DE1928016A1 - Process for the hydrogenative cracking of a hydrocarbon oil - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL.-ING. GERHARD COLDEWEY

Patent attorneys
MÖNCHEN 2 ^^^^^^^^^^^^^ HtEL EFON 34 50 67 ■ TELEG R AM M-AD RESS E: - IN VENT / MÜNCHEN - TELEX 5-29686

P 6408 (J / Ic) June 2, 1969

SHELL IlI'x'EHlUiDIOHALE RESEARCH ΜΑΑΪSOHAPPIJ U.V., The Hague, Netherlands

"Process for the hydrative splitting of a hydrocarbon" οbofföls "

Priority: June 4, 1968, Great Britain Registration itfr. :. 26 574/68

The invention relates to a method for hydrating splitting a hydrocarbon oil under special working conditions, a naphthenic kerosene is used as the feed and Füissig gas components as well as from the fission product a light gasoline fraction with a high ratio of Isoparaffins to normal paraffins with 5 to 6 carbon atoms and furthermore a heavy gasoline will be separated "

The refineries are supplied with crude oils in increasing quantities, which are strongly naphthenic. These are, for example, African crude oils, which have only recently become available became. Kerosene, which can be obtained from these crude oils by direct distillation, must be described as inferior warden »because they are not in the form of

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Sell first-class quality products, "for example as light oil or fuel for IT aircraft turbines, raid because of their low smoke points »also an improvement in quality Such kerosene through a complete hydrogenation has due to the high content of ring compounds of these products only a modest effect in terms of improvement of the smoke point. Eo lot therefore of particular interest, such Convert hydrocarbon oils into more valuable products »

This technical problem can be 3iched according to the invention by means of the 3 Solve multi-stage procedures.

The process according to the invention for the hydrogenative cleavage of a hydrocarbon at an elevated temperature and pressure in the presence of hydrogen and a catalyst which consists of Hicke 1, tungsten and fluorine in close association with an acidic carrier and by treating the carrier in Ilydrogelform with a solution of the relevant Metallea or, * the metals iat iat, is characterized in that a naphthenic kerosene charge with a total content of ring compounds of at least 50 wt _o # and a smoke point of at most 23 mm

a) elungskatalyaator over a Hydroentschwef at a pressure of at most 100 kg / cm and a temperature in the range 315-375 ⁰ C and treated reductively

b) then in the presence of a fluorine-containing hydrogel catalyst With a content of 0.1 to .14 wt >? £ nickel and

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0.1 to 5 Gev / tungsten .ϊί _B whose SiOg algo -Irägermaterial ^ i & SIOO consists of at least 60 wt * cleaved reductively at a pressure of at most 100 kg / cm and a temperature in the range 270-390 ⁰ C. will what

o) the reaction mixture withdrawn from the cleavage zone in Plüssiggaakomponenten, a light gasoline or «a light gasoline fraction with a high ratio of IsO-C ₅ and / or Cg paraffins to normal CV and other Cg paraffins and a final boiling point of 65 to 120 ⁰ O soui * a heavy gasoline or a heavy gasoline fraction whose initial boiling point corresponds to the final boiling point of the light gasoline or the light gas fraction, and possibly a residue fraction boiling above the heavy gasoline or the heavy gasoline fraction is separated, v / oak

d) in the cycle again in process stage (b) apßlst will *

The production of the invention for the hydrogenative cleavage Hydrogel catalysts used can be used according to the British Patent 1,059,692.

Under a kerosene or kerosene feedstock v / ill be within the scope of the invention off a Kohlenwasserst elve 1 nude ion having an ASTM boiling range of 150 to 280 ⁰ C understood ,, In general, such Ölfrsktion precipitated as directly distilled fraction during the distillative Anftrennung of crude at. Pur process of the invention a kerosene feedstock is used,

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which is heavily naphthenic and has a total content of ring compounds of at least 50 wt on haphthenes of more than 35% by weight

Preferably the kerosene charge contains caphthenes from 40 to 65 wt. # and in particular from 50 to 60 wt. * # The aromatics content of the feed is preferably from 10 to 25 wt. # And in particular 17.5 to 22.5

The kerosene suitable as a feed for the process of the invention can be obtained, for example, from African crude oils. In Table I some properties "of such directly-distilled kerosene are compiled ₉ which come from African crude oils". These kerosene are strongly naphthenic and have a bad smoke point due to the high content of ring compounds.

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- 5 Table I.

Properties of the
Kerosene wrapping A. B. 0 D. Density, d? ° 0.820 0.854 0.854 0.800 20th
Refractive index, nt 1.4550 - 1.4517 1.4469 Hydrocarbon, wt Paraffins 25.5 25.5 55.0 44.0 Naphthenes, 54.5 57.0 45.5 40.5 Aromatics (added) 20.0 19.5 21.5 15.5 (polycyclic) monoaromatics,
Moles / 100 g 12.2 χ
io- ² 9.6 χ
10 " ² 14.7 x
10 ~ ² 12.1 χ
ΙΟ " ² (polycyclic) diaromatics,
Moles / 100 g 1.8 x
10 ~ ² . 2.4 x
ΙΟ " ² 0.9 x
ΙΟ " ² 1.8 χ
10 "" ² Smoke point, mm 18.5 18.5 20th 25.5 Sulfur, parts by weight per million 557 550 154 1100 Total nitrogen per million 1.5 4.5 0.8 1 | 3 * Molecular weight 156 174 155 161 ASIM boiling range, ⁰ C Initial boiling point 166 198 162 179 10 vol. # 179 206 176 189 50 VoI. # 196 215 194 200 90 VoI 4> 222 255 220 229 Bnd boiling point 258 240 255 245

At least three different advantageous end products can be obtained from the product stream discharged from the hydrogenating cleavage zone, namely PlüssiggaekoMpoiienten, abbreviated as LPG, also a light gasoline and a visual gasoline clarify au * Dar liier frequently occurring term "iPlüssiggaakomponenten ¹¹ refers to C ^ - and G. hydrocarbons, which represent the Ausgamgsisaterial for Plüssig = gas · Such hydrocarbons can LPG aligetrennt in known Weiae from the product stream and condensed! Liquefied petroleum gas is a very important source of fuel and is particularly suitable for charging processes in which combustion fuels are obtained, such as hydrogen gas. ¹ * refers to a hydrocarbon de-stillate with a boiling point in the range from 65 to 120 ⁰ G. Instead of a single hydrocarbon de-stillate, one or more "Eeichtbenzinfractions" can be obtained from the product stream of the * hydrlerendöii cleavage zone, for example, a Destlllatffraktion having a boiling range of 30 to 80 ⁰ C and a further fraction with a boiling range 80-115 ⁰ C. the Axisirack _9: "rind" - in- 'refers to a Kohlenwasserstoffäestillat "which above half the boiling range. the light Benzines boils "the Endsieö ~ point of the heavy gasoline is in the range from 100 to 210 ⁰ C, but the initial boiling point depends on äem, final boiling point of the light gasoline" in the form of a Praktion the naphtha can be recovered with a narrower boiling range, for example, ala! Fraction with a boiling range from. T00 "to 115 ⁰ O ₅ ,

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Finally, it should be noted that in all cases, where temperature information in connection with boiling ranges and Boiling points occur; these temperatures are based on the ASTM distillation methods relate.

The process according to the invention is extremely adaptable, since the ratio of the various end products obtained from the cleavage product can be changed depending on the demand by varying the lower cut point for the cycle oil accordingly andsfraction with a boiling point above 180 ⁰ C recirculates, the liquid gas components, a light gasoline _{fraction C 5} -80 ⁰ C and a Sehvrorbenzinfraktion 80-115 ⁰ C in proportions of 16.8 GewefS or «24» 6 Gew.JS or _e 22.0 wt. jb obtained, but if all ^{material boiling above 150 0} O is returned to the circuit when the same kerosene charge is processed, then liquid gas components, light gasoline fraction and commercial gasoline fraction fall under identical working conditions in Eangen proportions of 18.5% by weight ₉ 9 wt. Or 25.1 Gevfo ^ an. If, with the same charge and under identical working conditions, all of the ^{material boiling above 115 0} O is recycled into the cleavage zone, the three above-mentioned end products are obtained in proportions of 29.7% by weight or 39.7% by weight or 33.0 wt. # _E In the latter case, the ratio of the end products separated from the cleavage product is practically 1 ί 1: 1 _β .

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therefore proceedings, the cleavage product is separated such that the final boiling point of the heavy gasoline fraction in the range of 100 to 120 ⁰ C, in which case everything boiling above this final boiling point material in circulation in the hydrogenating separation step is recycled.

In Introducing given example, a second heavy gasoline fraction is recovered having a boiling range 115-180 ⁰ C, if everything boiling above 180 ⁰ C material in the circulation returned Wiru, while a return of the entire above 150 ⁰ C boiling material, the heavy gasoline fraction having a boiling range of 115 to 150 ⁰ C. Aue of the drawing attached to the explanation, it is easy to see which end products and in which proportions are obtained when the lower distillation cut for the cycle oil is varied. In the graphic representation, the lower distillation section of the circulating oils, which ^{varies in the range from 180 to 115 °} C., is on the abscissa, while the yield of the) individual products in wt. #, Based on the freshly added charge, is on the ordinate applied. The area above curve A relates to the positive gas components _o The area between curves A and 0 relates to light gasoline and the area below curve C relates to heavy gasoline.In the special case shown in the drawing, two light gasoline fractions are obtained, namely an Oc - 80 ⁰ C fraction (area between curves A and B) and a ^{fraction boiling between 80 and 100 0} C (area between curves B and 0) o In the same way, two SchwerbenJüinfraktio.-

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ηβη separated, namely a ^{fraction boiling between 100 and 115 0} O (area between curves C and D) and a fraction with a boiling point above 115 ⁰ O (area under curve D).

The boiling ranges indicated in the drawing for the individual distillate fractions have al3 been chosen particularly favorably. Of course, the intersection points for the individual fractions can be changed depending on the requirements of the refinery in question. For example, the heavy gasoline fraction can having a boiling range 100-115 ⁰ C, which is of very high quality is "also separated together with the light naphtha fraction 80 to 100 ⁰ O as a single distillate fraction (boiling range 80 to 115 ⁰ C) or it can be with the gasoline fraction be blended to such a distillate fraction.

The inventive method has furthermore the advantage that the lighter hydrocarbons namely methane and ethane accumulate, in very small quantities, namely in amounts of less than 1.5 wt _o #, and often less than 0.8 wt. #, Based on the fresh feed fed in, so that only a small proportion of the feed is lost through the formation of these by-products in the hydrating cleavage zone. The end products separated from the cleavage product in the process according to the invention are also of very high quality. The obtained from the cleavage product © Oe - 80 ° Ö-Benjsin-

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fraction has an F-1-3 octane number in the range from 98 / to TQ2 _O. Because of its exceptionally high quality, such a light petrol fraction can be mixed directly with finished premium petrol. The heavy gasoline obtained as a further end product is a very good feed for a reforming plant due to its high content of ring compounds.After reforming treatment, such heavy gasoline can serve as fuel or as a feed for the production of aromatics, for example through an extraction treatment with solvents such as furfural sulpholane , liquid SO, or II-methyl pyrrolidone »

The inventive combined treatment of the kerosene charge in a hydration zone and a hydrating cleavage zone leads to a very stable mode of operation, especially as far as the catalyst for the hydrotreating cleavage is concerned 100 is returned to 120 ⁰ C boiling material in the circuit, if during the separation is Flüssiggaskomponentsn and one or more light petroleum fractions and a Sehwer "- gasoline fraction having a final boiling point between 100 and 120 ^{ο σ} by fractional distillation üea cleavage product, a side stream having a boiling range between 100 and 210 ⁰ O is subtracted. By taking off such a side stream, an accumulation of aromatic hydrocarbons can be avoided during the process. Due to its high aromatic content, the side stream obtained in this way can also be used as a blend component

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for Beasine to be used, »To get a good quality sidestream? to. gain without reducing the quality of the other prices, however, it is advisable that the sidestream be in an amount of 5 Ms 15 wt. and in particular from 8.5 "to 12 _f 5 Se \ r. "based on the hydrotreated feed, subtracted

In the process according to the invention, the is used as a charge used iiapiitlieabussian kerosene fraction before the actual hydrogenative cleavage over a hydrodesulfurization catalyst Treated with hydration * Any known hydrodesulfurization catalyst is suitable for this purpose. »Preferably contained Such catalysts as the active metal component one or more oxides or sulfides of metals of groups VI B and ¥ 111 of the periodic system of elements, especially the Iron group. These metals, especially molybdenum, tungsten, cobalt and nickel, can be used in combination with known stabilizers and promoters are used, the usual carrier materials being considered, such as aluminum oxide, silica, Eirkonoxyd, Titanaxyd and types of clay »like bauxite and Bentonite Mixtures of such carrier substances can also be used The carrier material should preferably have no or only a very low gap activity and from this The reason is strongly acidic carrier materials or mixtures of these Substances less desirable · Preference is given to using activated aluminum oxide as carrier material. Particularly preferred Metals are cobalt and molybdenum, each in their own form Oxides or Sulphides «, Commercially available Hväroentsohwefelungs-

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BATH ORIGINAL

Catalysts contain 1 to 5 # cobalt and 3 to 20 fo molybdenum on an aluminum oxide carrier. Such catalysts are particularly suitable for the purposes of the invention

During the hydrogenating treatment, a pressure in the range from 50 to 90 kg / cm and a temperature in the range from 335 to 365 ⁰ C are preferably used. The liquid hourly space velocity is generally in the range from 1 to 10 and preferably in the range from 3 to 7 parts by volume of kerosene charge 3rd part by volume of catalyst ^ e hour ,, The required hydrogen can be fed in at a rate of 100 to 2500 Kl 3e liters of charge «

By means of this hydrogenation treatment, polyaromatic hydrocarbons with a condensed ring system, which tend to deactivate the cracking catalyst based on an amorphous silica-alumina support, converted into less harmful monoaromatic polynuclear hydrocarbons. Ground through this hydrating treatment also converted compounds of the naphthalene type into tetralin Since the kerosene burnings under consideration here have already been carried out by Naturally only have a very low nitrogen content, the product stream flowing out of the hydrogenation zone does not need to be especially to be freed of ammonia, but the kerosene charge treated with hydrogenation can be hydrogenated directly into the » de cleavage zone (b) are fed in «This has the advantage that that both the hydrogenating treatment and the hydrogenating cleavage are carried out in a single reactor

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can, v / which contains different catalyst beds, wherein the first catalyst bed selected for the hydrogenation treatment. Palis, however, the kerosene charge is higher Has nitrogen content, it may be appropriate to discharge the product stream from the hydrogenation treatment in the usual way to treat to remove ammonia »

The hydrogenating pretreated kerosene feedstock is subsequently cleaved by hydrogenation over a Wolfrem and Hickel containing catalyst which has been suitably prepared according to the United Kingdom Patent Specification 1,059,692 · The hydrogenolysis is preferably carried out at a temperature in the range 310-380 ⁰ C und.einem Pressure in the range of 50 to 90 kg / cm. The liquid hourly tree speeds may range from 0.5 to 10 and preferably in the range of 1 to 5 volumes of feed mixture, d _c h ,, the Mi ^ ture of reductively treated kerosene feedstock and cycle oil, per volume of catalyst per hour are selected. The molar ratio of hydrogen to oil is expediently chosen in the range from about 5: 1 to 25 s 1.

The fluorine-containing catalyst for the hydrogenative cleavage is prepared, for example, by adding the acidic support material in hydrogel form with a solution of one or more nickel compounds in contact and then the hydrogel calcined, with tungsten and fluorine being stored in the hydro oil before calcination. Preferably the Metals are used in such quantities that the finished catalyst

009800/1484

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sat or contains 1 to 5% by weight of nickel and 1 to 3, 5% by weight of tungsten. The fluorine is preferably incorporated in such quantities includes class, the finished catalyst contains 1 to 3 percent by _e # fluorine. Particularly good results are obtained with a catalyst which has been ^ else produced in the above-described V / and its carrier to 78 percent by "5" of silica and 22 to Gmr _a $> consists of aluminum oxide.

Both the hydrodesulfurization catalyst and the catalyst for the hydrogenative cleavage are advantageously used in the sulfided form. Such a sulfidation is carried out in a manner known per se. In order to keep both types of EJatalyeator in the sulphided form, a sulphurous charge should be used in the aligemoinen. Ba jedoeli ä ± Q have here under consideration Kerosene usually has a low sulfur content, it is advisable to add one or more sulfur compounds, for example Sehwef © hydrogen!, Carbon disulfide and / or mercaptans, "This ¥ erMndungen the feed are practical before Incorporated hydrating treatment, yoke can add more amounts of. The sulfur compounds are added sulfur compounds even after carrying out the hydrogenating pretreatment _o ropes _s if required, be used in an amount of at least 100 parts per million sulfur "In the sail is a sulfur content of the hydrocracked hydrocarbon to be treated oil of at least 0.05 percent by . $ and preferably from 0.1 to 1.5 wt. $, based on the oil to be hydrogenated, in terms of weight.

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Since ä @ T catalyst depleted for the hydrogenating Spaltimg usually during Ihirehführaiig the process gradually fluorine *, it is advantageous aufreckt the necessary fluorine content to obtain one lnäem before Kerosinbe destiny or stage during the cleavage by hydrogenation in the process (b ) continuously or intermittently one or more fluorine compounds "adding Especially zweekmässig is such a fluorine additive in the range of O Ms 25 Sewoteilen per million _e are suitable for this purpose € Owd2lL inorganic and organic fluorine compounds * Preferably include those compounds selected which _f among the The conditions of the hydrogenative cleavage are sufficiently volatile to ensure a homogeneous distribution of fluorine over the gas phase of the reaction mixture. For example, hydrogen fluoride, fluorobenzene and fluorotoluene are suitable. * A particularly preferred organic compound is mfluoroethane. This fluorine compound is preferably added to the cycle oil before it is fed into the reactor

The eerosin feed can be fed into the individual reaction zones as a liquid, as a vapor or as a mixed vapor-liquid phase, which depends on the temperature, pressure and the amount of hydrogen ous mixed with the feed will come together with a big. Wasserst off excess in this zone introduced The excess hydrogen is generally Sm obtained from <d "r reaction mixture, which flows from the high pressure separator and at least Spaltzene in a to the rope in the zone of the cleavage by hydrogenation

returned,

After passing through the high pressure separator, the reaction mixture of the hydrogenating cleavage zone is separated in a fractionating column into a distillate, from which the liquid gas components, a light gasoline and a heavy gasoline can be obtained, as well as a residue fraction, which boiled above the final boiling point of the heavy gasoline have an initial boiling point in the range from 100 "to 210 ⁰ C, and it is fed back in the circuit into the hydrogenating gap zone and there combined with the kerosene feed treated in process stage a).

The !! temperature in the zone of the hydrogenating cleavage is generally adjusted such that the degree of conversion per pass of Beaehickungsmiechung least 40 is ßewo ^ · Preferably, the! Temperature to a Umwandlungegracl 50 bie 75 G ew _o #, based on the Contamination Mixture, Adjusted »To Maintain These Conversion Levels. the fresh feed is mixed with the cycle oil in such a ratio that the weight ratio of feed mix to fresh feed is at most 2.5: 1 for a 40 # conversion and for a conversion of 50 to 75 $> im Range varies from 2 % 1 to 1.3 J 1.

The hydrogenative cleavage can be carried out in a solid such as e.g. stationary, or a moving catalyst bed carried out

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will. In order to obtain the best results with a stationary fluidized bed, the catalyst is spray-dried during the production of the hydrogel to a particle size which can be fluidized. Bin catalyst having a Teilohengrössenverteilung, wherein less than 3 weight "$ of the less than Leuchen are large and not more than 15 wt αχ 20, $ 90 of the particles as _y gives very satisfactory results in the inventive method. Such a catalyst has an embossing agent * which consists of 88% by weight of silica, while the remainder is aluminum oxide. In addition, it contains 4 * 5% by weight of Hickel and 2.9% by weight of tungsten, while the fluorine content is 2% , 1 Gew “$ is.

Example 1 .

This example illustrates the beneficial effect of hydrogenation pretreatment on catalyst stability.

A product obtained from an African crude oil directly-distilled kerosene having a boiling range of 180 to 250 ⁰ C (oil B of Table I) is cleaved by hydrogenation in an operating with recycle procedure over a Pluor, tungsten and Hickel containing catalyst. The catalyst was obtained in the manner described above by incorporating the components in a hydrogel. The catalyst has the following composition: 2 _S 6 parts by weight of tungsten, 3.5 parts by weight of nickel, 2.6 parts by weight of fluorine per 100 Parts by weight of carrier material, which consists of 78% by weight of silica and 22% by weight of aluminum oxide.

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dried door of 525 ⁰ C in nitrogen and then for two hours "at 325 ⁰ C in a Gasmiachung vorerulf idiert, which © to 10 by volume. ^ of H ₂ S and 90 VoI · $ 6 auo Hg" exists. The hydrogenative cleavage is carried out under the following working conditions: pressure 75 kg / cm, liquid hourly space velocity 1.5 1 · »h" ~, molar ratio of circulating hydrogen to oil 10: 10 die 'temperature is adjusted such that the Uciwandlungsgrad to products having a boiling point below 180 ⁰ C for about 65- wt. # is "the feed are 650 Gev / oteile per MHion sulfur in the form of carbon disulfide and 5 parts by weight per million fluorine in the form of o-fluoro »toluene was added · the above 180 ⁰ G siedenäe heavy material is circulated in the zone of the hydrogenating cleavage. During a working period of 530 hours, the medium-sized" catalyst temperature can be increased from 326 to 330 ⁰ O, upright to the desired degree of conversion to obtain

Hach termination of this experiment, the same catalyst for the hydrogenolysis was a _r with hydrogen pre-treatment th kerosene feed B used These hydrogenated Beschik "= effect was by mild hydrotreating of Kcrosins over a commercially available cobalt-molybdenum catalyst at a temperature of 355 ⁰ C, a pressure of 75 kg / cm and

= 1 »1 of an hourly liquid space velocity of 5 1 * 1 ° h has been obtained * Before the practical use xrarde the catalyst in the usual way presulfidiex * t. As a result of the hydrogenating pretreatment of the nitrogen content of the Keroüinbeechickung was let to a value below 0.1 _e per million

0 0 9 8 0 8 14 8 4 BAD ORIGINAL

and the content of diaromatics has been reduced to 0.2 10 "* mol / 100 g. On the other hand, the concentration of polynuclear compounds increased mono aromatic compounds to 11.6 χ 10 mol / 100 g «

The hydrogenolysis was tested under the above conditions conducted the pressure, space velocity, the goal difference of recycle gas to oil, and the return of boiling above 180 ⁰ C material The Beschikkung were 5 parts by weight per million fluorine and 1000 parts by weight per million Schwof el ssugesetz; in addition, 3 parts by weight per million nitrogen in the form of butylamine were also added in order to match the conditions in the first attempt with regard to the nitrogen content of the feed. In this case, too, the temperature was set to a degree of conversion of 65 wt. "#"

Despite the nitrogen content in the feed the Katalysatoratabilität was quite excellent in this second trial · To the gevriinschten Unwandlung3grad to maintain the average Katalysatorfcemperatur had during an operating time of more than 1600 hours, only by 2 ⁰ C, namely from 327 to 329 ⁰ G, increase. This proves that the hydrogenating pretreatment of the kerosene charge before the actual hydrogenating cleavage had a beneficial effect on the catalyst stability

In Table II below are those in Experiments 1 and 2 end products obtained and their properties. The light gasoline produced was split into two fractions.

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separated, namely a Gc - 80 ⁰ C fraction and a 80 - 100 ^0C Group _o In a corresponding manner there was also the Sonwerbenzin in two separate fractions fractionated) namely a fraction 100-115 ⁰ O and a fraction from 115 to 180 ⁰ C. .

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Table II

feed untreated 5 0.4 hydrating
pretreated ; 0.3 6th i / n ratio Fission products * Gew _o # 2 16.2 16.0 P. 11.0 related to loading, 5 26.2 25.4 0 17.9 light gases (H ₂ S; Cj-JG ₂ ) 0 13.8 14.5 9 Liquid gas components
(IPG) 5 8 ₈ 6 8.0 5 Fraction G «-80 ⁰ C 34.1 31 ti "80-100 ⁰ G 5
5 "100-115 ⁰ G ^{11115-180 0} C .- Properties of the gap 0.660 Products 87.2 IPG
"""""nC ^ / iC ^ ratio 98.7 Density, d? ti / n-Yerhc 0.21 F-1-0 (octane number) f. 11.2 0.657 F-1-3 i 18.7 87.0 Total paraffins, wt. $ 78 77f 98.5 O ₅ - 44, 43 * G ₆ - 33, 34, Haphthene, " 19 » 19 Aromatics, " 2 » 2, Fraction 80-100 ⁰ G Paraffins, GtQM ^
Haphthene, "
Aromatics, " 40
57
3 42,
56 Paraffins, ßew _o $
Aromatics, "
Fraction ΘΟ ^ βΟ ^ Ο 29
58
13th 25th
56
19th Naphthenes * "°
Aromatics. ⁿ 29
55
18th 23
59
18th

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Confirm the above .Analysenergebnisse that produced three lüssiggaskomponenten a high content of isobutane, and in that the light gasoline fraction Gc-SO ⁰ C of the highest Qua «= · formality is · Fractions 80 -. 100 ⁰ C and 100 - 115 ° G Chins. Cuttings can be used for purposes of example. They are mixed in the product ratio with the C ₅ -80 ^ fraction, the leaded cetane number IP-1-3 of the light gasoline with a final boiling point of 100 ⁰ G is 9 δ.2 * Y ^ when mixing this beaain

ψ with the 100-115 ° G ~ Group in the production ratio of a gasoline with a Bndsiedepunkt of 115 G ⁰ UNAE a FI

Octane S4 »8 erhalten- By mixing the light gasoline" = fraction 80 - gives an excellent feed to a reformer (fraction 80 · => 180 ⁰ C) 100 ⁰ C with the heavy gasoline.

Example 2

The experiments in this example explain the effects of a variation in the lower distillation cut of the cycle _{oil Q}

To investigate the influence of the lower distillation section of the circulation oil distribution on the product and the properties of these Pro =-products to study the above 150 ⁰ G bsw _e is the above 115 ⁰ C boiling material long in two further tests returned in the circulation "Dm a degree of conversion au can be maintained by 65 per pass, which had Semperatur 340 bzwo 360 ⁰ C can be increased while the other conditions were kept constant gemäßs example 1 ,, the experiments were dureh to that used in example 1 catalyst

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BATH ORIGINAL

the experiments described here _r out which after the end a life of about 4750 hours without an intervening performed regeneration · had As the fluorine compound difluoroethane was added and, as in Example 1, the feed was 3 parts by weight per million of nitrogen was added a

The results of these experiments are shown below
Table III summarized »

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- 24 Table III

Lower distillation cut Cryo barrel oil Circulation oil 150 ⁰ C 115 C Fission products, wt, # 'related' to 'loading, light gases (KUSjC- + 0 «) 0.5. 1.1 Liquid gas components (LPG) 21.2 33.9 Fraction 0 ^ -80 ⁰ C 31.9 39.8 »80-100 ⁰ C 16.5 14.1 '♦ 100-115 ° ö 8.4 14.4 "115-15O ⁰ C 24.9 Properties of the gap Products LPG n-C ^ / i-C, ratio 0.20 0.26 Density, d | ° _- 0.6588 P-1-0 (octane number) 87.5 87.4 F-1-3 98.3 99.7 Total paraffins, wt 77.2 | i / n-Ver] • 77.1 jL / n vea C ₅ -, 42.6 j 12.3 , 44.1 j 9.0 Gg-- ⁿ 34.2i 19.1 32.6 I 13.8 Naphthenes, ⁿ 20.9 20.9 Aromatics, ⁿ 1.9 2.0 O Paraffin, GeW « fi 43.5 38.5 Naphthenes, ^H. 55.0 59.0 Aromatics, " 1.5 2.5 Fraction 100-115 C Paraffins, Gew _e ^ 24.0 24.0 Naphthenes, ⁿ 54.0 46.0 Aromatics, ^β 22.0 30.0 Paraffine, Sew _ö ? I 24.5 Naphthenes, ⁿ 54 Aromatics ^{,! L} 21.5 -. -

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B \ O H SC "ϊ"

The above Analyä end at s "to confirm that both the quality can be improved as well as the Ausoeute the Leichtbenzinfraction when a material of lower molecular weight in the circuit; is returned" If .beispielsweise the above 115 ⁰ C boiling material is recycled, are about 34 Gew ^ Flüasiggaskpmponenten and about 54- Gew ₀ ^ light gasoline in the boiling range Oc-IOQ ⁰ C produced, which a P-1-3-0 et number of
97 »O has» However, it is also possible to use 68 wt
O5-II5 ^o 0-light gasoline fraction with a P-1-3 octane number of
About 97 to be gained if you include the heavy ^{gasoline fraction 100-115 0} O in the light gasoline fraction “Palis das
Material boiling above 150 ^° C. is recycled
is, the 115-150 ° 0-praction is a good feed material for a deformation plant. These results show the high adaptability of the process according to the invention, whereby the most varied proportions of gasoline
high quality and can be generated from feed for a molding plant. The speed at which the
The decrease in catalyst activity under these severe conditions is limited, in particular if a ^{material boiling above 115 °} C. is recycled.

Example -3 '-_ ..,' ί ■% ■ ': ■ - ■ _; rv ■,;. ,., ■■■ This « example explains the influence of the purchase of a Seitan et roses la distillation section on the product distribution and the properties of the products * ΐ ^? _-:, r t \\> ,.

JSm to improve the catalyst stability and an enrichment

009808 / U84 ^BAD

If there is a lack of aromatics to be avoided, if ^{traction that is boiling above 115 0} CI is carried out in the ice skating, part of the 115-100 ⁰ G fraction is drawn in the form of a sidestream; disassembling the circulation . from "as a result, the aromatic drops close stop, the circulatory otromes from 60 to 43 Gevr ^ and 65 wt. ^ - weight conversion can be lowered to about 10 ⁰ C. the amount of the withdrawn Seitenstromeo is about 11 based on fresh feed.

The work sbeainguiigon during the hydrogenative cleavage with and without a decrease in the Seitenotroznes are the same as in Example 2. The charge is the hydrogenated pretreated kerosene B ₀ Everything boiling above 115 ⁰ O is recycled 350 hours long, and during this period, the temperature-had χ temperature for 65 $ strength conversion can be gradually increased from 366 to 373 ⁰ C · the experiment with decrease in a side stream was about made for 200 hours, the temperature-constant remain " · ■ '* ^: [

The results obtained are shown below in Table, 17;

set »=, .-.;.,. — ..-.

i '-: I ■■' ■ V BAD ORIGINAL

009808 / U84

Table IV

Circulation oil: fraction 115 ⁰ C ⁺ with side flow Working conditions Fission products, wt., $ without side stron 0.8 related to £ Ήθ 3 chickling 37.8 light GaSe (H ₂ SjC, + C ₀ ) 35 ₉ 5 Flüasißgaakompon (LPG) 1.1 16.9 FraJrtion C ₅ -80 ⁰ G 33.1 10.6 ¹¹ 80-100 ⁰ C 39.0 11.0 100-115 ° C 16.4 ^M 115-180 ⁰ C. 12.8 Properties of the gap - per dukie 0.6596 Fraction 0, - 80 ⁰ C 87.2 Density, d ^ 99.2 F-1-0 (octane number) 0.6588 78.6 | i / n ratio P-1-3 87.4 45.5} 11.3 Total paraffins, Gew _o # 99.4 32.4 * 16.1 78.2 | i / n ratio 19.5 C, - _t « 46.0} 10.0 1.9 Naphthenes, " 31.7 i 13.7 38.0 Aromatics, " 20.0 58.0 Paraffins, wt 1.8 4.0 Naphthenes, ^M. 36.0 Aromatics, ^M 60.0 23.5 100-115 ⁰ C fraction 4.0 51.0 Paraffins, wt. # 25.5 Naphthenes, ⁿ 1-5.0 Aromatics, " 50 _f 0 0.8107 Fraction 115-180 ⁰ G 35.0 84.0 Density, d | ° 93.5 F-1-0 (octane number) 11th F-1-3 42 Paraffins, Gew _o ^ -> - 47 Naphthenes, ^tf Aromatics, " -

009808/14

^{The fraction 115-180 0} O withdrawn as a side stream can be used for blending purposes. By mixing this fraction with the light gasoline fraction C ~ - 115 ⁰ O in the production ratio, a G ₁ - 180 ° C benein fraction with a cetane number F-1 is obtained -3 of 94 »8 in an amount of 73 * 8 wt. J & i based on fresh charge. Without removing the side stream, however, it is not possible to use a Qc - 180 ° 0 gasoline with the front. to obtain the good quality specified above without further treatment of this gasoline.

Example 4 '

In this example, the process stages of the hydrogenating Treatment and the hydrating cleavage combined with each other, whereby a semi-technical pilot plant with high space velocity is used.

Three different catalyst beds are arranged in a 2 liter reactor. The first bed consists of a commercially available aluminum oxide catalyst which contains cobalt and molybdenum. The other two catalyst beds contain the hydrogenating cracking catalyst also used in Example 1 with tungsten, iron and fluorine on a silica-aluminum oxide support. _{The fresh charge is passed over the Co / Mo / Al 2} O »catalyst together with hydrogen at an hourly liquid space velocity of 5 liters per liter of catalyst per hour, the resulting gas velocity being about 250 Hl / kg of charge. >. After the first

009808 / U8.4.

Catalyst bed, in flow direction, WbQT are fed to a separate heater, circulation oil with additional fluorine and circulation hydrogen gas.

—1 —1

Duration of 2 _t 5 1 ° 1 ° h ₉ "based on the feed rate, through the bed of the hydrogenating gap & atalysatorstf Έβά_ initer these conditions about 17QO 0tunSen under the above 180 ⁰ O si @ d © nö®a material« Me are. at the end of the Yerauches lrg®atiisse obtained are shown in Figure 2a "hereinafter beauty V * Mhrsnd the Tersuchsdauer had the average catalyst temperature of the catalyst for the hydrogenolysis for the purpose of Aufreshterhaltung a degree of conversion of about 65 $ of 321 34-6 ⁰ C increases"

0098Ö8 / U8 * BAD ORIGINAL

SOafcelle V

Pressure, kg / cm

First catalyst bed

Amount of catalyst used, charge

ml

Hittl »KatalyBat ort emperatur, G RaurBgesoh Speed l» l ~ ¹ «h ~ 'Gas velocity (1 pass) Hl / kg sulfur addition, parts by weight per million

Second and third catalyst beds

Amount of catalyst used, ml of feed

Pulled out of 1 "Batt ctige, Grew" $

Circulatory oil, Sew «$

Arte it sbe d in ^ n ^ en

Hittl »Kat alysatortemperatur, tree speed 1 · 1 ~ ^1" h ^"1 Speed Kreielaufgas, WI / kg Molverhältn.Kreislaufgas s oil fluoride supplement, weight _c parts per Killion

Fission products . ^ related to charging light gases (H ₉ S; G ₁ + C ₉ )

Fraction Ö _K - 80 ° S

"100-115" 0 «115-18O ⁰ O

Properties of spa products

Density rd ^, Jf-I ₁ -Q \ octane number) F-1-3 total paraffins, wt. ^

η ι »

Naphthenes »An
fraction

Paraffins, naphthenes, aromas, yraktion.jQO-J ^ I TaratfiSe, "* Naphthenes. Aromatics,

170 ^d * kerosene B

350-5 240 1050

250

346

1375

₉ 18.0

14.7

8.0 61

0.65-94 87.3 99.0

78 _$ 8 fi / s 44 * 3- 12 _ff 7 33.8 ί 20 ₉ 6 18 ₉ 5 2.7

59 * 5 3.0

5-

BATH ORIGINAL

The experimental data compiled here confirm that too a mode of operation with high space velocity is possible without the product quality being impaired *

Patent claims

009808 / U84

Claims (1)

Claims; ο Process for the hydrogenating splitting of a hydrocarbon oil a "at elevated! temperature and elevated pressure in the presence of hydrogen and a catalyst, which consists of nickel, tungsten and fluorine in intimate connection with an acidic carrier and by treating the carrier in hydrogel form with a solution of the metal in or _e of the metals has been established, characterized ge - Ψ denotes that a naphthenic keros commissioning destiny with a total content of cyclic compounds of at least 50 wt $ and a smoke point of at most 23 mm. a) hydrogenated over a hydrodesulfurization catalyst at a pressure of at most 100 kg / cm and a temperature in the range from 315 to 3.75 ⁰ C and treated b) followed by n in the presence of a fluorine-containing Hydrogelkatalysators? ith a Sehalt of 0.1 to 14 # nickel and 0.1 to 5 wt _o # tungsten, the SIO is ₂₂ j carrier material of at least 60 wt. ^ of SiO _2, with a Pressure of at most 100 kg / cm and a lempe temperature in the range from 270 to 390 ° 0 is cleaved by hydrogenation, whereupon c) the reaction mixture withdrawn from the cleavage zone in Plus gas components, a light gasoline or a light one gasoline fraction with high ratio of Iso-Oc- and / or 009808 / U84. Cg-paraffin ium to Hormal-G ^ - and / or Gg-paraffins and a End3iedepunkt 65-120 ⁰ G and a heavy naphtha or SChv / erbenzinfraktion whose initial boiling point corresponding to the final boiling point of the mineral spirits or "the light petroleum fraction *, and optionally a above the heavy gasoline bssw _e the Sefewerbe & ziäfraldiian boiling residue fraction is separated, v / elohe d) again fed into process stage (b) in the circuit willo 2g process according to claim 1 _S, characterized in that in process stage (c) a commercial gasoline or a heavy gasoline fraction with a boiling point in the range from 100 to 210 ⁰ G *, preferably from 100 to 12 G ° 0, is separated » 3ο The method according to claim 2, characterized in that a side stream of a product with a boiling range of 100 to 210 ⁰ G is taken off during the distillative separation of the reaction chamber withdrawn from the gap , Preferably 5 to 15 Ge \ h $, and particularly 8.5 accounted to 12.5 ßew _o? £ of hydrogenating treated in the process stuf © (a) Charging 4 · α The method of claim 1 Ms 3 _f dadureh in that a naphthenbasisches- Ausgangsiaaterial with a liaphtlaengehalt from 40 to 65 §ew _o $ _s Torsugsweise 50 to 60 GK, g $ or ο a halt close aromatic 10-25 _ 17 ₃ 5 Ms 22 ₈ 5 BAD ORiGINAL 5. Process according to Claims 1 to 4, characterized in that the hydrogenating treatment in process stage (a) takes place at a pressure of 50 to 90 kg / cm and a temperature in the range of 335 Ms 365 ⁰ O. 6. The method according to claim 1 to 5 »characterized in that the hydrogenating cleavage in the Terfahransstufe (to) takes place at a pressure of 50 to 90 kg / cm '" and a temperature in the range from 310 to 380 ⁰ J, 7 · The method of claim 1 to 6, characterized in that the hydrogenating _s cleavage at an hourly Raumg © · = speed 1-5 Mter feed mixture well and Eückführungsgut) 3θ liter of catalyst per hour follows · 8 «method Naeh claim 1 to 7 t ₉ characterized in that the gap catalyst 1 to 5 Gev7 _o $ liokel and 1 Ms 3.5 wt" $ tungsten aowie 1 to 3 wt Fluos _e ^? contains » 9ο Method according to claim 1 to 8, characterized in that the Katalyeatorträgsrmatarial su 78 G-ew »^ from SiOg 2u 22 Gev;» ¹ / ^ consists of AIgO- *, 1öo method of claim 1 bit 9 ₉ gekeimseiclmetj characterized in that the process stage (a) singe fed en Bepcliik · = kung previously firevrichtsteile at least 100 per million SEHV / e fei, preferably 0.1 ms 1 _B 5 Sew, fs sulfur train ₈ @a? "be szt» BATH ORIGINAL . - 35 - The method of claim 1 to 10, characterized in that _t be added before or in process step (b) hydrogenating the pretreated feedstock to 25 parts per million sulfur " 12c method according to claim 11, characterized in that the residue 3fraction of fluorine, which is returned to the cleavage zone, is added » 13ο Method according to claims 1 to 12, characterized in that 'That the hydrogenative cleavage takes place in a stationary fluidized bed took place 14. Process according to claim 13 _9, characterized in that process stages (a) and (b) are carried out in a single reactor which contains different catalyst beds 00 9 808 / U8 Blank page