DE1288569B - Process for producing a catalyst for the conversion of hydrocarbons - Google Patents

Description

1 '2'

The invention relates to a process for the production of the corresponding oxides by calcination thereof of a catalyst for the conversion of carbon, whereby these different constituents of hydrogen, which can be used separately or in a mixture after the final thermal parts Activation aluminum oxide, fluorine, boron oxide, cobalt can. The atomic ratio between molybdenum and oxide and molybdenum oxide. 5 Cobalt can vary within wide limits, e.g. B.

The method according to the invention is thereby between 20: 1 and 1:20, these limits also being the case

indicates that gaseous boron fluoride can be exceeded and undershot at one.

Temperature between 100 and 500 ° C, preferably except for the aforementioned essential components

200 and 400 ⁰ C, with aluminum oxide converted so long as the catalyst of the invention may also contain other is continued until the catalyst contain a fluorine content of io ingredients which do not harm the reaction

0.2 to 10 weight percent and a boron content of, or even favoring, e.g. B. other heat resistant

0.05 to 2 percent by weight and which in itself oxides as alumina, in particular magnesia, zirconium,

in a known manner, the molyb, titanium oxide and silica are introduced.

Danish and cobalt compounds in the catalyst before after introduction of the catalytic components or after the reaction between the boron fluoride 15, the catalyst is subjected to a heat treatment

and the alumina. Activation and conversion of the raw materials

The catalyst produced according to the invention is subjected to the catalytic components. This allows the conversion of hydrocarbons with treatment is advantageously carried out by heating to a low industrial and commercial value in temperature of 400 to 650 ° C. Presence of hydrogen in high-value products, 20 As mentioned above, with the catalyst prepared according to the invention, for example, the conversion of heavy carbons into gas oil can be achieved with a satisfactory level of hydrogen, such as fuels or gas oils with too low temperature and a low freezing temperature, high outflow - and freezing temperatures in gas oils or the conversion of light gasoline with improved characteristics or light low octane number in gaseous paraffinic hydrocarbons, especially those with a high paraffin content, hydrogen with a high content of iso- the below 200 ° C and preferably below 150 ⁰ C paraffins. The catalyst produced according to the invention can also be used for other hydrocarbon-converting substances with a high content of isoparaffins in the lungs, for example for hydro-. Β. Include 4 or 5 carbon atoms, as well as cracking, isomerization, recovery, hydro- 30 in gasolines of better quality, refining reactions. For these types of applications, the ratio is

The catalyst produced in accordance with the invention is the volume flow rate of processed liquid

more active and / or more selective than the catalysts without hydrocarbon per hour to the volume of the

Fluorine and / or without boron or also as the catalyst catalyst between 0.1 and 6 and preferably

goals, which at the same time by another procedure 35 between 0.5 and 3.

Introduced fluorine and boron contain, in particular the intensity of the side reactions of cracking

than according to the US Pat. No. 2,878,180 is due to the duration of contact with the

known processes produced catalysts. Ge catalyst. These side reactions can therefore

that can be reduced considerably by choosing a limited one from the above-mentioned USA patent

Known processes, the halogen is made by means of a 40 contact time.

aqueous halide solution, in the case of fluorine with- The catalyst is advantageously with a

for example in the form of an aqueous hydrogen fluoride temperature of 375 to 500 ° C and a pressure

acid solution, introduced. This mode of operation is limited to between preferably 5 and 150 atmospheres.

Boron fluoride not applicable as boron fluoride is used with.

Water decomposes. 45 It has now been discovered that the present catalyst

As mentioned above, the fluorine and sator can be used both in the

the boron in the catalyst before or after the course of its regeneration by oxidation of the

bringing molybdenum and / or cobalt into the clay deposits had a remarkable stability,

earth. These at high temperature which similar fluorine-containing catalysts

implementation happens in such a way that 50 did not have. This stability was' apparently due to that

beforehand with the molybdenum and / or cobalt connections special type of fixation of the fluorine according to the

fertilize treated or untreated clay invention attributed. So it's redundant, often

refill earth with the boron fluoride in the fluorine and boron given above.

Temperature range is brought into contact. That. . . .

Boron fluoride can be used alone or preferably

thins with inert gases such as air, nitrogen or a catalyst according to the invention is through

Carbon dioxide, can be used. Impregnation of in a size between 2 and

Of the various forms of alumina, the 8 mm extruded aluminum oxide grains are with a ?? - Form and its starting products, ζ. B. hydrargillite, aqueous cobalt nitrate solution, drying of the aluminum is preferred. 60 minium oxide, impregnation with an aqueous am-

To produce the catalyst, molybdenum monium para-molybdate solution, drying and active

and cobalt, preferably in the form of their compounds, four of the catalyst by heating for two hours

used, which was produced in the course of a later heat treatment to 550 ° C.

treatment, possibly in the presence of hydrogen, the catalyst has the following weight compositions

can be converted into oxides or sulfides. 65 Settlement: 4% cobalt oxide (CoO), 20% molybdenum oxide

Examples of such starting products are cobalt (MoO ₃ ), the remainder aluminum oxide,

salts, such as cobalt nitrate, cobalt chloride, and molyb- Then in an amount of 601 / hour. per liter

dänsäure or their salts, such as ammonium molybdate, the above-prepared and kept at 300 ⁰ C

Catalyst a mixture of boron fluoride and dry air in a ratio of 20:80 parts by volume fed. After one hour of treatment, the catalyst is allowed to cool and it is found that its fluorine content is 4% and its boron content is 0.75%.

Above this is arranged in a fixed bed catalyst, which is kept at the temperature of 43o ⁰ C, at a pressure of 90 kg / cm ^a, a stream of hydrogen and direct distillation gas oil is conducted with a high paraffin content and a boiling point at atmospheric pressure between 270 and 39O ⁰ C .

The amount of hydrogen reached 15001, based on normal conditions at temperature and pressure, per Liters of treated liquid hydrocarbon, the latter being used in an amount of 11 per liter of catalyst and fed per hour.

The hydrocarbon fraction of the “gas oil” type with a boiling point at atmospheric pressure between 240 and 390 ^° C. is separated from the effluent.

The following results are obtained:

Distillation interval ( ⁰ C)
Density (df)

sulfur
(in percent by weight) ...

Freezing temperature ( ⁰ C) ...

Starting oil

270 to 390
0.873

0.26

+12

Recovered gas oil

240 to 390 0.853

0.031

The catalyst is regenerated by firing under the following conditions:

In the course of a first stage, ^{nitrogen, which has been brought to 325 °} C. for 15 minutes beforehand, is added in an amount of 100 l / hour. per liter of catalyst passed over the catalyst.

In the course of a second stage, the nitrogen is replaced by a mixture of 2% oxygen and 98% Replaced nitrogen, which is introduced in the same amount as above. The temperature of the catalyst progressively increases and then decreases again.

In the course of a third stage, the temperature of the catalyst is brought to 475 ^° C., and the same mixture of oxygen and nitrogen as before is fed in. The temperature of the catalyst increases to about 550 ⁰ C and then decreases.

The catalyst regenerated in this way is analyzed. It is found that the fluorine content of the Catalyst is still 4%, which indicates that the result of the use of boron fluoride in The presence of boron resulting from the preparation of the catalyst stabilizes the fluorine of the catalyst.

35

40

55

Example 2
Through the same catalyst as in Example 1, a gasoline is allowed to flow, together with hydrogen, which has the following composition:

Paraffins 73.6 percent by volume

Naphthenes 19.1 percent by volume

Aromatics 7.1 percent by volume

Various substances 0.2 percent by volume

of which sulfur 300 parts by weight p. M.

df 0.715

Distillation interval 74 to 140 ⁰ C

Octane number

(clear research) 49

The temperature is 430 ° C., the pressure is 70 kg / cm ² , the flow rate of the liquid is 0.61 per liter of the catalyst and per hour, and the flow rate of hydrogen is 15001 per liter of the hydrocarbon treated.

The following are obtained per kilogram of the amount introduced: 210 g of propane, 114 g of isobutane, 87 g of η-butane, 560 g Gasoline of the following composition:

Paraffins 76.5 percent by weight

Naphthenes 13.5 percent by weight

Aromatics 10 percent by weight

Sulfur less than

10 parts by weight p. M.

df 0.693

Distillation interval 30 to 14O ⁰ C

Octane number

(clear research) 60

This gasoline can be hydrocracked again, which increases its octane rating is improved and new amounts of light hydrocarbons are obtained. After that gasoline Tetraethyl lead has been added, which improves its octane rating considerably, so it can as well as it is to be used as fuel.

The following comparison shows the superiority of catalysts prepared according to the invention (Catalyst A) versus catalysts prepared according to US Pat. No. 2,878,180 (Catalyst B) with regard to the catalytic effectiveness. The catalysts used for comparison were made as follows:

Catalyst A

11.8 g of molybdic acid (85% MoO ₃ ) are dispersed in 55 ml of water, whereupon 6.4 g of cobalt nitrate hexahydrate are added. 100 g of small aluminum oxide spheres are impregnated with this dispersion. After impregnation, the beads are fired for 11 hours at a temperature of 104 ⁰ C dried and then for 2 hours under air inflow at a temperature of 426 ⁰ C.

Through 50 cm ³ of the catalyst prepared in the manner described above, at a temperature of 300 ⁰ C at a rate of 3 1 / hour. a mixture of boron fluoride and dry air (in a volume ratio of 20:80) passed through. After half an hour of treatment, the catalyst is allowed to cool. Analysis shows that it contains 2% fluorine, 0.37% boron, 0.95% cobalt and 5.4% molybdenum.

Catalyst B

7.3 g of boric acid are dissolved in 75 ml of water. To 50 ml of the resulting solution are added 11.8 _{g of molybdic acid (85% MoO 3} ), 5 ml of 50% hydrofluoric acid and 6.4 g of cobalt nitrate hexahydrate. The volume of the solution is made up to 55 ml.

With this solution 100 g of ^ -aluminium oxide spheres are impregnated. After eleven hours of drying at 104 ^° C., the impregnated spheres are fired for 2 hours at a temperature of 426 ^{° C. with admission of air.} The catalyst produced in this way contains, determined analytically, approximately 0.37% boron, 2% fluorine, 0.95% cobalt and 5.4% molybdenum.

The two catalysts A and B were used to determine their catalytic effectiveness in the

tested in the manner described in example 1,
the following results were obtained:

Supplied
Gas oil Catalyst B Catalyst A Boiling range
CQ 265 to 390 245 to 390 245 to 390 Density id ¹ /) ... 0.872 0.859 0.856 sulfur
(Weight
percent) ... 0.28 0.03 0.03 Freezing
temperature
(° C) +11 +3 0

From the table above it can be seen that by the catalyst according to the invention in comparison with the known catalyst a 25% reduction in the solidification point of the treated This gas oil is achieved, which is extremely advantageous.

Claims (1)

Claim: Process for the preparation of a catalyst for the conversion of hydrocarbons, the after final thermal activation aluminum oxide, fluorine, boron oxide, cobalt oxide and ίο contains molybdenum oxide, characterized in that that gaseous boron fluoride at a temperature between 100 and 500 ° C, preferably 200 and 400 ° C, is reacted with aluminum oxide until the catalyst has a Fluorine content of 0.2 to 10 percent by weight and a boron content of 0.05 to 2 percent by weight and the introduction of the molybdenum and cobalt compounds in a manner known per se in the catalyst before or after ao the reaction between the boron fluoride and the aluminum oxide takes place.