DE2215665C3 - Process for producing gasoline and refined liquid hydrocarbons - Google Patents

Description

A large number of different hydrocarbon tol products to be produced optionally and thus depending on the circumstances.

The process of the invention is now characterized by the DAT oil hydrogenation employing 240-1440 m ³ of hydrogen per m ^a oil at a temperature of 350 to 450 C and a pressure of 17.5 to 3b0 kg / cm ² in the presence of a Subjected to hydrogenation catalyst prior to fractionation, the gas oil fraction of the hydrogenated oil resulting from the subsequent fractionation is catalytically cleaved, and at least a portion of the liquid products coming from the catalytic cleavage device is returned to the process while mixing with the starting oil before the hydrogenation is carried out.

Since it is thus possible according to the invention, the lamellar Crude oil, or a crude oil from which only the relatively volatile components have been removed. subject to hydrogenation before any other refining is carried out and this There is a substantial reduction in obtaining a variety of products, all of which are hydrogenated with regard to the complexity of the device compared to the state of the art, as there are no separate ones Hydrogenation plants are necessary. According to the invention, there is also a reduction in Amounts of coke, where applicable, and corresponding increases in the amounts of more valuable liquid products; low sulfur content in the liquid products and in each of the residual fractions Coke; reduced corrosion due to the sulfur removal prior to contact with the Crude oil tower, catalytic cracking device. Coking device and the subsequent processing units; high throughput in the entire device for hydrogen treatment or hydrogenation device; the light fractions are in a unit of hydrotreatment or hydrogenation which is no greater than that for conventional hydrotreatment or hydrogenation only the heavier fractions are required: and optionally lower olefin contents in heavy gasoline products, especially gasoline, in those embodiments where catalytic or coke heavy gasoline is returned to the proceedings.

According to the invention, gasolines are produced, and it optionally reformed gasoline with improved octane number and / or coke can be obtained. These Products find useful application as fuels for engines, such fuels with improved properties or carbon for making electrodes.

An embodiment of the invention is shown in the drawing and will be described in more detail below described. It shows

F i g. 1 is a schematic drawing of the invention in application of the refining system for hydrogen treatment b / w. Hydrogenation of crude oil and the catalytic cracking;

F i g. 2 a refining plant that also performs reforming Performed with the formation of gasoline with a higher octane number (reformate) and formation of Hydrogen, which is optionally used in the device for the hydrogen treatment or hydrogenation device supplied we: 0> n can;

F i g. 3 a refining plant in which a hydrogen treatment or hydrogenation and catalv table cleavage - as in FIG. 1 shown - performed is, however, in addition, a residual fraction coked to form coking liquids, which is optional may be recycled back into the process with mixing with the feed to the hydrotreating equipment or hydrogenation device.

Starting products

ίο Hydrocarbons: All crude oil will be the Subjected to hydrogen treatment or hydrogenation. Prior art methods have Water treatment or hydrogenation of residual products considered, d. H. Shares with a boiling point of z. B. 350 ° C and above, without that it was possible to achieve the advantages achieved here according to the invention. Particularly according to the invention Appropriate crude oils include those that have consistently high levels of sulfur. but lower salary

2c, on asphaltenic Pioduk'-n and heavy metals like a sulfur-containing crude from West Texas.

Instead of all of the crude oil you can also use light

distilled crude oils are applied, t. B. those.

in which the portion boiling below about 200 C is fractionated out has been.

The preferred gas oil fraction to be fed to the catalytic cleavage unit according to the invention is preferably that proportion of the mixed distillation products, both atmospheric and vacuum distillation, which after removal of the gasoline and the slight de> iiil.ii <· and is preferably within a range of 2t ' ^fA his () 20 C, preferably from 290 to 5 ¹ M) C and in particular from. ^{Boil 1} ^ " ¹ to 560 C.

Bottom fraction: The preferred bottom fraction for the coking according to the invention is that fraction which generally boils above about 480 ° C., preferably above about 540 ° C. and in particular above about 560 ° C. Liquid products of the catalytic cleavage unit:

A catalytic splitting unit leads to a liquid one Product that is conventionally fractionated into a variety of products, including catalan Gasoline, catalytic cracked milk distillates. catalytic cracked gas oil and an entrained catalytic converter containing slurry, all or part of the catalysts being separated and fed back to the catalytic cleavage cell.

Catalytic cracked gas oil: In many conventional operations, gasoline is obtained as the end product. vAobci the middle distillate and, or the catalytic Moving! returned to the catalytic cleavage unit will. According to the catalytischc Fission gas oil and optionally the middle distillate and / or gasoline for mixing with the crude oil feed applied to the hydrogen treatment device or the hydrogenation device. That catalytic cracked gas oil is generally in a range from 230 to 510 ° C, preferably from 260 to 500 (.

and in particular boil from 320 to 480 ° C.

liquid products from the coker: The selected for recycle into the process liquid products from the coker werderfreak generally from the total liquid product mi C _r, - consist or ( "hydrocarbons to the formed highest-Püssigcn products Da ¹ low molecular weight product, in particular. the C ₃ -. C, and possibly (",, - shares become 'more advantageous

5 ^J 6

separated for olefin recovery. All other llydrierdruck: Even if the pressure during de

The proportions of the liquid product of the coking and hydration reaction are not critical in the narrower sense.

If necessary, the device can also be used for one, but it should be 17.5 to 350 kg / cm ^!

separate use. It is preferred to 42 to 175 kg / cm ² and especially au

1 to 100 percent by volume, preferably 50 to 100 volumes, s 56 to 140 kg / cm ² .

percent and in particular 75 to 100 percent by volume of the hourly space velocity of the liquid

of liquid products (with C ₃ - and higher carbons - during hydrogenation: this speed win

Hydrogen) from the coking device generally granulates to about 0.5 to about 6, preferably aul

mend, mixed with the total crude oil, which is in the 0.5 to 4 and especially to 1 to 3 volumes of liquid

Hydrogenation process occurs. As far as coking io wedge per volume of the hydrogenation catalyst prc

If liquids remain, they can run for hours.

Convenient purposes, e.g. B. for gasoline and heavy catalytic splitting: The catalytic splitter

Fuels. is carried out under conventional conditions

Hydrogen: The water used according to the invention z. B. the ones as they det on pages 174 to 179 Hydrogen can be commercially available, September 15, 1970 issue of Hydrocarbon like that obtained through the reforming of heavy gasoline processing and in the literature referenced there will, e.g. B. are described by means of the reforming points. The catalytic cracking processes, as they are on pages 184 to 193 of the September catalysts, are generally mixtures of silica 1970 edition of the publication »Hydro- and alumina or magnesium oxide and contain pre-carbon Processing «, or of the 20 preferably crystalline compounds of silica and water This substance can be produced specifically for this purpose by using alumina, commonly known as "zeolites" or "molc," that water vapor is reformed or a kular sieve «are known.

Partial oxidation of hydrocarbons takes place - see Suitable catalytic cracking catalysts are

the same publication on pages 269/270. Written in Hydrocarbon Processing, Vol. 47, No. 2,

There are 240 to 1440 m ³ , preferably 480 to ^ 3 pages 125 to 132 (February 1968).

1190 m ³ and in particular 600 to 950 m ³ hydrogen coking: The coking is carried out under conventional

in application, each performed with an amount of per conditions, e.g. B. like them on the

m ³ oil feed for the hydrogenation device in p. 180/181 of the Sepxcmbcra edition 1970 of Hydro-

be moved. carbon processing and the lit-

Catalyst for hydrogen treatment or the 30 temperature points are described.

Hydrogenation: There can be a wide variety of different- Device: A conventional device can be used.

Licher hydrogenation catalysts are used for hydrogenation, distillation, catalytic

and this particularly includes those who applied Me-splitting, reforming and coking

metals from the group of nickel, molybdenum, and cobalt. If this also applies to the subject matter of the invention

Tungsten, or a compound containing such metals, is not required, can be used when using crude oil

fertilize, contain. with a high content of metals and / or particulate

Carrier for the hydrogen treatment or the shaped products in a conventional protective housing,

Catalysts used for hydrogenation: The preferred one filled with cheap catalyst, upstream

Catalyst supports are alumina, silica, magne- plus the main hydrogenation reactor,

siiimoxid or combinations thereof. In general, the more expensive main catalyst is used

think the wearer shouldn't be so pissed off that protect.

significant hydrogen splitting of the oil among the The invention is further preferred hereinafter Reaction conditions occurs. For example, on the basis of a number of exemplary embodiments Use explained in a working with a fixed bed: Examples 1 and 2 correspond to this Hydrogenation unit becomes a catalyst in the form of an object of the invention. Comparative Examples 1 and 2 Extrudates, pellets or spheres of this size illustrate the loss of the advantages of the invention applied that excessive pressure drop through in the event that crude oil and the in the process the catalyst bed is avoided, but the size of the recirculated stream cannot be hydrogenated. That is sufficient is small to a good transport the game 3 explains the use of heavy fuel as Oil in the middle of the 50 used feed for the reformer. Allow catalyst particles. General loading. Sizes from about 3.2 to 1.6 mm are preferred. At B e 1 s ρ 1 e 1 1 a moving or boiling bed, hydrotreating or hydrogenating the worker Hydrogenation reactor are extruded or velvet crude oil and catalytic cracking in the invented shaped particles with a dimension of 55 in accordance with the invention. 0.8 mm or less is advantageous. With reference to FIGS. 1, the overall

Hydrogenation temperature: Although the temperature of the crude oil 10 enters the desalination device 11 during the hydrogen treatment or the hydraulic type in which the inorganic halide removal reaction is not particularly critical, it should be removed. The desalted crude oil in the heat same but to values of 320-450 ⁰ C, preferably from 60 exchanger 12 heated, with additional hydrogen 14 and at 350-430 ⁰ C and in particular 360-415 ^r C in the process the recycled hydrogen 33 in amount. The applied temperature brought into contact. There is then still another one of the relative hydrodesulphurisation and heating in the furnace 13. The stream of hot hydrocracking activities of the special in application crude oil and hydrogen will depend on a catalyst bed and is nor- 65 from nickel-molybdenum catalyst in The hydrogenation times increase during a throughput device 15 at 370 ^c C, a pressure of 105 kg / cm ^{2 to} compensate for a deactivation of the catalyst and a space velocity of 1.64 h " ¹ and catalyst ... a hydrogen-oil ratio of 80 (1 m ³ / m » op-

leads. The hydrotreated or hydrogenated stream is cooled in the heat exchanger 16 and fed to a separator 17 which separates the gaseous from the liquid products. The gaseous products, starting from the separation device 17, are washed with removal of sulfuric hydrogen and ammonia from the hydrogen stream 33 to be returned to the process to avoid recirculated electricity. The liquid products coming from the separating device 17 are fed to the main distillation columns 18, where they are fractionated into product _{streams, namely gas 19 - consisting essentially of C 1} - to C hydrocarbons, which are fed to a conventional system for gas concentration - from gasoline 20 -, the same consists essentially of C ₅ - to C ^ - fractions which boil up to about 200 "C, and is fed to a mixing plant and / or catalytic reforming -, a middle distillate 21 - which can be more than one fraction and consists essentially of kerosene, diesel fuel and jet fuel -, a gas oil 23 - which consists of both atmospheric and vacuum gas oil - which is fed to the catalytic cracking device 43, and of the bottom fraction 22 which is fed to a conventional coking device alternately .

The catalytic cleavage unit 43 is at a Temperature of 485 "C, a space velocity on a weight basis of 2.14 h 'and one Catalyst / oil ratio (weight) of 5.6 operated using a catalyst.

The product coming from the catalytic cracking device is fractionated in the fractionation column 27. The upper distillate 28 from the column 27 is partially condensed with separation in the separation device 40 into an upper distillate 30, consisting essentially of C ₄ and lighter hydrocarbons, which are fed to the gas concentration, and a lower distillate stream 46, which essentially consists of hydrocarbons and above with a boiling range up to 200 ° C, and this product is mixed with gasoline or can optionally be mixed with the crude oil stream coming from the desalination device 11 for the purpose of returning to the hydrogenation unit 15. The fraction 44, starting from the fractionation column 27, consists essentially from hydrocarbons, the boiling range of which is about 200 to 320 ⁰ C and is used for mixing with diesel fuel, heating oil, kerosene and turbine fuel, or the product can optionally be mixed with the crude oil stream coming from the desalination device 11 for the purpose of returning to the hydrogenation device Fraction 45 coming from the fractionation tunnel 27 consists essentially of hydrocarbons with a boiling range of 320 to 450 ° C. and is returned to the process for the purpose of mixing with the product emerging from the desalination device. The residual fraction coming from the fractionation column 27 is cooled in the heat exchanger 49, and entrained catalyst is optionally separated off in the sludge removal device 47 for the purpose of returning to the catalytic cleavage unit 43 in the form of a trunk 29.

The crude oil 10 used according to Examples 1 to 4 is a sulfur-containing crude oil from West Texas and contains 1.67 weight percent sulfur. The sulfur contents of the various distillation fractions of the crude oil are shown below.

Table I.
crude oil

Ocstillalionsfraklion
C.

below 200.
200 to 320
320 to 560
560 plus ..

Volume percentage

18.96 22.13 38.00 20.91

Weight percent sulfur

0.16 0.63 1.65 2.62

The liquid products obtained after the hydrogen treatment or hydrogenation and fractionation have the composition shown below.

Table II
hydrotreated or hydrogenated products

Distillation fraction
C.

below 200.
200 to 320
320 to 560
560 plus ..

Volume percentage

18.66 24.38 41.64 15.32

Weight percent sulfur

0.01

.0.01

0.12

0.74

The process according to the invention thus leads to a substantial reduction in the sulfur content all liquid products including gas oil 23. which is subsequently used as feed product for the catalytic cleavage unit is applied. To the better. To show yields that are based on Reason of the splitting of the gas oil, which on the basis of the hydrotreated or hydrogenated Mixture of the gas oil from the catalytic cracking unit and the whole crude oil has been obtained is - compared to the gas oil obtained from the crude oil and the gas oil of the catalytic cracking unit, as in Comparative example 1 described - mixtures containing the same amounts (volume percent) of gas oil of the catalytic

Table IH

dry gas
(m ³ / m ³ ) ...

propane

Propylene

Isobutane

η-butane

Butylenes

C ₅ , 200 ⁰ C ...

200 to 320 ⁰ C

32O ° C plus ..

coke

(Weight percent) ..

I.
26.4 30.4 27.0 2.4 2.5 2.4 7.2 7.0 7.1 5.6 4.6 5.8 1.2 1.2 1.4 6.4 6.8 6.8 59.4 50.8 63.1 16.1 18.7 14.7 11.5 17.3 8.5 4.75 5.8 4.75

30.7

Lytic cleavage unit contained in crude oil, cleaved ¹ ) - for the product mixing and other conven- Gas oil flows again, since there is less gas oil, starting. The crude oil according to Example 1 is used together with

of the hydrotreated or hydrogenated 15 percent by volume of the condensate from the Verko charge, under equivalent cleavage conditions 5 kungsvorrichtung, as it is formed by conventional Verge will. The yields are obtained in the following coke at 520 ° C, along with soil table as a volume percent of the feed re-fraction from the crude oil according to Example 1, which according to unless otherwise noted. the conditions of Example 1 of a hydrogen

Comparative example 1 has been subjected to treatment or hydrogenation.

10 a hydrogen treatment or hydrogenation and

It serves to demonstrate the cleavage yields as they are subjected to catalytic cleavage, as described in Example 1 with reference to the conventional processing of. The coking unit is obtained with a gas oil, assuming a sulfur-containing temperature of 495 ° C. bed temperature with a single crude oil and not proceeding according to the invention. let temperature of the feed of 538 ° C operated. The gas oil described in Table I of Example 1, _s, the ratio of oil to water vapor feed is overall under the cleavage conditions of Example 1 amounts to 20.5 volumes of oil per volume Wasspalten. The yields of cleavage products are in the _ser The coking time is 9 hours. The represented by Table III. The additional use of catalytic cleavage of the 320-525 ° C gas oil 12 volume percent catalytic cracking gas oil in the fraction obtained yields ^1), wherein the gas oil-crude oil is equivalent to a conventional catalytic ₃₀ fraction from the hydrogenated mixture consisting of see splitting operation, wherein since the combined charge consists of 15 percent by volume of condensate from the coking charge ratio - total charge / refiner and 85 percent by volume of crude oil, charge - amounts to approximately 1.4: 1. A comparison _s j _cne Table III. equal to the yields using Example 1 and the

Comparative example 1 shows the markedly improved comparative example 2

Conversion and selectivity in gasoline as well as this shows the lower yield of gasoline that

reduced coke accumulation, as it results _according to the invention by conventional catalytic cracking of ur. Nitrogen and carbonization gas oil has been obtained

Example 2 ^is · where no treatment with hydrogen or

30 hydrogenation took place.

This example shows the advantages of the hydrogen _e j _n mixture of 15 volume percent Vcrkokungs-

treatment or hydrogenation of the condensate of the g ^ _ä \ _t see Example 2, and 85 volume percent crude oil. Coking device together with crude oil in see Example 1 is distilled to obtain a feed product for the gas oil fraction having a boiling range from 320 to catalytic cracking. ₃₅ 525 ° C. This gas oil is catalytically split, see

With reference to the F 1 g. 3 becomes crude oil 10 example 2. The yields are in Table III as in FIG. 1 processed to obtain a reproduced. The yield of gasoline (C ₅ carbon bottom fraction 22, which is used as feed for a hydrogen, 200 ° C.) is significantly lower than with conventional coking unit 60. _{Applying the method according to} the invention in which the 4O Example 2 obtained by means of the coking unit 60, and the accumulation of coke is greater, as a result of which products consist of coke 64 and a hot - a greater loss of valuable products in the form of steam flow, which cools and then in the separating _V on coke and thus a larger amount of air for the device 61 in a gaseous stream 62, which are displayed in the regeneration of the catalyst, consisting essentially of hydrogen and C] - C ₄ -Kohlen-

water materials, which have a gas concentration- 45 example

plant for the purpose of separating and processing trains- In this embodiment, the heavy load is split up, and a liquid gasoline is reformed to form a gasoline high current 63, which consists essentially of Q-hydrocarbon octane number and hydrogen, which are substances and higher-boiling in the treatment hydrocarbons are applied to _m j _t hydrogen and hydrogenation is at a boiling point of about 510 ⁰ C and can with _5O.

that coming from the desalination device II. Referring to FIG

Crude oil stream is mixed. Optionally, the _w j _e may be processed i _m Example 1, wherein the at hand dei liquid product stream 63 can be fractionated or exiting the main column or columns 18 Heavy be divided and produced only a portion of this stream with fuel 20 as feed to the catalytic Refordem from the desalter 11 ₅₅ mation unit 50 is applied The reforming stream are mixed, with the remaining proportion consisting of a hydrogenation reactor and

. various reforming reactors together with

·) The catalytic gap investigation in connection with the required furnaces and auxiliary equipment. _{The subject matter of the} invention is cooled in a small, stationary bed of the product stream and then in the working laboratory reaction equipment is carried out by means of separating devices 51 into a fluid: PrnHnW O hr.V, "," The yields are converted using " Rennvorncniung M in a liquid product 52 high unit factors defined as the yield in a refinery and a gas flow 53 divided, which consists of unit / yield in the laboratory unit, the more closely predominant hydrogen and partially as matched the yields which are returned to the reforming reactor in a catalytic stream 54 and the cleavage unit of a refinery with fluidized bed, _{partly as} stream 55 for use

harmonized conditions at about the same temperature, _Q .. \ "" 7. J ^erwe> iaung ar

are expected. In all examples the same sentence is used at ° ⁵ other miles, e.g. B. in the hydner unit 15, partially unit factors applied. is deducted.

1 sheet of drawings

Claims (4)

• ι patent claims: 1. A process for the production of gasoline and refined liquid hydrocarbons, starting from a total crude oil or a crude oil which has ^{been distilled with removal of a fraction boiling below 2 (K) 0} C, by means of cracks in a catalytic cracking device, characterized in that the oil subjected to hydrogenation using 240 to 1440 m ^{3 of} hydrogen per m ^{3 of} oil at a temperature of 350 to 450 ° C and a pressure of 17.5 to 350 kg / cm ² in the presence of a hydrogenation catalyst prior to the fractionation, which occurs in the subsequent fractionation resulting gas oil fraction of the hydrogenated oil is catalytically cracked, and at least a portion of the liquid products coming from the catalytic cracking device is returned to the process with mixing with the starting oil before hydrogenation is carried out. 2. The method according to claim 1, characterized in that the oil is ^{hydrogenated with 480 to 1190 m 3 of} hydrogen per m ^{3 of} oil at a temperature of 320 to 430 C and under a pressure of 42 to 175 kg / cm ² . 3. The method according to claim 1, characterized in that that gasoline-containing liquid products from the Catalylian spa equipment in part are fed to the oil before the hydrogenation, and at least a portion of the from the hydrogenation device emerging product is reformed. 4. The method according to Ansprrdi I, characterized in that that the coming from the hydrogenation products are fractionated, and at least a portion of the soil fraction is coked. 5. The method according to claim 4, characterized in that at least a portion 'ler liquid Products from the coking device are returned to the process with mixing with the oil fed to the hydrogenation. 6. The method according to claim 1, characterized in that that the hydrogenation catalyst is a metal from the group consisting of nickel, molybdenum, cobalt and Tungsten or a compound containing these metals is used. 7. The method according to claim 1, characterized in that both a gas oil and a middle distillate containing liquid products of the catalytic cracking device the oil before hydrogenation is fed. 8. The method according to claim 1, characterized in that that at least a portion of the hydrogen in the process to the hydrogenation device is returned. 9. The method according to claim 1, characterized in that that the hydrogenated product is divided into several hydrocarbon products and an oodenfraktion is fractionated, as well as at least a portion of the bottom fraction in a coking device is coked, the liquid coking product in a top distillate with Cj hydrocarbons and lighter hydrocarbons and at least one high-boiling stream with Cä hydrocarbons and heavy hydrocarbons is fractionated. The invention relates to a method for producing gasoline and refined liquid hydrocarbons starting from a total crude oil or a crude oil that boils below 200 C while removing one Fraction has been distilled by means of cracking in a catalytic cracking device. According to the state of the art that comes closest to the invention (Austrian patent specification 285 006) it is according to the so-called »J-Spaltverfah- ren «, a light catalytic gas oil to partially saturate under mild hydrogenation conditions with the formation of an easier-to-cleave Hydrocarbon streams. Tetrahydronaphthalene is much easier to break down than naphthalene. As a feed material ei.i catalytic oil must be applied by this process, having a high content of aromatics and having a boiling range of 300 to 45O ⁰ C. According to this it is not possible to use an untreated crude oil or a crude oil, from which only the slightly volatile components boiling up to about 200 ° C. have been removed, the other Processing. To explain the further, more general prior art, it should be mentioned that it has become known is a separate hydrogenation or hydrogenation of catalytic fission product streams to be carried out, see e.g. B. the publication by R. A. F 1 i η η and O. A. L a r s ο η - The Effects of Hydrogenation and Catalytic Cracking of Various Molecular Types and Middle Distillates ·., J. Appl Chem. 11, July 1961, pp. 271-276, and the publication by M.D. A b b o 11, R. C. A r c h i b a 1 d and R. W. Dorn, "Hydrogen Improves Catalytic Cracker Feed «. Petroleum Refiner, 37, pp. 161 to 166. 1958. The hydrotreatment or hydrogenation of Erdölrestprcdukten is described in the following publications (Dutch patent 6 916 218-Q). Here are procedures / to convert sulfur-containing, carbon-containing black oils in low-boiling, normally liquid hydrocarbon products with reduced sulfur content described, an integrated process is used in which a cleavage in the presence of hydrogen and catalytic desulphurisation takes place in a stationary bed. The Dutch patent specification 6 916 017-0 teaches the hydrodesulphurization of crude oil or reduced crude oil, the asphalt fractions contains, at low temperatures in the presence of a metal catalyst of groups VI ' VII of the periodic table arranged on alumina. The hydrotreatment or hydrogenation of the Total crude oil is described in detail in a Publication by S. G. P a r a d i s, G. D. Gould. D. A. B ca and E. M. Reed labeled "Isomax Desulfurization of Residium and Whole Crude Oil," which was given as lecture 31c on the occasion of the meeting of the American Institute of Chemical Engineers on February 28 to March 4, 1971 in Houston. U.S. Patent 3,562,800 is concerned with hydrodesulfurization of crude oil or reduced oil Oil without recirculation of liquid products from other units while mixing with the incoming one Crude oil feed. The invention is based on the object of creating a method of the specified type which enables, with reduced device and procedural requirements Effort, based on crude oil,