DE2052414A1 - Hydrocrack catalyst and processes for its production - Google Patents

Description

(08 869 861 - 27.10.69 15890 - 7519)

W. R. Orac & Co.

2 Hanover Square

New York, K.Y.A-St.A. Hamburg, October 13, 1970

Hydrocracking Catalyst and Process for its production »

The invention relates to an improved Hydroorack catalyst and especially an improved Hydroorack catalyst, which contains a crystalline aluminate to which a metal from groups Vi and / or VIII des Periodic table of the elements is applied

Hydrooraok catalysts that are used to convert higher molecular weight Hydrocarbon fractions are used to make more useful products * are well known. It Numerous hydrocracking catalysts have already been described been, which a hydrogenation promoting metal of groups VI and 'or VIII on an inorganic carrier material, E.g. amorphous Kieselshure, clay or a Kleselstture / toonerde hydrogel. In more recent times are Hydrocracking catalysts have also been proposed which, as a component of a crystalline aluminosilicate, i.e. a Zeollth included.

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The fact that zeolite has pronounced crystallite and With pure openings of about 6 to 12 pounds rubs into Hydrooraok catalyst, which compares 1 to the amorphous used up to now, yields superior activity and selectivity «« Iod dl · «eisten zeolites, 41 ·» or H # r »t * lluoe from Hydrocraclc-Katalyeatoren VTWndung found halMH» voo Paujaeiten derived, which have • in SUioiuedloxyd / Alueinlueoxyd-Ratn · of about 3d to 7t1. The "Faujasite" (which "in the Aueoafi set aside the initiation of criminality") and relatively unstable when the jarring temperatures are exposed. This means that the paujaelte present in the alkali form are "odiflxated" in order to increase their thermal stability before they can be incorporated into a hydrocracking catalyst "Particularly those characteristics which are valid in the Hydrocraok process are lost when" faujasites are subjected to thermal stabilization treatment, sB • la · * extensive ion exchange of alkali ions for equivalent ions that increase the stability of the flat ·

The load is due to the task of being improved. Metal of hydrocracking groups containing VI and / or VIII

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Develop catalyst, the great catalytic activity and has selectivity in addition to good thermal stability.

The invention accordingly relates to a hydrocracking catalyst, which is characterized by a content of

exchanged faujasites old of at least 3T1, of 0.1 to 15 based Gew.Ji (on the Faujaslt) rare earths of zones (printed £ a) 5 to 80 wt. of an old one rare earth Siliciuadioxyd / Alueiniuaoxyd-Verhöltnie as SB ₂ O ₅ ) contains,

b) O ₉ 5 to 15 Qetf. £ a hydrogenation promoting metal of groups VI and / or VIZZ and

c) 9 ^, from 5 to 5 percent, £ contains an amorphous Kleeelsäure / Tanerde matrix that up to 40 wt.% (based on the matrix) of alumina ·

The subject of the B & rfIndung is still a procedure for Manufacture of the Hydroeraok Catalyst, which thereby marked 1st »dafi man

1) a uniform suspension of a faujasite according to the Definition under a) in an amorphous silica hydrogel with a content of 10 to 40 wt. £ aluminum oxide manufactures »

2) washes the mixture obtained in step 1) »

3) impregnated the washed mixture with a solution,

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which "there" contains promoter metal, and k) the impregnated gene dries and calcins.

Finally, the invention relates to a method for cracking of hydrocarbons, since it consists of the Hydrocarbons in vapor form together with hydrogen under hydrocracking conditions above that according to the invention Catalyst conducts

The one preferably used in the context of the invention Zeolite is a paujasite of the type Y (PCY) partially exchanged with rare earths, which is described in the U.S.A. patent application Ser.No. 796,215 of February 2, 1969 (inventor McDaniel et al.) Is fully described 1st. This PCY is characterized by resistance to thermal decomposition at temperatures up to 927 ° C, an initial surface of 800 nn / g and a content of rare bonds (calculated as rare earth oxides) from about 0.2 to 10 wt

The silica / alumina hydrogel aatrlx, welohe according to the invention Is used, contains about 10 to 40 ew. £ Aluminum oxide. The hydrogel is made in general, by tine alkaline solution either with carbon dioxide or a mineral acid or with a salt of a mineral acid, such as alum, is brought to bloom. The silica / alumina hydrogel preferably has a surface

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from about 300 to 550 η / g and a nitrogen pore volume from about 0.4 to 0.8 »l / g.

The use for the production of the present catalysts Finding promoter metals are metals of groups VI and VIII of the Periodic Table of the Elements. In particular, chromium, molybdenum, Tungsten, bis-iron, cobalt, nickel, platinum and palladium for Production of the catalysts suitable. The promoter metals are mostly applied to the catalyst support in the form of soluble salts or in the form of complex compounds

In the production in general, the catalyst base stock Telle, that is, the pebble Sure / alumina hydrogel, and the zeolite is mixed with a solution of the desired promoter metals, brought into a suitable particulate form, and then calclnlert at temperatures from 427 to 649 ⁰ C, the erforderliohe physical strength and achieve hardness su.

In a typical production of the catalyst according to the invention, a paujasite, for example a PCY _{1, is added to} a gelled suspension of amorphous silica / alumina. As a result, the Oemisoh is thoroughly digested to produce a

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Achieve uniform distribution of the PGY in the Kleeels acid / alumina suspension, which is then filtered. The filter cake is then washed with water and ammonium in order to separate off all kinds of contaminants. The suepenslone can optionally be spray dried to obtain microspheres with an average particle size of about 50 to 75 µm . The spray-dried product is collected and washed again to remove alkali metal salts; then the product is finished by impregnation with the promoter metals.

QemKB a preferred embodiment of the invention, a PCY-containing hydrocracking catalyst is prepared by adding an alkali raujasite with a silicon dioxide / aluminum oxide ratio of preferably 3: 1 to 6: 1 to reduce the content of alkali ions, usually sodium ions, to a value of about 1 .5 to 40 weight percent (calculated as M ₂ O, where If is an alkali metal) is washed with an ammonium salt. The exchanged Faujaalt is then brewed in contact with a solution of salsa of rare earths until a content of rare earths (calculated as SB ₂ Ox) of about 0.5 to 10% (based on the Faujaslt) is achieved. The faujasite exchanged with rare earths is only partially loaded with rare earths inasmuch as the faujasite structure theoretically amounts to about 30 Ge *.

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on rare earths, but actually only about O ₉ I to 15 and means only 0 * 5 to 10 Qew. £ are incorporated. Following the exchange with rare earths, the zeolite is calcined at a temperature of about 571 to 87 ° C. for 0.1 to 3 hours. To achieve optimal results, the already exchanged zeolite is again with an ammonium salt solution, for example a
Ammonium sulphate solution, exchanged in order to bring the alkali content to a value below 1% by weight (calculated as alkali oxide), whereby the alkali metal is normally
Sodium is.

The promoter metals in the form of aqueous solutions of their salts or complex compounds are mixed with the carrier material to form a viscous mass. This mass can too
Pellets from 0.3 to 0.65 mm in diameter can be deformed. The material is then dried at temperatures from 121 to 204 ° C and then calcined at temperatures from 427 to 649 ° C in order to obtain solid, well-cohesive and abrasion-resistant particles.

The catalysts of the invention can be used in conventional hydrocracking plants. The application
Finding Hydrocraclc conditions are that the converted into the vapor state hydrocarbons at temperatures of 149 to 482 ° C, pressures from 35 to 210 atmospheres

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preferably 70 to 140 atttt, and throughput speeds from 0.5 to 5 * 0 volume of feed product / hour / volume Catalyst (OHSV) are passed over the catalyst. The preferred hydrogen / hydrocarbon molar ratios range from 10: 1 to 50 ι 1.

Virtually any hydrocarbon can be used as a base product Use when it is not pure

* It deals with aromatic compounds that do not contain any alkyl groups. Particularly suitable starting materials are straight-run Oasöle having a boiling range of about 204-427 ⁰ C, cycle oils from conventional cracking plants with a similar Siedeberelch as the Oasöle, Schwernaphthafraktionen and alkylaromatlsche hydrocarbons. The process for converting light and heavy oas oils into naphthas, which boil in the gasoline sector, and for producing heating oils of excellent quality is particularly valuable. When handling highly aromatic feedstocks

™, higher temperatures of, for example, 316 to 482 ^° C. are preferably used. When using products _f which consist in the main of waxing or naphthenic hydrocarbons, somewhat lower temperatures are preferred, for example, 260-427 ° C.

It has been found that in the presence of the Catalysts hydrocarbons to be particularly useful

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Lower molecular weight derivatives are cracked. Oils catalysts exhibit thereby an abnormally high activity at relatively low temperatures of about 316 ⁰ C. In addition, it appears that the activity of the catalyst even over long periods of use remains constant praktlsoh time.

The following examples are intended to illustrate the invention to serve:

example 1

A Hydroerack catalyst was prepared by combining 15% of a partially rare earth exchanged, aluminum-coated zeolite of type Y (PCY) with 85% of a synthetic amorphous silica / alumina hydrogel containing 15% of aluminum oxide . The PCY zeolite was prepared by first treating a type Y zeolite with an alumina / alumina ratio of about 4.7 t 1 with ammonium sulfate in order to reduce the content of sodium ions to a value of about 2 ow. This exchanged zeolite was then treated with a solution of rare earth chlorides (consisting of about 25 % lanthanum, 50 % cerium and 25 % of an Oemlsehes from other rare earths) to a SBgOyOehalt of about 1.5 Oew.J * (based on the Faujaslt). The old rare one

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Brden-laden paujaslt was then eaten at a temperature of 704 ° C. for 2 hours. The calcined product was exchanged again with ammonium sulphate in order to reduce the content of sodium ions to a value of less than 0.5 ow / f (calculated as Na ₂ O).

A sample of 49> 3 g of the PCY prepared as described above with a total volatile content of 12.6 pounds and 21 g of an amorphous KleseleBure / Fonerde hydrogel with a content of 13% by weight of aluminum oxide and a total content of volatile constituents of 26.9 % were ground together for 4 hours in a ball mill. 240 ml of a solution of 18.4 g Ammonlun-heptamolybdate (NH ^ JgMo ₇ O ₂ ^ .4H ₂ O in water was added to the ball mill, followed by milling was continued for another 4 hours in length. Thereafter, the Oemiaoh at 121 ⁰ C was Dryed for 16 hours and impregnated again with 200 ml of a solution of 23.7 S cobalt acetate Co (C ₂ H 4 Og) ₂ in water, This mixture was dried for 40 hours at 121 ° C. The dried product was dried with 4 Oew .jt "St" rotex "as an aid to offset Plllenherstellung and formed into pellets of 4.58 · 4.38 mm. The pellets · were ealoiniert for 3 hours at 538 ⁰ C, graded mesh to 14 to 20 and again a further 3 hours calcined for a long time at S38 ° C.

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Example 2

The catalyst prepared naoh the operation dea Example 1 was used in a Hydrooraok method "in which as the starting material a light Qasöl having a density of 24.5 ⁰ API, a boiling range of 2I7 to 34O ⁰ C, a nitrogen content of 20 ppm," a . ^ found Schwefelgehelt of 0.08 wt.% and a content of 55 wt, # of naphthenes and 18 wt aromatics use. The test conditions were a pressure of 88 atti, a hydrogen / oil ratio of 25 moles of hydrogen per mole of oil and a durometer ratio of 1.0 (liquid / hour).

In the test procedure, the catalyst was first ^{heated under a stream of hydrogen for activation to 4} ° C. for 24 hours. The temperature of the Reaktlonsgefäfiea was lowered to 216 ⁰ C and initiated the oil as a feedstock. The catalyst was conditioned with the starting product for a further 24 hours. The reaction temperature was set so that the density of the total product was 55 * 5 ° API, which corresponds to a conversion of about 70 to 7? It was found that an average temperature of 550 ° C was required to maintain this degree of conversion after about 30 hours of operation, while the temperature was increased to 354 ° C after 200 hours and

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- 12 Over 500 hours Ια remained essentially constant.

To "detection of the relative activity dee erflndungsgeelßen catalyst al · comparison, a Kobaltnolybdän catalyst used, the 19 Oetf. # A Z-14 U8 molecular sieve in place of 15 wt.% Of the PCY Molelcularsiebes contained and subjected to similar test conditions, and also the temperature was adjusted to maintain the same conversion in wt.%. It was found that for the comparison used for '~ ZH US Katalysatorbel an initial temperature of 335 ° C after 30 hours, had to be increased after 200 hours at 366 ° C, and that a further increase of about 0,56 ⁰ C. The 24 ^ idle hours were required to maintain the degree of unchanged. This indicates that a typical catalyst containing a Z-14 US molecular sieve is active initially, but loses its activity much more rapidly over a prolonged period of operation than the catalyst of the invention.

Example 3

A caleinated zeolite of type Y (PCY) partially exchanged with rare earths was produced as described in Example 1 _{, except that the RE 2} O, content was reduced to 9%

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was increased. The * exchanged Ztollth trurde 2 hours lane ρ · * 538 ° C and then ammonium sulphate exchanged, uu the NftgO content to below 0.2 wt. £ bring,

45.2 g of a sample of this PCY with an official volatile content of 8.0 % were mixed with 222.0 g of an amorphous KiealKureAocierde hydrogel which had an aluminum oxide content of 13% by weight and a total volatile content of 26% , 9 % . This vegetable was ground in a ball mill for 4 hours to obtain a homogeneous powder. 300 g of the powdery mixture were impregnated with 180 ml of a solution containing 15 g of ammonium heptamolybdate (NH ₂ ^ JgMo ₇ O ₂ ^ .4H ₂ O, in which the XugelmUh len treatment was continued for 2 1/2 hours · was then continued the mixture was dried for 16 hours at 121 ° C and again impregnated with 150 ml cobalt acetate CoCCgH ^ Og ^ ta water. This material was dried for 18 hours at 121 ° C and then 40ew «£" Sterotex "was added formed into pellets from 4.58 to 4.58 mm and 4 hours at 538 C ^O · ealolnlert The pellets were oalcinlerten mesh at 14 to 20 (U.S. standard) and classified again for 3 hours at 704 ° C · oalolniert

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Example "

The catalyst of the example ·? was after the same Procedure as investigated in Example 2 »Bine average Bydroeraek-Teisperatur of 3 * 9 ° C was after 20 operating hours required to maintain a level of change de »a · density you 55» 5 ° API of the total product corresponded. After 100 hours of operation the Temperature increased to 554 ° C, whereupon the degree of uranium conversion remained essentially constant for a further 200 operating hours.

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Claims (8)

2052AU - 15 - Patent claim 1 · hydrocracking catalyst, characterized by a content of a) 5 to 80% of a rare earth exchange faujasite with a silicon oxide / aluminum oxide ratio of at least 3 »1, which is 0.5 to 15%. Jfc (based on the faujasite) of rare earth ions (expressed as SE2O,) contains, b) 0.5 to 15 wt .5t of an amorphous kleselsic acid / alumina matrix which contains up to 40% (based on the matrix) of aluminum oxide · 2 · catalyst according to claim 1, characterized in that the paujasite has an initial surface area of more than 800 m2 / g . 3 «Catalyst according to claims 1 or 2, characterized in that the metal promoting the hydrogenation is an Oenisch of cobalt and molybdenum · 4 · Process for the production of a Hydrocraok catalyst, characterized in that on BAD ORIGINAL. 109821 / 204S 20524H - 16 - 1) a glelohaceous suspension of a Faujasite's Definition Yes. Claim 1. in elnea amorphous silica / ronenle drug which contains 10 to 4o Qew.jt of aluminum oxide, 2) wash the qeaisoh obtained in step 1, 3) the washed mixture impregnated with a solution, which contains the Proaotoraetall and 4) the impregnated Osalsoh dries and calcined. 5. The method according to claim 4, characterized in that the panjaslt is previously oalinated at a temperature of 371 to 871 ° C for 0.1 to 3 hours after the old rare earths have been exchanged. 6 · Method according to claims 4 or 5, thereby marked, that one is old to a watery Awaoniunlonen containing L solution washes ™ '7 · methods sub cracking hydrocarbons, characterized in that DAFL aan den hydrocarbon vapor r 11 ■ seed old hydrogen under hydrocracking conditions a catalyst Upper geeäfi to claims 1, 2 or 3 passes. 8. The method em claim 7 »characterized in that Then a temperature of 149 to 482 ° C, a 109821/2045 20524U - 17 - Pressure from 35 to 210 atf! and a high speed from 0.5 to 5 Volu »« n basic product / hour / Volume «! Using catalyst " ugs / era / r319 109821 / 2OAS