DE1645830C3 - Process for hydrogen refining - Google Patents

Description

The invention relates to a process for the hydrogenative refining of a gasoline fraction and at least one higher-siting fraction containing sulfur and / or nitrogen compound (s) contaminated hydrocarbon feeds boiling in the range of 28 to 599 ° C

a) reacting the hydrocarbon feed in a first reaction zone in the presence of a Catalyst with hydrogen under increased pressure and at a temperature of 260 to 427 ° C,

b) Separation of the volatile fraction from the higher-boiling hydrocarbon fraction by distillation from the reaction product mixture obtained and

c) further catalytic refining of the contained in the separated volatile fraction Hydrocarbon fraction in a second reaction zone under increased pressure and at elevated temperature.

A method of the type indicated above is known (U.S. Patent No. 2,340,922). This Known processes make it possible to use a wide boiling range in the gasoline boiling range from feedstocks Obtaining boiling, largely sulfur-free hydrocarbon fractions, however, is pretty complex and expensive. In particular, in this known process, from the reaction product mixture of the first reaction zone initially one in the gasoline boiling range and lower boiling components containing fraction separated by fractional distillation, from which the gasoline fraction is condensed, then carefully freed from the hydrogen sulfide dissolved therein by washing and finally being re-evaporated by heating before being fed to the second reaction zone can feed.

Furthermore, a process for hydrocracking and desulfurization of crude oil is already known, in which the crude oil after the admixture of hydrogen-containing gas and preheating in an upward flow passed through a first reactor, the effluent of this reactor in a vaporous and a liquid part separated, the liquid

3 4

Proportion returned to the first reactor and there under milder than those in the first reaction

K t ·· K ^ -uw ^{Γ αίαη} Ρ αοπηι & ^{Part of the} hydrogenation conditions used in the zone

considerable amounts of high-boiling components at a temperature of 260 to 399 ° C, below

with boiling points up to about 540 ⁰ C, in a pressure of 34 to 102 atmospheres and with a

fed into a second reactor and the effluent 5 space flow rate from 5 to nu ^ ¹ ™ * ^ ⁰ ™ with recovery of an ent- 10V / V / h in the presence of at least one

^s ™ ^f elth product is separated (USA.-patent metal from groups VI and VIII of

sennit Jiiv 765). According to this known method, the periodic table and / or at least one

Ren from the effluent of the second reactor containing a bond of such a metal

n ^e nf k ^ ¹¹ ^: ^ ⁰¹¹ ™ ^{still contain} about io catalyst hydrogen refined and

^D1 s 0.02 percent by weight sulfur and can 4) of which, if necessary with that in the process, then not directly in a reformer step 2) as a distillation residue.

^we " ^crv S ^{tet will} n. falling, higher-boiling, refined coal

Accordingly, the task of combining hydrogen fractions, in the process

green, em method for hydrogenating refining 15 step 3) resulting reaction product mixture

one separates in the gasoline boiling range and higher boiling hydrogen.

Feed containing hydrocarbons is preferably the effluent from the second

th boiling range to create that the explained reaction zone with that in process step 2) does not Has disadvantages of known working methods, falling, liquid, higher-boiling hydrocarbons and is more economical to carry out and 20 material fraction is added to a total product stream Products with excellent properties, especially those of hydrofined hydrocarbons contains a gasoline fraction with such low reduced sulfur content. Sulfur content leads to the fact that they are without further advantages.

In process step 2) the separated Ketormieranlage can be used as input material for a catalytic manure. a ₅ volatile fraction cut so that they 2 to

fcs has been found that the slope of 50 percent by volume of that under normal conditions impurities, such as sulfur and nitrogen compound components of the process step 1), contains during the hydrogenation from proportionally generated reaction product mixture, moderately heavy hydrocarbon fractions in It has been found that according to the invention in very

Naturally light hydrocarbons migrate more easily and simply with the least amount on which the known processes in terms of labor, process equipment, lack of investment and operating costs, presumably essentially essentially result in an effective run-down, at least in part on that of the hydrogenation - Sulfurization of hydrocarbon feeds reaction-related cracking of coals with a broad boiling range can be achieved. Is due at hydrogens and the inventions 35 solved object of a preferred embodiment as nachdung, ie before standing even closer explains is a comparison ^ w u ^To _J ^{AufarbeitungdesReaktions} - mix of the various effluent streams

product mixture provided from the first reaction column before the hydrogen separation. The mixture surprisingly obtained by a simple decompression can then be replaced in a suitable fractionation evaporation if one fractionates the usual type and then further treats them in a known manner in each case in the second reaction zone, specifically selected and coordinated works or used. Complies with operating conditions. For example, the gasoline fraction of the

The subject of the invention is thus a process of batch material separated from the combined effluent of the type indicated at the beginning, which is thereby identified and then directly, without any further intermediate sign, that treatment, catalytic reforming, is added.

3) The hydrocarbon ^{feed in the first is fed to produce upgraded} products therefrom in the gasoline reaction zone under a pressure of 34 to boiling point. 102 atü and with a room flow velocity. ^In this context it should be noted that

Density of 0.3 to 6 parts by volume of liquid in ^s ° previously known processes in which the charge per part space of catalyst and was tried to hydrogenate hydrocarbon charges with a broad hour in the presence of at least one metal boiling range, to light fractions tall from groups VI and VIII of the period - of extremely poor quality. When the systems and / or at least one compound previously known methods in the broad boiling Hyeines reached such a metal-containing catalyst ^5S drierung of hydrocarbon feedstocks with hydrofined, sulfur impurities from

0} mic Ha «, λοκ»; », Ι, _η η τ» 11 · j · the relatively high-boiling components in the

T ^ L · ^ ^ΡΙ ° ^ relatively low-boiling components, whereby

^{as Prad} "kt separated light (gasoline) fractions - were _tark s ^ ^ WI venmr gt that

wÄSmiSatSiBSw ^ C fr ^ß Τ ^β 7 ^ - work according to bcSnnten

lj _e " _t " Λ. «*« ;! » oci ^ ou ^ drive the light fractions thus obtained

.. ,,,, 65 each have to be re-hydrogenated in order to

r? i.S ?? ^ «n process step 2) materials obtained with a for re-normalization

to produce easily volatile fraction without further addition of satisfactory quality. With others

of hydrogen in the second reaction zone was a previous fraction

tioning stage is provided to convert the into a single-stage expansion evaporation zone wide range of boiling feedstock introduced into the hydrogen and proportionately agreed to break down fractions so that each one was light hydrocarbons from the heavier ones Individual fractions of a catalytic hydrogenation from hydrofined hydrocarbons are separated and different, precisely tailored to them. The amount of gaseous fractions withdrawn from the flash evaporation conditions should be a satisfactory reduction in sulfur on a liquid basis, preferably at least 2 and to bring about salary in each individual parliamentary group. a maximum of 50 percent by volume of the total discharge The invention, on the other hand, makes it possible to use the first reaction zone. If the To hydrogenate material with a wide boiling range without a gaseous stream making up less than 2 * / · is that that these shortcomings and disadvantages of known work are explained in more detail below have to be accepted. second reaction zone, as noted, in the

Under designations such as »materials broadly uneconomical. When in the flash boiling range, "" hydrocarbons containing gasoline. In the evaporation zone, a quantity of more than 50 material feeds with a broad boiling range or 1 lumens percent is separated off, can be considerable compartment »input material« or »charge«, the quantities of heavy components in the second are used interchangeably, the reaction zone are entrained, which means that the Straight run and / or cracked hydrocarbons have at least advantages of the process of the invention and mixtures of such hydrocarbons are lost to some extent. Habitual different refining processes in which these sympathetic heavy proportions become "0 Hch" Feeding into the process of the invention is to be understood as being suitable among the feedstocks prevailing in the second reaction zone. Refining processes that are not so relatively mild include crude oil desulfurization. The amount of fractionation, catalytically and / or thermally vaporized material is calculated on a liquid basis. Cracking of crude oil or crude oil fractions that as The volume percentages include below destructive distillation of wood or coal, the normal conditions gaseous components, such as Retort processing of shale oil, processes for hydrogen and hydrogen sulfide, not one. delayed and for fluidized bed coking and die in the flash evaporation zone from the various other pyrolytic reactions. Separated light in the outflow of the first reaction zone In any case, however, the feed material must be cut in such a way that the fraction should preferably be Boiling range for the process according to the invention that the 90 volume percent point of the dung contained in it a considerable amount of a light fraction of hydrocarbon fraction is about 204 ° C, tion, which is usually called "naphtha" or "gasoline" because the flash evaporation zone is referred to as equal fraction. Normally weight relief evaporation conditions arh the gasoline fraction has a boiling range of about 35, it may be appropriate or necessary to 71 to 204 ° C, however, even at certain temperatures, the temperature within it can be set so that Deviations from these limits are still a gasoline - that in the case of expansion evaporation only those in it fraction within the meaning of the invention. In addition to the gasoline fraction contained in the vapor phase required gasoline fraction, the charge must be brought.

In the second reaction zone, milder reactions will contain at least one other higher-boiling action conditions than in the first reaction zone fraction, e.g. B. kerosene, diesel oil or maintained. This relatively mild Be gas oil. It can also include C ^ and C _s -carbon conditions contain a temperature in the range of hydrogen. In general, therefore, feed materials suitable for the process of 45 and an hourly space air velocity in the invention include from 260 to 399 ° C., a pressure of 34 to 102 atmospheres, such sulfur-containing carbons liquid of 5 to 10 V / V / h. The amount of hydrogen present in the two hydrogen mixtures in the range from 38 to th reaction zone boils at 599 ° C. depends entirely on the one in the previous one, of course

The feedstocks of the aforementioned type are separated from the flash evaporation zone and, according to the invention, in a first catalytic reaction zone, which is passed on in the manner explained, from the relatively strict hydrogenation conditions. There is no other, subject to external infiltration. A proportion of hydrogen is preferably fed into the second reaction zone. nis of hydrogen to carbon from 0.09 to The charge of the second reaction ^{zone consists of 0.9 Nm s} H ₂ per liter of feed material applied, i.e. completely from the gaseous fraction, which can be known to carry out a hydrogenation 55 in the flash evaporation zone between the reaction has been separated at temperatures above 260 ° C to one of the two reaction zones

if diolefins are present. If both reaction zones have been found to have the same catalysts or there is a likelihood that their chemical and physical composition will be lighter feedstocks, for example those with a boiling point and nature. Suitable hydro range from about 38 to 288 ° C, contain noteworthy menining catalysts. contain at least one gene of diolefins, so that undesired metal from groups VI and VIII of the period polymerizations can take place, should therefore systems and / or at least one compound of such diolefin-containing feedstocks before such metal. Thus, the catalyst min-introduction in aas process of the invention contains at least one metal component from the group to be treated, e.g. B. by mild hydrogenation. Chromium, molybdenum, tungsten, iron, cobalt, nickel,

In the method of the invention, all of the rhodium, ruthenium, palladium, osmium, iridium effluent from the first catalytic reaction zone and platinum or mixtures of two or more

such components. Preferably are brought about so that about 10 percent by volume of the catalyst used, the molybdenum and min- through the line 16 inflowing material (not counting water vapor, a metal component from the iron group and hydrogen sulfide) in the periodic table. The molybdenum flash evaporation zone is separated and the component is generally withdrawn in a larger concentration an amount ranging from 1 to point 166 ° C. - "-." .., ..,. 6 weight percent is present, calculated as elemental The current flowing through the line 19 material which tares metal Preferably, the catalyst io relatively light hydrocarbons, typidie catalytically active (s) metal component (s) of the shear, in the boiling range of _C6 to 166 ° C , and contains the type specified above in association with sulfur compounds, is mixed with an inorganic carrier material. The metal components catalytically activated in the flash evaporation zone can be passed with any separated hydrogen and hydrogen sulfide in suitable resistant inorganic oxide to a reactor 20 which can be combined when relatively slower. These include B. aluminum is maintained under mild operating conditions. The beminium oxide silicon dioxide, zirconium oxide, thorium operating conditions in the reactor 20 include, for example, boron oxide, titanium oxide, hafnium oxide and a temperature of 343 ° C. and a pressure that mixes two or more of the named as it will also result from the normal pressure drop in the oxide Often more components between the reactor 15 and the reactor components with the metal components and the carrier 20 results. The hourly Raumströmungsgeschwinmaterial combines z. B. Halogens, such as fluorine and / or the liquid in the reactor 20 or chlorine 8.0 V / V / h, based on the in the relaxation

Material separated off according to a particularly preferred embodiment evaporation zone. As already

In the form of the invention, an input material which is mentioned is not additionally added

has a boiling range of C _n to 482 ° C, use hydrogen in the reactor 20 because there is enough hydrogen

Set and the first reaction zone with a temperature in the stream coming from the separating device 17

temperature of 385 to 413 ° C and a room air flow is available in order to hydrogenate the

flow rate of 0.5 to 1.5 V / V / h pulling 19 relatively light carbon

In this embodiment, hydrogen is removed from sulfur in the 30

the second reaction zone to feed a temperature of 322 to. In line 19 you can optionally

371 ° C and a room flow velocity heating devices (not shown) are

νήη fi up to 9 V / V / h applied moderately or may be necessary in order to

The invention is described below in connection with conditions for the conversion of sulfur compounds the drawing further illustrates in which 35 fertilize in hydrogen sulfide in reactor 20 «^ Enj ^^ jPUcJbild a preferred choice

ΪΓ & ΑwhS a coker distillate withdrawn with line 21 and preferably with the

a SSSch from C ₆ to 476 ° C, a relatively heavy hydrofimed carbon

S ^ hTefeleehalt of 0.52 percent by weight, one * ° mixed hydrogen, which from the separating

Bromine count of 28 and a nitrogen content of 17 flow off via a line 18. That in one

880 parts ^ c million (ppm) used. This mixture formed in line 22 is not represented by

sa ^ ma erial is cooled by a line 10 supplied equipment and in a separating

and if so ™ el hydrogen is passed from a line 11 device 23, in the hydrogen from the

It is assumed that a mixture ratio of 45 hydrofined hydrocarbons is separated off.

0 53Nm * hydrogen per liter of feed material. The separated hydrogen is transferred via the line

Keeps the GerSSh from hydrocarbons and 11 withdrawn and preferably for mixing

stop. The ^ ^e ™ ^sc "_ *" * _{Ld 12 a Er} . _{returned with} the input material. Since the

the e ^ uf 399 ° C, and hydrogenation a small amount of hydrogen (about

aem it, au contains 50 1 percent by weight) is consumed by

14 in "" ^ J ^ S ^ T'ST i Lit 25 Makeup Hydrogen Into the System

contains 50 1 percent by weight) is consumed by

eme line 14 in "" ^ J ^ S ^ T'SuT 2 2 Ge a line 25 make-up hydrogen into the system

emen catalyst of the un J- ^ J ^ Sertä- introduced. The hydrofined hydrocarbons

Weight percent cobalt and 5 ^ _£ ^ weight pr ^ g ^ ^ ^ _{separator 23 over eme Ld} _

^be - ₅₅

hold are.

■, λ η. · ■ a · "". ctiinriiirhp κ aumsirumuim »- A major technical advantage of the process

of 74.7 atu ^^^^ lr 60 rens according to the invention is based on the fact ^^^ ifZ ^^^ irfÄrdieine that the feedstock, which is a considerable

I weight percent of, a hydrofined

older about the bleaching print like the ke- 05 eiwa 1 i jc m .. »^ "&"*>" ■. ""» - '"« «y» »c

will age. Preferably there is no intermediate treatment of any kind, η a catalytic treatment

in line 16, and an out-reforming plant can be introduced. In the opposite

Equilibrium expansion evaporation set required the previously explained up to

Her known method in general an additional llydration of the gasoline fraction before this one is for introduction into a catalytic reformer had suitable quality. The invention is a technically improved and

10

created a much simplified hydrogenation process in which the gasoline portion of the feed boiling over a wide range is converted directly into a product of satisfactory quality for reforming purposes.

For this purpose, 1 sheet of drawings

Claims (4)

Patent claims: 1. Process for the hydrogenative refining of a gasoline fraction and at least one higher-boiling fraction Fraction containing, with sulfur and / or nitrogen compounds) contaminated Hydrocarbon feeds in one Boiling range from 38 to 599 ° C, through a) Reacting the hydrocarbon feed in a first reaction zone in the presence a catalyst with hydrogen under elevated pressure and at a temperature from 260 to 427 ° C, b) Separation of the volatile fraction by distillation from the higher-boiling hydrocarbon fraction from the reaction product mixture obtained and c) further catalytic refining of the contained in the separated volatile fraction Hydrocarbon fraction in a second reaction zone under elevated pressure and at elevated temperature, characterized in that one 1) the hydrocarbon feed to the first reaction zone under pressure from 34 to 102 atmospheres and with a space flow velocity of 0.3 to 6 parts by volume of liquid in the feed per volume of catalyst and hour in the presence of at least one metal groups VI and VIII of the periodic table and / or at least one compound of such a metal-containing catalyst refined by hydrogenation, 2) a volatile fraction from the resulting reaction product mixture separated from the higher-boiling components by single-stage flash evaporation, which is cut so that the 90 volume percentage point of the contained therein Hydrocarbon fraction in ASTM distillation does not exceed 260 ° C Cherishes. 3) the entire volatile fraction obtained in process step 2) without any further Addition of hydrogen in the second reaction zone under milder conditions than those in the first reaction zone applied hydrogenation conditions at a temperature of 260 up to 399 ° C, under a pressure of 34 to 102 atmospheres and with a space velocity from 5 to 10V / V / h in the presence of at least one metal groups VI and VIII of the periodic table and / or at least one compound of such a metal-containing catalyst refined and hydrogenated 4) of that, optionally with that in process step 2) as the distillation residue accumulating, higher-boiling, refined hydrocarbon fraction combined, im Process step 3) separating off the resulting reaction product mixture hydrogen. 2. The method according to claim J, characterized in that the first reaction zone per liter of hydrocarbon feed 0.09 to 0.9Nm ^{3 of} hydrogen are fed. 3. The method according to claim 1 or 2, characterized in that the processing of the Reaction product mixture from the second reaction zone resulting hydrogen in the first Reaction zone is recycled. 4. The method according to any one of claims 1 to 3, characterized in that in the process step 2) the separated volatile fraction is cut so that it is 2 to 50 percent by volume of that under normal conditions contains liquid components of the reaction product mixture generated in process step 1).