DE2516416A1 - NEW CATALYST FOR THE CONVERSION OF HYDROCARBONS - Google Patents

Description

New catalyst for the conversion of hydrocarbons.

The present invention relates to a new catalytic composition with exceptional properties in terms of selectivity and activity, but especially in terms of resistance against aging and with several successive regenerations when considering this catalytic composition used for the conversion of hydrocarbons.

In these processes, catalysts of the so-called bi-functional type are generally used. These are catalysts that simultaneously have a hydrogenating-dehydrogenating effect and a puncture, which are referred to as ^M acid ^M character.

Catalysts of this type are in the scientific literature and found very often in patents.

The standard type of catalyst most widely used to date generally has _a ) a base or support that

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usually carries the acid function, which can be modulated by introducing a suitable compound such as halogen or a halogen derivative, and _b ) at least one noble metal from group VIII, usually platinum - which has the hydrogenodehydrogenating effect.

The catalysts of this type usually give satisfactory results, however, they are generally poorly selective and poorly resistant to aging. To eliminate these disadvantages, nan has a new and numerous generation over the past few years invented by bimetal catalysts.

Recently, our work on developing a type of catalyst led on the basis of aluminum oxide, which may be a Contains halogen and at least one noble metal from group VIII of the periodic table and two metals from group VII B of the periodic table (rhenium, manganese) and / or IV A of the periodic table (Germanium, tin).

The addition of at least two metals from group VII B and / or IV A for the carrier not only gives it acid properties that are very favorable in terms of the selectivity of the end product, by very strongly inhibiting the cracking effect and at the same time preserving the isomerizing effect; moreover carries this addition helps stabilize the structure and texture of the final catalyst and consequently reduces one of the causes the aging of the catalyst and improves the dispersion of the noble metal of Group VIII, which is the dehydrogenating-hydrogenating Property bears.

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The catalytic composition according to the invention also has the advantage that in the order of magnitude of particles it is possible to manipulate which mechanical properties (friction, crushing) have that which are superior to an aluminum oxide without an additive. We have also found that catalysts consist of a support, a metal of Group VIII and a single metal of Group VII B or IV A (and not two metals of Group VII B and / or of group IV A), are in the form of particles, the fineness of which makes these catalysts hydrogenilizing, wherein at the same time there is a considerable tendency for the particles of these catalysts to sinter. If you according to the invention at least associating two metals of Group VII B and / or IV A, one can avoid a large part of these errors.

The catalytic composition according to the invention is much more active, more selective and especially more resistant to aging than the compositions described above, such as those which contain alumina and the following pairs: Pt-Ge, Pt-Sn, Pt-Pb and Pt-Mn.

The catalysts of the present invention can be used for a wide variety of hydrocarbon conversion reactions such as isomerization, dehydrogenation, hydrogenation, hydro-dealkylation, Hydro-cracking, dehydro-cycling, polymerisation etc ..

Very often these catalysts are used in processes at where several of these reactions take place at the same time.

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An example of this type of process is catalytic ^ Reforming or the recovery of aromatic hydrocarbons (Aromatization "Aromizing"), in which one by the catalyst a petroleum fraction passes, which generally consists of a mixture of paraffinic, naphthenic and aromatic Hydrocarbons.

The catalytic converter is located

1. either in multiple fixed bed reactors, where appropriate the possibility exists that a replacement reactor is provided, which is set in puncture, while the catalyst of the regenerating a fixed bed reactor;

2. or in one or more liquid bed reactors;

3. or - which usually turns out to be one of the best solutions, if you want to work continuously for a long time - in at least one reactor with a mobile bed; the method (described in the French Patent No. 2 160 269) consists in that the charge and the hydrogen are circulated through at least one reaction zone, e.g. a granular one Contains catalyst introduced progressively through one of the two ends of the reaction zone and progressively through the other of the both ends of the reaction zone is withdrawn, whereupon the progressively withdrawn from the reaction zone catalyst in a Regeneration zone conducts the catalyst, once regenerated and reduced in the presence of a hydrogen stream, progressively reintroduced at the end of the reaction zone opposite that end through which the catalyst is withdrawn

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replace the catalyst withdrawn from the reaction zone, so that an increased and practically constant level of activity is maintained at every point in the reaction zone.

The entire batch and the catalyst are subjected to such conditions that isomerization and dehydrocyclization of the Paraffins and a dehydration of the naphthenes is effected and a product rich in aromatics with increased octane number is obtained.

An example is the hydro-dealkylation of aromatics Mentioned using similar devices, e.g. that of! Toluol zu Benzene or that from methyl naphthalene to naphthalene.

Another example is isomerization. You can also in similar devices containing the catalyst, with suitable Reaction conditions a hydrocarbon charge that is rich is an n ~ paraffins, convert to products that are rich in isoparaffins or you can get an aromatic batch that is rich in Cg hydrocarbons and has a composition very different from the thermodynamic equilibrium, convert it into a product, whose composition is closer to that of equilibrium.

All these foregoing reactions v / ground usually in a temperature range of 300 - 600 ⁰ C performed. As for the reforming reactions in particular, they are generally

at a temperature of about 450 - 600 ⁰ C under a pressure of βίο
wa 5-20 kg / cm carried out, with the hourly throughput at

0.5-10 parts by volume of the liquid charge (naphtha, which is at approx

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60-220 ° C distilled) per part by volume of catalyst. As far as the dehydrogenation reactions of saturated hydrocarbons (e.g. those with 5 - 40 carbon atoms per molecule) are concerned, these reactions are usually carried out at a temperature of 300 - 60O ⁰ G under a pressure of 0.1 - 20 kg / cm ² carried out, the hourly throughput being 0.1-30 parts by volume of the liquid charge per part by volume of catalyst. The molar ratio of hydrogen / hydrocarbons at the reactor inlet is usually 0.1-30. In the dehydrogenation reactions of saturated hydrocarbons (and uaphthenes), the catalyst usually does not contain any halogen.

The catalyst according to the invention contains

a) an aluminum oxide carrier,

b) at least one noble metal from group VIII of the periodic table, i.e. from the group platinum, palladium, iridium, ruthenium, rhodium and osmium,

c) a metal pair of group VII B (manganese or rhenium) or group IV A (germanium or tin), the pair consisting of the combinations Manganese-germanium, manganese-tin or rhenium-manganese "can exist.

The catalyst according to the invention preferably contains (based on the weight of the catalyst support) 0.005-2% by weight, in particular 0.05-1% by weight of at least one noble metal from group VIII of the periodic table and 0.01-10% by weight, in particular 0.1-5% by weight any of the above two Group VII B and IV A metals, i.e. manganese, rhenium, germanium and tin. All percentages are

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pull on the metallic elements.

The catalyst optionally also contains 0.1-10% by weight or more, preferably 0.2-5% by weight (based on the catalyst support) of a halogen such as chlorine or fluorine.

The structural properties of the catalytic carrier can also be of importance. So that you can work with sufficiently high flow rates during reforming and the Avoiding the use of reactors with too large a capacity using a prohibitive amount of catalyst, the specific upper

ρ ρ

surface of the carrier greater than 5 m / g, preferably 50 - 600 m / g, in particular 80-300 m / g. The porous volume of the support is generally greater than 0.2 cm / g.

The catalyst can be prepared according to the classical methods, the support being impregnated with the solutions of the metal compounds to be introduced. Either a common solution of these metals is used or separate solutions are used for each metal or group of metals. Aqueous solutions or solutions in hydrochloric acid or in alcohol are preferably used. If several solutions are used, intermediate drying and / or calcinations can be carried out. Usually it ends with a calcination zBbei about 500 - 1000 ⁰ C, preferably in the presence of free oxygen, for example by performing air purge.

Examples of compounds of germanium and tin are

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mentions the chlorides, nitrates, bromides, sulfates or any other Salts of these metals which are soluble in water or hydrochloric acid. Complex salts should also be mentioned here, e.g. the oxal-germanium and citric acid complexes, acetylacetonates, organometallic complexes Etc..

Examples of manganese compounds are the nitrates, chlorides, bromides, fluorides, sulfates or acetates of manganese or any other manganese salt that is soluble in water or hydrochloric acid such as manganese chloroplatinate.

Examples of rhenium compounds are rhenium heptoxide, Ammonium perrhenate, acetylacetonate or other complex derivatives, which are soluble in water, acids or other suitable solvents.

The platinum can be used in any known form, e.g. as hexachloroplatinic acid, ammonium chloroplatinate, platinum sulfide, Platinum sulfate or platinum chloride.

The halogen can originate from one of the abovementioned halides or can be introduced in the form of hydrogen chloride or hydrogen fluoride, ammonium chloride, ammonium fluoride, gaseous chlorine or as halogenated hydrocarbons such as, for example, CCl ,, CHCl ₇ or CH ^ Cl.

A first method of preparation consists zBdarin by impregnating the carrier with an aqueous solution containing the metal of group YIII, zBPlatin with using a solution of hexachloroplatinic acid, followed by drying at 120 ⁰ C and a few hours

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a temperature from 300 to 600 ⁰ C, preferably about 500 ⁰ G, calcined in air; then followed by a second impregnation with an aqueous solution of nitrate or other compound of germanium, tin, rhenium or manganese, whereupon at 110 ⁰ C dried and several hours at a temperature of 450-700 ⁰ C, preferably at about 550 C, calcined in air.

Another method is to impregnate with a solution which also contains the following components:

1. platinum (e.g. hexachloroplatinic acid);

2. Hangan, germanium, rhenium or tin (e.g. a chloride, bromide, Fluoride, sulfate, acetate etc. of manganese, rhenium, germanium, Tin or any other salt of these elements that is soluble in water or hydrochloric acid such as manganese chloroplatinate, ammonium oxal germanate, Platinum-tin-II or IY complexes etc.);

3. optionally chlorine or fluorine.

Another method is to get the platinum last introduces after having already the other metals of group YII B and IV applied A to the carrier.

A preferred process for preparing the catalysts of the invention is that in the first stage on the Carrier first one of the two metals of the above-mentioned combinations or also part of the other metal of these combinations brings up. Subsequently, in a further stage, the noble metal of group VIII and is brought together or separately the other metal of this combination or an additional

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Amount of the first metal in this combination that you put on the Carrier had applied in the first stage.

This last-mentioned production method for catalysts consists in first applying the selected support in the first stage applies at least part of at least one of the two metals of the combination selected from the above group, so that a carrier hereinafter referred to as "modified carrier" is obtained.

The metal (s) added at this stage is called "modifying Element "or as" modifying elements ",

In this first stage, this preparation is preferably added method to a single of the two metals of the chosen combination (i.e. a single modifying element), with the entire Metal is introduced during this first stage.

The modifying element (s) can be mixed directly by dropping them together on the chosen carrier, or they can be added by impregnating the chosen carrier with a solution containing the chosen modifying element or contain the selected modifying elements in a suitable amount, followed by drying and calcining.

In this first stage, preference is given to using a carrier which consists of aluminum oxide with a specific surface area of 80 - 300 m / g and a porous volume of 30 - 80 cm / g. Hereinafter a table is given for illustration in which Art

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some modified carriers are listed. The table contains in Compact JOrm the compound used for the modifying element and the final treatment required to recover the modified carrier.

The impregnations are generally carried out dry, d.fy with an amount of the modifying element-containing solution equivalent to the porous volume of the selected support is.

üodi & adorned carrier with 0.2 Wt% made of Temperature and
Duration of dry Hours. Temperature and
Duration of the calc Hours. Mn nens renation «Al ₂ 0 with 0.2 Wt% Manganese nitrate 100 ° C / 4th Hours. 600 ° C / 4th Hours. Ge Al ₂ O with 0.4 Weight % Oxal germanium 100 ° C / 4th Hours. 600 ° C / 4th Hours. ! Sn acid LkIpCU with 0.2 Weight-76 Oxalotin acid 100 ° 0/4 Hours. 550 ° C / 2nd Hours. re Al Oj Ammonium perrh 100 ° C / 2 55O ° C / 1st I. nat

In the first stage of the preferred method for preparing the catalysts, 0.01-10 % by weight (based on the support), preferably 0.1-5% by weight, of at least one of the two metals is added to the selected support selected combination from groups VII B and IV A. Preferably, 0.01-10% by weight (based on the carrier), in particular 0.1-5% by weight of a single

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gen of these two metals of the chosen combination.

In the second stage of this preferred method for preparing the catalysts according to the invention, the noble metal of group VIII of the periodic table and at least part of at least one of the two metals of the selected combination are introduced onto the modified support. Preferably, apart from the Group VIII metal, one of the two metals of the selected combination is introduced in this second stage, while the other metal has been applied to the support during the first stage. In the second stage, 0.005-2% by weight, preferably 0.05-1% by weight of platinum and 0.005-10% by weight, preferably 0.05-5% by weight, are added (based on the weight of the support) ? i> of at least one of the two metals of the selected combination of groups VII B and IV A. Is preferably carried out in this second stage, from 0.005 to 10 wt -.% T preferably 0.05 - 5 wt .-% of a single one of the two metals of a selected combination, the total amount of the first metal of this combination on the support during the first stage was applied.

In this second stage, the Group VIII noble metal and the Group VII B and / or IV A metal (s) become more common Way introduced by a suitable method, as it has already been indicated above, e.g. by co-precipitation or successive impregnations.

In the following examples, the invention is explained in more detail without that it should be limited to this:

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example 1

Two catalysts A and B are prepared, one specific

ρ · ζ

Have a surface area of 220 m / g, a porous volume of 55 cm / g and a chlorine content of 1.05 %.

These catalysts are prepared as follows: for catalyst A, which is not a catalyst according to the invention, an aluminum oxide with a specific surface of 240 m / g and a porous volume of 56 cm / g is used.

100 g of this carrier are mixed with 100 cm of an aqueous solution, which contains the following components:

1.90 g concentrated hydrochloric acid (containing 37.5% HCl), 14.00 g of an aqueous solution of chloroplatinic acid with 2.5 G-ew.-tf platinum,

30.00 g of an aqueous solution of the oxal-germanium complex with 1.7% by weight germanium.

It is left in contact for 5 hours at room temperature, with mechanical homogenization every 5 minutes. It is then dried in air for 2 hours at 100 ⁰ C and then calcined for 2 hours at 53o ⁰ C with a stream of dry air (over activated alumina dried).

The catalyst obtained contains (based on aluminum oxide): 0.35% by weight of platinum,
1.05% by weight chlorine,
0.5 wt% germanium

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Catalyst B according to the invention is prepared using the preferred manufacturing method described above. The same aluminum oxide is used as for catalyst A and modified with manganese in the form of acetate by dry impregnation in the presence of excess acetic acid. The mixture is left 6 Matured for hours at room temperature.

Then it is dried at 110 ^° C. and calcined for 4 hours at 700 ^° C. with dry air (dried over activated aluminum oxide).

100 g of this manganese-aluminum oxide (0.4% by weight of Mn) are mixed with 100 cnr of an aqueous solution containing the following components:

1.90 g of concentrated hydrochloric acid (containing 37.5% HCl), 14.00 g of an aqueous solution of chloroplatinic acid with 2.5 wt -.% Of platinum,

30.00 g of an aqueous solution of the oxal-germanium complex with 1.7 wt. ~: # germanium.

The whole is left in contact for 5 hours at room temperature, with mechanical homogenization every 5 minutes. It is dried in air, then 2 hours at 100 ⁰ C and then calcined for 2 hours at 53o ⁰ C with a stream of dry air (over activated alumina dried).

The final catalyst contains (based on aluminum oxide):

. 0.4 wt -% of manganese (manganese in the catalyst is substantially in the form of the oxide before; this also applies to all other examples, the number% number manganese refers to the metallic element.) 509844/1087

0.35 Ge% platinum
1.05 wt% chlorine
0.5 wt% germanium

The behavior of these two catalysts is being tested with n-heptane investigated.

The reaction conditions used are as follows:

Pressure 10 "bar

Hydrogen / hydrocarbons molar ratio 8

Weight of n-heptane / weight of catalyst / hour 4

The temperature at the reactor inlet is 51O ⁰ C. The product obtained is analyzed in the 20th and 120.Stunde the test period.

In Table I, for the catalysts A and B used, the molar yield is toluene and the amount of light hydrocarbons obtained and the light hydrocarbons / toluene ratio indicated, whereby the selectivity of the catalyst is characterized (under light hydrocarbons one understands the Fraction Cj - C.).

The selectivity of the catalyst is the better, the lower the amount The ratio of light hydrocarbons / toluene is.

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Table I.

Kataly
sator Composition (wt .-%)
"based on aluminum
oxide Pt Ge j Cl 1.05 Time
(Stun
the) %
toluene
(mol) % slightly
te KW
(mol) easy
KW / To-
luene A. Mn 0.35 i
0.5 1.05
ί 20th
120 25th
18th 35
35 (mol) B. 0 0.35 0.5 20th
120 25th
24 33.5
31 1.4
1.95 0.4 1.34
1.29

This table shows that the use of catalyst B instead of the catalyst A markedly improves the selectivity. The catalyst B has a better stability of the dehydroziklisende Acts as the catalyst A.

Example 2

With regard to example 1, one might think that with the Catalyst B obtained better results than with catalyst A because manganese was simply added to catalyst B. Compares one now in Table II (in a test with n-heptane under the same reaction conditions as in Example 1) that with the catalyst B results obtained with those of catalyst C, which contains more manganese than catalyst B (0.5% instead of 0.4%) and which was prepared in the same way as Catalyst B, it is found that Catalyst B is better Achieved results, but with the catalyst C better results

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nits than the catalyst A provides.

The heptane test was also ^{repeated with a catalyst B 1} , the composition of which is identical to that of catalyst B, but which was prepared by a more classic method as follows:

The catalyst B 'is obtained by adding 100 g of aluminum oxide 100 cm of an aqueous solution containing the following components:

1.90 g concentrated hydrochloric acid (containing 37.5% HGl), 14.00 g of an aqueous solution of chloroplatinic acid with 2.5

Wt .-? O platinum,
30.00 g of an aqueous solution of the oxal-germanium complex with 1.7% by weight of germanium,

9.60 g of an aqueous solution of manganese acetate with 5 wt .-? O Manganese.

The rest of the manufacturing process is the same as for the other catalysts A and B.

The final catalyst B ¹ (based on alumina): 0.35 wt -% platinum.
0.5 wt% germanium
0.4% by weight manganese
1.05 wt. 56 chlorine

The results obtained with catalyst B ^{1 are} somewhat less than with catalyst B.

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Table II

Kataly
sator Composition (wt .-%)
based on aluminum
oxide Ge Mn Cl Time
(Stun
the) %
toluene
(mol) % slightly
te KW
(mol) easy
KW / To-
luene B. Pt 0.5 0.4 1.05 25th
24 33.5
31 (mol) C. 0.35 0.5 0.5 1.05 20th
120 .25
22nd 33.5
32 1.34
1.29 B ' 0.35 0.5 0.4 1.05 20th
120 25th
23.1 33.5
32 1.34
1.48 0.35 20th
120 1.34
1.38

Example 3

One might nonetheless think that the properties of the final Catalyst B are the consequence of the special method of introducing manganese into aluminum oxide and that the presence of germanium is not absolutely necessary.

The present example shows that the absence of germanium leads to a considerable decrease in activity and selectivity the catalyst leads. In Table III are the results of n-heptane tests under the same reaction conditions as in reproduced in the preceding examples. The catalyst D is prepared in the same way as the catalyst B, but contains no germanium.

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The catalyst D is made from the same modified carrier as the catalyst B prepared (manganese-aluminum oxide) in the same Yfeise as the catalysts A and B. 100 g of the carrier 100 cnr of a solution containing the following ingredients are added contains:

1.90 g concentrated hydrochloric acid (containing 37.5% HCl), 14.00 g of an aqueous solution of chloroplatinic acid with 2.5 Wt% platinum.

The method of preparation of the catalyst D is the same as that of the previous catalysts.

The solid obtained contains ( "based on aluminum oxide): 0.4 wt .- o manganese is combined with aluminum oxide 1.05 Grew -% chlorine?.
0.35 wt. 96 platinum

Table 'III

Kata
lysa
gate carrier
behan
delt Composition (wt .-%)
based on aluminum
umoxyd Ge Mn Cl Time
(Stun
the) %
Tolu
oil %
easily
te KW easily
te KYf /
toluene Around
Wall
lung with Pt 0.5 0.4 1.05 (mol) (mol) (mol) B. Mn 0.35 0 0.4 1.05 20th
120 25th
24 33.5
31 1.34
1.29 94
92 D. Mn 0.35
j 20th
120 21
20th 33
30.5 1.57
1.53 93
89

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Example 4

According to the technique used for the preparation of catalyst B, catalysts E and P are shown, the composition of which and the results obtained with these catalysts are shown in Table 17, as are the results with catalysts E ^f and P ¹ which do not contain manganese contain.

The catalysts E, P, E ^f and P »all contain 1.05 wt .- ^ chlorine.

Table IV

!
Kata- Composition (wt .-%) Ma 3rd element Time % % Around easily lysa- based on aluminum 0.4 0.5% rheni (Stun Tolu easy- Wall te KW / umoxyd around the) oil I te KW lung toluene !gate Pt 0 0.5% rheni (mol) (mol) (mol) -77 » 0.35 around 20th 25th 34 94 1.36 0.4 0.5% tin 120 23.8 31.4 91.5 1.32 E ' 0.35 20th 20.6 33 93 1.6 0 0.5% tin 120 19th 30.5 89 1.61 P. 0.35 20th 25.8 33.8 94.5 1.31 120 24.9 32.6 93 1.31 ί p. 0.35 20th 21.5 33.3 92.8 1.55 120 20.1 32 88 1.59

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Claims (1)

Claims Catalyst, consisting of (a) an alumina carrier, (b) at least one noble metal from group VIII of the periodic table, namely platinum, palladium, iridium, ruthenium, rhodium or osmium, (c) a metal pair from the combination group manganese-germanium, manganese-tin and rhenium-manganese. 2. Catalyst according to claim 1, characterized in that it (based on the catalyst support) 0.005-2 wt .-% at least of a noble metal and 0.01-10% by weight of each of the two metals of the combinations mentioned. 5. Catalyst according to claim 2, characterized in that it (based on the catalyst support) 0.05-1 Gev /, -% at least of a noble metal and 0.1-5% by weight of each of the two metals of contains the combinations mentioned. 4. Catalyst according to Claims 1 to 3, characterized in that it also contains 0.1-10 % by weight of halogen (based on the catalyst support). 5. Catalyst according to Claims 1 to 4, characterized in that the noble metal is platinum and the metal pair is manganese and tin used. 6. Catalyst according to Claims 1 to 4, characterized in that the noble metal is platinum and the metal pair is rhenium and Manganese used. 50984A / 1087 7. Process for hydroconversion of hydrocarbons in the presence of a catalyst according to claims 1 to 6. 8. A method for reforming in the presence of a catalyst according to Claims 1 Ms 6. 509844/1087