NL7908588A - METHOD FOR CATALYTIC CRACKING OF HYDROCARBON OILS AND CATALYST SUITABLE FOR THIS METHOD. - Google Patents

Description

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METHOD FOR THE CATALYTIC KRAKEH VM HYDROCARBON OIL EU SUITABLE CATALYST FOR THIS METHOD

The invention relates to a process for catalytic cracking of hydrocarbon oils in the presence of a catalyst containing at least one crystalline zeolite, and to such a catalyst.

The non-prepublished patent application 7901288 relates to a process for catalytic cracking of hydrocarbon oils in the presence of a catalyst containing at least one crystalline zeolite and contaminated by small amounts of at least one heavy metal and in addition 0.01-2.5 wt. % drill contains,

Zeolite-containing cracking catalysts are widely used in industrial cracking plants for the manufacture of motor fuels or components thereof. The crystalline zeolite-containing catalysts differ from the amorphous conventional cracking catalysts consisting of alumina and silica in that they have greater activity and selectivity. A drawback, however, is that the zeolite can be subject to contamination by heavy metals, such as cobalt, molybdenum, tungsten, copper and in particular vanadium, nickel and iron. The latter three metals in particular are present in certain crude oil fractions which must be catalytically cracked.

Although methods are known for removing such heavy metals from crude oils or fractions thereof, it remains desirable to look for means that eliminate the need for this removal for the required conversion of hydrocarbon oils. During the catalytic cracking of hydrocarbon oils, the contaminating influence of heavy metals is felt in the form of a gradual decrease in the activity and selectivity of the catalysts and an increase in the O '780 85 8 8 *' '2 coke formation, which Kook's · forms an undesirable by-product. The deterioration in the desired properties is accompanied by a gradual increase in the heavy metal content of the cracking catalysts.

According to the non-prepublished patent application 7901288, the adverse effect of the heavy metals on the cracking catalysts can be reduced by incorporating a small amount of hear in the catalyst.

It has now been found that this adverse effect can be reduced even further if the catalyst contains tin in addition to boron.

The invention therefore relates to a process for catalytic cracking of hydrocarbon oils, the cracking being carried out in the presence of a catalyst containing at least 1 crystalline zeolite, small amounts of at least one heavy metal, 0.01-2.5 wt. . # drill and 0.01-2.5. wt # of tin.

The catalyst preferably contains 0.1-1.5 wt. Boron and 0.1-1.5 wt.% Tin, which percentages are based on the weight of the fresh catalyst. The amounts of heavy metal contaminants, especially vanadium, nickel and iron, usually range from 0.1 to 2.0% by weight, calculated in the form of the total amount of metals, based on the weight of the fresh catalyst.

The catalytic cracking process is suitably carried out at a temperature between 100 and 650 DEG C. at a pressure between negative pressure and a pressure of several hundred bar. A fixed bed, a moving bed, a liquid catalyst and a suspended catalyst can be used, while a riser may also be used. Hydrogen is not added and the specific conditions depend on the nature of the food and the desired products. The feeds fed to the cracker are hydrocarbon oils derived from petroleum, shale oil and / or tar sands, which have an initial boiling point above the final boiling point of gasoline 7908588 X-r 3. Suitable feedstocks are, for example, gas oils, fuel oils, deasphalted oils, paraffins and residual oils.

The present process uses a catalyst formulated with a naturally occurring or synthetic crystalline aluminosilicate, namely a zeolite.

The zeolite component of the catalyst is suitably ion-exchanged with non-poisonous metal ions, such as rare earth metal ions, which enhance the activity of the catalyst.

The boron and the tin can be incorporated into the catalyst both before and during the cracking treatment by methods known per se, for example ion exchange, dry mixing, impregnation or precipitation. Boron and tin are very suitably incorporated by adding volatile boron and tin compounds or solutions of organic or inorganic boron compounds and solutions of organic or inorganic tin compounds in water or organic solvents to the gas used to regenerate the catalyst, to the hydrocarbon feed or the recirculation oils, or the steam used for regeneration to strip the catalyst. During the regeneration of the catalyst, the boron and the tin or the boron and tin compound are almost invariably converted into boron oxide and tin oxide.

The treatment agents used in the method according to the invention contain boron and tin compounds. These can be organic or inorganic.

Examples of suitable tin compounds are (il) chloride, tin (IV) chloride, tin naphthenate, tin (II and IV) nitrate, tetraethyltin, tetrabutyltin, tetraphenyltin, dodecyltin, dibutyl-30 tin dilaurate, tetraoctyltin, tin citrate, tin tartrate and mixtures of these compounds . Examples of suitable boron compounds are orthoboric acid, tetraboric acid, boron pentasulfide, boron trichloride, ammonium biborate, kaleium borate, diborane, magnesium borate, methyl borate, butyl borate, tricyclohexyl borate, 2,6-35 ditert-butylphenyl dibutyl boronethylcyclohexyl-methyl-88-hexyl-methyl-8-methyl-8-yl thereof. Treatment agents containing significant amounts of sodium, such as sodium tetraborate or treating agents containing other known cracking catalyst gifts, are less desirable.

The normal performance of the cracking process is not affected by the presence of boron and tin in the catalyst, so that it is possible to choose the usual values for the cracking and regeneration temperatures, the feed rate of the hydrocarbons, the ratio of feed and recirculation 10 oil and other parameters.

EXAMPLE

In the presence of a cracking catalyst containing faujasite-Y

a series of cracking tests were carried out under the following conditions: 15 pressure 1 bar ö reaction temperature kQ5 0

regeneration temperature 600 ° C

feed Kuwait distillate · throughput 6, l · kg / kg / h 20 The relative selectivity (S) of the conversion during

K

the cracking treatment .is determined according to the formula: SR = -

PC

where P_ is the total weight of the product fraction. . C-221 ° C 13 P

expressed in the form of a percentage based on the diet and P is the total amount of coke by weight expressed in the form of a percentage calculated on the diet.

Iron naphthenate (0.5 wt% Fe), vanadium naphthenate (0.2 wt% V) and nickel naphthenate (0.1 wt% Hi) are added to the catalyst by impregnation.

The elements boron and tin are added to the cracking catalyst by adding it with butyl borate and

Impregnate qdibutyltin dilaurate.

The results of the tests are reported in the table, # 7908588.

v 5

V

which also includes for comparison the results of the catalytic cracking tests in which only boron or only tin or none of these metals was added to the cracking catalyst.

TABLE

Tin Drill ΡΏ Pn S

.D ϋ II

wt. % wt. % 0 0 44.1 12.1 3.65 0 0.4 46.5 10.6 4.4 0 0.6 46.6 9-3 5-0 0 0.8 42.8 9-9 4.35 0.3 0 45.0 10.5 4.30 0.3 0.4 46.5 9.4 4.95 0.3 0.55 46.4 8.T 5.35 0.3 0.6 46.5 8.6 5.40 0.3 0.8 46.2 8.8 5-25 0.4 o 45.1 10.2 4.4o 0.4 0.35 46.2 9.3 4.95 0.4 0.5 46.5 9-2 5.05 0.4 0.65 46.6 8.8 5.30 0.4 0.8 46.2 8.8 5.25 0.55 0 45.1 10.2 4.40 0.55 0.35 46.3 9.6 4.80 0.55 0.5 46.3 9-2 5.05 0.55 0.6 46.3 9.1 5.10 0.55 0.8 46.0 9.1 5.05; r 'V * v {r;' 7908588

Claims (5)

A method of catalytic cracking of hydrocarbon oils, characterized in that the cracking is carried out in the presence of a catalyst containing at least one crystalline zeolite, small amounts of at least one heavy metal, 0.01-2.5 wt., $ 5 hear and 0.01-2.5 wt% tin. 2. Process according to claim 1, characterized in that the catalyst has 0.1-1.5 wt% hear and 0.1-1.5 wt% tin. Process according to claim 1 or 2, characterized in that the catalyst has vanadium, nickel and iron as heavy metals. 10 k. Process according to claim 3, characterized in that the heavy metals are present in total amounts between 0.1 and 2.0% by weight. Crystalline zeolitic catalyst suitable for use in the process according to claims 1-U, characterized in that it contains small amounts of at least one heavy metal 0.01-2.5 wt.% And 0.01-2 .5 wt.% Tin. 6. A crystalline zeolitic catalyst according to claim 5, characterized in that it has 0.1-1.5 wt% and 0.1-1.5 tin. ff '. % - i I 7 ® 0 8 5 β 8