DE1199739B - Process for the production of a spray-dried, flowable cracking catalyst containing silicon dioxide, aluminum oxide and magnesium oxide - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

BOIj

Int. α .:

German KL: 12 g

Number: 1199 739

File number: A 34059IV a / 12 g

Filing date: February 24, 1960

Opening day: September 2, 1965

The present invention relates to a process for the preparation of a cracking catalyst, the silica, Contains aluminum oxide and magnesium oxide, with aluminum oxide and magnesium oxide in the finished catalyst composition in a weight ratio of in each case 1: 1 to 8: 1 available.

In the older German patent specification 1067159 already disclosed a method for producing a cracking catalyst by mixing together one Calcium and / or magnesium silicate and an aluminum salt solution suggested. In this procedure however, the magnesium salt solution becomes a liquid sodium silicate solution first and then to the reaction solution obtained is in turn the solution of a water-soluble salt of aluminum and added to an aqueous ammonia solution.

From French patent specification 1112 397 a silica-magnesium oxide catalyst is known which contains 28 ¹⁰ ZoMgO and 3% Al ₂ O ₃ . In this case, however, the aluminum oxide was only added to improve the filtration properties of the silica base before the magnesium oxide was added. This catalyst has a significantly shorter service life and stability and also gives considerably poorer yields of propylene and butylene compared with the catalyst obtainable according to the invention.

The process according to the invention for the preparation of the new cracking catalyst consists in that a silicon dioxide-aluminum oxide gel containing between 10 and 30% aluminum oxide, based on the finished catalyst composition, is used ^{for at least 1} 1/2 hours at a temperature between about 30 and about 75 ° C is reacted with so much finely divided magnesium oxide that a magnesium oxide content between 1.5 and 15%, based on the weight of the finished catalyst, is obtained.

The silica-alumina component can be made by any one of skill in the art known method, such as the method described in U.S. Patent 2701793, getting produced.

According to one such method, hydrated silica can be obtained from an aqueous solution of an alkali silicate, for example from commercially available water glass, by acidification with eini Mineral acid, for example sulfuric acid, are precipitated. The precipitated hydrated silica can then in an aqueous solution containing an aluminum salt, such as aluminum sulfate or. Aluminum nitrate, to be suspended, and that

Process for the production of a silicon dioxide,
Aluminum oxide and magnesium oxide
containing, spray-dried, flowable
Cracking catalyst

Applicant:

American Cyanamid Company, New York, N.Y.

(V. St. A.)

Representative:

Dr. F. Zumstein,

Dipl.-Chem. Dr. rer. nat. E. Assmann

and Dipl.-Chem. Dr. R. Koenigsberger,

Patentanwälfe, 'Munich 2, Bräuhausstr. 4th

Named as inventor:
Maiden Ward Michael, Stamford, Conn .;
Robert Matthew DeBaun, Old Greenwich, Conn .; William Beveridge Innes, Stamford, Conn.
(V. St. A.)

Claimed priority:
V. St. V. America dated February 24, 1959
(795 046,795 095)

Hydrated alumina can then be added to the hydrated silica by adding a basic Compound, such as ammonia, are precipitated, creating a silica-alumina slurry is formed. Of course, the usual filtration and washing steps are used to remove undesirable substances such as sodium salts, sulfate ions and the like. to remove or reduce to a tolerable minimum.

The magnesium oxide is used in such amounts as to achieve a content of between about 1.5 to about 15% magnesium oxide, based on the final weight of the catalyst, is necessary is. As mentioned, the silica, alumina and magnesia components should in the flowable composition in an amount

509 659/454

'-. 1 199 73 $ ■ ·, - ■■

3 4

must be present that meet the weight '. "'." \;. Example'

Corresponds to percentages, but must additionally if

the unexpected advantages of the present invention 2.81 kg of sodium silicate, the 0.80 kg of sulphate

manure should arrive, the aluminum oxide and contains, were in a mixing vessel to 11.3 kg

Magnesium oxide is added to the water by weight given above and heated to 40 ° C. Under good

Ratios to one another, namely - each between - stirring was 25% sulfuric acid up to one.

see roughly 1: 1 to 8: 1. . pH 5 added and the mixture for 1 hour

The finished catalyst particles are shaped, aged.

by passing the composition through a nozzle or towards the end of the aging period, 246 g Naüber a spray wheel in contact with hot gases ίο trauma aluminate solution, then 490 g of alum will. Such drying can be added with the solution. The final pH was 4.6. the Slurry from any suitable spray dryer was filtered in a filter pot leads to be. and washed with 18 kg of water. The filter cake

The catalyst composition will be at least again in an equivalent amount of water

^{Aged for 1} Iz hour, although times up to 20 15 slurried, filtered and treated with 18 kg of water.

Hours were applied, after which the 3-compo wash. The filter cake was picked up again.

nentert catalyst systera is dried again, slurried in. · an equivalent amount of water that

preferably by a rapid method such as pH adjusted to 6.6 with ammonia, then

Filtered with the aid of a spray dryer or a peel-off dryer and washed with 18 kg of water. The out

voltage device. 20 cake remaining from the third filtration was in

The catalysts made according to the invention are re-slurried a small amount of water

can be, like other commercially available, synthetic and spray-dried. The catalyst obtained is

Table cracking catalysts are used, containing 12% Al ₂ O ₃ (solids basis) and about 16%

for example like silica-alumina-ca- moisture »

catalysts in catalytic cracking processes (especially 25 358 g of this substance, which contains 300 g of solids

other fluidized bed process)., in which one held high boiling, were in. one. Mixing vessel for 5.4 kg of water

the crude oil hydrocarbon is catalytically given to form, and on. 60 ° C heated. 20 g dry ma

a high octane gasoline is cracked. In g Magnesiumoxvdpulveji were added, and the

such a mixture, which is well known to the person skilled in the art, is allowed to react for 2 ^{hours at 6O 0} C »

Process the catalyst particles with a 30 left. It was then drained and:

Dried vapor stream of the hydrocarbon in contact.

The resulting catalyst contained 6% magnesium in a range between about 370 and 540 ° C, oxide, 11.3. ⁰ Ai aluminum oxide * the remainder was silicon preferably caused between 480 and 540 ° G or dioxyd-. The: MumMurnoxydr-magnesium ratio carried out. 35 was 1.9: 1.

The use of the inventively * produced. To the present invention in terms of

Catalysts in such cracking processes leads, turning of catalysts, the inorganic Silikafr-

As already mentioned, “to describe the unexpected and add-ons”, wufiäe a dec-

full advantage that, in general, the gasoline-like catalytic converter, in the

hives ^{1 are} increased / without a noticeable 40 benen way-produced.

Change or even = a. Loss of the more valuable 1.1'8 kg sodium silicate (Philadelphia quartz "N"

Gases such as propylene and butylene showed. One takes fire) were -in, a mixing vessel with 11.3 kg of water

indicates that given when using the cage according to the invention. = 4.9 kg of kaolin clay were added

catalysts when cracking high-boiling crude oil coals and the mixture carefully: stirred, to make a di-

Hydrogen fuels ensure these advantages of the high level of gasoline emanation of the ion. The mixture

booty without loss of propylene and butylene was mainly 40? € heated · ,. 25% sulfuric acid to

neutrally at the expense of the less valuable gases, such as added to a pH of 5 and the mixture:

Methane, ethane, Athens-u. Like ·., can be achieved. ! For hour; aged.

In the figures of the drawing, those with- Am; At the end of the alimentation period, 143 g of Na-

Catalysts according to the invention achieved yield- 50 triumalurainatlösung.huizugetzt, then-312 g

Improvements in gasoline, propylene and butylene in the alum solution. This resulted in a pH of 4.6. The: Compared to the corresponding, Ausheuten, the; with slurry, was filtered in a: filter pot

one. Standard containing 12% aluminum oxide and washed with 18 kg of water. The filter cake

obtained catalyst, were shown. was in-an equivalent amount of water again

Although the present invention is slurried on 55, filtered, and treated with 18 kg of water

wash the main components of silicon dioxide,

Magnesium oxide and aluminum oxide and - in addition - The filter cake obtained was again in a:

view of the critical equivalent amount of water-re-slurried between them,

Quantitative ratios have been described, the pH should be set to 7 with ammonia! Then it should be noted that the catalyst produced according to the invention was filtered and _; with. Washed 18 kg of water. The lyzers also add small amounts up to one amount in this case. Filtration- remaining. Filter cake was

Holds about 1% of other, catalytically active substances in a smaller amount of water

Substances such as manganese ^ beryllium, zirconia and spray-dried. The catalyst obtained

kon and titanium, or substantial amounts feinteili- was from 12 ° / tt, aluminumoxy; dj.50 ⁰ / o clay, und.der

ger. may contain inorganic silicate additives. 65 ResCwarSüiciumdioxids. ^r : V:

The following example is intended to illustrate the invention. 358 g of this substance; the 3.00 g: solid

The parts and percentages are based on weight, more than ₅ in a mixing vessel became: 5.4 kg of water

unless otherwise stated and ·, to 6QP G water: heatable. Man 'added

10 kg of dry magnesium oxide were added and the mixture was allowed to react at 60 ° C. for 2 hours. It was then drained and dried.

The catalyst obtained contained 3% magnesium oxide and 12.1% aluminum oxide. The relationship Aluminum oxide to magnesium oxide was 4: 1.

Although the present invention is directed primarily to Mieß cracking catalyst compositions has been described, catalysts can also be used in ball, pill, bead, press and others Shapes are used.

It should be made clear that the aluminum oxide specified in the present description and amounts of magnesia relate essentially only to the combined form, d. i.e., alumina and magnesia are chemically bound to the silica, in contrast to the free or unbound state. In this regard, it is noted that the presence on free or unbound aluminum oxide or magnesium oxide in general the coking properties adversely affect the final catalyst compositions.

Claims (1)

Claim: Process for the production of a silicon dioxide, aluminum oxide and magnesium oxide containing, spray-dried, flowable cracking catalyst made from a silica-alumina gel, with aluminum oxide and magnesium oxide in the finished catalyst composition in a weight ratio of 1: 1 to 8: 1 in each case are present, characterized in that the gel, which is between 10 and 30% aluminum oxide, based on the finished Icatalyst composition, contains at least ½ hour long at a temperature between about 30 and about 75 ° C with so much finely divided magnesium oxide is implemented that a magnesium oxide content between 1.5 and 15%, based on the Weight of the finished catalyst. Considered publications:
German Auslegeschrift No. 1067 159;
British Patent No. 827,440;
French patent specification No. 1198 499,
397. 1 sheet of drawings 509 659/454 8.65 © Bundesdruckerei Berlin