DE1954002C - Process for the conversion and desulfurization of a sulfur-containing hydrocarbon feed - Google Patents

Description

b) SraS SJÜLhÄ kauly ratio
hk

SraS SJÜLhÄ kauly- ns ^ S «« ??

4. · u π ι. · Ι. · · Τ-, ι 3 ° if more than 150 parts ie million total metals, be

table reaction zone at a pressure of wchi ^ i <"=> γ« ^iCllc J ". ,. . ',

more than 68 atm reacts with hydrogen, but Ψ *** in the single state but a high one

c) the resulting ReaktionszonenausfluR in sulfur content, especially at or above 2 Geeiner first separation zone at about the same wight percent, and a high content of heptanchen pressure as the insoluble catalytic re asphaltenes ^. ^"m *" ™ _r ^ £ action zone in a first vapor phase and ^{35 percent h} f ^under ^ ¹ ? " ⁸ ^ ™ ^ "ί ££" a first liquid phase separates ^because hydrogen products have reduced hydrogen

d) reSflÄ, «^ Sr second separating ^ aUs, ^ * ™ das. KaU« ^ »^^. zone at about the same pressure as in ™ ^{enal na <*} F ^rh ™ ⁸ ^ «ner catalytic Reder first separation zone but at a reduced $ ^Uonsz ™ ^at £ ^rh ° ^{htem PRINT} \" l presence of temperature in a hydrogen-rich second ⁴ ° hydrogen to Schwefelverbindun removal of vapor phase and a second liquid phase 8 ^{e "and} generating tiefersiedender hydrocarbon separatory ^{materials to} g ^{replaces them> the} resulting reaction mixture

e) at least a portion of the first liquid separated and thereby obtained liquid portions of a Phase in a non-catalytic thermal cracking reaction with subsequent mixing reaction zone cracks, subjected to work-up of the reaction products

f) the outflow of the non-catalytic react.

tion zone in a fractionation zone introduces such, according to their usually deep dark to

and there a heavy hydrocarbon ™ black coloration, also called black olives, which boils completely or largely above carbon hydrogen feed materials such as raw oils, separates 343 ° C and ^{extracts 5} ° ^and especially those from tar sands

g) this heavy hydrocarbon stream in residues, topped crudes, yakuumriickstande a third separation zone at a verringer- "· ^ά & Verbmten also contain nitrogen-containing pressure ranging from unteratmosphä- f ^un 8 ^{s u. nd} . Organmetallic complexes high molecular pressure up to 3.4 atmospheres in a distilled S ¹ ^ T * ¹ ??; I · ^{meta hs} _u ^che "^ P ^ ^ent Jalten bare comprising hydrocarbons third ⁵⁵ of nickel and vanadium as main objective metallic liquid phase and a residue concentrate components. Such a material has in general _separating ° mean a specific gravity greater than about

0.9340 to 15.6 ° C and a Conradson

2. The method according to claim 1, characterized by coking residue of more than 1.0 percent by weight; indicates that the second liquid phase ^6o a large part of the black oils has a Conradsonin the fractionation zone at a point above coking residue above 10%.

the place where the outflow from the not kata- As examples of such Schvvarzöle are the

lytic reaction zone is introduced, introduces. Bottom products from crude oil distillation columns

3. The method according to claim 1 or 2, characterized in that, for. B. a bottoms product with a specific characterized in that one part of the first ⁶ 5 weight of about 0.9705 at 15.6 ° C and a liquid phase in such an amount in the content of impurities of about 3.0 weight of feedstock traces back that in the percent sulfur, 3830 parts per million total nitrogen adjusted liquid feed to the catalytic converter, 85 parts per million total metals and about

3 4

11.0 percent by weight asphaltenes. Another can. Such hydraulic cracking works, the same typical feedstock is that from a vacuum - if catalytic; In the case of this execution column, the bottom product obtained from a central eastern form of the known is then a two-stage crude oil. Such a vacuum bottoms product has catalytic conversion processes in both e.g. B. a specific gravity of 1.0291 at 15.6 ° C, 5 levels. However, such an approach is not sought in the method of the invention having an average molecular weight of about 620. ASTM 20.0 Volurnprozeat distillation temperature In the same literature reference is also found from about 557 ⁰ C and a content of about Note that the hydrocracking reactions with 4000 parts per million of nitrogen, 5.5 percent by weight of a relatively low risk of catalyst sulfur , 100 parts per million vanadium and nickel io coking more slowly and even at 288 ° C through and 6.0 percent by weight of heptane-insoluble can be passed. However, these are asphaltenes. only about the results of the laboratory. These scientific investigations in abundance on the market about the lower low-value input materials offered or their temperature ranges of the start of the reaction of the interhigh molecular components can largely only be as 15 eating reactions; an indication of the ver-road asphalt or - in the case of dilution with a higher method of operation with a distillate hydrocarbons that work with high conversions - as very the industrial process, low-quality heating oil is to be used from this note. There is no winning. Accordingly, a pronounced technical interest in the same literature reference is pointed out in the, that higher temperatures of similar black oils into desulphurized lower-boiling ones are used in the case of usable and economical conversion of the ao technical processes.

Hydrocarbon products. Also the references in the literature reference that with The main difficulty with the previous absence of metal impurities in loading methods is the lack of sufficient catalyst life of 100 days the sulfur stability of the catalysts, if this can be achieved by 5 or more, and that bifunk feed large quantities of asphaltic sub-tional catalysts by pretreating the trees contains. Since the process with such a high charge with hydrogen or by execution drive must be carried out that at the same time - the hydrocracking in two stages with different times with the conversion of sulfur-containing borrowed catalysts in the two hydrocracking stages Compounds in hydrogen sulfide and carbon can be protected from contamination, Hydrogen a conversion of non-distilling give no indication of the mode of operation according to the cash shares, the asphaltic mate tends to regulate the invention.

rial dispersed in the feedstock is used for thermal cracking processes for conversion Accumulation and polymerization, so that its conversion from hydrocarbons to lower-boiling product in more valuable oil-soluble products have long been part of the state of the art is practically excluded. Furthermore divorce (Gruse and Stevens, Chemical Technology of The Sulfur-Containing Polymerized Asphaltic Petroleum, 3rd Edition, New York, Toronto, London, Complexes on the catalyst, resulting in a I960, p. 344). In the case of the procedure of the contractor Increase in the rate of deactivation of the prescribed working method, however, contains talysators leads. These difficulties are exacerbated further from the catalylic reaction stage to the re-enactment and more involved in such feedstock action zone of further cracking implementation materials that contain large amounts of metals. Since flowing material inevitably requires considerable amounts such feed materials have such high metal contents as hydrogen. From this reference is not to Containing 700 parts per million, the catalyst will take like one out of a rate of catalytic reaction deactivation to such an extent there would be considerable amounts of hydrogen flowing through it accelerates that processing with production containing material in connection with particular Lower-boiling hydrocarbon products are economical - separation and recycling measures in a wide range The reaction stage is no longer acceptable and has not been catalytically converted - hydrocracking process and the can occur in the process, so that the particular results with the reactions are quite generally known (Kirk-50 method according to the invention aimed at. Encyclopedia of Chemical Technology, benefits and benefits can be obtained. 2nd edition, Vol. 15, 1968, pp. 35 to 37). It is therefore the object of the invention to provide an underlying However, the process is not all-too-far to create in a simple and economically common way therefore, a hydrocracking process in a back-Hcher way an extensive conversion, z. B. Stand materials for their desulphurisation to 55 of 80 percent by volume and above, such turn, but it should be the effluent of the catalytic black oils in largely desulphurized distillable Reaction zone further permitted in the presence of considerable hydrocarbons, from the known ones Amounts of hydrogen, as this inevitably results from interference with conventional processes by asphalts catalytic reaction zone with in the next tene is free and a conversion of the asphaltenes Reaction zone arrives, and in connection with loading 60 in high quality products with a long service life correct separation and recirculation measures around the catalyst in the catalytic conversion will. How this is done in detail brings with it.

has, cannot be inferred from the literature reference. This problem is solved by a method There is only the indication that a catalyst of the type mentioned at the beginning, according to the invention table desulphurized "synthetic oil" is then characterized by the fact that one further hydrocracking according to one of the procedures as used for feed obtained by distillation - a) the feedstock to a temperature in the beech are subjected to being heated from 260 to 399 ° C,

5 6

b) the heated feedstock in the catalytic passage of the feedstock and the hydrogen through Reaction zone at a pressure greater than the catalyst bed. In many cases a ge-68 atü reacts with hydrogen, know temperature control by applying a

c) the resulting reaction zone effluent is brought about in a cooling stream. A technically first separation zone at about the same pressure 5 and economically usable catalyst life as that of the catalytic reaction zone in the long run is achieved when the maximum catalyst a first vapor phase and a first liquid temperature, which practically separates the phase, corresponds to the product outflow, below 427 ° ^C C.

d) the first vapor phase is kept in a second separation. According to another preferred zone at about the same pressure as in the io feature, the reaction zone effluent enters the first first separation zone, but at a reduced temperature separation zone at a temperature in the region of 371 temperature in a hydrogen-rich second steam to 427 ° C to ensure that the proportion phase and a second liquid phase separates, the resulting first liquid phase, the subsequent

e) at least part of the first liquid phase is subjected to thermal cracking following, about 10.0 to about 40.0 mole percent dissolved water ion zone in a non-catalytic thermal reaction cracks, contains substance.

f) the outflow of the non-catalytic reaction- Preferably the reaction zone is under a zone introduces into a fractionation zone and held there pressure of 68 to 272 atmospheres. The coal one Heavy hydrocarbon stream, the hydrogen feedstock can pass through the catalytic converter boils completely or largely above 343 ° C, 20 with an hourly space velocity separates and the liquid from 0.5 to 10.0, based on the

g) this heavy hydrocarbon stream is passed into a fresh hydrocarbon feed excluding a third separation zone at a reduced pressure of any recycled diluent in the subatmospheric pressure range. The hydrogen concentration of 3.4 atmospheres in a distillable hydrocarbon ion should be in the range of 890 to 8900 standard m ³ str-ffc comprising third liquid phase and one per 1000 liters. The combined feed residue concentrate separates. ratio, defined as total volumes of liquid

Charge per volume of hydrocarbon fresh

This creates a process that, in charge, should be in the range of about 1.1: 1 to easily and economically a very wide range of about 3.5: 1.

going conversion, for example of 80 volum- der in the catalytic fixed bed reaction or

percent and more, of such black oils in the far-conversion zone, the catalyst contains extensively desulphurized, distillable hydrocarbons, a metal component with hydrogenation activity is permitted in substances, and this with a long service life bond with a suitable high-melting point of the catalyst in the catalytic conversion 35 carrier material based on inorganic Oxides of grade. Due to the special connection of the background, either synthetic or natural origin, the interconnection of catalytic conversion and the exact composition and the individual thermal cracking with specific separation and applied processes for the production of the carrier recycling measures in compliance with special materials do not represent features of the invention Pressure and temperature conditions are thereby 4 ° it should be noted, however, that a silicon composite process is created B. from 88.0 percent by weight of neter desulfurization and production of lower-boiling aluminum oxide and 12.0 percent by weight of silicon fractions a conversion of the asphaltenes into dioxide, or 63.0 percent by weight of aluminum oxide high-quality products with low hydrogen consumption and 37.0 percent by weight of silicon dioxide or 68.0 consumption and in which, among other things, 45 percent by weight of aluminum oxide, 10.0 percent by weight, the separations almost exclusively by means of an extremely high level of silicon dioxide and 22.0 percent by weight of boron, simple phase separations of gaseous and fluorophosphate are generally preferred,
siger phase in technically and economically suitable metal components with hydrogenation activity

very simple separators can be carried out. are those based on metals of the groups

Preferably, the second liquid phase 50 VIb and VIII of the periodic table (periodic table) is also introduced into the fractionation zone at one of the elements according to EH Sargent & Company, position above the position at which the effluent from the 1964 was introduced. Such catalysts can be introduced into a cracking zone. several metal components from the group molyb-

The total feed to the first preferably contains Danish, tungsten, chromium, iron, cobalt, nickel, platinum, fixed bed catalytic reaction iridium, osmium, rhodium, ruthenium and gezone, mainly made from fresh feedstocks thereof. The concentration of the rial, a recirculated part of the first liquid catalytically active metal component or -kompo phase, a recirculated hydrogen-rich components depends primarily on the vapor phase and supplementary hydrogen in the individual case, the selected metal and the present in the individual case, supplement the in the overall process, consumed 60 physical and / or chemical properties of hydrogen and to maintain the pressure of the feed. For example, which is required, is preferably heated to a Group VIb metal component in general temperature in the range from 343 to 399 ° C in an amount in the range from about 1.0 to about The temperature is in the aforementioned range 20.0 percent by weight and the ferrous group metals are controlled by monitoring the temperature of the product effluent 65 in an amount ranging from 0.2 to 10.0 weight of the reaction zone. Since the main percent is present, while the noble metals of the neuter conversion reactions are strongly exothermic group VIII, preferably in an amount in the range, there is a temperature increase at the rate of 0.1 to 5.0 percent by weight, whereby

ι. a- "Knmno stands for use as a return stream for the

all values are calculated as if this compo ψ ^ Unite _{with the} fresh black oil feed Mate ducks in the catalyst in the elemental state ^ '^ _{Bmane UMJ} would re _heavy carbon existence. . Hydrogens in the cold separator-condensing-For clarification are eimge below: largely liquid in the wa ^^ phase from available documents _ Bgnffe used the _separator removed.

ned. The expressions »largely * ™ Ρ * ° ™ 6« Mind ^^ ^ ^ _{HeLßabscheid} e _r will

"Largely liquid" characterize every gstan ^ emes ^ _{association with the} multiple carbon

in individual cases, the present current ^ ff at ^{RTEM ae} _{wassersto e} INSAT _Z material recycled, so that they

Main antxil of the components present be. no diluent for the then located

times or standard conditions »o ™ gf ™ Jl h ingredients serves The amount of in

Main antxil of the diluents present for which then befil mal- or standard conditions »o ™ gf ™ J pressure is used for heavier constituents. The amount that is in shape or normally in liquid form. The expression "branched off liquid phase is so" about the same pressure as "or a similar ^ ^ _{ratio in the} combined Be-formulation indicates that the pressure from a B _{to the catalytic} reaction zone, defining the subsequent vessel, is kept the same as ^ Total volumes of liquid feed, the pressure in the preceding vessel. -5. " _{u liquid feed} preferential rinaert only to the pressure drop, which as a result of the j ^ ^ ^ ^ ₁ ^ ^ . _{χ The} media flow through the system" fiitt V ^ n at _{de Td} , _{the largely} liquid phase from for example the first ^ tab ' The reaction zone in the hot separator is placed in a reaction zone or at a pressure of about 197 atmospheres. The thermal cracking coil is introduced to the first separation zone, ie a hot separator. to e . _{ Pressure in the range of 13.6 to a pressure of about 193 atmospheres; Ansdrjg- £ - «new, ™ .. £ _{Tem of} 371b; _{s 399} o c. the dike temperature w, e «or« ™ «higher for ^ _thermal ^ _{product flow is indicated in the} formulation. that there is only one Tenipratorv «Tmge_ _{Fraktionierzon} e or distillation column arrangement, which on the normal Tempe ^ urrucK ^. ^^ _{Temperat and Pressure} . ₂ ane as a result of the flow of material from an accumulation g ^ ^ _6n ^^ _that i _eic hte_ no, male Γη. Another or ^on ^ 'VTS exhaustion gaseous hydrocarbons and in gasoline sensible heat into latent heat through expansion fc β hydrocarbons, which have a nominal or "flat evaporation", if ^ c ^ m pressure ^ _boiling point of 204-C, as over-: .bfaH occurs, is based. Under Jm "desJHierDaren _{koDffraktion,} middle distillate hydrocarbons in the proportion of those Einsat7.mater.als ^ ^oh \ ^ENW ^ _{r" Si} e _deb rea 204-343 ° C to be understood as Seitenschmtstoffe that ■ at a temperature below. ^ ^^^ _{^ 30c boiling antcile to be distilled as} half 566 ^ C lconn n. Since aas ω _{soil fraction} are deducted, set material asphaltic ^Ko ^ P ^on . ^{e "th} ^^^^^ As _{is erläutcrt detail} below in connection of the Drawing These mt temperature, from a practical Ge m dhtspuma _och, the second we.t-, ine limitation is to represent Vjtanderaig ^« _{flüssi phase from the} Kaltabsche.der With regard to the """" ^ residue, the product is also appropriately placed in the distillation column. from which the asphalt rucki tanu -nt _mh ^ _{md has} been removed at a point between the trigger. analyzes have, however, _so one middle distillates and the like Emfuhrungsstelle Siedeendpunkte 503-621 C give ^ thermally cracked product effluent. The measures ^ s will be experienced ^ h * ^ _{30 c} ^^ _Mat ^ _{vird nl} ,, -, Hihung exemplary information & en ifugt de be, one

The measures ^ s will be _{learned ^ ^ 30 c} ^^ _Mat ^ _{vird nl} ,,,

agile using exemplary. Anga & en _{vacuum flash column} introduced, de be, a Dr jo .;

., nd values further illustrated. _{20 feis 6OmmH} g is absolutely held

The entire product outflow from the kattuy _vacuum flash zone serves as a third separation zone

• ical reaction zone is, be. e.ner maximum _task in enrichment and extraction

Temperature of 427 ° C and preferably = «n« vMa ^ S asphaltic residue, which is essentially

A mali temperature of 413 ° Cm «P ^^ Jj ™ ² ^ free of distillable hydrocarbons _tt t, lies

oeleitet to as "Hei ^ß ^ ^s * ^e 'S _d ^ _In general, from the Vakuumgasolstrome be below

zee net will. The main task of the Matactad « _Vakui f _{mflashkolonne} - _{m form} a separate

consists in using the mixed-phase product consisting of vacuum gas oil and a heavy vacuum

eS giving way to vaporous ^ ** ™ ± £ ⁵ Ss decreased, in some cases, however, can

Is hydrogen, and a largely liquid phase _{D a} vacuum gas oil is withdrawn,

the 10.0 to 40.0 mol percent dissolved Wasa ^ tott ^ _{Γ (3 according to dner} ^ _{ν0ΓζαΕΐεη} execution

contains to separate. Preferably, the entire reprocessing is carried out in a suitable wax-reaaUproduto ^^^ ₅₅ Sj ^ stream, hereinafter referred to as "Slop-wax stream

used to denote its temperature m «» »J ^ ™ ¹ ™ ^, which is in a temperature range of

371 to 427 ° C and preferably below ^ 399 CD _Q ^^ ^ _fe ν ^^, ω ^

lower. The largely vaporous ^ e ™ £££ withdrawn, with at least part of it back-

the hot separator is m «ne ^ eite separation zone s β ^ _{the Μδο1ιβη} KoWenwasserstoffem-

ping, which in the following is united as the old section of the "f _{atzmateria1".} Preferably she does

is drawn. The ^^ "SäSS, ^ but returned amount 1 to 20 · /. Of the total amount

the same pressure as the «« ^^^ S of the peeled off slop wax. At one of the

with much lower T ^ JJ ^ Jg. like return, the amount of stop

wise in the range of 16 to 60 C. The ^ «aosen z ^ ^ ^^ ^ _{fa de lgten} ρ ^.

which serves to enrich the water flow in _the ⁶ _catalytic reaction zone the

second largely vapor width JM ^ g _{00 ratio of} the components including the ζυ-

hydrogen-rich, vaporous ^ fi ° 'w ^ _roze n _t recirculated portion of the first liquid phase

Mole percent hydrogen and "» ^ ^a ^ f ₀ Jf, 5 _mfa ß, the hot separator in the one given above

Propane and heavier Konienw 209 683/371

Range from 1.1: 1 to 3.5: 1 remains. According to a multiple flow diagram, in which details,

other embodiment may be part of the slop- die for explanation and understanding of the

Wax and / or the heavy vacuum gas oil to work measures are dispensable, omitted

recycled and with the first liquid phase that were.

introduced into the thermal cracking reaction zone 5 In processing, the feedstock should be so will be united. In this way, as far as possible, returned to distillable coals Amount is chosen so that the combined hydrogens are converted by the usual feed ratio of the thermal distillation and commonly used frac cracking reaction zone flowing material above tioniereinrichtungen can be obtained. The 1.2: 1 and generally no more than 4.0: 1 io feed is placed in a fixed catalytic bed. Conversion zone mixed with about 1780 stan-

One of the main advantages of the process according to the dard-m ^{: 1} hydrogen per 1000 liters of fresh charge

Invention consists in an extension of the consumption-processed. The charging occurs at a catalytic converter

Capable catalyst life at a catalytic satorbett inlet temperature of about 363 ° C and

Fixed bed reaction zone. This is mainly due to an inlet pressure of about 180 atmospheres. The hour

on the fact that a desulphurization on values lent space flow velocity of the liquid,

less than about 1.0 weight percent based on fresh batch only is 0.5

catalytic reaction zone at a ratio and the combined feed ratio

moderately low operating severity is achieved, with on the entire liquid charge, is about

the result that a formation of sulfur corresponds to 2.0: 1. In the illustrated embodiment

holding polymeric products, as they are otherwise soiien as product streams with a gasoline fraction

from the presence of insoluble hydrocarbons an end point of 204 ° C, a kerosene cut of

borrowed asphaltenes results, to a minimum of 204 to 260 ° C, a middle distillate fraction in the boiling

is returned. The low operating sharpness in the range of 260 to 343 ^ C, and a gas oil flow,

catalytic fixed bed reaction zone continues to have an initial boiling point of about 343 ° C.

to a dissolution of hydrogen in the one at Norwee and all other distillable hydrocarbons

Malbedingungen liquid contains a heavier proportion of the pro-substance of the product outflow

duct discharge, at least a part of which is called loading.

Feed to the thermal cracking reaction zone The feed is in an amount of about

is used. Furthermore, the vacuum flash 30 572 000 liters / day through a line I in the

kolonne be kept much smaller, since the drive was introduced. The input material is about

Fraction in the zone for separating the product outflow 2.0 percent by volume of a slop wax recirculation fraction

the thermal reaction zone and for concentration from a line 2, 572,000 liters / day from one

tration of the material boiling above about 343 ° C coming into a hot separator liquid stream

rials is used. This means an additional 35 from a line 3, and one returned

Advantage in terms of process technology and gas flow rich in host hydrogen from a line 4

economic efficiency of the overall procedure. The introduction (about 1780 standard m ^{3 of} hydrogen per 1000 liters)

the second largely liquid phase from the cold mixed. The mixture flows through line 1

separator in the distillation column at one point in a heater 6. The total charge is

between the take-off point of the middle distillates and 40 kung for the heater 6 initially through conventional

the point of introduction of the thermally cracked pro- lent heat exchange with different hot

The duct outflow also ensures that the outflow from the soot flows to a temperature of around

Floor withdrawn stream heated the lowest possible amount 335 ° C; for simplicity this is in the

contains material boiling below 343 ° C. Drawing not shown. In the heater 6 is

Since the coals boiling below about 343 ° C, the temperature of the feed mixture is increased to 363 ° C

Hydrogen proportions increased separately in the distillation zone, then the heated mixture flows through

are obtained, a much smaller line 7 in a catalytic fixed bed reactor is sufficient.

Vacuum flash column. gate 8.

To further illustrate the explained, the product outflow leaves the reactor in mixing features is hereinafter in connection with the 50 phase through a line 9 at a temperature of Drawing as an example the conversion and de- 419 ° C. The outflow is called tub exchange sulphurisation of the bottom product a vacuum medium is used to bring its temperature to 399 ° C column to lower the full boiling range from a crude oil before entering a hot separator 10 at originated, described. The vacuum bottoms product enters a pressure of about 177 atmospheres. From the has a specific gravity of 0.9881 to 15.6 ° C, 55 hot separator is a largely vaporous one an average molecular weight of about 600, a phase withdrawn through a line 11 and, after ASTM initial boiling point of about 460 ° C, with cooling by conventional means, in a KaItetwa 44.0 percent by volume at a temperature of separator 12 at about 38 ° C and 173 atm. 566 ° C can be distilled, it contains 4600 parts each. A largely liquid phase is drawn off from the AbMillion nitrogen, 1.92 percent by weight sulfur, 60 separator 10 through a line 15 and 105 parts per million vanadium and nickel, it has a part of it (572000 liters / day) is made by the a Conradson coking residue of 12.8 Ge line 3 branched off, for unification mh the weight percent, and it contains about 3.45 weight fresh feed from line 1 and the hopper percent Asphaltenes insoluble in heptane. Wax return flow (1040 liters / day) from the line

The description is based on an approximation2. The remainder continues to flow through line 15

technical system with a throughput of in a thermal reaction coil 16, with a

about 636 m ^s / day (636,000 liters / day). In the drawing pressure of about 19.5 atü and a temperature of

The procedure is based on a combined approx. 399 ° C. A hydrogen-rich gas phase is established

taken from the cold separator 12 through a line 4 using a compression device, not shown. After addition of make-up hydrogen from a line 5, the gaseous mixture flows on through line 4 to combine with the liquid feed mixture through line 1. A liquid phase is removed from cold separator 12 through line 13 and introduced into a distillation column 14 .

In Tables I and II below there are component analyzes of the currents which occur during the separations in the. Hot separator 10 and result in cold separator 12, listed. In the specified analyzes, in mol percent, various return flow and / or cooling flows are not included. The analyzes for the largely vapor phase of line 11 and the liquid phase of line 15 are compiled in the following table I:

Table I.

Analyzes of the currents from the Hot separator ing
Il Lei ti
15th Ingredient, mole percent
nitrogen 44.5 * 84.4 hydrogen 9.3 Hydrogen sulfide 0.7
11.7
33.8 ** 13.7 Q Q 0.5
1.36
0.04 ρ " ρ ' ^ 4 .i
r -399 ° C ο
399 "C and above

* 38.0 mole percent is hydrogen.
** About 17.1 Vo residue.

Approximate analyzes for the liquid phase of line 13 and the vapor phase of line 4 are summarized in Table II:

Table II
Analyzes of the flows from the cold separator

Ingredient, mole percent

nitrogen

hydrogen

Hydrogen sulfide ..

C ₁ -C ₃

₄₃

C "- 399 ° C

399 ° C and above

management
4 I 13

86.0

13.6
0.3
0.1

47.6 is to meet the specified conditions in the distillation column for forming the desired product cuts. In the embodiment shown, which is useful for many applications, the fractionation column 14 is operated to form an overhead fraction, which consists of a small amount of normally gaseous components and the hydrocarbons in the gasoline boiling range that are liquid under normal conditions (below-

half boiling at about 204 ° C); this leaves the column through a line 18. A kerosene fraction which boils in the range from 204 to 260 ° C. and a middle distillate fraction which boils from 260 to 343 ° C. are passed through in the embodiment shown

Lines 19 and 20 withdrawn. It should be noted that the discharge point of the Middle Desüllatfraktion is above half the point of introduction of the liquid from the cold separator. Since in the example explained the highest boiling point of the desired product

ao dukisiröme from the fractionating column is 343 ° C, the fractionating column is maintained at conditions at which the concentration of the material boiling above 343 ° C and flowing off through line 21 becomes as great as possible. The thermal

The cracked product effluent from line 17 is therefore cooled to a temperature of about 427 ° C.

The heavier fractions are introduced into a vacuum flash zone 22 at a temperature of about 427 ° C., which operates at about 30 mm Hg absolute.

The vacuum flash column serves to concentrate a residue fraction which flows off through a line 25; this can be done with the heavy gas oil fraction (454 to about 527 ° C) of line 24 and at least part of the slop wax fraction (527 to 621 ° C),

which is not returned through line 2, are mixed. This mixture of slop wax residue and heavy vacuum gas oil works well as heating oil as its sulfur content is clear within the usual specification of 1.0 percent by weight

located. A light vacuum gas oil is withdrawn from the vacuum flash zone 22 through a line 23. The relatively small amount of hydrocarbons that boil below 343 ° C. is drawn off from the vacuum flash column by conventional ejectors or the like, not shown in the drawing.

The total product yields and the product distribution are compiled in Table III below:

16.2
4.7

31.0
0.5

55

The largely liquid phase from the cold separator 12 is introduced through the line 13 into the fractionation column 14 at a point which is above the point where the thermally cracked product effluent is fed through the line 17 into the column . The thermally cracked outflow has a pressure of about 3.9 atm and a temperature of 499 ° C. These are - the same applies to the temperature and the pressure of the liquid coming out of the line 13 from the cold separator - changed as much as that required table ΙΠ Yields and product distribution

Component yield Ammonia, weight percent 0.15 Hydrogen sulfide, weight percent 0.70 C ₁ -C ₃ , weight percent 3.63 Butane, volume percent 2.31 Pentanes, volume percent 1.47 Hexanes, volume percent 2.29 C _7-204 ° C, 11.19 percent by volume

204-260 ° C, volume percent 11.44

260-343 ° C, volume percent 21.18

343 ° C and above, volume percentage 37.02 Backlog 18.61 -

Furthermore, it should be pointed out that the C ₇ - 204 ° C fraction has a specific gravity of 0.7941 at 15.6 ° C and a sulfur

content of less than 0.1 percent by weight. The 204 to 260 ° C fraction has a sulfur content of 0.20 percent by weight and a specific gravity of 0.8524 at 15.6 ° C. The 260 to 343 ° C fraction has a specific gravity of about 0.8783 at 15.6 ° C and contains about 0.2% sulfur. The proportion of 343 ° C and above has a sulfur content of 0.25 percent by weight and a specific gravity of 0.9402 at 15.6 ° C.

With the added amount of fresh feed of 572,000 liters / day, there is 86.9 percent by volume of the total of C ₄ and higher-boiling coal

Hydrogen formed product from distillable components, that is 497068 liters / day. If the A residue of 18.61 percent by volume is mixed with the heavy vacuum gas oil to form a heating oil,

the total yield of usable products that are liquid under normal conditions is approximately 604500 liters / day. It is essential that that this in the illustrated embodiment with a hydrogen consumption of

ίο only about 156 standard m ^s per 1000 liters of fresh feed, which is about 1.31 percent by weight, is reached.

1 sheet of drawings

Claims (6)

ι 2 lyric reaction zone a ratio of Claims: 1.1: 1 to 3.5: 1 results. 4. The method according to any one of claims 1 to 3, 1. Process for conversion and desulfurization, characterized in that a sulfur-containing hydrocarbon 5 hydrogen fraction with an end boiling point of feedstock is used, of which at least 10 ° / o above about 343 ° C from the fractionation zone boils at 566 ° C and that subtracts a ratio point above the point at which the second moderately low metal content, in particular the liquid phase, is introduced,
less than 150 parts per million total metals, 5. The method according to any one of claims ι bi54, calculated in the elementary state, but one characterized by the fact that one at least high sulfur content, especially at or part of the third liquid phase in the Einüber 2 percent by weight, and a high content of recycled feedstock of several heptane-insoluble asphaltenes 6. The method according to any one of claims 1 to 5, percent by weight, with the formation of deep boiling, characterized in that part of the distillable hydrocarbon products 15 third liquid phase in an amount in the first reduced sulfur content in which the carbon liquid phase is returned that the hydrogen feed after heating in a unified feed to the non-catalytic catalytic reaction zone at an elevated pressure reaction zone has a ratio of above 1.2: 1 in the presence of hydrogen for removal,
of sulfur compounds and production of deep ao
Reacted boiling hydrocarbons, the resulting reaction mixture separated and thereby ■ liquid fractions obtained from a further cracking reaction with subsequent work-up the reaction products are subjected, »5 The invention relates to a process for converting characterized in that one ment and desulfurization of a sulfur-containing