DE1938978A1 - Process for hydrotreatment and a catalyst for carrying out the process - Google Patents

Description

LAWYERS

DRJUR-DIi ⁵ L-CHEM-WALTERBEIT

DR. JUR. HANS CHR. BY S. ^: FRANKFURT AM MAIN-HOCHS? AOBUMiSWASSEÄ. - ■ "__ ■..; _" ■ .- .: ·. . ; ".- .. ■ - _/ : - ^:.

Our Kr ₀ 15 685. "" .. -. .'.- ". X ', - ^Λ ' ■ - ": ■■ "

Chevron. Research.
San Prancisco ^ GaIe ■, V *, - St · A -,.-.-

Process zlii- HVdroBehandlting and ".'ein- -. for the execution of the procedure

The subject of the invention is. the catalytic reaction: Hyd £ okr.aekung. -von Ijrdöldest-illa.ten and 'deasphalted by Iiosunggialttel-' Eüclcstänänen with the production of _: high quality tiger 'fuel products including jet fuels. and gasoline. "-" -. ^: . . ^:

It is "known that a catalyst - from. A crystalline zeolitic molecular them" b-component: in conjunction with other catalyst components. It is also known that at least some of these "other;catalyst" components can be present in an embedding material (matrix) in which the molecular sieve component: is dispersed. "Such Eatalysatoren: can '. Acken Kr-bekänntlicjli -As for reactions katalytisehes, - Hydrokraeken -uiid'- Hydro-SJntschwef Contro l used werdeiio' As, examples, corresponding Patentachriften in which a ^7; or more of these -Segenstände. treated ", - are- to be 'taken'.'- - - -" - - "■ '■■""- ... -:" - "-.

Ü QBB Q B ns

BATH

1338978

^: / U. S, Patent 3,140,251 ^: .,; Λ: ■ \

U.S. Patent 3 HO 253 -. ■; "■". -;. - .. ".. '■

Brit ", patent specification 1,056,301. . "-,. ■ / -.; '■ ■ .:

Tranz "" Patent 1 503 063 ... ' _ ^: - -

Pranz. -ta tent very if t. 1 506 793 ν " _ _. ''

The further improvement of such catalysts, in particular for hydrocracking and hydrofining, is "constantly" being worked on. are, and the EichtTorpragbarkeit ^ ied by the increased - * number of possible modifications of catalysts with a - ■■ -. -. additional molecular sieve Kompcai.ente not reduced »Rarely ;. : - can - v; although this is also a very: aimed goal -. "; already before the" request a considerably improved result ... .- ".-. from. the request with a modified - catalyst with - one. molecular sieve components and other analyzer components _.; ... can be predicted, and this is especially true of ... ". Use of such catalysts in. Eydrokraek and. Hydrofinic processes «,". ".. ■. - .. -.

The aim of the invention is then to create an enhanced catalyst from a crystalline zeolite hollow sieve compartments in conjunction with other catalyst components : "■■■ Catalysts'"

1 ». An improved Eydrokrack -" / irksainkeit and.

20 an improved effectiveness in nitrogen removal through Hydrogenation (hydrodenitrifxcation). -. -

having" . ■ ■. "

Those are serene goals. Creating using this improved catalyst to be carried out hydrocracking and .Hydrofining processes and combinations thereof,. Those with high. Divesting high quality jet fuel - as well as -

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other valuable fuel production works.

The. The present invention and its advantages will be based on explained below in conjunction with the accompanying drawing. ■

Fig. 1 shows in schematic form the system and paths for carrying out the method - according to various embodiments of the present invention. ^o in the case of the catalyst according to the invention is used in direct throughput, in order to achieve a hydrocooling charge of a hydrocirculation and hydrogenation which takes place at the same time. Subject to nitrogen removal mater the formation of more valuable products, some of which can be further refined by catalytic reforming or catalytic hydrocracking, if necessary,

The Fig, Z also shows in thematic form the system and Plieesbahneiigur implementation of the process according to further details of the present invention, wherein the inventive catalyst for the simultaneous hydrofinishing and hydrocracking of a hydrogen column charge is used _? the hydrofinier-hyilrocracksone in circulation .Tjetrejiben will come and certain parts of the effluent from the hydrofinier-hydrocracking zone can optionally be catalytically reformed or catalytically cracked.

It has now been verified that the above-mentioned aims are achieved with the aid of a catalyst: * v / erder., E. A unique combination of catalytic constituents contained in precise amounts, including molten earth, alumina, a component of the YI group des periödicciieix Sys.-tems, a component of Group VIII and a crystalline molecular sieve — Ivoiiiponente, which ± u v-? s rii.tlicr.eii in the or 'hydrogen bela /! _ere - _a Porni x "is present and practical no catalytic loaded metal or ^ri etalle er.Oiiäl *. Sege'cenen if in aem Katslysaxor ivach a Uc ^ poiiente of the IV,

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.Group contain / be-. If such a component is present, / These can be litan, zircon, thorium or hafnium or one Combination of these metals - be that in metal, oxide or Sulphide form or in a combination of these forms in an amount from 1 to 10, preferably from 5 to 9 wt. net as metal) of the ^ ichtmolekularsieb-Kompoiaenten des Catalyst present.

According to the flow control, in particular a catalyst is used create that out

A. a geIfarmigen embedding device from:

a) at least 15% by weight of silica,. "■■ _ ■

b) Alumina, in an amount such that an alumina: silica weight ratio of 15 'x 85 to ^{80:20 is present;} . . v

c) Micke! and / or cobalt or in metallic, oxidic and / or sulfidic form in an amount of, calculated as metal, 1 to 10, preferably 5 to 9 wt .- $ the embedding material,

d) Molybdenum and / or tungsten in metallic, oxidic and / or the sulfidic form in an amount of calculated as "lie tall, 5 to 25» preferably 10 to 20 wt .- # the bedding material;

B, a crystalline zeolitic molecular sieve found in essentially in ammonia or hydrogen-laden form is present, which has essentially no catalytic be- Contains charged metal or metals and that continues in In the form of individual parts and in the embedding

Z material is dispersed, ^

v / obei, the Hat - Iyoator by an average pore diameter of less than 10 Angstroms and «.turc-h. a surface area of over 200 m / g is characterized.

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The gel-like embedding material is preferably made of nickel and tungsten in metallic, oxidized and / or sulfidic form. The molecular sieve can in. a length of 1 to 50 wt .: -φ, based on the "'G-eniisQja, be present.

Another catalyst according to the invention consists essentially of:,; *.>;.; ..- ■ "" ■ "■". ^:

A ₀ a porous xerogel from:, ■ '

a.) at least 15 G-ew .- ^ silica,. "-. '. - ■ -. -' ■ - ¹ ^ ;. '

b in an amount such that) clay, ^a: Donerde. : KieBelerde-. ü-weight ratio. from. .1: _5:; 5 85-to BQ.S2Q is available,. .

c) Hickel in, metallic, ^: ; oxydls.cher: and / or smliiaei33her form -in one.quantity -νοη, -.computed as. Metal, 1- ^ to 10,

-preferably 5., to 9 xxew »- ^. of; Xerogels ,. : vv. ^: -. ä) Wolf ram-in metallic,: oxidic and / or. more sulfidic. Form, in., An amount ^ of,;. Calculated '/ as ^ metal, :: 5 to. "25j preferably IQ to, 2G: öew _.; ^ Jäes X; erogelsr ~

B "a crystalline zeolite molecular acid in an amount / from 1 to 50% of the catalyst, which is essentially in ammonia or hydrogen-laden 3POrIn, -intentially no catalytically-laden metal or contains such metals - and is practicing rhlhaüs' in 'the form of individual parts ■ ^exists; di © dlspergiert are in the xerogel ^,::.....'; """..-_""._ ■.. :. - ^; . S _ '-' -

wherein the catalyst has a pore diameter of less than 100 Angstroms and a surface area of about. "- 2OO m / g.

Further in accordance with the present invention there is provided a hydrotreating process which consists in having a hydrocarbon feed which is essential. Includes amounts of about 93 ⁰ G-boiling substances and rdöidestillaten from ^ by liösungs- medium entagpi ^ ai-kietv-fcQft Brdöl-fiüokständen, shale oil or coal tar distillates at "-" eiii "he Tempieratur-from 204 to 51O ⁰ O , a pressure of -56 ^ ■

00 98Ό8 / 1517

1938970

? keitsraumgeschwindigkeit from 0.1 to ϊ, 0 vol / foil / STDE and a hydrogen feed rate of 35 · ".61 - 3561 m ⁵ m ⁵ Wasserstoff'Je charge (200-20000 S (XF by; barrel) in a reaction zone Bringing hydrogen and the catalyst described above into contact and that the hydrotreated products are obtained from this reaction zone ... The hydrocarbon charge can contain a considerable amount of organically bound nitrogen, since the catalyst according to the invention is both opposite or- ': ganischem nitrogen extremely as well as to ammonia tolerant behaves and is catalyst a powerful catalyst in hydrodenitrogenation, "nitrogen removal by hydrogenation and hydrocracking using the Katalysatcrfs take place simultaneously and on .wirksame ^ else, ^the catalyst. can be used as a hydrodenitrification catalyst in a zone preceding the hydrocracking zone, the % drokracksone a similar or different hydrocracking catalyst containing a high \ - valent jet fuel product can be gevronnen äaim, "if the catalyst for the Hydrokr ^ ckung a _suitable: J.ueh feed is used, a b.ochv, iertige Feed to a catalytic reformer can then be made; when the catalyst is used for hydrocracking. The effluent from the hydrocracking system ^£ roduct boiling above the boiling range of gasoline, or in the hall of the extraction of a jet fuel above. Boiling range of the jet fuels can be catalytically cracked for the production of many other valuable products.

2er regard to a crystalline zeolitic molecular sieve, ^"containing substantially no catalytic metal loaded ', or loaded metals" means that the molecular sieve based on the sieve, no more than 0.5 weight ₉ - $ ~ catalytic metal or having catalytic metals. The catalytic metal or metals of this type include the etalia of Tf * _t VI, and VIII ,. Group of the periodic table, including sodium,

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BADOHIGINAt.

The weight ratio of catalytic metal in the high molecular sieve portion of the catalyst to catalytic metal in the molecular sieve portion of the catalyst is high Catalyst achieved. It has been found that such catalysts are inferior to the catalyst of the present invention.

In the process according to the invention, the feeds for the hydrofining hydrocracking zone consist of petroleum distillates, solvent-deasphalted petroleum residues, shale oils or coal tar distillates. The feeds contain substantial amounts of materials boiling above 93 ° C, vorzugsv / eiae in the range 177-510 G _#, and in particular in the range between 2Ö4- and 482 ⁰ C * Suitable BeBchicküngen are those heavy distillates commonly known as heavy immediately distilled gas oils and heavy cracked circulating oils (oycleoila) as well as conventional FCG feed and parts thereof. Cracked feeds can come from the thermal or catalytic cracking of various raw materials, EB from materials obtained from petroleum, gilsonite, shale and coal tar. Because of the better hydrofining activity and stability of the catalyst according to the invention, it is not necessary to subject the feeds to hydrofining before use in the present hydrofining / hydrocracking process. The feeds can in the present case be up to several thousand ppm organic contain bound nitrogen, the content of organically bound nitrogen is preferably below 1000 ppm.

The crystalline zeolite Molekulareieb component of the 'Hydrofinier-hydrocracking KatalyBators can be any kind

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Known in the art as a useful component of a conventional · V hydrocracking catalyst _m ± a crystalline zeolitic molecular sieve component ". Preferred is a decat ionized molecular sieve cracking component. Particularly suitable are faujasite, especially" Γ "* · And ♦ 'X ^ -Faujasite, as well as mordenite in the ammonia or hydrogen-laden form.

The molecular sieve component of the catalyst can be according to any conventional known processes.

The molecular sieve component can in a conventional manner in an embedding material made up of the other catalyst components by coagulating these other components around the ι molecular sieve components are dispersed around »

The most heavily loaded with ammonia or hydrogen Porm. present molecular sieve component can - as according to the invention required - essentially catalytically by this loaded metal or such metals kept free; that the molecular sieve component is in a slurry of the precursors of the other catalyst components dispersed at pH 5 or above. Form a ; Uatrium form of the molecular sieve component one, the 'starting - * fabrics, this can be done through before uniting with the others : Ion exchange taking place in the catalyst components Ammonia- or hydrogen-laden form can be transferred. But you can also with the other catalyst components j combined and then by ion exchange into the ammonia or Hydrogen-laden form can be converted. In none of the

In both cases, however, the molecular sieve component should be combined with the - precursors of the other catalyst components at a pH value of less than 5 »-

Optionally, the finished catalyst can be based on conventional .j way to be sulfided before use. If the catalyst *

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tor is not presulfided, it will be carried out during execution of the process through any "possibly in" hydrocarbon feed tends to sulphidation.

The hydro, finishing hydrocracking zone containing the catalyst according to the invention operates at a temperature between 204 and 510 ⁰ O, preferably between 260 and 454 ⁰ C, a pressure between 56 and 246, preferably 70 and 211 atmospheres and a liquid space velocity of 0, 1 to 5.0> preferably from 0.5 to 5.0, in particular from 0.5 to 3.0 vol / vol / hour. The feed rate of all of the hydrogen introduced into this zone (treatment and circulating hydrogen) is 35 »6Ί to 3561, preferably 356.1

"Z ¹ X-

up to 3561 m of hydrogen per m of hydrocarbon feed (200-20000, or 2000-20000 SOT / barrel).

In the operating conditions of the hot-rolling zone and catalytic Cracking zone in various embodiments, the present invention is. Customary, in the Technique known conditions.

According to FIG. 1 of the drawing, according to an embodiment of the present invention, one is described above Hydrocarbon feed, boiling above 204 C in this case, and a substantial amount of organic Can contain nitrogen compounds, 'introduced via the line 1 in the Hydro'finier hydrocracking zone 2, the inventive contains catalyst, 'The charge will be in% -drokraokzone 2 "under the aforementioned conditions hydrocracked in the presence of V / water fed in via line 3. Under these conditions hydrodenitrification takes place at the same time until the feed is practically denitrified is. The product flowing out of zone 2 is introduced into separator 5 via line 4, from which hydrogen separated from the treated feed via

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; the line 6 is returned to zone 2. In the separator

5 water entering through line 7 is used to wash ammonia and other impurities out of the incoming hydrocarbon stream. Line I removed from plant 5. The total will be from the Annex 5 - washed, hydrocracked substances introduced via line 9 into the :: \ distillation column 10, they w'o in fractions. '. i are separated, e ins chi ie s si i a fraction C * ~ ", which is withdrawn via line 15, a fraction 0 ^ -82 C, which is removed via line 16, a fraction 82-204 ⁰ C, the is withdrawn via line 17, a fraction of 160 ° -288 C, the "-about line 18 is removed, and a fraction 160 ⁰ G, which is withdrawn via line nineteenth Both via line 16; ;; ; withdrawn fraction O ^ - 82 ⁰ G is; a quali-; tatxY high-quality light petrol * The disconnected via line 17; headed fraction 82 ° - 204 ° 0 forms a high quality cataly- ■; table reforming filling, which takes place in the reforming zone 20

can be catalytically reformed, from which one can derive a high-quality catalytic reformate via line 25. The withdrawn via line 18 fraction 160 ° - provides 288 ⁰ C -. A qualitatiY quality jet fuel is the above i line 19 remote fraction 160 ⁰ C is a valuable j hydrocracking feedstock in the J% d _r okräekzone 26 in & e -. in the presence of a conventional hydrocracking catalyst and: hydrogen introduced into zone 26 via line 27

can be catalytically hydrocracked. From the hydrocracking ^r '■ zone 26 a ^ Spills, Masserstoff 30 via line 28. Hydrogen may roduct i removed in separator 29 is removed therefrom via line into hydrocracking zone 26, are recycled. The said fraction 160 ⁰ G ⁺ can j. also be catalytically cracked in a catalytic cracking zone under conventional catalytic cracking conditions,. Hydrocracked substances can from the separator 29 via the '\ recycled into the distillation column 10, 35, and 9 leads are where they AIIF the above-described ^v' may be broken down into fractions else. '■' -

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According to Fig. 2, a

of the kind described above, ..- which ^{boil in the be ^ aIIe above 204 0} C and considerable amounts of organic. Nitrogen compounds-may contain, introduced via line 50- into the Hyflrofinier-Hydrokrackgione 51, which contains the catalyst according to the invention · The feed is in the zone 51 under the conditions specified above in the presence; of hydrogen supplied via line 52: hydrofined and hydrocracked at the same time. The product flowing out of zone 51 can pass through line 55 i * ¹ to hydrocrackers 54

: Wercfen introduced 'of this as' the same conditions as in zone 51 i * i the presence of a hydrocracking in - be ataiysators \ hydrocracked käiin - ^. ^{B for} the hydrokraek catalyst ^; Zone 54 can be. act the same catalyst, \ as used i ^ ^ ^ of zone 5 or it may be a manufacturing ι kömmlicher HydrokräGk catalyst be used ,, the group consisting of a crystalline 1-zeölithisehen .Molekülarsieb Krackkomponen- | In both cases the product flowing out of zone 51 can be introduced into zone 54 via line 53 without the interposition of a stage for removing impurities, but none of the hydrocracking catalyst in zone 54 Contains crystalline zeolitic molecular sieve component, an intermediate stage for removing ammonia and other impurities is preferably interposed between zones 51 and 54. The zones 51 and 54 can be arranged in separate header housings, which can be operated with different pressures... - -, "'." - ■ '.. ■. "-. ■" .-

The zones 51 and 54 can, however, also be arranged as separate catalyst layers - in a single ruckgehause 55 ", and the product exiting zone 51 can be without Interposition of a pressure release, condensation or Removing contaminants are introduced into zone 54; This is especially true of the pail that the zone 54 is equipped with the inventive catalyst or

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contains a conventional catalyst composed of a crystalline zeolitic molecular sieve component. Is emerging from the zone 54 ^r roduct passes via line 56 to separator 57 from which hydrogen via line in the Hydrofinier hydrocracking system 51 is returned, optionally, the entire recycled hydrogen or parts thereof via line 59 into hydrocracking zone 54 passed will. In separator 57, water entering through line 60 is used to scrub ammonia and other contaminants from the incoming hydrocarbon, unless these "contaminants have already been removed between zones 51 and 54; ammonia, water and other contaminants are removed via the line withdrawn from zone 57, ^ the product emerging from zone 57 passes via line 66 into the distillation column 67, where it is broken down into fractions, including

which is discharged via line 68, a fraction C / ", a fraction Cj-- 82 ⁰ C, which is withdrawn via line 69, a fraction 82 ⁰ -204 0 °, which is removed via Leitung'70, a fraction 16O ° -288 ° C., which is discharged via line 71, and a fraction 160 °, which is separated off via line 72. In a preferred mode of operation, the fraction discharged via line 72 is returned via lines 73 and 74 to the hydrofining hydrocracking zone 51. If necessary, the entire fraction or part of this fraction can be returned to the hydrocracking zone 54 in line via line 75. The fraction withdrawn via line 69 is C, -82 ° C To a high quality light gasoline, the fraction 82 ° - 204 ° C removed via line 70 represents a high quality catalytic reforming ^ eschickung, which can be subjected to catalytic reforming in the -Äeformieraone 76 ", from which a valuable one via line 77 catalytic -tefo rrnat can be derived. Fraction 160 ° - 288 ° C withdrawn via line 71 results in a high quality fuel. The fraction 16O ^{0+ carried} via line 72 can be wholly or partially transferred

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Line 78 are fed to the catalytic cracking zone 79, in which these under conventional catalytic cracking conditions in the presence of a conventional catalytic cracking catalyst, a catalytic insult to valuable fuel products can be subjected, which can then be removed via line 80 ... from zone 79.

The following examples illustrate the requirements Catalyst, its division and its "use in the pre-, lying method, 'without restricting the invention.

Example 1, "-.._ ■ -;

Production of a gelated catalyst (catalyst A) the following composition:

Components wt .- ^ of the total catalyst

HiO '-: ■ "' ^: - '■"' 10.0 -.- ■■■ , -

24 ', 5- ■■.'. '

₃ ■ ■. 29.0

₂ ; 25.5

• Crystalline zeolitic "
Molecular sieve, "Y ^{! L} -I'Orm '■ -.--: - 11.0

total - 100.0

The itatalysatorhörstellung was made in the following stages, the different starting materials were used in such an ^H narrow that the weight percentages of the above ingredients reached des'.fertigen Katal.ysators were. '' - .. '. - - ^: - -

1 ο Production of the aqueous acidic solution with content of AlCl ₃ , NiOl ₂ and acetic acid,. . -

2. Preparation of three alkaline solutions: Ca) a sodium 11cate solution
(b) a sodium tungstate solution .and

. (c) an ammonia solution containing ammonia in such excess , 003808/1517 ■■ / /; λ, - '

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shot contains that after. Combination of the alkaline solutions with the acidic solution at a neutral pH value of about 7 a common precipitation of all metal-containing Components of the solutions occurs.

3. "Association of acidic and alkaline solutions and common Precipitation of all metal-containing components of the two solutions at .a pH value of about 7 below Formation of a slurry.

4. Addition of the crystalline present in finely divided form zeolitic molecular sieve of the type Linde ammonium "Y" to the slurry. . ■■ -

To be contained under Gewrmiung of the molecular sieve, the molecular sieve 5. Remove filtering the slurry containing the hydrogel filter cake was washed repeatedly with dilute ammonium acetate solution ionic l ^N latrium- and chloride contaminants both from the hydrogel as well as from the molecular sieve contained therein «

6β drying the hydrogel containing the molecular sieve in an air circulation oven and then activating it in an air stream for 5 hours at 51O ⁰ O.

': ■.: ■ ^: - ■■■. ■■■

The finished catalyst was characterized by a surface of 417 m / g, a pore volume of 0.4 cm / g and one mean pore diameter of 38 Angstroms a ȣ, where the Molecular sieve component essentially no catalytic Metals, i.e. practically the combined nickel and The volfram content of the catalyst was rather in its Gel content than in its molecular sieve component *

A gelatinized catalyst (catalyst B) was exactly v / ie 'in Example_1, with the exception that the molecular, sieve in an ammonia water before incorporation into the slurry

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- 1 ρ -.

The NiClp solution was pre-soaked in order to load the molecular sieve with nickel. The starting materials were used in such an amount that the finished catalyst had the same percentage by weight of the constituents as the
catalyst of example 1.,.

bainite, the only difference between the catalyst and ι was this that of Example 1 that the I contained in the catalyst Nickel distributed over the gel component and the molecular sieve component was.

Example 5

A gelatinized catalyst (catalyst C) was prepared exactly as in Example 1, with the exception that no molecular sieve components were incorporated; li'ie- starting materials were used in such an amount that the finished catalyst
the same proportion of non-molecular sieve components as the catalyst of Example 1. Remaining
The catalyst had the following composition:

Components G-ev. ', - $ of the total catalyst

NiO 11.2

27.5
\; 32.6

28.7

C.

total 100.0

The ^ ev.'iehtspröaentsatz each Niclit-Iiolekular-sieve component of the catalysts A and B thus amounted to 89 '> ft _t based on the ü'ewichtspronentsatz the same Korapqnente "of the catalyst C, wherein the further 11 Ge'..'.-? 5 of the catalysts A and B of
the molecular sieve component were contributed.

Example 4

The catalysis parts A, B and C of Examples 1 - 3 were

00980871517

the separate '!' rush for hydrocracking Californian oil feed in direct throughput, used. .

The gas oil feed had the following properties:

Boiling range spec. weight Organic nitrogen content

,O.

260 to 482 G 0.9402 3,000 "ppm

H. hydrocracking conditions:

Total pressure of total hydrogen supply Liquid space velocity conversion per pass into products with boiling point below 288 C (#) 'starting temperature in C

176 atü

1780.5 vi? Ixs?

0.8 vol./vol./hour,

as indicated below.

The hydrocracking activities of the three catalysts were turned on the initial temperatures measured, which were required to achieve the given conversion per cycle:

catalyst

Δ ■.

i ^ s temperature in G

'385 399 413

The nozzle manufacturectOffprodakt with boiling range from 149 "to 288 ⁰ C had ii: joc.; M -'all 'in this respect the same sufficient quality

when the smoke point was 21 mm each time

and the

is below -70 ⁰ C.

In each ^x 'are all free of oragaiiischen nitrogen compounds, ~ the liquid hydrocracked product in lateral w - ~ which it is apparent that the hydrocracking depending lesmal i: ^r, essentially complete nitrogen removal by hydrogenation

runfr ^{% is} accompanied.

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This example showed that

1) the hydrocracking activity of the gel catalysts with molecular sieve (Catalysts A and B) that of a molecular sieve but otherwise identical I-ataly3ators (catalyst C) is superior to _ _ ".

2) hydrocracking activity of the gel catalyst mi t of a molecular sieve without metal loading (catalyst A) of the one having a metal-loaded molecular sieve equipped, but otherwise identical gel catalyst (catalyst B) is superior and

3) the ^ el catalyst with an i-iolekularsie bicomponent e without Metal loading means »essentially complete hydrodenitrification at a lower temperature in the winter than the catalysts. 3 and C.

Example 5 - - - -

Sin other part of the catalyst A of Example 1 was used to hydrocracking a entssphaltderten solvent hydrocarbon oil with boiling point above 288 ⁰ C and a content of organically bound nitrogen of 5,500 ppm in -...; used in a direct throughput. Subsequently, this part of the catalyst A was used for the Ilydrocracking of another part of the same, ejatasphalted by solvent. Oil downstream of the ext inlet ions circulation of the 3 products boiling over 288 G is used. ., - - - '. ; . j

. Hydrocracking conditions after the operating equilibrium has been reached

Catalyst A, Catalyst A, Direct Recycle Rate -. - ■ ■, .. '■ -' ·

Temperature in ⁰ C total pressure, in atü '. Gesaiiit-exhaust gas ratio

PlüssiglceitsraurageschWindig * - " - speed, VoI _r / VoI ₀ /S.tde ^.: 0.8.;. '

Conversion into product with

■ "427 -J- 427 : -1.76 / ■ ' : 176 10,000: '^ 10,000

Group 149 ° - 288 ⁰ G as -Düsenkraftstoffprodukt;

Catalyst A, Catalyst A,

Direct through-circulation

sentence

30.0. 50.0 20th 30.0 -54 -57 17.0, 37.0 68.0: 54 * 0 15.0 9.0

* Yield ^ in ^: cold point, mm freezing point in ⁰ G paraffins, vol- '/ o naphthenes, Vbl-jä aromatics, vol- $

^! As this example shows, a high yield of high quality jet fuel is obtained from the solvent-deasphalted hydrocarbon oil feed both in direct throughput and in circulation operation. \ Furthermore, it is seen that the circulating operation to a higher ^F Kydrokr ckaktivität ^ j. Leads thereof and quality, which is due to the fact that the normal paraffins of the eiitasphaltierten solvent oil are ¹ eil concentrated in the high boiling ¹ J-, to extinction in the jet fuel range overall \ be-cracked: yield of jet fuel. _: «

j Example 6. -

The fraction 288 ⁰ C from the direct throughput operation of the; Example 5 is treated further in a subsequent hydrocracking or catalytic cracking stage "This roduct ^r represents a valuable, refined Seschickung for such Weiterbehandelung represents -. _{-

The invention is not aimed at explaining any theory the unexpectedly improved hydrofining and hydrocracking ; performance of the present catalyst bound. It will come on, ' taken that favorable results in unmatched ways largely due to the special combination of the kata used

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lytic components associated with a relatively high ratio of catalytic metals in the fricht molecular sieve shell of the catalyst compared to the catalytic "metals in the molecular sieve fraction of the catalyst and at the same time with a low absolute amount of katalytiseheη metals in the molecular sieve fraction of the catalyst.

Although only specific embodiments are described, the invention can be modified in various ways without departing from the scope thereof

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BATH

Claims (1)

_; ₂₀ _ -. 1938378 P A T .Ε 'xi T A Il PROVERBS: " Ίο ■ method for hydrotreatment, characterized in that daso roan a hydrocarbon charge that contains significant amounts of ^{substances boiling above 93 0} C and made of earth. oil distillates, petroleum residues deasphalted by solvents, slanted oils or hard coal tcer distillates. bestent, b in a reaction zone, egg a .Temperature -'510 of 204 ⁰ C, a pressure from 56 to 246 atmospheres, a liquid, keitsraumgeuch-wirdigkeit of 0.1 to 5.0 vol / vol / STDE. and a hydrogen feed ratio of 35.61 3561 ra. hydrogen per feed with / ordering hydrogen and the catalyst . . . : "■ - ..... .A., A gel-like embedding material a) at least 1J wt _o - ^ silica, fo): ^f üör.er / e!. . to such an extent that a Touerde: silica There may be a ratio of 15:85 to 80:20, c) Nickel and oxide cobalt in metallic, oxidic and / or sulfidinciier form in -a! - close of. 1 to . 1 ^ j% by weight of the egg ■ d) .KoIy bdän and / or Wolf ram, in meta-lli3cher, oxydi scher and / cder suliidi:, c ': er form in an "i.onr-e from 5 to .-' i of the embedding material,.. ... - _ '\ - _ B. a crystallized zeolite Hclekularsieb, which in ; Substantially in ammonia or oxygen-laden form : present +, essentially no catalytically loaded. Me- ^; t & ll or such; _: .e ^; : contains all, is present in the form of individual parts and dispersed in the embedding material 00Ü808 / 151 7 BATH ORIGINAL 2. The method according to -Anspruch- 1, characterized in that one misunderstood a carbon dioxide charge, the one ■ contains substantial ["close, organically bound nitrogen and that one ammonia from the emerging from the reaction zone Product removed. ■ ■ .- 3e method according to claim 1, characterized in that one boiling above the gasoline range part of the product exiting from this reaction zone in a second reaction zone at a temperature of 204 "to 510 C, a. Pressure from 56 to 246 atmospheres, liquid space velocity from 0.1 to 5.0 vol / vol / hour and a Viassorutoff feed ratio from a total of 35.61 - 3561 ".ία hydrogen each m charge in the presence of hydrogen and one ■ hydrocracking ^lv atalysator hydrojirackt. "' 4. Catalyst for. Implementation da :: ^v experienced: s. according to claims 1-3, consisting of .. ", ■ A ₀ a gel-shaped insertable material made of ■. ". .- - a) at least 15 G-ev ·; ..- ^. Silica, ■ ~. - ■ "..-.- b) Tor-erdo in such a tightness that an alumina: silica-G-ev.f-Chtsv.arhaltnis of 15 * 85 to 80: 20 is present. c) liickel and / ο-ler cobalt in metallic, oxidic and / or sulfidic form in an amount of calculated al .; hstall, ΐ 'to 10 G-ew .- ^ of the embedding material, d). Molybdenum and / or tungsten in metallic, oxidic unä, · or sulphidic form in an amount of, calculated as ilatall, 5 to .25 &ev; .- / ä of the embedding material, B.O a crystalline zeolitic molecular sieve, which is im essentially in Afiimoniak- or WaisserstOff-laden j? orm is present, essentially no catalytically charged metal oil contains such metals, in the form of individual "parts present and dispersed in the embedding material is, · . . - ■ -.-'- · - ■ -. - .- ■ "" ' wherein the catalyst "continues to have a, middle pore-- 009 80 8/15 17 diameter γοη less than a ^ s 100 angstroms and a surface is characterized by over 200 m / g. 5, catalyst according to claim 4 »characterized in that that the gel-shaped sealing material made of nickel and tungsten consists, which is in metallic, oxidic and / or sulphonic Form is present, ■ 6, catalyst according to claim 4 »characterized in that. that the content of the crystalline zeolitic molecular sieve 1 to 50 wt .- / 3 of the mixture is. 7 o Catalyst according to Claim 4, characterized in that it essentially consists of A, a porous xerogel a) at least 15 wt. -, -> silica, b) alumina in such:.: eiige that a i'oner e: ilieseler-ie-Gev / ICRI ^ sverhältnis of 15 85 to 80: 20 is ^present,:: ■ ■ -.-._ c) liickel in metallic, oiiydiseher and / or; sulfidisciier Porra in an amount of, calculated as ^ etall, 1-bis 10 wt .- / y of the xerogel, - ". - - . d) v / olfran in inetallischer, oxydiacher and / or sulphidic form in a narrow ^ of, calculated as metal, 5 to 25 wt - ^c ß> of the xerogel; 3, - dem- crystalline zeolitic molecular sieve in a ΐ. from 1 to 50 wt .- ^ of the catalyst. : ' .- ■> For; - Chevron Research Company: San i'rancisco.j CaI., V ₀ St ₀ A ₀ - Lawyer ... : 009803/151 7 BAD