DE1192159B - Process for activating hydrocracking catalysts - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

159 Int. α .:

BOIj

German class: 12 g -

Number:
File number:
Registration date:
Display day:

1192 159
U 7785IV a / 12 g
February 11, 1961
May 6, 1965

Destructive hydrogenation, which is also called hydrocracking as a difference from simple hydrogen addition denotes unsaturated bonds between hydrocarbons, encloses certain Structural changes and can therefore be referred to as cracking under hydrogenation conditions, so that the lower-boiling products of the cracking reactions are much more saturated than without being present of hydrogen or hydrogen-supplying raw materials. Destructive hydrogenation processes are mostly used on coal or heavy oil residues or distillates for the purpose of producing substantial yields of low boiling saturated products and to some extent also for the production of intermediate products used as household fuels. Even heavier cuts can be made for Lubricants can be obtained. These hydrocracking processes can either be clearly thermal Be operated on the basis of or in the presence of a catalyst. A large number of substances are considered Catalysts have been used as have the iron group metals including iron, nickel and cobalt and the oxides and sulphides of chromium, molybdenum, and tungsten, which are the metals of the left row of the Represent group VI of the periodic table. There are also numerous mixed metal and metal oxide catalysts as well as less common metal salts have been tried.

Hydrocracking is relatively important for the treatment of cracked gasoline, particularly thermally cracked gasoline, either alone or in admixture with direct-made gasoline. Selective cracking is highly desirable because it normally results in a product with improved anti-knock properties. In general, the lower molecular weight products will have higher octane numbers and therefore a lower average molecular weight gasoline end product will usually have a higher octane number. Furthermore, isomerization or some other molecular rearrangement occurs during the cracking reaction, which also leads to products with higher anti-knock properties. The selective cracking is of particular advantage for converting a feedstock with boiling above about 204 ⁰ C components to those in boiling below about 204 ⁰ C ingredients. It will therefore be understood that the selective cracking results not only in a better quality product, but also in an increase in the amount of the desired product.

The selective cracking must not cause the decomposition of the normally liquid in processes for the activation of to any significant extent
Hydrocracking catalysts

Applicant:

Universal Oil Products Company, Des Piaines,

JH. (V. St. A.)

Representative:

Dr. H.-H. Willrath, patent attorney,
Wiesbaden, Hildastr. 18th

Named as inventor:

Mark Joseph O'Hara, Mount Prospect, JU.

(V. St. A.)

Claimed priority:

V. St. ν. America 12 February 1960 (8224)

normally lead to gaseous hydrocarbons. It generally consists of splitting a heavier hydrocarbon molecule into two molecules, both of which are normally liquid hydrocarbons. To a lesser extent, it includes the conversion of methyl, ethyl and propyl groups into methane, ethane and propane. However, the removal of these radicals is minimized by controlling the catalyst composition and, to some extent, the reaction conditions. On the other hand, non-selective cracking leads to decomposition into normally gaseous hydrocarbons, e.g. B. from normal pentane to methane.
Furthermore, uncontrolled cracking leads to the more rapid formation of large quantities of coke or carbonaceous material which is deposited on the catalyst and destroys its activity.

The invention has therefore set itself the task of creating a catalyst that meets all requirements to a selective hydrocracking, as set out above, corresponds to and a favorable product yield supplies. As mentioned, hydrocracking catalysts are known which result from cracking activity having multicomponent carrier and at least one active metal of the groups incorporated by impregnation VIa and VIII of the periodic table exist in an amount up to 20 percent by weight. According to the invention

509 568/426

3 4

Particularly active hydrocracking can now be obtained in a similar way, but not necessarily as catalysts, by preparing the catalysts with equivalent results,
The used metal of Group Via and / or VIII hydrogen charge for 1 to 8 hours in a is with the solid support generally in an oxygen-containing gas in a temperature range 5 total amount of about 0.01 to about 20 Weight of 700 to 76O ⁰ C and then up to percent, calculated as metal, by formation of an hour in the range from 260 to 54O ⁰ C reduced aqueous solution of platinum chloride, palladium chloride, are. This specially guided activation includes nickel chloride, molybdenum chloride, chromium chloride, as the last step in the completion of the hydrochloride, platinum bromide, palladium bromide, nickel cracking catalysts; because if the components io bromide or molybdenum bromide or a nitrate, have only been combined with one another, z. B. nickel nitrate, molybdenum nitrate or ammonium the catalyst does not yet have the ability to promote selective molybdate, further dilution of the solution and addition-1-hydrocracking within the meaning of the invention. the resulting dilute solution to the cracking

The activation of a palladium-aluminum component is now combined in a steam dryer. In miniumoxyd-Rcformierungskatalysators in such a manner, 15 to another method, separate aqueous that the catalyst in an oxygen-containing gas solutions added to the metal compound and ammonia, at least about 15 hours at a temperature of hydroxide, is heated to the resulting solution an at least about 649 ⁰ C , giving a pH in the range of about 5 to about 10. Temperature of about 649 to 816 ° C is preferred. If the active constituent contains several metals, this activation can, if desired, be followed by a hydrogen reduction which is customary in the carrier. with cracking activity added in a single solution. In the reforming of gasoline, however, there are forms in which the metals are used. Reactions which can differ considerably from hydrocracking are colloidal solutions or suspensions, whereby a breakdown of the molecules, for example of cyanide, hydroxide or sulfide, is to be avoided. In addition, with the known activation processes, the concentration of the active metal is preferably around 0.01 to around 10 percent by weight for palladium-aluminum oxide reforming,
After combining all the catalyst components, heating of at least about 15 hours is required, while according to the invention, the heating of the impregnated carrier is dried with or longer in a steam dryer for about one hour to about 8 hours and the oxidizing gas is terminated in 1 to 8 hours 30 is then in air or other oxygen-containing gas. for a period of about one hour to

It was found that the temperature at which about 8 hours at a temperature in the range of

the impregnated mass is oxidized, oxidized to achieve about 700 to about 76O ⁰ C. Then the

the greatest efficiency of the catalyst essential catalyst during a period of about one

is borrowed. 35 half to about an hour at one temperature

Aside from the support of the catalyst is in the range of about 260 to about 54O ⁰ C in the presence of

of at least one metal or metal oxide, as reduced by hydrogen. The reduction of the catalyst

Chromium, molybdenum, tungsten, iron, cobalt, nickel, sators can also be put in place by means of a

Palladium, platinum, ruthenium, rhodium, osmium hydrogen purge at a temperature of about

and iridium. Suitable carriers are, for. B. of course 40 315 ° C can be made after the catalyst

Occurring aluminum silicates, especially after sator is introduced into a hydrocracking zone and

acid treatment, and man-made masses before the material to be treated is introduced into them

from silica-alumina, silica-zirconium oxide, becomes.

Silicic Acid-Alumina — Zirconia, Silicic Acid — Ma- As noted above, the catalysts are the

gnesia, silica-alumina-magnesia, silica-45 formed according to the method according to the invention

Alumina — thoroxide and alumina — boron oxide. The loading, particularly suitable for use in the

preferred solid carriers ordered from an artificial hydrocracking of gas oil or its fractions.

A mass of silica and clay. The exact working conditions depend partly

If the cracking ingredient is at least two of the character of the feedstock and partially refractory Has inorganic oxides, the 50 may wise on the activity of the catalyst. In all-mass c in any suitable manner, such as separate, the method is shared with a spatial sequence or common precipitation methods, speed (defined as the volume of liquid getting produced. of the oil charge per hour and volume of catalyst

The preferred cracking ingredients, consisting of silica in the reaction zone (from about 0.5 to about 20)

Acid-Clay Crdc and Silica-Alumina-Zirconia 55 or more. The hydrogen is from

are preferably made by introducing an external source or within the

an acid, such as hydrochloric acid or sulfuric acid, recycled with the process. With the preferred

commercially available water glass under precipitation conditions, sufficient hydrogen is generated

for silica mixed with acidified and left in the circuit so that no extraneous water

Water or other washes with a 60 cloth is required.

Aluminium salt and / or zirconium salt mixed. The hydrocracking process using the

and either a basic precipitating agent, such as a catalyst according to the invention, takes place either in

Ammonium hydroxide, or the desired individual charges or preferably in continuous

Oxide or the oxides by thermal decomposition Lichem operation. In this mode of operation, the

of the salt forms. The silica-alumina-zirconium 65 hydrocarbons continuously through a fixed

oxide cracking component can be formed by creating a catalyst layer upstream or downstream.

the aluminum and / or zirconium salts are passed together. In the case of continuous operation with a

or added separately. The other cracking components removed from the bed become catalyst and hydrocarbon

substances passed through a reaction zone either in cocurrent or in countercurrent. With a continuous Operation with suspension are catalyst and hydrocarbons as a sludge by the Reaction zone out.

The following examples serve to further illustrate the catalyst and process according to the Invention.

example 1 Table I.

Oxidation ^{temperature (0} C) ..

Conversion (volume percentage,

distilled at 204 ⁰ C)

catalyst

A I B I C I D

538

649
17th

704
20th

760

40 According to the following table, the catalysts were used under otherwise identical conditions, but at different temperatures. The transformations to be compared (volume percent, distilled at 204 ⁰ C) were as follows:

Table II

IO

790 g of water glass (28% SiO ₂ ) were diluted with 1580 cm ^{3 of} water and added to 315 cm ^{3 of} hydrochloric acid plus 630 cm ^{3 of} water with stirring. The acid-silica sol was added to 4075 cm ^{3 of} Al ₂ (SOi) ₃ solution (specific gravity 1.28) _{prepared from iron-free Al 8} (SO ₄ ) S "H ₂ O crystals. The sol was then incorporated vigorous stirring to 1850 cm ^{3 of} ammonium hydroxide (28%, NH ₃ ). The final pH was 8.2. The pH was then ^{increased to 8.5 with 65 cm 3 of} ammonium hydroxide. The gel was filtered, in small pieces cut and ³ of 1.5 N ammonium hydroxide is washed in a Pyrex tube for 24 hours with 7.61 of water plus 150 cm per hour at 8O ⁰ C, about 16 hours at 15O ⁰ C dried and shaped into pills of 3.2 mm. then the pills additional 3 hours at 65O ⁰ C was annealed. the composition contained about 63 weight percent alumina and 37 weight percent silica.

2.0 g of purified palladium chloride was dissolved in 250 cm ^{3 of} water plus 12 cm ^{3 of} hydrochloric acid. The solution was then ^{diluted to 300 cm 3} with water and poured over 300 g of the silica-alumina base into a rotating steam dryer. The pills were dried for 2 hours in a steam dryer and 1 hour in a drying oven at 150 ^° C., broken down into four parts and oxidized for 1 hour in a muffle oven at various temperatures. The first part (Catalyst A) was oxidized at 538 ° C, catalyst B at 649 ⁰ C, the catalyst C at 704 ⁰ C and Catalyst D at 760 ° C. Then, all of the catalysts in a glass tube in the effluent of hydrogen per 28,3Nl Hour at 427 ⁰ CV for ₂ hours. The catalyst layer was purged with hydrogen at room temperature.

These catalysts were used to hydrocrack a white oil feed with a boiling range of 371 to 482 ° C. 100 cm ^{3 of} catalyst A, B, C and D were each run in four runs under similar conditions, namely a catalyst temperature of 274 ° C, a pressure of 102 at, a space velocity of 1 and a circulation of hydrogen in a ratio of 535 m ³ per cubic meter Loading needed. The reaction vessel was lowered into a molten salt bath which was maintained at approximately the same temperature as the reaction vessel. The results of these tests are summarized in the table below.

Umw
d
A. indlung (
estilled t
Katal)
B. Volume prc
at 204 ⁰ C
reator
C. «Ent,
)
D. Working temperature
288 ⁰ C 20th
43 29
45 39
55 46
59 302 ⁰ C 62 73 80 80 316 ° C

The same catalysts were also used in passages in which the conversion (percent by volume distilled at 343 ⁰ C) was determined. The results at four different operating temperatures are given in Table III.

Table III

Umw
d
A. indlung (
estilled 1
Katal;
B. Volume prc
> at 343 ° C
fsator
C. «Ent,
D. Working temperature ..
274 ° C 44 57 69 288 ° C 52
72
92 59
74
93 68
82
95 76
84
98 302 ⁰ C 316 ° C

It is seen that the Catalyst D which had been calcined at 760 ⁰ C, results in a substantial increase in the hydrocracking of the feedstock to the desired products at milder operating conditions (lower temperatures of 274 ⁰ C and 288 ⁰ C) than the catalysts, which had been annealed or oxidized at lower temperatures.

It was also found that the use of catalysts that had been oxidized at temperatures of 816, 871 and 927 ⁰ C, led to relatively good conversion rates. However, the use of these calcining temperatures causes a shrinkage of the catalyst with the consequence of an increase in the apparent bulk density, which results in the need to use a larger catalyst weight. For example, four catalyst portions of 100 cm ³ , which had been produced under otherwise identical conditions but calcined at different temperatures, had the following relative weights:

Table IV

60

Weight of 100 cm ³

Oxidation temperature for 76O ⁰ CI 816 ° CI 871 ⁰ C1927 ° C

73

80

Example 2

A catalyst was prepared in a manner similar to that given in Example 1 above. 78 pills

were poured with a solution of 1.0 cm ^{3 of} platinum stock solution with 0.311 g of platinum per cubic centimeter in 90 cm ^{3 of} water plus 2 cm ^{3 of} hydrochloric acid in a rotating steam dryer and dried for 2 hours. The catalyst was then broken down into three parts. Catalyst E was oxidized I hour at 649 ⁰ C, catalyst F at 704 ⁰ C and Catalyst G at 760 ⁰ C in a muffle furnace. The catalysts were then reduced in hydrogen at 427 ^° C. for ¹ l for _{2 hours.} The hydrocracking activity of these catalysts differed in the same way as the analogous catalysts B, C and D.

Example 3

A silica-alumina catalyst base was prepared according to Example I. Five separate hydrocracking catalysts were then prepared by oxidizing nickel nitrate on the silica-alumina at various temperatures. Catalysts I, II and III were prepared by Nickclnitrat was placed on the silica-alumina, so that 1 ° / o nickel in the finished catalyst was present and it was oxidized at 593, 649 and 704 ⁰ C. Catalysts IV and V were obtained by nickel nitrate of the silica-alumina was added, so that the finished catalyst 6% nickel _au fd _it silica-alumina contained, and it was oxidized at 704 or 76o C ^0. In each case, the oxidation was followed by a reducing treatment with hydrogen, as indicated in Example 1. The hydrocracking activity of these catalysts was tested by treating a white oil in a similar manner, ie a sample of 100 cm ^{3 of} catalyst I, 11, 111, IV and V was run in passes at 274 ° C, a pressure of about 102 at, a space velocity of I. and tested with circulating hydrogen supply in a ratio of 535 m ³ per cubic meter of initial charge. A catalyst which had 0.4% palladium on silica-alumina and whose relative activity for hydrocracking was set at 100 was used as a standard for the hydrocracking activity.

The influence of the oxidation temperatures on the activity is shown in the following table:

Table V

catalyst Oxidation temperature
( ⁰ C) Relative activity I.
11
111
IV
V 593
649
704
704
760 100
109
133
214
254

55

It is readily apparent that the catalysts which had been oxidized at temperatures ranging from 704 to 760 ⁰ C, have a much higher hydrocracking activity than the catalysts that were oxidized at lower Calcinicrtcmperaturen.

Example 4

A catalyst base similar to that in Example 1 was prepared, and ammonium molybdate was added in such an amount that the finished catalyst contained 3% molybdenum. The catalyst was a long oxidized at 427 ° C and the other at 704 ⁰ C for 1 hour in a muffle furnace and then reduced V ₂ hours in hydrogen at 427 ⁰ C. The hydrocracking activity was determined by processing of a white oil with a boiling range of 371-482 ⁰ C for 100 cm ³ of each catalyst at 316 ° C, a pressure of 102 at, a space velocity of 1, 2 and 4, and with a cycle of 535 m ³ of hydrogen gas determined per cubic centimeter of charge. The catalysts were compared on the basis of the space velocity which results in a 60 ° / ₀ by weight conversion with a boiling point of 343 ⁰ C. These catalysts were compared to a reference catalyst containing 0.4% palladium on silica-alumina and having a relative activity of 100%. The molybdenum hydrocracking catalyst, which had been oxidized at 427 ⁰ C, shows a relative activity of 14 compared to a value of 68 for the molybdenum catalyst had been oxidized at a temperature of 704 ⁰ C.

It has thus been found that catalysts which operate at temperatures in the range from about 700 to 760.degree have been calcined, have higher hydrocracking activity than those below this temperature range have been annealed.

Similarly effective hydrocracking catalysts with a mixture of a metal from Group VJa and a metal from Group VIII were by impregnating a silica-alumina base, which had been prepared according to Example 1, with a mixture of nickel nitrate and ammonium molybdate in an acidic or basic medium, oxidizing the prepared in this way Pills are obtained by heating in a muffle furnace at a temperature of about 704 ^° C., holding at this temperature in air for a period of one hour and treating the oxidized pills with hydrogen in the same way as in Example 1.

Claims (1)

Claim: Process for the activation of hydrocracking catalysts, which consist of a multicomponent support having cracking activity and at least one active metal of groups VFa and VIII of the Periodic Table incorporated by impregnation in an amount of up to 20 percent by weight, characterized in that the catalysts before any contact with the hydrocarbon feed 1 to Oxidized for 8 hours in an oxygen-containing gas in a temperature range from 700 to 76O ⁰ C and then reduced in the range from 260 to 540 ^{0 C for up to one hour.} Documents considered:
German Auslegeschriften No. 1 055 510, 1 031 454. 509 568/426 4.65 O Bundesdruckerei Berlin