DE1926478A1 - Integrated low pressure hydrogen refining hydrocracking process - Google Patents

Description

DR. BERG DIPL-ING. STAPF

PATENTANWÄLTE 8 MÜNCHEN 2. H I LBLESTRASSE 2O

Dr. Berg Dipl.-Ing. Stapf, 8 Munich 2, Hilblestraßa 20 Your sign Our sign

Dahim

May 25, 1969

Lawyer file Io 4 , 2ο
Be / A

ESSO Research and. Engineering Company, Linden, IT. J., USA

"Integrated low pressure Y first off refining hydrocracking

Yerfahren

Earlier hydrocracking processes were operated at pressures above approximately 140 atmospheres (2000 psig) using catalysts used, the various metal hydrogenation components, combined with amorphous metal oxide cracking base materials, contained. Then newer hydrocracking

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β [081T) * 5 16 20 81 telegrams ι PATENTEUIE Mönchen Sanki Bayerreehe Vereltubank MOndien 453 TOO Pp «t» ch «ckt MOndien i53

Catalysts developed by one or more relatives the group of platinum metals contained on a large-pore, crystalline aluminum silicate zeolite carriers were deposited. With these catalysts it was possible suitable conversions to gasoline and other premium petroleum fractions at about 105 atmospheres (1500 psig). Recently, there has been a catalyst that uses a low-noble metal hydrogenation component contained on a synthetic zeolite material, used for hydrocracking (see for example U.S. Patent 3,394,074) <> It is now known that a nickel-tungsten-zeolite catalyst is a Palladium catalyst in the treatment of raw feeds containing large amounts of nitrogen at 105 atmospheres (1500 psig) is largely superior.

The subject of this invention is a V / a ss he st off conversion process, that contributes to a good conversion of petroleum fractions

ο
Pressures below about 74 kg / cm (1050 psig), preferably at

Provides 20-70 kg / cm ² (300-1000 psig). This pressure range enables equipment to be used in which manufacturing metals and other materials that are available at a lower cost can be used for reaction vessels, tubes, valves, etc. In addition, the hydrogen refiner and hydrocracker can be operated at the same pressure and within essentially the same temperature range.

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vierungssyatem, d. h, starting system j and a single one Catalyst reactivation system, d. H. Regeneration system, can be used for both treatment units, especially when the two treatments are within a single reaction vessel envelope.

The use of hydrocracking pressures below 70 atmospheres (1000 psig) makes it possible to convert existing hydrogen refiners to hydrogen refiners and hydrogen crackers with a minimum of capital investment and additional labor costs. If the daily output should be greater than the capacity of the existing hydrogen ^{refining facility, the unit is coupled in series with a Grass-Roots M} hydrocracking reactor designed to operate within the same operating limits.

To maintain the catalyst activity satisfactorily in hydrocracking is to achieve it necessary for a large part of the organic nitrogen compounds from the feed because these materials will permanently deactivate the hydrocracking catalyst. It has heretofore been believed that severe conditions are essential to remove nitrogen, including Pressures in excess of about 75 kg / cm (1000 psig). It has now been found that a pressurized hydrogen refining and

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Low-pressure hydrocracking process over a very long operating time with feeds of the typical medium boiling point area with a very low temperature increase through

ih]
Maintain (400 ⁰ F) products.

can be led to a good conversion to Cc-204 ° C-

The flow diagram shows one of the most preferred embodiments the invention.

Briefly summarized, the method of the present is directed to Invention of a nitrogen-containing petroleum feed, such as a gas oil, and hydrogen over a bed of the ' conventional hydrogen refining catalyst a mild hydrogen refining temperature and pressure, e.g. B. 21-74 atm (300-1000 psig), and conducts then the effluent from the hydrogen refining unit via a bed of hydrocracking catalyst, which Nickel and tungsten on a crystalline alumina silicate zeolite are essentially the same Conditions and thus wins conversion products including gasoline. The hydrogen refining and hydrocracking catalysts are both activated at the same time and with the same materials.

Suitable feeds for conversion by the present process are hydrocarbon fractions having a boiling range of 150 - 54O ⁰ C (300 to 1000 ⁰ F), preferential 909881/1308

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wise ^{200-400 0} C (400-750 ⁰ F), or heart slices of such fractions. The fractions contain up to 800 ppm, usually from 10-300 ppm, nitrogen in the form of organic nitrogen compounds. The fractions usually come from "virgin" petroleum fractions or partially refined petroleum fractions. Specific sections include catalytic etc Rückflußöle, Virgin gas oil fractions Verkokungsgasöle, fractions from visbreaking .. The feed may some sulfur, usually 0.25 to 2 wt ₀ ^ included. The fractions contain from $ 20 to $ 60 aromatic hydrocarbons, and it is an advantage of the process that. these materials do not become hydrocracked or saturated to any appreciable extent when treated under the conditions used;

Typical examination results for loads are:

Table T Description test results

Weight, ^Ü API
Nitrogen, ppm
Sulfur, wt "$
Aniline Point, ⁰ G ₁ ( ⁰ F)
Bromine, - g / 100 g
number

Light catalyt «, Easy "Virgin" Reflux oil Ga söl LCCO LV (JO ■ 27.9 33.0 60 110 0.25 0.72 46.7 (116) 68.9 (1st 56) 4.7 2.5

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Table 1 continued

Distillation (ASTM) Light 'catalyt. Light "virgin" - O _n / Ό ^, - ν reflux oil Ga s oil

Initial boiling point 214 (426) 200 (392) 5 i> 241 (466) 238 (460) 10 249 (481) 256 (492) 20th 257 (495) 270 (519) 30th 263 (508) 281 (537) 40 269 (518) 288 (550.) 50 276 (530) 295 (563) 60 283 (542) 301 (574) 70 291 (556) 307 (585) 80 301 (574) 315 (598) 90 314 (596) 325 (617) 95 323 (613) 337 (636) Bnd boiling point 333 (632) 349 (660) <$> Rewind 98 98 io rest 1 1

Catalysts contemplated for use in the hydrogen refining step fc of the process include a hydrogenation component such as the oxides and / or sulfides of metals of Group VI-B and / or VIII, which on a suitable Carrier material, such as aluminum oxide, silicon dioxide-aluminum oxide, Bauxite, diatomite and the like are stored. Salts of cobalt, molybdenum, nickel, tungsten are preferred, and nickel molybdate catalysts are particularly preferred or cobalt molybdate on aluminum oxide or silicon dioxide stabilized Alumina. Conventional, im

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Commercially Available Hydrogen Refining Catalysts are satisfactory for nitrogen removal.

The catalyst "used to carry out the hydrocracking step of the present invention as indicated above contains a nickel-tungsten hydrogenation component combined with a cracking base material of a crystalline alumina-silicate zeolite having a faujasite crystal structure, a uniform pore size and a silica to alumina molar ratio greater than about 3. Zeolites having the desired faujasite structure are either natural or synthetic in origin and, when dehydrated, should conform to the following formula?

0.9 i 0.2 Na ₂ O ι Al ₂ O ₅ : X SlO ₂ ,

wherein X can be 3 to about 6 or even more when the Zeolite subjected to selective alumina removal processes Suitable methods for effecting the removal of alumina from crystalline zeolites are known to those skilled in the art known. A particularly preferred form of the crystalline alumina-silicate zeolite is the zeolite Y, the commercially available from the "Linde Division" of the "Union Carbide Corporation" is available.

To find a useful form for carrying out the invention Procedure to obtain the sodium form of the

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Zeolites modified by cation exchange with a hydrogen ion or an ion that can be converted into a hydrogen ion, such as ammonium ion, according to exchange processes known to the person skilled in the art. It is generally desirable to replace a sufficient amount of the initial sodium ion so that the exchanged zeolite preparation contains less than 1.8% by weight of sodium, preferably less than 1.3% by weight.

Pie nickel-tungsten hydrogenation component is different in the crystalline alumina-silicate zeolite optional methods introduced. For example, it is possible to use the impregnation processes that have been customary up to now use to produce amorphous-based nickel-tungsten-type catalysts. With these procedures, the Catalyst base material treated with solutions containing nickel and tungsten, either separately or combined in a single solution, so that these ketalytisehen materials be deposited on the surface of the base material. See U.S. Patents 2,690,433, 3,232,887 and 3 280 04-0 refers to the introduction of nickel and tungsten into various types of catalytic support materials pointed out.

It is also possible to use the nickel-tungsten catalyst by converting the nickel into the cation

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Substitution sites for the sodium or, more preferably, the ammonium form of the crystalline aluminum oxide-silicate zeolite This is achieved when you mix the zeolite with a aqueous solution of an exchangeable nickel salt, such as Hiekel chloride, treated. The resulting nickel-exchanged Ammonium zeolite is then mixed with an ammonium tungstate solution treated, whereby a finely distributed intimate Uickel tungsten deposit at or near the exchange » represent the ammonium form of the aluminum oxide silicate achievedo This can then be brought to disintegration, as a result of which one disgusting ifram on the hydrogen SOrm of the alumina-silicate-zeolite receives.

While the manufacturing process of the catalyst for the Operability of the hydrocracking stage of the present invention is not critical, it is assumed that the latter Process in which one has a first exchange stage with Low-carbon ions and subsequent treatment with ammonium tungstate are used to obtain catalysts that are superior Have properties of maintaining activity, and accordingly it is such a manufacturing method preferred. . .

In every palle, the manufacturing process should have a catalyst provide from 1 to 8 wt. $, preferably 1 to 4 wt. $ nickel, (based on the metal form, although not

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necessarily present as such) and from 3 to 18 wt. ^, preferably 6 to 12 wt. $ tungsten, (based on the metal as above).

The embodiment of the invention in which the hydrogen refining, Hydrocracking, activation and regeneration are performed in the same reaction vessel now described in connection with the flow diagram «

A light "virgin" gas oil with similar properties, like those in table 1, lines 1 and 2 passed into the head of the reaction vessel 3 «, fresh hydrogen from line 4 and circulating hydrogen from the Line 5 is filled with the oil to form the feed mixture mixed. A liquid recycle stream can also be added to the feed mixture. The treatment gas contains 70 to 100 vol. $ hydrogen. The feed mix becomes downward in the mixed liquid-vapor-gas-as-phase via the hydrogen catalyst bed into the hydrogen refining zone 6 headed. A suitable catalyst is sulfided nickel molybdate on aluminum oxide »Before After sulfiding, the catalyst contains 5.7% by weight NiO, 13.0 Grew. # LIoO-z and the rest silica stabilized Alumina. The catalyst can be in the form of an extrudate, tablets, or any other suitable form to have. Typical hydrogen refining and hydrocraok -'-

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Conditions bind given in Table 2 below.

Tabel 2 Preferred - 68 area •
Wider area 31.6 975 , 6 Pressure atü 14 - 70 450 - 454 ^M psig 200 - 1000 316 - 850 Temperature ⁰ C 260 - 540 600 - «° p 500 - 1000

Throughput speed
Vol./hour./enol.

1-5

Gas velocity NmVm ⁵ 712 - 1780

SCF / bbl. 4,000-10,000

1.5-2.5

1068-1424 6000-8000

Initially , the process temperature is from 300 to 400 C (600-740 ⁰ P). In proportion as the catalyst is deactivated slowly, the temperature of the reaction vessel is increased to convert to the desired height, a 30 to 70 conversion #ige ie in the hydrocracking zone of the material having a boiling point above about 20O ⁰ G
(4-0O ⁰ P) to achieve a material with a boiling point below approximately 200 ⁰ G (400 ⁰ P).

Hydrogen refining is an exothermic reaction and if the feed becomes too hot to contact the pulp refining catalyst, the medium will be activated

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a quenching medium introduced via line 7 The quench medium can be a gas or a liquid petroleum fraction.

In the hydrogen refining zone, the nitrogen content of the feed is reduced by 50 to 99 ° / °. The sulfur content is reduced by 50 to 99 ° / ° and the other non-hydrocarbon components are removed just as well. There is a slight hydrogenation of the aromatic compounds and one of very little conversion, usually less than 5 $, to a material having a boiling point below 200 ^° G (400 ^° P).

The hydrogen refined feed, which still contains 40-200 ppm nitrogen, for example, is now fed into the Hydrocracking zone 8 passed. The treatment conditions in this lower zone are essentially the same as they are given in Table 2 above «It will "a hydrocracking catalyst that uses nickel and tungsten on crystalline aluminum silicate zeolite and is similar to that previously mentioned. The first reaction is cracking in the presence of hydrogen. The hydrogen saturates the chain fragment when it is broken off. Polyaromatic compounds are hydrogenated

The treated effluent is passed through line 9 to the separator 10 headed. The separator becomes the gas phase

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via the line 11 to the gas cleaning unit 12. After separation using conventional means, H _? S and UH, removed from the system via line 13. “Purified hydrogen is fed into the circuit via line 5. The liquid products are conveyed from the separator 10 to the fractionator 15 via the line 14. A gas fraction is obtained via the line 16. A gasoline fraction, with a boiling range of C, - 82 ^O C (180 ⁰ I ¹⁾ through the line 17 'a heavy fuel fraction having a boiling range from 82 to 221 ⁰ C (180 - 43o ⁰ P) is the Line 18 and a bottom fraction with a boiling range above 221 ⁰ O (43O ⁰ I ¹ ) via line 19 obtained. The whole or any part of 221 ⁰ C (430 ° F) + material can be circulated back to the inlet of the reaction vessel via the lines 20 and are guided. 1 The in the range 0 - 221 ⁰ C (430 ⁰ F) boiling material contains at least 10 fo aromatic hydrocarbons "The hydrocarbons may be the gasoline fraction are added for octane improvement, or it may be an aromatic fraction are passed to reforming and solvent extraction to give pure To win aromatics.

If new catalysts or freshly regenerated catalysts are to be activated, they can be activated with the same Treatment agents are processed. For example, both the hydrogen refining catalyst and

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and the hydrocracking catalyst activated by v / ground in that a 0.5 to 5.0 G-ew.% of sulfur-containing oil over the catalyst bed passes, with the temperature slowly raised to about 37o ⁰ C (700 ⁰ P) Sulphiding agents such as HpS and CSp can also be used. Therefore, the sulfiding and conditioning of the hydrogen refining catalyst and the hydrocracking catalyst can be carried out simultaneously under the same conditions without special equipment.

Similarly, the two catalysts are regenerated at the same time. Referring to the flow diagram of the I ¹ Iießen of the feed mixture is stopped and an inert gas from line 21 and air from the line 22 up through the hydrocracking catalyst bed and then passed over the catalyst bed Wasserstoffraffinierungs. The gas is circulated via line 23 and compressor 24. Part of the gas is cleaned via line 25. The regeneration can be carried out partially, ie by a stripping gas, or completely, ie using an oxygen-containing gas in order to burn off the coke from the catalysts. The temperature is maintained below about 480 C (900 F) during regeneration.

example

The procedure was carried out in a continuous at the same time

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Temperatures working test facility tested »A bed with 20 g of hydrogen refining catalyst, the KiO
(5.7 wt. 6) and MoO, (13.0 wt. #) On silica stabilized alumina was placed in the reaction vessel over a bed containing 50 g of hydrocracking catalyst, this being 1.4 Wt. $ Ui and
9.8 wt. F6 W on a faujasite base material. A light catalytic recycle oil (40 ppm nitrogen) and a light "virgin" gas oil (100 ppm nitrogen) were used
brought into contact with hydrogen in a process which took place for days. 70 atmospheres (1000 psig) were used during the first 50 days of the procedure and 38.7 atmospheres (550 psig) for the second 50 days. The results obtained using the lower pressure are reported in columns 1-3 of Table 3 and these results can be compared to the high pressure operating method at 105 atmospheres (1500 psig) in column 4.

Table 3
'"' _1 2 3 4

Loading '"' LCCO LVGO LVGO LVGO
Working conditions - '"-'
Temperature ⁰ C. ... "J

Il J!

Throughput rate • Vol./hour/vol.

Pressure atü "psig

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, 360 357 380 360 680 675 715 680 1.3 1.3 1.3 2.1 70 70 38 105 1000 1000 550 1500

Continuation of table 3

1 2 3 4

feed LCCO LVGO LVGO LVGO working conditions io H ₂ , Mol. # 96 96 96 90, ι Gas velocity Nm ³ / m ⁵ 1246 1246 1246 1246 SCF / bbl. 7000 7000 7000 7000 Conversion Vol. $, Initial boiling point 200 ⁰ C (400 ⁰ P) 60 60 40 60

o Aromatics, volume $ in C ₅ -2OO ° C (400 ⁰ F)

14.2 17.4 13.4

After 100 working days (50 days at 70 atmospheres = 1000 psig and 50 days at 38.7 atmospheres = 550 psig), corresponded to the maximum loss of activity 11.,. 1 ⁰ C (20 ° F) or less, whereby the 2iotwendigkeit the increase in the overall temperature (bulk temperature-increasing need = GTEB) of 0.11 ⁰ C / day (0.2 ⁰ F) or less results. The GTEB at 38 atm was discriminated with only about O, 11 ° C / day (0.2 ⁰ F) from the insignificant at 70 atm (1000 psig) (550 psig). This shows that the activity is retained very well at very low temperatures. The activity level is sufficient for reasonable throughput rates above 1.0.

An excellent conversion to products with a boiling range of 0, - 200 ⁰ C (400 ⁰ F) can therefore be achieved from batches which are in the range of 200 - 370 ⁰ C (400 -

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700 3?) Simmer «Furthermore it can be seen that the procedure is effective on feeds containing 10-200 ppm nitrogen.

It can also be seen that the amount of aromatics in the products increases as the pressure is decreased. At 105 atm (1500 psig) the product contained 13.4 # aromatics, at 70 atm (1000 psig) 14.2 # aromatics, and at 38 atm (550 psig) 17.4 rf aromatics. The low-pressure working method is therefore a suitable means of increasing the aromatics for gasoline with a higher octane number or for petrochemical use "

The low-pressure working process also leads to acceptance the hydrogen consumption o This factor is a further plus point for the process.

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Claims (13)

Patent claims: 1 _β Integrated low pressure hydrogen refining hydrocracking process, characterized in that one (a) a feed mixture of hydrogen and a nitrogen-containing petroleum fraction with a boiling range of 150 to 540 ⁰ C (300 to 1000 ⁰ F) over a bed of a hydrogen refining catalyst which contains a hydrogenation component from a salt or salts of metals of Group VI B, group VIII metals and / or mixtures thereof supported on a suitable carrier material containing, at a pressure in the range of Η to 70 atm (200 psig to 1000) and a temperature in the range of 260 to 54O ⁰ C (500 to 1000 ⁰ F) conducts, (b) all of the effluent from step (a) at substantially the same temperature and pressure range as in step (a) over a bed of hydrocracking catalyst conducts, which contains a crystalline alumina-silicate zeolite, the uniform pore diameter, a Faujasite crystal structure and a silica to alumina molar ratio greater than about 3, with the crystalline alumina-silicate zeolite a hydrogenation component containing nickel and tungsten is connected, and 909881/1308 -19- (c) a liquid product that is at least 10 vol. # aromatic Contains hydrocarbons wins. 2. The method according to claim 1, characterized in that the flow of the feed mixture is stopped periodically, a regeneration gas is passed in sequence through the bed of the hydrocracking catalyst and the bed of Was.serst.offraffinierungs-catalyst until the catalyst is reactivated, then the regeneration gas flow
turned off and steps (a) and (b) of claim 1 are carried out again. 3. The method according to claim 2, characterized in that the regeneration gas contains a mixture of an oxygen Gas and an inert gas. 4. The method according to claim 2, characterized in that the regeneration gas is a mixture of air and steam
(Water vapor) is. . 5. The method according to any one of the preceding claims, characterized in that both the bed of hydrogen raffle activation catalyst and the bed of hydrocracking catalyst with the same activation medium activated with the same activation conditions. 6. The method according to claim 5, characterized in that 909881/1308. _ ₂₀ _ the activation involves contacting the catalyst with a sulfiding agent. 7. The method according to any one of the preceding claims, characterized in that the zeolite component of the Hydrocracking catalyst has hydrogen cations in at least a portion of its exchangeable cationic sites having. 8. The method according to any one of claims 1 to 7, characterized in that the temperature increase requirement in continuous processes up to 100 days is less than 0.11 ° C / day (0.2 ⁰ F) for both catalyst beds. 9. The method according to any one of claims 1 to 8, characterized in that that the pressure is in the range of 31.6 to 68.6 atmospheres (450 to 975 psig) and the flow rate at least 1 vol./hour./vol. through both beds. 10. The method according to any one of the preceding claims characterized in, that steps (a) and (b) are carried out in the same reaction vessel and the feed mixture down first over the bed of hydrogen refining catalyst and then passed over the bed of the hydrocracking catalyst » 11. The method according to one of the preceding claims 909881/1308 -21- by "characterized in that at least 30 $ of the petroleum fraction is converted to hydrocarbons with a boiling range of G _c -200 ° C (C (-400 P)) o 12. Integrated low pressure hydrogen refining hydrocracking process essentially as described here with special reference to the drawing and the example. 13. Liquid hydrocarbon with a content of at least 10 vol according to the method according to any one of claims 1 to 12. 909881/1 308 Blank page