DE2437037A1 - HYDROCRACK PROCESS AND ASSOCIATED CATALYST - Google Patents

Description

Hydrocracking process and associated catalyst

The invention relates to the hydrocracking of heavy oil feedstocks for the production of a middle clestillate and has set itself the task of a hydrocracking process and an associated one Catalyst to propose.

Much of the effort in the field of catalytic hydrocracking in recent years has been directed to the development of catalysts for converting gas oils to gasoline-boiling products. Because of the better use of middle distillates compared to the feed materials of such hydrocracking plants and other economic considerations based on seasonal and geographical factors, a need for additional middle distillates has arisen "in order to satisfy the demand for products such as turbine and diesel fuels. A major source of Middle c ^ stillate

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BATH ORIGINAL

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are materials that contain high-boiling distillates with a boiling point between 340 to 370 and 59O ° C.

The invention has the object of hydrocracking catalysts to develop the high-boiling oils such as high-boiling under atmospheric pressure and high-boiling under vacuum, heavy Convert gas oils and circulating oils in such a way that the proportion of gasoline and lighter products as low as possible and the proportion of middle distillate is as large as possible. For converting middle distillate In gasoline, the best catalysts are those that contain a highly active cracking substance, such as crystalline Zeolite combined with a highly active hydrogenation component such as palladium or platinum. These catalysts are the least suitable for converting heavy oil feedstocks in middle distillates. Conventional hydrofining catalysts such as nickel-molybdenum-alumina catalysts have one Found limited application in this area but give low yields. When trying the nickel-molybdenum-alumina catalysts to be used for a complete conversion of heavy oil feedstocks into middle distillates, by completely recycling the unconverted oil, the problem arose of maintaining stable hydrocracking temperatures, which enable an economically viable term. Analyzes of the returned oil showed an increasing Formation of heavy polycyclic condensed

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Aromatics known as coke precursors and catalyst poisons. These catalyst poisons do not arise from the components such as heating oil or one of the other original fractions of the heavy oil used. Nor are they in larger amount in unreacted oils from conventional catalytic cracking, coking, thermocracking or the like Find processes. The evidence currently available suggests that such connections are due to the proportionate high working temperatures and the relatively low hydrogenation and cracking activity of the catalyst used are formed in the first catalytic reaction zone.

It has been found that a highly active and selective hydrocracking catalyst for middle distillates can be produced by activating a Group Vla transition metal - preferably a nickel-molybdenum-aluminum oxide system with an amorphous inorganic gel, which is formed by cation exchange of a gel with the formula 0.9 - 1.3K ₂ O. 3-8 SiO ₂ . Al ₃ O ₃ . 0 20 H ₀ O with calcium, magnesium, noble metal or transition metal ions together with ammonium ions, which can be converted into hydrogen ions (releasing NH ₃ ) when heated. For the sake of simplicity, this amorphous, large surface area, inorganic gel is referred to below as VK-3. As described below,

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the VK-3 can also be manufactured in a shape where instead of the K “O as a cation, a mixture of K“ O and Na “0 is present.

The process of the invention serves to convert a mineral oil feedstock with a relatively high boiling range into a middle distillate with a lower boiling range by bringing the feedstock into contact with a hydrocracking catalyst in the presence of hydrogen under hydrocracking conditions. The method is characterized in that a mixture is used as the catalyst, which (a) aluminum oxide, (b) an oxide or sulfide of a metal of group VIa and a transition metal and. (c) an amorphous inorganic gel with the general formula 0.9-1.3 M ₂ O. 0.3-8 SiO ₃ . Al ₃ O ₃ .0-20 H ₃ O, where M is a cation which is at least partially calcium, magnesium, noble or transition metal and also ammonium and hydrogen and possibly residual potassium or residual potassium and sodium.

With Group VIa metals are chromium, tungsten and molybdenum, and with transition metals are metals other than chromium, tungsten and molybdenum, commonly referred to as transition metals, and particularly meant nickel, chromium and iron.

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The catalyst according to the invention is tailored to hydrocracking feedstocks, which have a larger proportion of hydrocarbons with a boiling point above about 340-370 C and up to 590 C to give a product obtained that boils below 340 C, with as large a proportion of the products as possible boiling between 160 and 340 C. Feedstocks of this type are usually products of crude oil vacuum distillations and final asphalting of residual oils, as well as cracking circulating oils "from catalytic cracking or coking distillates. The term "conversion to 340 ° C" is defined as actually converted. Input product, that is to say 100 minus the percent by weight of input product which, as a product Tmi-t, has an onset of boiling at 340.degree get back. The selectivity refers to the weight ratio, expressed in%, of the products with a

¹ O

Boiling range between 160 and 340- C for all products a boiling point below 340 C. - -.

A typical feed product has that shown in Table 1 Composition.

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Table 1

Kuwait vacuum gas oil
API grade 21.0

Boiling range ASTM D-1160, boiling temperatures converted from 1 torr at atmospheric pressure

Start of boiling 416 ° C 5% 431 ° C 10% 434 ° C 50% 458 ° C 95% 521 ° C End of boiling 538 ° C Sulfur 2.91% by weight Nitrogen 0.08 wt.%

An essential and inventive feature of the invention is the use of an amorphous, large surface area, inorganic gel described above and with VK-3 has been designated. A large part of the pores on the surface of this silica alurainate has a diameter from 40 to 50 S. The VK-3 and its ion exchange forms are characterized by a large in the area between

300 and 900 m / g horizontal surface. Furthermore, the VK-3 has no crystalline structure, which means the absence of maxima shows in the X-ray diffraction analysis. The wide surface distribution of the VK - 3 is similar to that of an amorphous silicon

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dioxia-alumina hydrogel cracking catalyst with the difference, that a larger part of the pores falls in the range with a diameter between 15 and 50 Å. A pore size distribution, at which a large percentage of the pore diameter is in the range between 15 and 50 A is for cracking catalyst mixtures very advantageous. The broad surface distribution of the VK-3 is in sharp contrast to the typical ones crystalline zeolites of the faujasite type, which always have a sharp distribution maximum below 14 A.

The manufacturing process for this alumina silicate does not form part of the invention and has been described earlier. (US Pat. No. 3,775,345) It is characterized by the production of a slurry which contains Si0 ₉ / Al “0_ / K ₉ 0 in water. The reactants are combined in such a way that the following constituent ratios result:

0_ - 8 to 30 K ₂ O / SiO ₂ - 0.30 to 0.8

H 0 / K ₂ O - 20 to 45

./ - ■ This slurry of reactants is left between 1 hour and 4 days at temperatures between 16 and 43 C react. ·

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The aluminum silicate VK-3 is normally produced from a _{slurry containing SiO 9} / Al ₂ O ₃ / K ₂ O in the potassium form. However, it can also be produced in the sodium-potassium form, which means that the Group I metal is not just potassium but a mixture of sodium and potassium. The sodium-potassium form of VK-3 is produced by producing a _{slurry containing SiO 2} / Al O ₃ / K "O / Na ₂ CO ₃ ~ and can also be used to produce the ion-exchanged VK-3, the one. Component of the catalyst mixture according to the invention is used. In the cation-exchanged form that is used for the mixture according to the invention, the cation is calcium, magnesium, noble or transition metal, in particular a transition metal of the 4th and 5th periods or else ammonium. However, some of the cations can also be potassium or a mixture of sodium and potassium left over from the manufacture of the VK-3 starting product. The production of VK-3 in the sodium-potassium form is described in US application 419 154, which is also to be registered in Germany.

The VK-3 is converted into the calcium / ammonium form by adding it is treated with an ammonium chloride solution containing calcium chloride. The solution together with the VK-3 becomes a Stirred for hour at elevated temperature, filtered and washed. The calcium-ammonium ~ exchange-VK-3 ~ product becomes using ammonium chloride of another ammonium

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subject to exchange treatment. The end product is then filtered, washed free of chloride, dried and heated at 427.degree roasted. Other forms such as the Mg, Group VIII, or transition metal forms can be made in the same way v / earth, using these metals instead of calcium will.

The VK-3 promoter will work with the one acting as the base material Alumina hydrofining catalyst mixed. The VK-3 portion of the composite mixture is 5 to 90% by weight. Any method of mixing the two materials will give satisfactory results Results. A particularly good method is dry blending for about 1/2 hour in a conventional commercially available one Mixer followed by milling and extrusion of the milled ones consisting of promoter and alumina Mixture. - "

In the next process step, the compacts are dried at 120 to 165 ° C. for 2 to 16 hours and then roasted at 510 to 565 ° C. for 2 to 16 hours. The roasted compacts are then impregnated with a solution containing the salt of a metal of Group VIII, preferably with a nickel molybdenum salt solution. The nickel content is 1 to 6, preferably 3.5%, calculated as NiO, and the molybdenum content is 5 to 25%, preferably 16.5%, calculated as MoO ₃ . Although nickel

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and molybdenum, preferably present as oxides, are also used the sulfides obtained satisfactory results.

Hydrocracking conditions generally believed to be most advantageous are at a reaction temperature between 260 and 480 ° C, preferably 260 and 455 ° C at a Pressure of at least 35 atmospheres, preferably 70 to 350 atmospheres, and a liquid flow rate of about 0.1 up to 10, preferably 0.3 to 5 per hour (LHSV). The proportion of free hydrogen in the reaction zone should be at least 14 generally about 14 to 566, preferably 28 to 140 normal cubic meters per 0.1156 m of reactor charge.

The inventive hydrocracking catalyst was in a Hydrocracking plant tested at a temperature of 400 C and a weight throughput rate (WHSV) of 1 per hour, The pressure was 140.6 atmospheres and the conversion and the selectivity were recorded.

example 1

100 g of an amorphous VK-3 promoter were added to a solution of 100 g of ammonium chloride (NH.Cl) in 800 g of water. The solution was carefully stirred and a solution of 10 g calcium chloride (CaCl ₂ .2H ₂ O) in 200 g water was added. The solution was then stirred at 60 ° C. for one hour, filtered

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and washed. This VK-3 product was then subjected to a further ammonium exchange treatment using a solution of 100 g of VK-3 and 100 g of ammonium chloride in 1000 g of water. The exchange treatment lasted one hour at 60 ⁰ C. The (Ca, K, NH ₄₎ -VK-3-finished product was then filtered, washed free of chloride, dried and roasted at 427 ° C.

The catalyst mixture was prepared by dry mixing 87.5 g (80 g dry matter) of this VK-3 product for one hour with 421 g (240 g dry matter) of a slurry of alumina in a Pattersori-Kelly mixer. The resulting

animal mixture was with the addition of 25 cm glycerol and

3
Milled 54 cm of deionized water for half an hour.

The paste was pressed into 1.6 mm thick pellets, dried at 149 ° C. for 14 hours and roasted at 538 ° C. for three hours. The roasted compacts were impregnated with an ammonium-containing nickel / molybdenum solution, dried at 149 ° C. for four hours and roasted at 538 ° C. for three hours. The product contained 3.5% NiO, 16.5% MoO ₃ and 25% VK-3-Ca ⁺⁺ in the finished catalyst. The rest was alumina.

The Kuwait vacuum gas oil shown in Table 1 was at one throughput of 1 part by weight per hour, a pressure of 140.6 atü and a temperature of -399 C subjected to hydrocracking. The catalyst was in the form of 1.6 mm thick pellets.

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used. The test facility was operated for 24 hours. A series of experiments was carried out with a VK-3 catalyst, carried out a catalyst with 20% particularly stable zeolite of the faujasite type and a catalyst without a promoter. The values obtained in this series of tests are summarized in Table 2 below.

Promoter type

G ew.% PhD in
Alumina

Wt% NiO
Wt% MoO ₃
Catalyst age (hrs.)

Throughput (parts by weight per hour)

Temperature in ⁰ C

Tabel 2 US sieve no promoter VK-3-Ca ⁺⁺ 20th __ 25th 3.5 3.5 3.5 16.5 16.5 16.5 50 25th 50 ' 1.0 1.0 1.0 399 399 399 140.6 140.6 140.6

Pressure (atü)

Transformation

(Wt%) 38.7 39.6 23.4

Conversion to 340 C

Product distribution (Wt.% ) 7, 8th 19 7th 4th , 4 Start of boiling until 1 60 ° C 29 9 20, 9 17th , 9 160 ° C to 340 ° C 61, 3 60, 4th 76 , 6 H- 3 4 O ⁰ C

Middle distillate
(160 to 34O ° C)
Selectivity (wt%) 77.5 52.6 76.5

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The values obtained clearly show that the VK-3 catalyst converts approximately the same amount of feedstock, but that the yield of the desired middle distillate is significantly higher than with the catalyst with the particularly stable zeolite as proiaotor. The selectivity of the catalyst without a promoter Although it is comparable to that of the VK ~ 3 ~ catalyst, the yield is much lower.

Example 2

100 g of the amorphous VK-3 promoter were added to a solution which contained 100 g of ammonium chloride in 800 g of water. . · The resulting solution was carefully stirred. It was a magnesium chloride solution prepared by adding 10 g of magnesium chloride (MgCl “) were added to 200 g of water. This solution was added to the VK-3 ammonium chloride solution. The solution was then heated to 60 ° C., stirred at this temperature for one hour, filtered and washed. The magnesium and ammonium containing VK ~ 3 then underwent another ammonium exchange treatment subjected using a solution of 100 g of VK-3 and 100 g of ammonium chloride in 1000 g of water. These ■ Treatment was carried out at 60 ° C for 1 hour. The end product (Mg, K, NHJ.-VK-3 was ... then filtered, chloride-free washed, dried and roasted at 425 ° C. The .VK-3 product was in a Patterson-Kelly mixer "with aluminum oxide .ge ~

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mixed by adding to 89 g (70 g dry matter) of the VK ~ 3 product 162.5 g (130 g dry matter) of an aluminum oxide from Boehmitt type were added. The table continued for an hour. The resulting mixture was added

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ground by 25 cm of glycerine and 54 cm of deionized water for half an hour. The resulting paste was pressed into 1.6 mm thick compacts. These were then dried at 149 ° C for 14 hours and then roasted at 538 ° C for three hours. The roasted compacts were impregnated with an ammonium-containing nickel-molybdenum solution, dried at 149 ° C. and roasted for three hours at 538 ° C., so that a catalyst with 3.5% NiO and 16.5% MoO ₃ resulted. The finished catalyst also contained 35% VK-3-Mg. The rest was alumina.

The activity of the catalyst was tested using the feedstock according to Table 1 in a hydrocracking plant and compared with a catalyst which contained the same amounts of nickel and molybdenum oxides and, as a promoter, 40% of a zeolite of the faujasite type in the H form with an SiO ₂ / Al "O" ratio of 4.8: 1.

The plant was operated with a throughput of 1 part by weight per hour and under a pressure of 140.6 atmospheres. The comparison was set up to compare the temperatures

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were "in which equally large yields were obtained. In addition, the selectivity of both catalysts in relation to the middle distillate boiling between 160 and 34 ° C. compared. Table 3 shows the results.

Px'motor type

Promoter in aluminum oxide (% by weight) ■ 35 40

Catalyst age (hours) 50 50

Tabel 3 /O VK-3-Mg ⁺⁺ , 9 35 50 399 ■ 36 4th 30th 64

Temperature ( ⁰ C) 399 371

Conversion to 340 ° C (wt%) ■ 36 35.6

Onset of boiling up to 160 ° C. (% by weight) 4, O 20.1

160 to 340 ° C (wt%) '. 30.9 14.6

+ 340 ° C (% by weight) 64.0 64.4

Middle distillate (160 to

340 ° C) selectivity (wt.%) 86.0 ⁼ 41.0

The data show that although the hydrogen activated faujas sitolite catalyst was more active, i.e. it gave the same yield at a lower temperature, the selectivity of the VK-3 magnesium activated catalyst is much better. More than double the amount of input product was required Converted middle distillate fraction.

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Claims (10)

Expectations 1. Process for converting a mineral oil feedstock with a relatively high boiling range in a middle distillate with a lower boiling range, by the Feedstock in the presence of hydrogen under hydrocracking conditions in contact with a hydrocracking catalyst is brought, characterized in that the catalyst used is a mixture which (a) aluminum oxide, (b). an oxide or sulfide of a Group VIa metal and a transition metal; and (c) an amorphous inorganic Gel with the general formula 0.9-1.3 M ₂ O. 3-8 SiO ₂ . Al ₃ O ₃ .0-20 H ₃ O contains, where M is a cation which is at least partially calcium, magnesium, noble or transition metal and is also ammonium or hydrogen and possibly residual potassium or residual potassium and sodium. 2. The method according to claim 1, characterized in that there is a feed product with a boiling range of 350 to 600 ° C is used and that a distillate with a boiling range of 150 to 370 ° C is obtained. S09807 / 0907 243703? 3. The method according to claim 1 or 2, characterized. that one fractionates the product leaving the reactor to the middle distillate with the lower boiling range to win, and the unused input product with returns to the higher boiling range in the hydrocracking plant, 4. The method according to claim 3, characterized in that one hydrogen in such an amount through the cracking zone circulates that in the cracking zone 28 to 560 normal ■ "'■■" "- ■ 3" ■' - " cubic meters of hydrogen per 0.12 m input product before * - are in hand. 5. The method according to claim 1 to 4, characterized in that, that a pressure of 35 to 350 atmospheres and a temperature of 260 to 4 80 ° C. are used as hydrocracking conditions. 6. The method according to claim 1 to "5, characterized in that that a mixture is used as a crack mixture which contains the alumina and the inorganic gel and which is impregnated with salts of the desired Group VIa metal and the desired transition metal. 7. The method according to claim 6, characterized in that there is a crack mixture consisting of ⁵ shaped bodies B0t807 / 09Q7 verv / ends which is a mixture of the alumina and the contain inorganic gels and those with the salts of the desired metal of Group VIa and the desired Transition metal are impregnated. 8. The method according to claim 1 to 7, characterized in that a cracking mixture is used in which the metals of component (b) are molybdenum and nickel. 9. Hydrocracking catalyst, characterized by a content of (a) aluminum oxide, (b) an oxide of a metal Group VIa and an oxide of a transition metal not belonging to group VIa and (c) an amorphous inorganic one Gel with the general formula 0.9-1.3 M ₂ O. 3-8 SiO ₂ . Al ₃ O ₃ . O - 20 H ₃ O, where M denotes a cation, the at least partially calcium, magnesium, noble or transition metal and also Ammonium or hydrogen and possibly residual potassium or residual potassium and sodium. 10. Hydrocracking catalyst according to claim 9, characterized in that that it consists of a mixture which contains the aluminum oxide and the inorganic gel and which B09807 / 0907 with salts of the desired metal from group Via and of the desired transition metal. has been impregnated. 1. Hydrocracking catalyst according to claim 9, characterized in that that it consists of shaped bodies which are a mixture of aluminum oxide and inorganic Gels contain and those with the salts of the desired Group VIA metal and the desired transition metal, preferably impregnated with molybdenum and nickel salts have been. ue: ka: kö B0 9807/090 7