DE1938978B2 - CATALYST FOR THE TREATMENT OF HYDROCARBONS WITH HYDROGEN AND THEIR USE - Google Patents

Description

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The invention relates to a catalyst for treating hydrocarbons with hydrogen based on a crystalline molecular sieve, a hydrogenation component from group VI A and the Group VIII of the Periodic Table of the Elements and an embedding material obtained by manufacture a slurry of embedding material or the precursors of the embedding material, dispersing a crystalline zeolite molecular sieve component in this slurry and washing and drying the product obtained and its use for hydrodenitrification and / or hydrocracking of hydrocarbons. By using the catalyst according to the invention can Petroleum distillates and residues deasphalted by solvents with the production of high-quality fuel products including jet fuels and gasoline, hvdroffecrackt.

It is known that a catalyst consists of a crystalline zeoiythischen molecular sieve component can exist in connection with other catalyst constituents. It is also known that at least some of these other catalyst components may be in the form of an embedding material into which the Molecular sieve component is dispersed Such catalysts can be known for reactions such as catalytic cracking, hydrocracking and hydro-desulphurisation can be used as examples, respectively Patent specifications dealing with one or more of these subjects are to be named:

U.S. Patent 3,140,251
U.S. Patent 31 40 253
GB-PS 10 56 301
FR-PS 15 03 063
FR-PS 15 06 793

So are z. B. from FR-PS 15 03 063 catalysts based on a molecular sieve, a hydrogenation component from Group VI A and Group VIII des periodic system of the elements and an embedding material already known, the crystalline Molecular sieve component dispersed in the slurry of the embedding material and the obtained Product is washed and dried. According to the FR-PS, this is made up of molecular sieve and alumina hydrogel (Embedding material) existing product after drying with the hydrogenation component ned.

Furthermore, in de <US-PS 32 64 208 a catalyst, consisting of aluminosilicates containing manganese cations and protons or proton precursors, either alone or in intimate admixture with a porous matrix.

According to this US-PS the molecular sieve is with the hydrogenation component, i. H. Manganese, this activated Catalyst is primarily a cracking catalyst, which consists of a molecular sieve that is present in the bedding material is dispersed, but which in such cases does not contain any hydrogenation components

On the further improvement of such catalysts, especially for hydrocracking and hydrofining continuous work It is known that the results of modifications of the catalysts are often largely unpredictable. The increased number makes the unpredictability more possible Modifications of catalysts with an additional molecular sieve component are not reduced. Seldom can - even though this is a very desirable goal - before the attempt is made Significantly improved result from the experiment with a modified catalyst with a molecular sieve component and other catalyst components can be predicted, and this is especially true for the use of such catalysts in hydrocracking and hydrofining processes.

The aim of the invention was therefore to create an improved catalyst made from a crystalline zeolite Molecular sieve component in conjunction with other catalyst components, the opposite of similar known catalysts

1. improved hydrocracking efficiency and

2. improved effectiveness in nitrogen removal through hydrogenation (hydrodenitrification)

and the use of this improved catalyst in hydrocracking and / or hydrofining processes while achieving high yields

high quality jet fuel and other valuable fuel products.

The catalyst according to the invention is characterized in that it is obtained by adding a silicon compound, an aluminum compound, a nickel and / or cobalt compound and a molybdenum and / or tungsten compound in an amount to produce the slurry of the embedding material or the precursors of the embedding material the in the finished catalyst at least 15 wt .-% silica, an alumina: silica weight ratio of 15:85 to 80:20 and, calculated as metal, 1-10 wt .-% of the embedding material of nickel and / or cobalt and 5 to 25 % By weight of the embedding material corresponds to molybdenum and / or tungsten, precipitated or kogelier: is, the crystalline zeolite molecular sieve component is used in sodium form or in ammonia or hydrogen-laden form and is added to the slurry present at pH 5 or above, wherein the molecular sieve component, optionally used in sodium form, after dispersing by Io exchange can be converted into the ammonia or hydrogen-laden form and the molecular sieve component is used in an amount that the content of the crystalline zeolite molecular sieve is 1 to 50% by weight of the mixture, and the product obtained after drying is then activated and is optionally sulfided before use.

The catalyst of the invention has a unique combination of catalytic components in precise Amounts of, including silica, alumina, molybdenum and / or tungsten, nickel and / or cobalt as well as a crystalline zeolite molecular sieve component, which is essentially in the ammonia or hydrogen laden form and virtually none contains catalytically active metal or metals. Optionally, one can also be present in the catalyst Component of group IV of the periodic table should be included. If such a component is present, then so this can be titanium, zirconium, thorium or hafnium or a combination of these metals, which in metal, Oxide or sulfide form or in a combination of these forms in an amount from 1 to 10, preferably from 5 up to 9% by weight (calculated as metal) of the non-molecular sieve components of the catalyst are present.

The catalyst according to the invention consists of

A. a gel-like embedding material made of:

a) at least 15% by weight silica,

b) Alumina, in such an amount that an alumina: silica weight ratio of 15:85 until 80:20 is available,

c) Nickel and / or cobalt in metallic, oxidic and / or sulfidic form in one Amount of, calculated as metal, 1 to 10, preferably 5 to 9 wt .-% of the embedding material,

d) Molybdenum and / or tungsten in metallic, oxidic and / or sulfidic form in one Amount of, calculated as metal, 5 to 25, preferably 10 to 20 wt .-% of the embedding material,

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B. a crystalline zeolite molecular sieve in an amount of 1-50 wt .-% of the catalyst, which is essentially in ammonia or hydrogen-laden form, which contains essentially no catalytically active metal or metals and is still in the form of individual parts and is dispersed in the embedding material,

wherein the catalyst has an average pore diameter of less than 100 Angstroms and a surface area of over 200 mVg

Another inventive catalyst consists essentially of:

A. a porous xerogel made of:

a) at least 15% by weight of silica,

b) Alumina in such an amount that an alumina: silica weight ratio of 15; 85 until 80:20 is available,

c) Nickel in metallic, oxidic and / or sulphidic form in an amount of. calculated as metal, 1 to 10, preferably 5 to 9 wt .-% of the xerogel,

d) Tungsten in metallic, oxidic and / or sulphidic form in an amount of calculated as metal, 5 to 25, preferably 10 to 20 wt .-% of the xerogel,

B. a crystalline zeolite molecular sieve in an amount of from 1 to 50 percent by weight of the catalyst which is essentially ammonia or hydrogen in the loaded form, there is essentially no catalytically active metal or such metals contains and is also present in the form of individual parts that are dispersed in the xerogel,

wherein the catalyst has a pore diameter of less than 100 angstroms and a surface area of over 200 m ² / g

The reference to a crystalline zeolite molecular sieve, »which is essentially no catalytic active metal or active metals "means that the molecular sieve, based on the sieve, has no more than 0.5 wt.% catalytic metal or metals. The catalytic metal or such metals include the metals of IV., VI. or VIII. Group of Periodic Svstcms, including Sodium.

The weight ratio of catalytic metal in the non-molecular sieve portion of the catalyst to catalytic Metal in the molecular sieve fraction of the catalyst is high. In certain known catalysts, a low loading of the molecular sieve component in the catalytic metal only at the same time very achieved low metal content of the non-molecular sieve fraction of the catalyst. It was found that such catalysts are inferior to the catalyst of the invention.

The crystalline zeolite molecular sieve component of the hydrofining hydrocracking catalyst of the invention can be of any type known in the art as a useful component of a conventional hydrocracking catalyst with a crystalline zeolite molecular sieve component is known. Is preferred a decationized molecular sieve cracking component. Faujasite is particularly suitable, especially "Y" and "X" faujasite, as well as mordenite in the ammonia or Hydrogen laden form.

The molecular sieve component can be prepared by any conventionally known method.

The molecular sieve component can in a conventional manner in an embedding material from the other catalyst constituents dispersed ν ground by Kogeiierung these other ingredients to d> e molecular sieve component around.

The molecular sieve component which is essentially present in ammonia or hydrogen-laden form can - as required according to the invention - thereby essentially of any catalytically active Metal or such metals are kept free, that one has the molecular sieve component in a slurry of the precursors of the other catalyst component dispersed at pH 5 or above Forms a sodium form of the molecular sieve component one of the starting materials, this can be done before combining with the other catalyst components carried out ion exchange converted into the ammonia or hydrogen-laden form will. But it can also be combined with the other catalyst components and then through Ion exchange can be converted into the ammonia or hydrogen-laden form. In none of the In both cases, however, the molecular sieve component should be used be combined with the precursors of the other catalyst components at a pH below 5.

The finished catalyst may optionally be sulfided in a conventional manner prior to use will. If the catalyst is not presulfided, it becomes during the operation of the process by any, possibly in the hydrocarbon feed tends to sulphidation.

The catalyst of the invention can be hydrocracking and hydrodenitrifying at the same time a direct flow hydrocarbon feed to produce more valuable products some of them by catalytic reforming or catalytic hydrocracking can be further refined if necessary. The catalyst can also be used to run at the same time Hydrofining and hydrocracking a hydrocarbon feed are used, with the hydrofining hydrocracking zone is operated in circulation. Certain proportions of the effluent from the hydrofining hydrocracking zone can optionally be catalytically reformed or catalytically cracked.

The catalyst of the invention can, for. B. be used in a hydrotreatment process, according to which a hydrocarbon feed containing substantial amounts of above 93 ° C, preferably in the range between 177 and 510 ° C, boiling substances and from petroleum distillates, solvent-deasphalted petroleum residues, or shale oils Coal tar distillates, at a temperature of 204 to 510 ° C., preferably 260 to 454 ° C., a pressure of 56 to 246 atmospheres, preferably 70 to 211 atmospheres. a liquid space velocity of 0.1 to 5.0, preferably from 0.5 to 5.0, vol / vol / hour. and a total hydrogen feed rate of 35.61-3561m ³ hydrogen, preferably 35 (i, l to m ³ hydrogen per m ³ feed in a reaction zone with hydrogen and the catalyst described above is brought into contact. The hydrocarbon feed can be a substantial amount of organically bound nitrogen r> 5, because the catalyst according to the invention is extremely tolerant of both organic nitrogen and ammonia. The catalyst can be used as a hydrodenitrification catalyst in a zone preceding the hydrocracking zone, the hydrocracking zone being a hydrocracking catalyst of the same type or different If the catalyst is used for the hydrocracking of a suitable feed, a high quality nozzle fuel product can be obtained or a high-quality feed for a catalytic reformer can be produced It is not necessary to subject the feeds to a hydrofining treatment prior to use in the hydrofining-hydrocracking process. The feeds can contain up to several thousand ppm organically bound nitrogen, but the organically bound nitrogen content is preferably below 1000 ppm. The feeds can also contain several percent by weight organic sulfur.

The following examples explain the catalyst according to the invention, its preparation and its Use.

example 1

Production of a gel-coated catalyst (catalyst A) with the following composition:

Components Wt% of Total catalyst NOK 10.0 WHERE ₃ 24.5 AI2O3 29.0 SiO ₂ 25.5 Crystalline zeolitic Molecular sieve, "Y" shape 11.0 All in all 100.0

The catalyst preparation was carried out in the following stages, with the various Starting materials were used in such an amount that the weight percentages given above of the components of the finished catalyst have been achieved.

1. Preparation of the aqueous acidic solution containing AICI3, NiCl ₂ and acetic acid.

2. Preparation of three alkaline solutions:

a) a sodium silicate solution

b) a sodium tungstate solution and

c) an ammonia solution containing ammonia in such an excess that after combination the alkaline solutions with the acidic solution at a neutral pH of about 7 a joint precipitation of all metal-containing components of the solutions occurs.

3. Combination of acidic and alkaline solutions and common precipitation of all metals containing them Components of the two solutions at a pH of about 7 to form a Slurry.

4. Addition of the finely divided crystalline zeolitic molecular sieve of the NH ₄ -Y form to the slurry.

5. Filtering the slurry containing the molecular sieve to obtain a molecular sieve containing hydrogel filter cake, which is repeated with dilute ammonium acetate solution has been washed to remove ionic sodium and chloride impurities from both the Hydrogel as well as from the molecular sieve contained therein.

6. Drying of the hydrogel containing the molecular sieve in an air circulation oven and ι ο subsequent activation in an air stream at 510 ⁰ C.

The finished catalyst was characterized by a surface area of 417 mVg, a pore volume of 0.4 cmVg and a mean pore diameter of 38 Angstroms, the molecular sieve component in contained essentially no catalytic metals; d. H. practically all of the nickel and tungsten content of the The catalyst was mainly in its gel portion.

Example 2

A gelatinized catalyst (Catalyst B) was prepared exactly as described in Example 1, with the Exception that the molecular sieve is in an ammoniacal NiCb solution prior to incorporation into the slurry was pre-impregnated to load the molecular sieve with nickel. The starting materials were in used in such an amount that the finished catalyst had the same percent by weight of the constituents like the catalyst of example 1.

The only difference between the catalyst and that of Example 1 was that the catalyst contained nickel was distributed on the gel component and the Mülekularsiebomponent.

Example 3

A gelated catalyst (Catalyst C) was prepared exactly as described in Example 1 with the Exception that no molecular sieve component was incorporated. The starting materials were in such Amount applied that the finished catalyst has the same proportion of non-molecular sieve components like the catalyst of Example 1. The finished catalyst had the following composition:

Components

Wt .-% of
Total catalyst

NOK
WHERE ₃

SiO ₂
all in all

27.5

32.6

J28 lbs

100.0

ter portions of a California gas oil feed used in direct throughput.
The gas oil feed had the following properties:

The weight percentage of each non-molecular star component of Catalysts A and B is important thus 89%, based on the percentage by weight of the same components of the catalyst C, the other HGw .-% of the catalysts A and B from the Molecular sieve component are contributed.

Example 4

Parts of the catalysts A, S and C aar Examples I -3 have been tt the hydrocracking

Boiling range 260 to 482 ° C Specific weight 0.9402 More organic Nitrogen content 3,000 ppm Hydrocracking Conditions: Total pressure 176 atü Hydrogen supply out of a total of 1780.5HWm ³ Fluid space speed 0.8 VoiyVoUStd. Conversion per pass in products with Boiling point below 288 ° C (% By volume) 60 Starting temperature in C " As follows specified.

The hydrocracking activities of the three catalysts were measured at the starting temperatures, the To achieve the specified conversion, the following were required for each pass:

catalyst

Starting temperature in ° C

A. 385 B. 399 C. 413

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S5

60 The jet fuel product with a boiling range of 149 to 288 ° C was of the same sufficient quality in each case in that the smoke point was 21 mm in each case and the freezing point was below -70 ° C.

In any event, the liquid hydrocracked product is essentially free of organic nitrogen compounds, from which it can be seen that the hydrocracking of essentially complete Nitrogen removal was accompanied by hydrogenation.

This example showed that

1) the hydrocracking activity of the gel catalysts with molecular sieve (catalysts A and B) that of one molecular sieve-free but otherwise identical catalyst (catalyst C) is superior

2) the hydrocracking activity of the gel catalyst with a molecular sieve component without metal loading (Catalyst A) that of a equipped with a metal-loaded molecular sieve component, but otherwise identical gel catalyst (catalyst B) is superior and

3) the gel catalyst with a molecular sieve component Without Metafl loading, an essentially complete hydrodemtrifcation in im Much lower temperature than the catalysts B and C causes

Example p

Another part of the Kss A of Example 1 for solvent hydrocracking

Deasphalted hydrocarbons with p above 288 "C and a content of organic nitrogen oxide * of 5JSQU mm in

Throughput used. Then this part of the hydrocracking catalyst A became another Part of the same oil deasphalted by solvent circulating the oil boiling above 288 ° C Products used.

Hydrocracking conditions
Operating equilibrium

after reaching the

Catalyst A,

more direct

Throughput

Catalyst A, recycle

Temperature in ⁰ C 427 427

Total pressure in atü 176 176

Total exhaust gas, 10,000 10,000

relationship

Liquid space - 0.8 0.8

speed,

VoL / VoiyStd.

Conversion into product 40 75

with boiling point at

288 ° C, vol-0 / o

Fraction 149 ° -288 ° C as a jet fuel product

Catalyst A,

more direct

Throughput

Catalyst A, recycle

Yield,% by volume 30.0 50.0

Smoke point, mm 20 30.0

Freezing point, ⁰ C -54 -57

Paraffins,% by volume 17.0 37.0

Naphthenes, vol% 68.0 54.0

Aromatics, vol% 15.0 9.0

As this example shows, a high throughput is obtained both in direct throughput and in circulating operation Yield of high quality jet fuel from the solvent-deasphalted hydrocarbon -oil loading. Furthermore, it can be seen that the circulation operation leads to a higher hydrocracking activity, Jet fuel yield and quality leads, which is due to the fact that the normal paraffins, which are concentrated in the high-boiling part of the solvent-deasphalted oil are cracked into the jet fuel area.

Claims (2)

Patent Claims: 1. Catalyst for the treatment of hydrocarbons with hydrogen based on a crystalline molecular sieve, a hydrogenation component of Group VIA and Group VIII of the Periodic Table of the Elements and one Embedding material obtained by preparing a slurry of embedding material to or the precursors of the embedding materialb, dispersing a crystalline zeolite molecular sieve component in this slurry and washing and drying the product obtained, characterized in that it is obtained by making the slurry the embedding material or the precursors of the embedding material a silicon compound, an aluminum compound, a nickel and / or cobalt compound and a molybdenum and / or Tungsten compound in an amount that contains at least 15% by weight of silica in the finished catalyst, an alumina: silica weight ratio of 15:85 to 80:20 and, calculated as metal, 1-10% by weight of the embedding material of nickel and / or cobalt and 5 to 25% by weight of the Embedding material corresponds to molybdenum and / or tungsten, precipitated together or kogeliert is, the crystalline ieolythische molecular sieve component in sodium form or in ammonia or Hydrogen loaded form is used and the slurry present at pH 5 or above is added, the molecular sieve component, optionally used in sodium form after dispersing by ion exchange in a form loaded with ammonia or hydrogen can be transferred and the molecular sieve component is used in an amount that the The content of the crystalline zeolite molecular sieve is 1 to 50% by weight of the mixture, and that product obtained after drying is then activated and optionally before use is still sulfided. 2. Use of the catalyst according to claim 1 for hydrodenitrifying and / or hydrocracking of hydrocarbons,