DE1244317B - Process for the hydrocracking of a hydrocarbon oil originating from petroleum with a high nitrogen content and boiling above the gasoline range - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. Cl .:

Clog

German KL: 23 b-1/04

Number: 1244 317

File number: U 8005IV d / 23 b

Filing date: May 9, 1961

Opened on: July 13, 1967

Hydrocracking consists of a combination of catalytic cracking and hydrogenation, which serves to convert high molecular weight hydrocarbons, such as middle distillate and higher boiling fractions of petroleum, into lower boiling products, e.g. B. from the gasoline boiling area to convert. In a known hydrocracking processes such a hydrocarbon oil feed having a nitrogen content below 2.5% "is preferably from 0.05 to 0.5 ° / _0, catalytically cracked under hydrogen additive, wherein the preventing effect of the nitrogen compounds is reduced by use of a reaction temperature which is in is directly related to the nitrogen content of the feed. It was stated that ζ. B. a feed containing more than 0.24% nitrogen by acid treatment in a nitrogen content of about 0.07 ° / ₀ is to be placed before the hydrocracking is carried out. For a gas oil distillate, a nitrogen content of 0.009 percent by weight is considered permissible. Such starting mixtures boil in the middle distillate range, ie in the range from 204 to 343 ° C. The hydrocracking takes place in a range from 400 to 510 ° C, depending on the nitrogen content. Under the most favorable conditions, this hydrocracking process gives a gasoline yield of 63% with a run of 2 hours and a temperature of 427 ° C from a light oil of the mentioned Art.

In contrast, the invention relates to a hydrocracking process for a temperature above 343 ° C., ie above of the middle distillate range, boiling oil. While oils from the middle distillate boiling range still have a considerable Have market value, are the starting materials of the invention due to their high boiling point and Content of asphaltic and tarry impurities as well as high-boiling organic nitrogen compounds of very low market value. They usually contain 0.12 to 0.4 percent by weight Nitrogen and more.

In another known process, heavy gasoline and middle oils with a nitrogen content of less than 0.1, preferably below 0.05% or below 0.01 ° / ₀ , are mixed with hydrogen at 440 to 560 ° C, preferably above 480 ° C, subjected to hydrocracking under a total pressure not exceeding 100 atm.

The subject of patent 1 131 346 is a process in which the catalytic conversion of nitrogenous Heavy gasoline or non-cracked gas oils with a boiling point of up to around 287 ° C through catalytic Hydrofination, subsequent removal of ammonia, treatment of at least part of the

Process for hydrocracking a petroleum product
high nitrogen origin and
boiling above the gasoline range
Hydrocarbon oil

Applicant:

Universal Oil Products Company,

Des Piaines, JIl. (V. St. A.)

Representative:

Dr. H.-H. Willrath, patent attorney,

Wiesbaden, Hildastr. 18th

Named as inventor:

Charles Henry Watkins, Arlington Heights, JIL;

Mark Joseph O'Hara,

Mount Prospect, JIL (V. St. A.)

Claimed priority:

V. St. ν. America 9 May 1960 (27 697)

purified liquid product in an intermediate zone below cracking temperature in contact with a silicon-containing cracking catalyst and catalytic hydrocracking of the product from the intermediate zone is carried out. The intermediate treatment on the silicon-containing contact is considered essential,

30 'to extend the active life of the catalyst.

According to another older proposal, residual hydrocarbon oils are on the way in Gasoline and other fractions that converted the heavy residue oil under coking conditions is treated, with a nitrogen-containing distillate fraction boiling above the gasoline range and a heavy gas oil is produced, at least part of the nitrogenous distillate fraction to remove the nitrogen content down to one at 0.001% lying total content catalytically hydrofined and the fraction freed from nitrogen a catalytic Is subjected to hydrocracking. It is essential to carry out the coking and Separation of the coking product into two different fractions.

The invention has the task of providing a method for hydrocracking a petroleum with Hydrocarbon oil with a high nitrogen content and boiling above the middle distillate range to develop, which is able to by appropriate choice of temperature and pressure in

709 610/466

3 4

of the cracking zone at least 80 ° / ₀ below 343 ⁰ C in order to reduce the nitrogen content of the oils to less than 0.0001% boiling or at least 60% below 204 ⁰ C. These nitrogen impurities such as boiling, normally liquid product deliver. Pyrroles, amines, indoles, etc. can be obtained from the loading process. A solid catalyst which contains a hydrogenation charge oil, for example a metal component which has activity due to its treatment, and a metal component with a relatively concentrated sulfuric acid, preferably made of silica - be removed in order to form a carrier known in the art as white oil containing acid and alumina, in an known product. Another pretreatment known to be used. The invention is lungsmethqde is to Hydroraffinierbehandlung, the particular knowledge of, the oil in the presence of hydrogen over a that when an above 343 ⁰ C boiling as catalyst is passed, the organic stick-oil substantially as a starting material, the nitrogen content Substance compounds in ammonia and a carbon remover, as was previously considered necessary, converts hydrogen residue. Then he will have to be humbled. Stripped ammonia.

Accordingly, the invention provides a suitable catalyst for carrying out the

Process for hydrocracking, in which a above 15 hydro refining reaction are supported using catalysts

343 ⁰ C boiling oil with a previously less than iron group metals, their oxides or sulfides

0.0001 weight percent reduced nitrogen content including compositions in which the

in the presence of a hydrocracking catalyst among iron group metal with a metal, metal oxide

a hydrogen pressure of at least 75 and or. a Group VI metal compound such as

at most 136 atmospheres and a temperature between 20 tungsten oxide or chromium oxide

Hydrocracked at 288 and 454 ° C. is. A molybdate or thiomolybdate is preferred

Preferably the hydrocracking is the less of nickel and / or cobalt.

than 0.0001 percent by weight nitrogen containing In the process of the invention there is the

Hydrocarbon oil in the presence of a hydrofoil variable that interacts with the

Cracking catalyst causes the nickel and / or temperature is decisive, in the pressure of the hydrogen.

Cobalt in a total of 1 to 20 weight- As evidenced by numerous hydrocracking runs

percent or 0.01 to 3 percent by weight of palladium, the hydrogen pressure has a pronounced influence

on a pre-annealed, from 37 to 88 weight percent on the conversion of the charge mass and the

Silicic acid and 63 to 12 percent by weight of alumina yield of product boiling in the gasoline range,

Contains existing carrier. In the case of a particularly 3,) obtained in the conversion. At temperatures

preferred embodiment is the hydrocracking from 288 to 454 ⁰ C, the conversion into product

of less than 0.0001 percent by weight of nitrogen from the gasoline range essentially above 60 vol-

Containing · hydrocarbon oil in the presence of lum percent when the hydrogen overpressure

a hydrocracking catalyst which is 0.01 to above 75 atmospheres but not above 136 atmospheres;

1 weight percent platinum on a 0.01 to 3.0 level because the conversion drops at pressures above

weight percent bound fluorine and / or chlorine and below the above limits rapidly.

containing clay. The proportion of boiling in the middle distillate range

In contrast to the prior art methods product (namely the end product of the gasoline as the method according to the invention not only to the overall 204 ⁰ C to the end point of kerosene, or about a product, which predominantly in the 40 343 ⁰ C winnung) is also much boiling greater than the proportion in the gasoline range, but also so operated the products of conventional catalytic cracking that primarily a material from the luminescent oil process, namely the yield of intermediate range for use as jet fuel is obtained distillate at the expense of heavy distillate products. For the solution of the given problem, besides and residual oils, which boil above the luminous oil in the extremely low nitrogen content of the 45 range, are increased.

Carrying out hydrocracking in the lower part The invention is illustrated in the following examples

of the cracking range, namely between 288 and 454 ⁰ C, further explained that the critical effect of the water

essential. Even if the material pressure is exceeded, this affects the yield of hydrocracked gasoline

the stated limit of 0.0001 percent by weight, and middle distillate fraction when using different

z. For example, at 0.0006% nitrogen, the conversion drops to 50 of the catalysts and a feed mass

result in desired product within a few hours with less than 0.0001% nitrogen,

quite considerably. .

As starting materials [for the process according to B e 1 s ρ 1 e J 1

Invention come z. B. the high-boiling soil various types of hydrocracking

products from the fractionation towers of catalytic 55 gates were tested to determine how these hydrocracking

Crackers, such as heavy cycle oils, fuel oils, catalysts for nitrogen impurities in the

Address vacuum cycle oils and other petroleum hydrocarbons feedstock. With every attempt

Substance fractions, for which, because of their high, a white oil with less than 0.0001% total

Boiling point and content of asphalt and tar only nitrogen, which ranges from about 365 to about 468 ° C

there are few possible uses. Im 60 boiled (consisting of a mixture of C ₂₀ - bis

they generally contain high-boiling organic, for example, C ₃₂ paraffin and naphthenic hydrocarbons),

Nitrogen compounds that are needed for their occurrence in the as feed mass. One determined the

Asphalt residues are responsible. These oils, proportion of the charge (expressed as a percentage by volume),

which often contain 0.12 to 0.4% nitrogen, which was converted in the first place normally

Although a desirable starting source for the hydro-liquid ^{material boiling below 204 0} C (motor gasoline)

cracking process according to the invention with respect to the second, and a normally liquid, at 343 ⁰ C

Boiling range, but they have to be used in the boiling product (including in the gasoline range

Technique known methods are pretreated, boiling material) [luminous oil fraction]. The white oil

charge had a specific gravity at 15.6 ° C of 0.8838. In each experiment, the white oil and the hydrogen were simultaneously introduced into a reactor tube at the bottom, which was covered with a fixed layer of different catalysts. The liquid portion was introduced at a rate of 1.0. The reactor tube was surrounded by a circumferential heated salt bath keeping the temperature constant and uniform at a preselected height within the range of 274 to about 371 ⁰ C. Hydrogen was fed in together with the feed in the ratio of 534 Nl / 1 white oil under 102 atm. This pressure appears to be the most favorable pressure for the various catalysts tested. Although each catalyst was tested in the test series at different temperatures in the range from 274 to 371 ^° C. from the point of view of the greatest yield and highest conversion into liquid product, a temperature of 357 ^° C. was found, which proved to be the most favorable in a separate test series , used to determine the independent influence of the catalyst composition on the results obtained by comparative results. In experiment no. 1, the catalyst consisted of 2% nickel and 6% molybdenum on a pre-annealed carrier made of 63% alumina and 37% silica. In experiment no. 2, the catalyst consisted of 2% cobalt and 6% molybdenum on a pre-annealed carrier made of 63% alumina and 37% silica. In experiment no. 3, the catalyst consisted of 0.4% palladium on a preannealed support with 63% alumina and 37% silica. In Run No. 4, the catalyst consisted of 0.35 percent platinum, 0.3 percent by weight chlorine and 0.3 percent by weight fluorine on an alumina support.

In each experiment, a mixture of hydrogen and white oil feedstock under 102 was atm subjected at 357 ⁰ C of the hydrocracking, the reaction products were cooled under the pressure prevailing in the hydrocracking zone pressure and the uncondensed, consisting mainly of hydrogen gases were separated and recirculated. The liquid product was stripped under air pressure in order to remove constituents boiling ^{at approximately 25 ° C.}

The liquid residue was found to be the desired one

liquid product obtained. Table I gives the observed values for the experiments using of the above catalysts. In each run, the hydrocracking reaction continued for about 40 hours and then the influence of nitrogen addition to the extent of 0.0005% pyridine addition for each

i.s catalyst determined, taking the conversion continued under the existing pressure and temperature conditions for a further duration of the process, which is given in Table I.

Table I.

Attempt no.
2 j 3

catalyst

Ni + Mo

on
SiO ₂ -Al ₂ O ₃

Co + Mon

on
SiO ₂ -Al ₂ O ₃

Pd

on

SiO ₂ -Al ₂ O.

2— "iavs

Pt

on

Al ₂ O ₃ -Cl-F

feed
Oil ing
H ₂ in g

conversion

Duration in hours

product

Liquid in g

Gas Nl

Fluid properties

Specific weight at 15.6 ^° C

distillation

Initial boiling point in ⁰ C

% up to 204 ⁰ C

% up to 343 ° C

1030

34

32

885
70.8

0.7711

49
65
80

1050
26th

30th

840
113.3

0.7669

76
70
84

1060
28

758
87, i

1010
30th

39

910
73.6

0.7467

0.8109

100

113
35
83

Influence of the addition of 0.0005% total nitrogen as pyridine after 40 hours in the stream, 102 at and 357 ^° C.

Attempt no.
¹ I ² I ³ I ⁴ ' 70
61
17th
0 86
63
10
0 35
21st
5
0 Conversion into product from final boiling point 204 ⁰ C
in 40 hours in the stream
after _{addition of N 2} at 5 hours afterwards
N ₂ addition 65
58
15th
1 at 10 hours following the addition of _{N 2}
at 20 hours following the addition of _{N 2}

It can be seen that any hydrocracking catalyst provided useful hydrocracking as long as the feed was substantially nitrogen-free, although the pre-annealed silica-alumina-supported palladium catalyst was particularly effective. In any event, if the nitrogen content is increased even to 0.0005%, the activity of the catalyst will decrease rapidly, and even after an additional process time of 5 hours under hydrocracking conditions which have been found to be useful for white oil feeds with little or no nitrogen contamination, Thus the conversion with the preferred palladium catalyst fell from 86 to 63 ° / ₀ and further to practically 0 after 20 hours on stream. The deactivation is also evident after contamination z. B. with ammonia, amines and pyrrole compounds, as was found by adding them to feed masses. With only 0.0001% total nitrogen under the above reaction conditions, however, the hydrocracking activity of the catalysts declines hardly noticeably over time, so that the process can be operated with a practical level of performance and catalyst life in excess of what can be achieved in conventional cracking operations can.

Example 2

The critical relationship between percentage conversion to products of gasoline and Leuchtölsiedebereich and the hydrogen pressure during the conversion is detected in a series of tests on the white oil with a boiling range of 365 to about 468 ⁰ C of the hydrocracking conversion over a catalyst comprising 0.4% palladium was subjected to a carrier of 12% alumina and 88% silica under various overpressures from 34 to about 204 atmospheres at 274 to 371 ⁰ C using 534 Nl / 1 hydrogen, which was fed into the fixed catalyst layer together with the liquid charge. The latter was introduced with a passage speed of 1.0. The supported palladium catalyst was selected as being particularly useful among several catalysts from Example 1 and others with different silica / alumina ratios in the substrate. This catalyst is also able to maintain its activity for long periods of time and after processing the feed contained less carbon build-up than any other catalyst tested. The white oil feed had a specific gravity at 15.6 ° C of 0.8838 and contained less than 0.0001% total nitrogen.

As in Example 1, in each experiment white oil and hydrogen were introduced at the bottom into a reaction tube which was filled with the palladium-alumina-silica catalyst and was heated externally by a salt bath. The reaction products were cooled under the reaction pressure and the gases were separated from the liquid product, which was then stripped off at atmospheric pressure. The residue, which consisted of the desired liquid product of the hydrocracking reaction was separated out by distillation in a petroleum fraction having a final boiling point of 204 ⁰ C and a fraction having a final boiling point 343 ° C. The remaining residue was distilled further in order to determine the final boiling point of the product. Table II reproduces in part the results of these tests, and these and other results are plotted graphically on the diagram. These curves show clearly the critical relationship between the hydrogen pressure and the percent conversion to products with final boiling points of 204 and 343 ⁰ C.

Table II
Influence of the pressure on the transformation

Tpinnp pressure In the product In the product attempt with with FcltUr at Final boiling point Final boiling point 15 No. ⁰ C 204 ° C 343 ° C 1 274 34 16 37 2 288 18th 40 3 302 23 47 20 4 316 28 53 5 274 54.5 19th 43 6th 288 26th 52 7th 302 38 61 a ₅ ⁸ 316 75 52 73 9 274 32 55 10 288 30th 62 11 302 43 70 12th 316 10? 64 79 30th
13th 274 30th 60.5 14th 288 41 70 15th 302 56 83.5 16 316 150 83 96 35 ₁₇ 288 41 58 18th 302 52 67 19th 316 204 71 81 20th 288 31 40 40 21 302 38 48 22nd 316 54 55

The diagram contains the values from Table II.

The curves in the lower half show the conversion into liquid product from the final boiling point 204 ° C (plotted along the ordinate X), obtained at various overpressures (plotted along the abscissa P in atm) at a constant temperature of 274, 288, 302 and 316 ⁰ C. the curves in the upper half respectively show the conversion in normally liquid product having a final boiling point 343 ⁰ C (Y plotted along the ordinate.) in relation to the press P.

These values confirm the critical character of the pressure range between 75 and 136 at during hydrocracking at different temperatures and the fact that the most favorable pressure is approximately is 102 at and converting the feed to both gasoline and gasoline products decreases from the luminous oil boiling range at a pressure of 102 atm on both sides. Same tendency in the Conversion level is practically the same for other catalysts (including another preferred Catalyst made of nickel with a pre-annealed silica-alumina base), which is one of the catalyst composition or temperature independent effect.

Claims (3)

Patent claims: 1. Process for the hydrocracking of a hydrocarbon oil originating from crude oil with a high nitrogen content and boiling above the gasoline range at elevated temperature and overpressure in the presence of added hydrogen and a solid catalyst, the metal component having a hydrogenation activity and a carrier having cracking activity, preferably consisting of silica and alumina contains, characterized in that an ^{oil boiling above 343 0} C with a nitrogen content previously reduced to less than 0.0001 percent by weight is hydrocracked in the presence of a hydrocracking catalyst under a hydrogen pressure of at least 75 and at most 136 atmospheres and a temperature between 288 and 454 ° C . 2. The method according to claim 1, characterized in that the hydrocracking of the less than 0.0001 percent by weight of nitrogen-containing hydrocarbon oil in the presence of a hydro 10 Cracking catalyst is effected, the nickel and / or cobalt in a total amount of 1 to 20 percent by weight or 0.01 to 3 percent by weight of palladium on a pre-annealed 37 to 88 percent by weight silica and 63 to 12 percent by weight alumina carrier contains. 3. The method according to claim 1, characterized in that the hydrocracking of the less than 0.0001 weight percent nitrogen-containing hydrocarbon oil in the presence of a hydrocracking catalyst is effected, the 0.01 to 1 weight percent platinum to a 0.01 to 3.0 weight percent Contains bound fluorine and / or chlorine-containing alumina. Considered publications:
German Patent No. 848 351;
U.S. Patent No. 2,911,356. Legacy Patents Considered:
German Patent No. 1 131 346. A priority document was displayed when the registration was announced. 1 sheet of drawings 709 610/466 7.67 © Bundesdruckerei Berlin