also edge due to electroosmosis a solution of the active silicate are obtained, wherein then the silica sol is obtained in the anode emitter Am active ·· Silica sol can also by electrolysis of a active sodium silicate solution in a cell with a lead anode and a mercury cathode can be obtained

Active · KleaelaBureverbinrtungen of the general formula (Ma ₂ O) _n -SiO ₂ -XH ₂ O alt an η value from 0 to O ₉ 5 and a value for X of 0.1 and more, can by adding sodium hydroxide in active silica and / or silicates have a higher η value and can be used directly in the production of the zeolites. In this way, active di- and tetrasilicates are produced, as indicated, for example, in Tables 5 * 6, 7 »9 and 10,

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To determine the number of activities that an arbitrary Value based on the yield of Zeollth * for a star represents the roasting process "is based on an implementation" the pure zeolite X with active silica with a minimum act ivi did of about 10 units results. For this purpose nuts the molar proportions of the reactants must always be the same, such as.

SlO ₂ ZAl ₃ O ₃ >> 3.85

47.00

As an alumni supplier, Hatrlunalunlnat. used in liquid state. If an inactive silicate is to be used as the diluent, then commercially available Hatriundlsllikat with the approximate composition Na ₂ O, 2 SlO ₂ 14.1 HgO is used. A total of three tests can be carried out; Test 1 applies to an active range of 0 to at least 10 units and the silicic acid or silicate product to be examined is the only silicon-containing compound. Test 2 concerns the investigation of silicic acid or a silicate with an activity number of 10 to 100 units and here 10 % of the silicic acid to be investigated (calculated as SIO ₂ on a molar basis) can be used together with an inactive silicate as a diluent. Test 3 is for testing silica or silicates with an activity number in the range from 100 to about 1000

109828 / U69

Units thought, whereby 1% of the silicic acid to be investigated is present in connection with inactive »dis & lkat. In these investigations, a material with an activity of 0 does not give any notable amounts of zeolite X (only very small traces of zeolite B or zeolite C are allowed). A material with an activity of approximately 10 units results in essentially pure zeolite X in experiment 1 and about 30 μl of zeolite B and / or zeolite C together with zeolite X in »Versuoh 2. A material with an activity of 100 units results in 1» essential pure zeolite X in test 1 and and zeolite X with about 40 % zeolite B or C in test 3.

Am material BiIt an activity of 1000 units or more results in 1 »essentially pure zeolite X in» tests I, 2 and 3-The X-ray values for zeolites X, B and C are in the Table 4, where "d" is given in ftigetröm Distance »between the Xbenes and" i * mean the intensities which have been determined visually, with the strongest line being assigned an intensity of 10.

for exact activity tax numbers, standard conditions must be adhered to Units selected as standard and Runtgenbllder the pro products made according to tests 1, 2 and 3. By comparing the • eugungsbilder of test products »according to standard images the activity la range from 0 to 1000 units was determined

109828/1469

are »For activity numbers of more than 1000 units must exact tests also at even higher dilutions than in the test be performed.

In the Zeollth-X reactions for tea 1 to 3, the substance to be investigated (silica or silicate) is dissolved or suspended in about half the total amount of water required, which contains sodium hydroxide and, if necessary, sodium disilicate. This process must be carried out in a temperature range from 15 to 30 ^° C. so that there is no loss of activity of the silica. The mixture is stirred vigorously for 10 minutes to achieve a good mixture and then sodium aluminate solution is slowly added along with the remainder of the required water, after which the mixture is stirred vigorously for a further 10 minutes until a homogeneous mass is obtained. This is then heated to 90 to 95 ⁰ C under -kräftigem stirring and left for 3 hours under these conditions. The solid product obtained (

is filtered off and washed until the filtrate has a pH of shows about 10 and then dried at 80 to 120 ° C. The material is then examined with X-rays. Usually works on in a 1 liter jar. Examples of tests 1, 2 and 3 are given below, with hydratlsierta silica as Test material is used. In the case of silica with another Water content or, in the case of sodium silicates, the equivalent weight must be used to keep the molar ratios at the desired value

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T «et 1, activity range 0 to at least 10

69.67 g of silica gel (SiO ₂ 6.85 H ₂ O) were dispersed in 245.5 ml of water with a content of 30.5% sodium hydroxide. After stirring vigorously for 10 minutes, a solution containing 59.8 g of aluainate and 100 g of additional water was added over the course of 5 to 3 minutes with vigorous stirring. After mixing for 10 minutes, the temperature was increased to 95 ° C. with vigorous stirring. These conditions were maintained for 3 hours. The solid product was filtered off, washed until the pH of the filtrate was about 10, then ^{dried at ISO 0} C and then examined with X-rays.

Test 2, activity range 10 to at least 100

7 * 3 g of silica gel were in 265 S water together with 73 * 2 g ftatriundisillkat and 17.6 g sodium hydroxide i dispersed. To For 10 minutes of vigorous stirring, the procedure was continued as in Test 1, after which hatriura aluminate and more water were added admitted.

109828/1469

- 17 -Tea «3, activity range 100 to at least 1000

0.73 g of silica gel was dissolved in 265% of water along with 81.0 g Hatrlumdlsillkat and 16.2 g of sodium hydroxide dispersed. To For ten minutes of vigorous tubing, the procedure was as in Test 1 continued, nKmlloh by adding sodium aluminate and more water.

Manufacture of the zeolites

The flow of the current numbers, in particular with regard to zeolite A and zeolite X translations, results from experiments as summarized in Table 5. In these experiments, the participants in the reaction were vigorously stirred and, with the exception of Example 7, which serves as a comparison for a method according to the prior art, no aging was carried out. Experiments 1 to 5 show that the desired zeolite was obtained more quickly if active silicic acid components were used. When trying 4, the Inactive silica yielded not even the desired zeolite X, while the active! 'Ieseleäurehaltige component provided the zeolite X in only 3 hours, as compared with the tibllohen procedure of Example 7 where 17 hours pre-aging at 25 ⁰ C and 3 hours "erforderlieh was at 95 ⁰ C while ensuring aulte be worn dal a thermal or mechanical agitation was avoided.

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B * it is assumed that the advantages of selecting the active silicon component in the production of the zeolites A and X are based on the ability of this component to react very quickly with the aluminum component and to provide a homogeneous aluminum silicate gel which delivers the desired products much more quickly than the oils made from common silica. It has also been found that the active silica component is used according to the invention, just as the active silicates according to the above-mentioned earlier applications, can be used directly to carry out zeolite reactions in the desired manner, when these together with inactive silicone components, for example Water glass or even free silica can be used. Provided that a reasonable amount of active silica or active silicate is used, all of the advantages of the active component in the reaction, namely increased reaction rates and selectivities, are retained. The molar ratio of active silica or silicate to inactive * containing silica «! The material should, based on an olar SiO ₂ -BaSiS, be in the range from 1.0 to 1.0 to 76,000 and preferably in the case of zeolite X from 1.0 to 1.3 to 7,000. This Bereioh is affected by the Auemaß the activity of the active silicic acid or de · active silicate and for products with an activity of 100 units of this Bereioh "reads wipe 1.0 t 0 and 1.0 t 7.0.

1Q9828 / U69

For the division of zeolite A and zeolite X according to the invention leaan the active silica or silicate used a single active compound or, for example, a Danish form of hydrated silica either ala solution or all coarse or finely divided QeI together with other active ones KieselsMuriferous. Connections such as those British parallel application 591,679.

In the production of zeolite A and X, the Reaktionsgetaieoh from Natrlum is / namely long "until crystals form Aluminlum / Kieselsiture and water at temperatures in the range of 20 to 120, and held preferably 80 to 100 ⁰ C and the desired the

ohemlsohe composition and the X-ray blinds of the concerned Yield zeolites

In the previous process for the production of zeolite A in which used as KieselsKurekomponente substantially water glass was', they worked with Re £ ktionstemperaturen of 50 ⁰ C ₉ wherein the Utasetzung verlauftj very slowly when using the active Kiesel Sture geaUß invention ν ar the reaction after 24 Hours finished. The results of the experiments to explain this feature are shown in Table 6.

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I am compared with the previously known process according to British patent specification 973 933 for the production of Zeollth X s "lgt" because it had not been possible to manufacture this product in the pure state on a large scale, provided that it did not age for a long time (up to 9 Days) for the aluminum gel at room temperature. Even after such a stop Runge tent, it was necessary that Oemioch about 3 hours without stirring to 10O ⁰ C to heat · The use of a silica according to the invention notional 1st it possible a ?. pure zeolite X can be obtained in less than 3 hours without an Altormig but with or without stirring, preferably stirring in order to allow better mixing and faster reaction «

If an active silica with an activity number of Etehr is used as 100 units, the reaction times will be greatly reduced and with se! ir much lower Active silicic acid compound concentrations according to the invention and work together with normal commercially available water glass.

The results of the tests for the preparation of Zeollth X in pure form using active silica are given in Table 7. This table shows that the use of inactive silica Zeollth an X is obtained only after prolonged aging at about 25 ⁰ C and without agitation, wBhrend in the active silicic acid or active silicates, a zeolite X very

109828/1489

soneil without any difficulties that arise when stirring, is obtained. In the experiments shown in Table 7, the molar ratios are as follows

Si0g / Al _{2 o 3} »5.85 Na ₂ 0 / Si0 ₂ « 1,? 4

* 47.00

If a reactive silicic acid or a reactive silicate with an active number of more than about 80 units is used, even very low concentrations of active material can combine with in & ktl / en Kieealöureltoraponentai. be used. The effect of the alloy number on the concentration of the active KiesslsSurematerial required for the production of essentially pure zeolite X is shown in Table 8. The first two tests are comparison tests without the use of an active silicauaskotaponente. The molar ratios given above were maintained in all of these reactions. The results show that the presence of only inactive silica particles in the zeolite X conversion according to the preferred process according to the invention, ie without aging and strong BtKiras at reaction temperature, practically no zeolite X is obtained, but only a contaminated zeolite B results. If , on the other hand, suitable concentrations of active silicic acid are present, the silicate and the same inactive silicic acid component are present

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essentially pure zeolite X obtained.

Tables 9 and 10 show the advantages that are achieved in the production of zeolite Y when an active silica component according to the invention is used, in Table 9, experiments 1, 2, 5 and 6 show the advantages that are achieved when an active silica gel is used instead of a commercial colloidal silica, while experiments 3 and 4 show the advantages of active sodium tetrasilicate instead of commercial tetrasilicate. From Table 10 it can be seen that it is advantageous to use active silicic acid or an active silicate together with active silicic acid instead of inactive silicic acid with an active silicate. In experiments 1, 2 and 3 according to Table 10, the reaction time is reduced by a factor of 2.6 by using only active silicic acid-containing material. Experiments 4 and 5 also show the increased reaction rate

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Table 1 - Implementations with .active imß. inactive silica

In the experiments la and l ^; VMRD © as silica product ^w Syton X "Monsanto used which was" sin colloidal silica sol having an activity of O.

In experiments 2a and 2b, the product "Aerosil" from Degussa was used, nKraliclieine foggy or rough pebbles Silurs Biit extremely small violets and an activity of O.

In Experiment 3, a KieseXs-Acid was used which was produced in an earlier application by AnsKuraa won active catalytic asilicate and foestsnd from coarse KisselsM.uret; s Liehen and had an activity of 100.

10982 8/1463

T & bSll © 1

composition

Eeakfcl onsto

Aging up to 25 ° C in hours

Response time at

9 5 ° C in Stan »

product

39.8 g N & triumalurainate * 13.6 g KufcriumhyarOxya 2Ql, Q g colloidal silica ***

water

16

16c

Zeolite 3 Zeolite'C

39 * 8 g E & trluBjaluiainat.

! 3 »6 S Natpltiratoyä

60.0 g "Aerosil ·

2O g of water

39.8 s

2-3 »ο S sodium hydroxide 126.0 g of active silica gel, 206.0 g of water 160

1β

olith B

Zaolite Y-

Y-

* ■ molar composition 1.3! Yes ₀ O Al ₀ O, 12 Ho molar composition Siö ₂ .T, ö5

molar composition

3.67 K2O %

2 - Production of active Kisaelsätsi * © by adding Si & sre au aktiv! ®

! Attempt j activity ye »SHr. Sodium silicate

pH value is established

Reactiosis- s ^ το <

temperature pebble

säur® Im

Activity of

sstpökneten

Silica

! 10ÜÜ

iODO
1Ό00

300

J WV ^

7.5
7.5

T, O
T, O

10.5

30th

35

20th

30th
30th

81.0

5Ö0 200

300

At dsn tryaii. 1 and 4-11 became the slip to the solution and feel d © ri attempts 2 vsta 3 zv. a f © st © n Stispönsion Geg © b © a · Bei.de2 & Versueheß 2. -9? ä «^ öe. the pE-'fe ^ t asit HOl with acetic acid and in the experiment Il taifc nitric acid. © ioge'ß & llt What is certain that there was still!

l, at ©

the claim 10

Table 5 - Hersfcellxaig vosi active pebbles sEii ^

The £ oil constricting Try ^ aMe tesi Versucfe 1 © ift & a silicate-nit of activity. 250 Blnheitssi *; eroded. Add? Removal of the Kafcloäea sjurda the solution of the -is silicate kit "Zeolcspfo SS5 ^Ö « ßtsr Klihlimg

Bai Experiment 2 -mvd® also a liatFiuiBsili ^ at wife of Ak &ivii; Hfe 250 used, whereby 700 ml of a SQsactive 'j? At anthalteraden Lösimg öijrch "geolmrb 225"& @ i b3srenatter_ perkollert

In experiment 5 a 'NauriuiBsiliEait -iait; ά. *. Activity 0' - / - ar lands, whereby commercial Katrlusssilika't slt "Zeokarb 32y ^W: -ιΐ-closed and the HeaIctiGnstellnelH3er geldSill; vairäass. Dia working conditions were like · Foists

attempt

pH of the sol

6 1

20th

Klesel-

la

$ P

kXK'j ^^ - ι ¹ I> mii mi Il Ι "ι

BATH

109828/1469

X-ray values for zeolites X, B and C - table

■ 1., 111IWtIiI ¹ M) '. I ■ - "■ = ■ ¹ J- 1 Μ j" J
2 * ttith X Zeolite B d U.5 8.8 7.5 9 4.8 4.4 3.95 3.78 3.3 3.02 2.90 2.85 2.78 2.70 2.62 2.58 I. 10 9 6th 2.19 4th 4th 2 9 8th 4th 4th 8th 2 7th 4 " d 2O2 <: 38 2.22 4th 2.17 2.09 1.92 1.90 I.84 I.80 1.77 1.74 1.70 1.61 1.55 V 2 © ollth G * I. 2 6th 2 3.18 4, 4th 4th 4th 2 2 4th 4th 6th ? f Z a 7.1 > · · 4.1 10 2.90 2.6ö 2.52 2.36 .2.? ~> 1.-: ι <· « 1.54 I. 7th Ö 1.36 3 fl ' 2 4th 1 5 > ■ 4th d 1.48 1.41 1.38 4th 1.23 ■ I. 4th 4th 3 3.0
3.05 4th d 6.67 4.8 3.9
3.95 7th I. 10 2.5 5

* The diffraction lines for zeolite C were mostly diffuse and it was found that this material is often metastable and even converts to zeolite B after about 48 hours in the solid state.

0 98 28 / U69

Table 5 - Influence of activity on hydrated silica or sodium sulfate

Attempt no.

Type of silicate

Activity!

Mole ratios

SLO

g Ha ₂ O

Reaction time in hours at - 95 C.

product

Commercially available colloidal KI- _ Selsic Acid "Syton X *

1.46

2.12

68.7

0.5

2.0

amorphous Zeolite A

active colloidal silica

50

1.46

2.12

68.7

0.5

Zeollth A.

i active sodium dislicate

! 4 '

colloidal pebbles

tre "Syton X *

1.46

2.12

68.7

O ₅ S

sMuregel

3.95. I.

i 52

Zeolites A

Zeollth B.

Seolite .C. amorphous

Zeollth X

for β

active ii disillkat.

3 ·

commercially available

Sodium clisilicate

L-KimtM · !.

3 * 95 j

! ■ 'I

'$ 3 I.
f
i ·

Ij

bsi

Table 6 - Zeolifch A at 50%

attempt

O CU OO

Type of silicate

commercially available

in

>, I SiO,

95 ₉ '

24 60

fe & i

11

active

disilicate

commercial

colloidal pebbles «.

active colloidal silica

9 * ϊ.7

500

H

5, 7

Seolite A

4 I.

. 2eolite Af

6 CD

Table J - Preparation of Zeolite X at 90 · »95 ° C

attempt
Hr, ', used @ tzt @ 8
Sililcat Activity
of the silicates Reaction
time in Stön. Aging
at 25 ° C stir product 12th colloid · Kie
sic acid 0 3.0
5.0 no
1? Moan. Yes
no Zeolite B
Zeollth 'Σ 13th a & taves Kie
selsäuresol 3.0 nope Yes , Zeolite X 3.4 KatriUBdlsili- 0 3.0
5.0 kat ⁿ pyr «mid
Fire" 3.0 no
I? Stan. Yes
n © in • i- eaorpfe
Zselith X 15th active hatriun
üisilitcat no Yes Zeollth'X '

Table 8 - Influence of the activity number on the concentration of active silica for Manufacture of zeolite X

attempt
No. Kind of turned
put silicate UCtlVlt & tS-
bald Reaction participants Reaction * - product
permanent at
95 ⁰ C in hours Zeolite B +
aaorphic 16 commercially available
Natriundisttik & t 0 39.8 g of sodium aluminate (1.3Na ₀ O. Al ₀ O ,.
12 H ₂ O) ^d *
82.6 g sodium disilicate
(Na ₂ O.2SlO ₂ .14.1.H ₂ O)
16.1 grams of sodium hydroxide
394.0 grams of water 3 Zeolite B ♦
Zeolite +
amorphous commercially available
Sodium silicate »
inactive pebble
acid gel 1 0 39.8 g of sodium aluminate
73.2 g of sodium silioate
7.3 g of inactive silica gel
17.6 grams of sodium hydroxide
365 * 0 g water 3 Zeolite X 18th active pebble *
acid gel 2
commercially available
Sodium disilicate 100
0 39.8 grams of sodium aluminate
73.2 grams of sodium silicate
7.3 g active silica gel 2
17.6 grams of sodium hydroxide
365.0 g of water 3 Zeolite X *
approx. 10 %
Zeolite C 19th active pebble *
acid gel 3
commercially available
Sodium disilicate 500
0 39.8 grams of sodium aluminate
81.0 g sodium disilicate
0.73 β active silica gel 3
16.2 grams of sodium hydroxide
365, OgWa ₈ SeP 3 Zeolite X 20th active silica
acid gel 4
commercially available
Sodium diailicate iooo
0 39.8 g sodium aluminate
81.0 g of soda silicate
0.73 g Kleselsturegel 4
16.2 grams of sodium hydroxide
365.0 g of water 3

The silica · «·! · 1 * 4 all have the composition 3102. 6th 85 H ₂ O 100828/1469

Table ) »Active silicic acid and silicates compared to inactive forms

when implementing zeolite Y

Verse.
No. Silicon grain
component - composition Oxide-
JiOo 16 • Ratio
Na ₂ O skills
H ₂ O D. Aging stir Reactions
time Product; 1 colloidal
Silica
approx. 30JiSiO ₀ -_
"Sy ton 2X * ⁿ * 79.6 grams of sodium alumi
nat (1.3Na ₉ O.Al ₉ O ,.
12 Hy ₂ O) <
320 «0 g colloidal grain
sic acid
17 * 6 g sodium hydroxide
200.0 g of water 16 SiO ₂ 55 (a) O
(b) 24.0 (a) yes
'b) no Approx) 16
(b) 72 (a) zeolite
B + C +
amorphous $ 90
Zeolite Y 2 ^: active
Silica
gel
(SlO ₂ , 6.85H ₂ O) 8th !> 55 0 16 $ 100 Zeo
lith Y <
SiO ₂ ZAl ₂ O ₅ 3 active tetra
silicate ** 79.6 g sodium alurainate
292.0 g of active silica ¹ . 8th
Acid gel J
17 »6 g of sodium hydroxyci
250.0 g of water 5 0.3 45 0 Yes 48 9Ο5έ Zeo -
lith Y SiO ₂ i 4 commercially available
Tetrasilicate ** 39.8 ε sodium aluminate
428.8 grams of active tetra
silicate
973.0 grams of water 0.33 45 0 Yes 48 Zeolite S 5 active pebble
acid gel
(SiO ₂₁ 7.78H ₂ O) 39.8 grams of sodium aluminate
428.8 g of sodium tetrasi
likat
973.0 grams of water 0.33 30th 0 2.0 lOOJ & Zeo-
lith YSiO ₂
/ Δ Λ f \ * » ¹ ^ 1 6 ' colloidal kie
sic acid "Syton 39, ö g sodium inate
100.0 g of active silica
acid gel
15.6 grams of sodium hydroxide
93.5 g of water 0.7 0 2.0 amorphous Uctivi
does 39, ö g sodium aluminate
100.0 g colloidal pebbles
15.6 grams of sodium hydroxide
93.5 g of water 0.7 0 500 250 6th 250 0

Na ₂ 0.4 S10 ₂ T43 H ₂ O

-P

C? -P

U SOOM CVICV53)

£ 3 Zi ßJ ία

HSr

WtOWtO OO OVO O

Claims (1)

Claims 1. Process for the production of a connection d © 2 * Forrael (Na _g 0) SiOg.Xl ^ Op ia which iC sr.iien Wsr-fc ve »0.1 and more and η has a fourth from 0 to 0 * 5, vmau & Xch * * possesses active properties as a result of which ■ sck @ nna © islmet _s ilafj mm partially or completely removes the cations oa stEctivem sodium silicate of the formula (tits ^ ß}, StQp ^ IiJb. ■ , wefeei m in the range of 0.5 to 1.5 and "has a value of -0.05 and more, the temperature being set to 60 ° C or less. 2. The method according to claim 1, characterized in that Removal of the cations by SHurszug & ibe ssu - active silicate at temperatures from 0 to 55 ° C takes place in the finally, soluble salt is removed and the product will. Process according to Claims 1 to 2, characterized in that the cations are removed by means of Xonenaustaiischer sm active sodium silicate at a temperature in the range of O föis oS ° G. 109828Λ1469 BATH ORIGINAL - ¹ ST- is 4. The method according to claim 2 to 3, characterized in that the temperature during the removal of the cations is in a range from 20 to 40 ° C. 5. The method according to claim 1 to 4, characterized in that the product after the cation removal is dried at temperatures in the range from 15 to J55 ° C. 6. The method according to claim 2, 4 to 5, characterized in that that the cations are removed with hydrochloric acid. 7. The method according to claim 2 and 4 to 6, characterized in that that the pH of the active sodium silica & ts with acid on a pH of 8 to 10 is set. 8. The method according to claim 3, characterized in that the ion exchange unit is carried out by a Slurry of the ion exchange resin with a solution of the active sodium! likats and the realst ion participants cools while stirring. 9. The method according to claim 3, characterized in that one. carries out the ion exchange by passing a solution of the active sodium silicate through an exchange column, wherein the reactants are cooled during the passage. 10 9 8 28/1469 10. Method according to Änspruoh 8 to 9 » .by .getattui & eleimet, that one contains a small amount of alkali and afcfcitren egg which from the ion exchange reaction: 11. The method according to claim XO *, characterized in that the addition of alkali is so toasted that the active -KieHelsiSfflPoso: a SiOg / alkali ^ örhMltnis of 6b au 1 fcis 130 sa 1 is obtained. 12, process according to claim 1, star production © Ines as silicic acid sol, characterized in that oil © liit of the cations by electrolysis © tar solution " from ac'tiy © sa silicate in a rope with a lead and cathode .is carried out. Process according to claim 1 for -H © rstteilung.- © Ines active Sie.jel ~ säuresols, characterized in that the removal of the cations takes place by electroosmosis of a LSsmig active Katriutasilikats. Process for the production of crystalline-s ^ -thetiseher 2@ol.itiiissan -A or zeolites X mlt'.Molekulrrsiebeigenschr.ft € n '«nd - D« «: © naws ·» ". ^: Exchange properties-, thereby g @ k®nns © iehnet, 4ass ttian an aqueous solution Natriuroalutnlnat and a -KleselEisurekosnponeutö mixes in order to obtain solutions whose MoJ ratios are in the following range; 109828 / U69 Na ₂ OZSiO ₂ ο, οβ "Ms 4.00 0.70 Ms 20.00 15 * 00 until 200.00 2 _s 00 Μ » 3OjOO 0.40 DlS 6.50 10.00 Ms 150.00 where a part of the kiesels &tare'ialtigea component is a compound of the formula (8Ja ₂ O). SlOg.O _g 0 with a sra n value from 0 to 0.3 and X a meaning of O ₃ 1 and mobs * mxa active properties according to definition, whereby the proportion of active Sillciuiakosaponsnt® from other Silloiuo! Ko & ipanent @ n is up to 1.0 au 76, QOQ in the range from 1.0 to 0, being crystallized at temperatures of ⁰ to 120 C J50 olm © aging the Bsaktionsgeiaisches at temperatures below the Kristallisattionstemperatur. 13. The method according to claim 14 for the production of a zeolite A, at which the molar ratio of a reality participant in the the following area is « ₅ '' from 0.19 to 2.70 = 0.85 to 9 »70 gg = 3000 to. 200.00 and the proportion of active sill compor ^ nte among others 10 98 287 U6 9 .. ■■■■ ■. . . - 3 " ... ■■ .: - ■ Slllelunkomponenten ita Baraish from 1 _S O zv * O to I ₃ O su?, - a lies. 16. The method according to claim 15 aar production of g®ollt> i X. whereby the biological relations of the re & ktionteilnshsatsr in folssn Area lie? SiO ₂ Al ₂ O ₃ = .2,80 '' to S ₃ OO Na ₂ 0 / = Si0g. - o »7O to 5.00 ₂ O - 35 * 00 to ISO-OO, and the proportion of active silicone cojaposesite au sillciuuäcoQiponenten is in the range of 1 _e 0 su.O to 1.0 s? i T. 17 · Process for the production of Isoiith Y vem higher with SiOg / Al ₂ O, "¥ increased from more a3.s 3 to © Indestsns- 6 _Ρ 2 by intimate mixing of the reaction parts - 'jser, marked by the fact that. an aqueous® LSsmis © in®! ¹¹ ISsliehen AluraiiaiW. ^ -Component and a Slllciua & o & ipGnente, as at least partially-a connection d © r Poris © l (Ka _? 0). SiO ^ .XIi ₂ öeatnS2: t ₃ at the η a value of 0 bia 0.5 and X eiiim-W ©? & Νοη O ₃ I and more and an activity vcn s?. © hr than 10 Binhsitea, the proportion of active SllieivskosspoKiants zv, silicon components in the range -'ven l _s 0 & \ i 0 to l _s 0 s * a 6., CCiD, where sin Reakfeionsgeslsch with M half of the following ranges established * ?; 109828/1469 Ha _g 0 / S 10 g D. 0.2ö - 0.30 IT - 14th 2) 0.30 - 0.31 8th -· 16 3) o, 3l - 0.32 8 ■ .- 20th 4) 0.32 - 0.335 8th - 40 5) 0.335 - 0.4 7 - 50 6) 0.4 - 1.0 5 '- 30th 7) 1.0 - 2.0 8 _: -. • TO so - TO 20th - 90 12th - 90 12th - 120 12th - 120 12th - 120 whereupon the reaction mixture is obtained, preferably under "at a temperature in the range from 30 to 120 ⁰ C until a crystalline product. 18. The method according to claim 1 characterized ?, gekeisiseichnet that the active Silioiutnkomponente vcn an activity swert having rainäestens 100 units, and the proportion of the active silicon component sur inactive 3iliciunBkes; pon € r _£ th in the range of I to ₉ O 0 to 1.0 is 7.0. uetbb y, ■ 10 98 28 / U δ 9