DE1667313B1 - Method of making a catalyst - Google Patents

Description

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The invention relates to a process for the production of hydrolysis products of aluminum sulfate

a catalyst mass of silica and alumina, the partial hydrolysis obtained according to the invention

optionally in a mixture with a crystalline product characterized in that it is clear in water

Aluminosilicate. This catalyst solution according to the invention results.

Sator masses are solid, thermally stable and abrasion-resistant, 5 Although as a base in the inventive method

so that they are used with advantage in catalytic cracking processes, for example alkali and alkaline earth metal hydroxides

can be used in which the catalyst or carbonates can be used

alternating in a hydrocarbon conversion one expediently ammonium hydroxide, which one with

zone and a catalyst regeneration zone introduced the aluminum sulfate in a molar ratio of

is, the catalyst particles high temperature io about 4: 1 mixed. The mixing takes place purposefully

temperature changes and mechanical abrasion forces moderate with vigorous stirring to a uniform

get abandoned. To obtain reaction mixture and an intimate

From the USA. Patent 3,131,156 a contact of the reactants is to be ensured. The drive for the production of a cracking catalyst from the exchange of two of the three sulfate residues of the aluminum silicic acid and alumina known, in which one 15 niumsulfates against hydroxyl residues is essential for the process according to the invention with an aqueous solution of aluminum sulfate, since the aim of the formation of a base Partial hydrolysis product of the aluminum invention reacts neither with a fully hydrolyzed miniumsulfate, this partial hydrolysis product aluminum sulfate nor with a partial hydrolysis product with an aqueous suspension of hydrated aluminum sulfate, in which only one silica is mixed, the gelation is completed 20 sulfate residue is replaced by a hydroxyl residue.
and so then the silica-alumina thus obtained. The aqueous slurry of the hydrated mass is isolated and dried. Substantial differences Silica can include both silicic acid hydrosols as this known process compared with the inventive silicic acid hydrogels. Thus, the process according to the invention can consist in the fact that in the case of the partial hydrolysis product of the aluminum sulfate either the former in the partial hydrolysis product a maximum of 50% ^a 5 with an aqueous suspension of a silica of the three sulfate residues of the aluminum sulfate in hydrosol are mixed, whereupon the hydroxyl residues are then exchanged, the mixing of the Silicic acid hydrosol is completely gelled, or instead of partial hydrolysis product with the aqueous slurry, the silicic acid hydrosol can also be used before the munging of hydrated silicic acid at a pH. The partial hydrolysis product of the aluminum value above 6.2 is added and the partial hydrolysis sulfate gels in the process.

product is already completely hydrolyzed. As a result . The isolation and drying of the catalyst mass these differences occur in the previously known is done in a conventional manner. For example, will Process for catalyst masses whose abrasion resistance - the silica-alumina mass is filtered and washed, The ability and thermal stability of those of the invention to remove the soluble salts. The filter cake According to the prepared catalyst masses essentially 35 can then be slurried in water and the spray underlay are. drying are subjected to catalyst particles

The object of the invention was therefore to obtain catalyst in a certain size range. Even

The spray-dried material can then be used to obtain masses of silica and alumina

compared to the known comparable catalyst- are re-slurried and washed several times

masses improved abrasion resistance and heat to reduce the soluble substance content to the

have persistence. This goal can be achieved by bringing the desired concentration. Used in this

the method of the present invention. ion exchangers are usually used to initially

This inventive method for the purpose of removing trium ions and then sulfate ions,

position of a catalyst mass made of silica and the drying then takes place, for example, at about

Alumina by reacting a base with an aqueous 45 150 to 370 ° C.

igen solution of aluminum sulfate with formation. In the process according to the invention, this is part of one Partial hydrolysis product of aluminum sulfate, hydrolysis product of aluminum sulfate before it Mixing this partial hydrolysis product with a complete hydrolysis evenly with the hydratiwaqueous Slurry of hydrated silica mixed together as it was a clear solution acid, completion of gelation, isolation 5 ° forms. In addition, the partial hydrolysis product is in the and drying the silica-alumina layer thus obtained, with its hydroxyl radicals chemical bonds The mass is characterized in that the base is formed into the hydrated silica before with the aqueous aluminum sulfate solution in one it gelled, so that a more uniform catalyst Quantity ratio with each other converts that satorverbindungen than by known methods a soluble partial hydrolysis product forms in which 55 gets.

two or three sulfate residues of A1, (SO ₄ ) ₃ against hydroxyl A further improvement of the catalyst masses

residues are exchanged, the partial hydrolysis product with according to the invention is obtained by inclusion of natural

the slurry of hydrated silica, borrowed or synthetic crystalline

optionally in a mixture with a crystalline aluminosilicate, such as from zeolites. With the so far

Aluminosilicate, in a known process not exceeding about 5 for the production of similar catalysts

pH-value mixed, the resulting mixture ages sator masses of silica and alumina with a

and then final crystalline aluminosilicates were obtained by adding a base to the mixture

the partial hydrolysis product is completely hydrolyzed. Difficulties, since the aluminosilicates are unstable,

The partial hydrolysis product probably has a pH value below 3.5 to 4.0 if it has a long period of time

Formula Al ₂ SO ₄ (OH) ₄ , although it is also possible to be exposed to 65. But this difficulty is caused by

that it is present as a chemical complex, but in which the process according to the invention eliminates. It goes

in any case about two hydroxyl groups on one one advantageously so that one finely divided

Aluminum atom come. Compared to other partially divided crystalline aluminosilicate in a silica

3 4

Säuresol dispersed, the mixing with the partial hydrolysis product, for example, by acidification

of sodium silicate adjusted with a mineral acid up to about 3.9 to about 4.3. As a crystalline aluminum

a pH of about 4.0 to 4.5 was obtained, minosilicate can expediently be a finely divided faujasite,

the silica sol gels and the silica gel is used in chabazite or mordenite,

in the alkaline range, then the pH value of 5 The silica-alumina mass is expedient

Adjusts gels to about 3.5 to about 5.0, separately therefrom subjected to an exchange with a base, as in the case of

Ammonium hydroxide and aluminum sulfate in one for example with aqueous ammonia and / or one

mixed with one another in such a molar ratio that an aqueous solution of a compound of calcium,

the above-mentioned soluble partial hydrolysis - magnesium, manganese, vanadium, chromium, cerium, aluminum

The product of aluminum sulphate is obtained with ionium, lanthanum, praseodymium, neodymium, samarium or

the silica gel, which contains the crystalline alumino- other rare earths, these aqueous solutions

contains silicate, mixed, and after aging, complete solutions have a pH value of around 4.5 or more

constantly hydrolyzed and the catalyst mass should then. The material exchanged with the base becomes

isolates and dries. then washed free of water-soluble substances,

The silica sol is after the finely divided 15 dries and at a temperature of about 260 to

crystalline aluminosilicate was dispersed therein and 815 ⁰ C in an inert atmosphere, such as air, ac-

after it has gelled, activated to an alkaline pH.

Value, preferably about 7.0 to 7.5, adjusted, where- To demonstrate the increased abrasion resistance

by forming a complex that the silica compared to catalysts according to the prior art

hydrogel and crystalline alumino-20 dispersed therein became one according to Example 1 of the USA patent

silicate includes. After this complex sufficient 3 131156 produced catalyst with regard to the

has been aged for a long time at the alkaline pH value, abrasion resistance with a according to Example 1 of the Er-

In order to develop a suitable pore structure, the catalyst produced is compared. 45 g each

to a pH of about 3.5 to about 5.0, preference of the catalyst to be tested were in the presence

wise about 3.9 to 4.3, adjusted and then with the as of 5 g of water with an air circulation of 429.75 1 /

Partial hydrolysis product of aluminum sulphate which, like hours, is heated to 600 ° C. Weight loss after

was prepared above, at a pH of high-12 hours and after every additional hour up to

at least about 5 and at least about 3.5 mixed. The end of a total of 42 hours was determined. the

The pH value of the hydrogel is expediently compared with the results below:

Heating time

Weight loss

Catalyst according to

U.S. Patent 3,131,156

Catalyst according to the invention

0 to 12 hours
12 to 42 hours
'0 to 42 hours

total of 12.8 percent by weight

0.44 percent by weight hourly

26.0 weight percent total

a total of 8.7 percent by weight 0.19 percent by weight hourly 14.4 percent by weight in total

The following examples are further explanations of 15 ° / _o ammonia zusetzte to the aluminum

tion of the invention. sulfate hydrolysis to complete. After an hour

Example 1 aging at this pH was about 161

Sludge containing about 1000 g of solids as silica

A silica hydrosol was contained by the addition of 45 alumina, ³ large filter 9850 cm ³ / ^s oig filtered through a 2250 cc of a 6.9 N aqueous ° waterglass solution surface. The filtration rate of this to 1179 cm ^{3 of} 25% sulfuric acid in a continuous silica-alumina gel, which was prepared after the thoroughly stirred reaction vessel using the invention, the pH of the resulting mixture was about 4.5 with the filtration rate of a silica was. Gelling occurred within about 3 minutes compared to 50 clay gels after which on sale. The pH of the resulting slurry for equal to 1 conventional Verwurde described later by the addition of 40 cm ³ of 15% was recovered drive strength ^n.
Ammonia at about 39 ⁰ C adjusted to 7.1. Of the . .
Sludge was 1 hour at this temperature
ages, with the pH in the meantime rising to 7.5 55 This example describes the production of. The pH of the sludge was then adjusted to a conventional method, ie with aluminum sulfate 5.0, ^{by adding 51 cm 3 of 25% strength sulfuric acid.} Then a partially hydrolyzed instead of a partial hydrolysis product of aluminized aluminum sulfate became the stirred silica sulfate. A silicic acid hydrosol was added by adding sludge, the pH being lowered further by 60 of 9850 cm ^{3 of} 6.9% strength water glass in an aqueous solution to about 4.3, and the resulting solution to 1179 cm ^{3 of} 25% strength sulfuric acid in one Sludge was aged for about 1 hour. The partially stirred reaction vessel was added, the pH-hydrolyzed aluminum sulfate being about 4.5 as a result of the rapid addition of the resulting mixture, would ^{add 15% ammonia solution from 1348 cm 3.} Gel formation occurred within about 3 minutes. 3070 cm ^{3 of} a vigorously stirred aqueous alum solution 65. Thereafter, the pH of the resulting stirring was obtained for about 1 hour. The sludge by adding 40 cm of 15% Amg-aged sludge was subsequently adjusted to a moniaks at about 38 ° C to 7.1. The pH value of 6.9 was set by adding 550 cm ^{3 of} sludge for 1 hour at this temperature.

Claims (1)

5 6 ages, the pH of the sludge rose in the adjusted to 7.7 at about 38 ° C. The mud was meanwhile to 7.5. Aged, the pH of the slurry for 1 hour at this temperature, the pH was then quenched by addition of 51 cm ³ of 25% strength ^e r of the sludge rose to 8.1 in the meantime. Sulfuric acid adjusted to 5.0. The pH of the sludge was then added by adding 3070 cm ^{3 of} an aqueous alum solution to the ^{silica sludge stirred in from 51 cm 3 of} 25% strength sulfuric acid to 5.0, whereby the pH was adjusted. Thereafter, 1935 cm ^{3 of} an aqueous waiter was reduced to about 2.5, and the resulting alum solution to the stirred silica sludge was aged for about 1 hour. At the same time, the pH value was thereby further closed to about 3.1, the sludge was reduced to a pH value, and the resulting sludge was adjusted to 6.9 by adding 1798 cm ^{3 of} 15% strength to about 1 Aged hour. Then the ammonia was added. After aging at lstündiger sludge to a pH of 6.9, adjusted by this pH value was about 161 sludge containing about one cm ³ 15 zusetzte 1275 ° / ₀ ammonia. After 1000 g of solids as silica-alumina contained, aging for 1 hour at this pH value, as in the previous example, they were ^{filtered through a 161 mud containing about 1000 g of solids as silica-2250 cm a} filter area. In the present 15 clay contained, ^{10.6 minutes of area filtered through a 2250 cm 2} filter case for the initial filtration as in the previous example, compared to 7.4 minutes for the material of Example 1 that won in Example 2 and Comparative Example 2 - required, whereby in both cases the same filtrate- nenen catalysts were deactivated with steam, amount was gained. In both cases the was made by getting a 55% mixture of steam in air Filter residue again slurried in 81 water at a temperature of 760 ° C for 12 hours and filtered under identical conditions. In front of the catalytic converters. Then the catalyzers became The case was 16 minutes compared to 9 misses compared to a freshly prepared tin nut for the material of Example 1 evaluated according to the standard catalyst: A synthetic silica process the invention required. acid-alumina catalyst containing . 25 13.9 percent by weight of alumina, for which the volume B e 1 s ρ 1 e 1 2 activity was arbitrarily set at 100 and the A silica hydrosol was was not deactivated by the addition of steam, has been standard 11200 cm ³ 6.9 ° / oig ^em water glass in aqueous solution as a catalyst. to 1360 cm ^{3 of} 25% strength sulfuric acid in a continuous The method of evaluation consisted in that one Thoroughly stirred reaction vessel prepared, wherein 30 a gas oil with an initial boiling point of about the pH of the resulting mixture about 4.3 260 ° C poured into a tubular reaction vessel made of rust. Gel formation occurred within about 15 minutes, sending free steel 25 cm ³ of that to be tested. The pH of the resulting sludge was contained catalyst in a fixed layer, then by adding 90 cm ^{3 of} 15% ^en · Ammo- The gas oil was adjusted to 7.65 at a rate of about niaks at about 38 ° C. The sludge 35 was ^{fed in at 100 cm 3} per hour, and the reaction vessel was aged for 1 hour at this temperature, the temperature being maintained at 500 ° C. Converting to gasoline the pH rose to 8.1 during this time. The and gas was measured. The catalyst VolumenpH of the slurry was then activity by addition, expressed as a percentage, the Vervon was 100 cm ³ ig ^he adjusted with 25% sulfuric acid to 5.0. ratio of the hourly space velocity of the Then a partially hydrolyzed aluminum 40 liquid (liquid parts by volume of fed sulfate added to the stirred silica sludge, oil per hour per unit volume of catalyst), which by adding 475 cm ^{3 of} a 28% am- with the Steam-deactivated experimental catalyst monia solution to 1935 cm ^{3 of} a vigorously stirred solution was required to obtain the hourly space-velocity aqueous alum solution, whereby the liquid, which was further reduced to about 3.9 with the fresh standard, required 45 catalyst, to give the same conversion and the resulting sludge was about 1 hour development, with the ratio multi-aged at 100. The mud was then poured onto one. The pH value of 6.9 was adjusted by adding 400 cm ^3. 15% ammonia was added in order to complete the catalyst produced with an activity of sulfate hydrolysis. After 1 hour 50-42% and for the aging according to Comparative Example 2 at this pH value, about 161 catalyst had an activity of only 35%.
Sludge, which contained about 1000 g of solids as silica-alumina, through a 2250 cm ³ filter.
area filtered. Comparative Example 2 55 1. Method for producing a catalyst from silica and alumina by reaction This silica-alumina catalyst was after a base with an aqueous solution of aluminum dsm conventional process, i.e. nium sulfate with the formation of a partial hydrolysis pro- with aluminum sulphate instead of with a partial hydrolysis product of the aluminum sulphate, mixing this product of aluminum sulfate according to the invention. 60 partial hydrolysis product with an aqueous on-on Silicic acid hydrosol was made by adding slurry of hydrated silicic acid, 11 200 cm ³ 6.9% ig ^sn water glass in aqueous solution complete the gelation, isolation and to 1360 cm ^{3 of} 25% strength sulfuric acid in a drying of the silica-alumina thus obtained stirred reaction vessel obtained, the pH value being mass, characterized in that of the resulting mixture was about 4.3. Gelation of the base with the aqueous aluminum sulfate formation occurred within about 15 minutes. solution in such an amount ratio mitein-Thereupon the pH of the resulting Schlam- was reacted other that a soluble Teilhydrolysemes ^e mi ammonia product forms by addition of 90 cm ³ of 50% strength, in which two of the three sulfate radicals 7 8 of the Al ₂ (SO ₄ ) S exchanged for hydroxyl residues and then aged by adding a base to the are, the partial hydrolysis product with the Auf- Mixture the partial hydrolysis product completely hy- slurry of hydrated silica, dehydrated. if necessary in a mixture with a crystalline aluminum 2. The method according to claim 1, characterized in that miniumsilikat, with a not exceeding about 5- 5 indicates that the base is ammonium hydroxide the pH mixed, the resulting mixture used. 109 516/362