DE1804768A1 - Process for improving petroleum fractions through catalytic hydrogenation - Google Patents

Description

DR. GERHARD RATZEL PATENT ADVOCATE

68 MANNHEIM 1, October 13, 1968 Seckenheimer Str. 36 α · Telephone 46315

Poit "ch" cklconto> Frankfurt / M. No. 8293 Lanki Ocutsdi «Bank Mannheim No. 72/00066 T · I · g r. Cod «ι Gtrpar

1804763

INSTITUT FEiLNGAIS DU PETROLE DES OAEBUBANTS ET LUBEIPIANTS 1 & 4, avenue de Bois-Preau 92 EUETJi-MALMAISON / France

Process for the improvement of petroleum fractions by catalytic hydrogenation.

The petroleum fractions resulting from the direct distillation of the crude oil and the products of pyrolysis operations such as the 'steam cracking' ¹ , the "coking" and the "visbreaking operation" are mainly due to unpleasant odor properties and their instability and corrosion properties, as well as other disruptive properties, are generally not marketable.

The refining by hydrogenation has therefore aims to improve these products so that their properties and its value correspond to the requirements \ refining is carried out by passing the feed in the presence of hydrogen over

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Catalyst which - expressed in summary - has two functions j the function of bringing about the hydrogenation and the function a cracking effect.

The catalysts of the cobalt or molybdenum f type, which on a Aluminum oxide carriers with a large specific surface, for example one of more than 120 m / g, are arranged and have a considerable cracking activity, so to speak represents the first generation of refining catalysts; Although these catalysts still have a certain usefulness, the Multiplication of the fractions to be treated and the increasing The strictness of the regulations to be observed have changed the problems; on the side of classic hydro refining (Elimination of sulfur, nitrogen, traces of metal and hydrogenation of unsaturated products) it has become necessary the treatment method is less harsh, but to a greater extent selective with regard to the treatment of possibly more unsaturated Products.

Of these less severe or vigorous methods of treatment, without this signifying a limitation, the hydrostabilization of certain pyrolysis waste gases should be mentioned, in particular the hydrogenation of diolefinic compounds that are present in the outflowing gases, as well as the hydrogen treatment of oil fractions with the aim , their improvement, for example with regard to color and color stability, also with regard to their viscosity properties, their oxidation stability, etc. Oil fractions are understood in particular to mean the distillates which boil ^{at 76 cm Hg above 35O 0 O.}

In practical application it has been shown that the classic refining catalysts for this type of selective hydrotreatment, which with certain. Batch types is necessary, do not fully satisfy. In fact, the classic catalysts have a number of disadvantages

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ORIGINAL INSPECTED

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with himself. In the case of the pyrolysis products, one observes an inevitable Polymer formation from a batch that contains highly unsaturated compounds, with deactivation also occurring very quickly the catalyst enters; one is therefore forced to frequent regenerations of the catalyst; in the case of the oily Distillates cause excessive cracking of the feed, which takes place on the catalyst supports in general, in particular Loss of yield due to a greatly increased formation of light products and a decrease in certain qualities, for example the Viscosity of the oils.

It has now surprisingly been found that when you transfer of petroleum fractions, for example an oily fraction or a fraction that consists of a

"Coking", a "visbreaking operation" or a "steam cracking" originates in the presence of hydrogen over a catalyst which has been produced by treating metals from groups VIA and Vllldem aluminum oxide with a specific surface area between 40 and 100 m / g and a pore volume between 0.4 and 0.8 cm-vg and preferably between 0.6 and 0.8 cm / g. with more than 75 % of the pore volume having pores of a diameter between 100 and 2000 angstroms, the acidity being weak or zero _r incorporated ", it is possible to obtain refined products with selectivities and yields which are substantially better than those which are can be achieved with the use of classic hydrogen treatment catalysts with a high specific surface area.

Furthermore, the catalysts prepared by impregnating the alumina just described have a hydrogenation activity even in the presence of sulfur, without significant cracking or coke formation taking place, which is the case to a considerable extent when conventional catalysts using ordinary alumina are used.

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The catalysts of the invention are therefore particularly suitable for Interesting stabilization treatments that precede a classic Treatment mode can be switched, such as hydrodesulfurization; however, their availability is not limited to this case.

The aluminum oxides to be used according to the invention can be different Manner, for example according to the procedures described in the French patents 1,386,364 of December 2, 1963 and 1,449,904 of July 9, 1965 are described

These methods consist in that aluminum oxide treated with a large specific surface in an autoclave with water at a temperature of the order of magnitude of 150 to 25O ⁰ O, optionally in the presence of an acid. The aluminum oxide is then calcined.

In this way, the specific surface area is reduced and the macroporous volume is increased, while at the same time creating good mechanical strength. Further, the activity is an aluminum oxide produced in this way in general ^v my very low. You can go through this if necessary. Reduce the incorporation of alkali compounds or alkaline earth compounds, such as NapO, CaO, KgO, even further.

On the other hand, any other process that leads to an aluminum oxide, which has the properties described above, leads, can be carried out.

The activity of the aluminum oxides is determined by measuring the heat of adsorption of ammonia on alumina under a pressure of

—4
Measured 10 mm Hg. This value is calculated on the basis of the microgravimetric weight determination and the thermal measurement using differential thermal analysis.

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- Sheet 5 The formula for calculating the heat of adsorption AH is:

ΔΗ heat released (expressed in κ calories per κ ΑΙ , -, Ο ,.) amount of adsorbed HH, (expressed in millimoles

⁰ per gram A)

These measurements are made at the temperature at which the corresponding catalyst is to be used (for example at 340 ° 0 in the case of example 1),

This heat of adsorption gives the mean strength of the acidic centers • the carrier.

The aluminum oxides used according to the invention with weak activity have a ΔΗ of less than 0.04-.

A support is therefore used with a weak acidity or one of zero acidity, which in any case is considerable specific surface, i.e. a surface of more than 4-0 m / g. Everyone proves this "intrinsic neutrality" other measure than superior, for example the addition of alkali metal.

As examples of metals of groups VI ^ and VIII that can be incorporated of the periodic system which are added to the aluminum oxide according to the invention are cobalt, iron, nickel, molybdenum and Called tungsten.

Preferred pairs are the nickel-molybdenum pair and the cobalt-molybdenum pair others of their group may be present on the aluminum in the form of their oxides or sulphides.

As for the continuous detailed technique of making the erf indungsgemäss As catalysts to be used, it must be said that this is well known in the art and a detailed description is not necessary here. These

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The procedure generally consists in that aluminum oxide, which has the properties given above, is impregnated with a solution of the metals of groups VI ^ and VIII or with two specific solutions and then the carrier impregnated in this way is dried and then at a temperature of preferably above 50O ⁰ O calcined. The catalyst obtained in this way can be reduced with hydrogen and, if appropriate, treated with a sulfur compound, for example by means of a stream of hydrogen sulfide, before it is actually used.

The batch to be treated can be very different in nature; it can, for example, as already stated above, from an outflowing The medium of a "visbreaking operation", a "coking" or a "steam cracking" can also be made of oil-like There are fractions of a vacuum distillation, preferably with a solvent for the purpose of extraction of aromatic Connections has been dealt with.

The catalysts produced by the impregnation of the carrier generally contain from two to twelve percent by weight of a Group VIII metal and from 5 to 16 percent by weight of one Group VI metal ,, these metals being calculated in the form of their oxides, for example as CoO and MoO ,,.

It is allowed to these petroleum fractions over the catalysts disclosed at a temperature between for example 150 and 450 ⁰ C and preferably between 250 and underline 35O ⁰ C, and a pressure between 1 and 100 atmospheres.

The hourly volume throughput of batch to be treated per unit volume of catalyst is generally between 0.05 and 10 liters per liter and hour.

The volume ratio of gaseous hydrogen / liquid charge is generally between 50 and 500 (measured at normal temperatures

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temperature and pressure conditions) 5 higher ratios can also be used exist, although these are less advantageous.

The following examples illustrate the subject matter of the present invention, but are in no way limiting in nature.

Example 1:

An oily fraction obtained by distilling crude oil in vacuo is treated with for the purpose of reduction Hydrogen. This fraction, which is called "cylinder raffinate", was previously treated with methylethyl acetone for the purpose of extraction treated with aromatic compounds. The resulting product, which has not been freed from paraffins, was then in the presence treated by catalysts based on cobalt and molybdenum, which are arranged on the aluminum oxide support.

Two identical experiments were carried out, namely one with a catalyst A, which is produced using classic aluminum oxide with a large specific surface and the other with a catalyst B, which was produced using an aluminum oxide with a reduced specific surface area but its macroporous volume was significant and its acidity decreased. The comparative properties of these two aluminas are as follows Table I given.

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Sheet 8 O) TABLE I

properties classic aluminum
oxide Aluminum oxide
according to invention Specific upper
area in m / g 220 70. Pore volume in
cmVg 0.70 0.60 Pore diameter 30 % pore volume ent
speaking pores of
more than 2000 2. Pore volume ent
speaking pores
of a diameter
between 100 and
2000 A Medium Adsorp
tion heat
g cal / mmol NH, 0.06 0.03

In both cases the catalyst contained 6 percent by weight cobalt and 6 percent by weight molybdenum, calculated as oxides GoO respectively.

The process conditions of the hydrotreatment were as follows:

- Total pressure: 60 kg / cm

- Temperature: 340 ° 0.

- Throughput: 1 liter batch per liter of catalyst and

hour

- Throughput of EUs 150 liters per liter batch (measured at

Normal conditions).

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The characteristics of the batches and the products obtained from these two cases are given in Table II below.

TABLE II

properties Before the water After hydrotreating With cata
gate B according to
invention 15th
Density d ^. fabric treatment With a catalyst
A. 0.895 Viscosity at
50 ⁰ C in cSt 0.899 0.892 124 colour
ASTM-D-1500
- in front of the old woman
tion *
- according to the Al
treatment 139 118 3.5
4.5 Sulfur in Ge
weight percentage I.
00 03 5
6.5 0.57 0.87 0.56

♦ Please see the explanation following Table III.

It should be noted that in the process according to the invention, that is to say when the batch is treated in the presence of catalyst B, which was prepared using aluminum oxide which has the properties given in Table I, the loss of density of the raffinate is significantly lower than in the case of Use of the classic catalyst. This shows that when the catalyst B is used, cracking is reduced. Furthermore, both the color and the color stability of the product that is produced using the inventive catalyst

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tors manufactured, very much improved compared to the properties of the product made using the classic catalyst.

Example 2;

Catalysts A and B were again used, which are used at a temperature of 520 ° C. and otherwise identical process conditions as in Example 1, transferred batches that consisted of a light naphthene vacuum distillate.

The results obtained are summarized in Table III below .

TABLE III

properties Before the water After hydrotreatment; Catalyst B
(according to the invention) Density ₄ ¹⁵ st off treat
lung Catalyst A 0.905 Viscosity at 0.912 0.901 57 ⁰ O (in cSt) 21.8 50 ⁰ O (in cSt) 24.1 20.5 15.5 colour 14.7 12.9 ASTM-D-1500 - in front of the old woman
tion * 1.5 - according to the Al
treatment 8th 1.5 4.5 Sulfur wt% 8th 4.5 1.15 1.6 1.05

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♦ Aging "consisted of keeping the test pieces for 16 hours" at a temperature of 12O ⁰ O in an oxidizing atmosphere (test TJOP method 359-59).

Example 3 t

Two catalysts 0 and D were made that were 2.5 weight percent Nickel oxide NiO, 12.5 percent by weight molybdenum oxide MoO, and 85 percent by weight aluminum oxide.

The supports are the same as those used in the preparation of catalysts A and B, respectively.

The cylinder raffinate from Example 1 was treated with hydrogen in the presence of these two catalysts. The procedural conditions were the same as in Example 1.

The results obtained are summarized in Table IV below ·

TABEL

Properties of the with
Hp treated Raffi
nats Classic cataly-
0. Catalyst D
according to invention 4 ⁵ 0.890 0.892 Color before the old
tion
Color according to the old one
tion 3
4th 2
3.5 Viscosity at 50 ⁰ O
(cSt) 105 109 Sulfur in wt .- # 0.42 0.43

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It can be seen that the catalyst D is essential to a greater extent, compared with the catalyst 0, the viscosity and the color of the batch is improved, with the degree of desulfurization is very cheap.

It should be noted here that Examples 1 to 3 were used to to provide evidence that, in particular, the color and color stability of the batches have been significantly improved; the Desulfurization run is not an essential part of these examples.

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The amount of the hydrotreated fractions, both in the process according to the invention and in the classic processes, is significantly below the prescribed tolerance limits; In addition, the remaining sulfur is in a harmless form; If the desulphurisation is carried out too far, the oils even become unstable.

Example 4:

It became the outflow of a "visbreaking operation", which occurred in the interval 150 to 26O ⁰ C si '
treated with hydrogen.

Boils interval 150 to 26O ⁰ C and has a density of 0.807,

The hydrotreatment was carried out in the presence of catalysts E, F, G, each containing 8 percent by weight of NiO and 8 percent by weight MoO, arranged on an aluminum support, contained »carried out.

As far as the first two catalysts E and F are concerned, their aluminum supports are already above in their properties and correspond to columns II and III of Table Ϊ.

The carrier of the catalyst G is the same as that of the Catalyst E; in all cases the heat of adsorption of the aluminum oxide was initially 0.06 and was increased by the incorporation of Na ^ O reduced to 0.035 g calories / mmol NH; the remaining properties remained unchanged.

After 300 hours of operation, the maleic anhydride index became

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(Test UOP 326-58), the bromine index (ASTM-1159 AP II) and the stability measured against the oxidation at effluent from this hydrogen treatment.

The results obtained with regard to these three catalysts are summarized in Table V below.

TABLE V

properties Batch Catalyst E. Catalyst P Catal
gate G Maleic an-
hydride index 20th 0 0 0 Bromine index 60 50 39 45 Oxidation stabil
lity ♦ * 6 h 24 hours 48 h 30 h

** One measures the time in hours it takes to produce two milligrams of rubbery product per. 100 cm ^ of the product by blowing air into a specimen kept ^{at 82 0 C.}

It can be seen that only the catalyst F, in which all properties of the wearer comply with the provisions of the present invention, leads to good results.

If the catalyst E is used, the product obtained still has an increased bromine index and low oxidation stability.

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When using catalyst G the results are slightly better, however not yet satisfactory.

So you can see that the conditions given above (specific Surface, pore volume and pore distribution, acidity) all have to be fulfilled in order to make the progress according to the invention to achieve.

- ^ - / Claims:

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Claims (6)

- Sheet 15 - - Patent claim e 1.) Improved process for the treatment of petroleum fractions, in which these fractions are formed in the presence of a catalyst deposited on an alumina support from metals of Groups VI ^ and VIII of the Periodic Table of the Elements, in contact with hydrogen brings, characterized in that the aluminum oxide has a specific surface area of 40 to 100 m / g, a pore volume of 0.4 to 0.8 cnr / g, with more than 75% of this pore volume having pores with a diameter of 100 to 2000 Angstroms, as well as an acidity which, at the application temperature of the catalyst, corresponds to a heat of adsorption of less than 0.04 g-calories per millimole of NH. 2.) The method according to claim 1, characterized in that the pore volume is 0.6 to 0.8 cmvg, with more than 90 % of the pore volume pores having a diameter of 100 to 2l00 Angstrom. 3.) Process according to claims 1 or 2, characterized in that that the petroleum fractions consist of lubricating oils. 4.) Process according to claims 1 or 2, characterized in that the petroleum fractions from the effluent of pyrolysis opera ations, such as the "visbreaking process", the "coking" or the "steam cracking" exist. 5.) Process according to claims 1 to 4, characterized in that the catalyst 2 to 12 percent by weight of metal, expressed as metal oxide, namely cobalt, iron and nickel and 5 to 16 percent by weight, expressed as oxide, 9098 20/12 - Sheet 16 contains molybdenum and tungsten 6.) Process according to claims 1 Ms 5> characterized in that the contact at a temperature of 150 to 450 ⁰ C, a pressure of 1 to 100 atmospheres with an hourly volume throughput of liquid petroleum JFraction of 0.05 to liters per liter Catalyst and a gaseous hydrogen / liquid ratio. Petroleum fraction of 50 to 500 liters per liter measured under normal conditions. 909820/124 1