DD151877A5 - METHOD FOR ALKYLATING HYDROCARBONS - Google Patents

Abstract

The invention relates to a process for the alkylation of hydrocarbons having 4 C atoms, olefins and / or saturated hydrocarbons to form hydrocarbons of high octane numbers and is characterized in that as a catalyst aluminum-modified silicas with porous crystal structure and a specific surface of at least 150 m & exp2 ! / g of the general composition Si (0.0012-0.005) Al.Oy, wherein y represents a value of 2.0018 to 2.0075.

Description

Berlin, the 14.4.1980 divisional application

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Process for alkylating hydrocarbons Field of application of the invention

The invention relates to a process for the alkylation of hydrocarbons, nit 4 C-atoms, olefins and / or, saturated hydrocarbons ** to form hydrocarbons of high octane numbers.

Philosophy F ^e , K ^e , ^ ^a . ^{n, nt: en tecnn} ^ ^sc h ^er 'solutions

There are a number of methods for the alkylation of hydrocarbons known »They work for the most part with metal salts of organic and inorganic acids as catalysts.

On the other hand, a number of modifications of crystalline silicic acid or SiO _{2 are} known, such as cristobalite, tridium with keatite, etc., which can be prepared in a known manner. From Heidemann in Min. Petrog., 10, 242 (1964), it is known to react an amorphous silica with 0.55 % KOH at 180 ^° C. in 2/5 days to obtain a crystallized silica "Silica X" , their specific surface

is about 10 m / g, but has poor stability, since it ages to cristobalite within 5 days and eventually converts to quartz.

From Flanigen et al., Nature, 271, 512 (1978), the Her-,. Position of crystalline silicic acid known, "silicalite", which has a hoho specific surface area and due to their hydrophobicity is suitable for water treatment, in particular for the deposition of organic substances.

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It is an object of the invention to use modified crystalline silicas for the alkylation of hydrocarbons.

The object of the invention is to use aluminum-modified crystalline silicas of high stability as catalysts or for the preparation of catalysts.

It has surprisingly been found that substances with a very high ratio of SiO ₅ ,: Al _p O "can be obtained, which however are not zeolites, since the minimum amounts of aluminum contained therein are insufficient for a structure of silicoaluminate,

The new substances differ from crystalline silicic acids in that tiny quantities of aluminum can produce a wide range of acidity. Such substances have a protonic acidity which at least corresponds to the protonic form of the zeolites, while possessing a very high structural stability intrinsic to crystalline silicic acid, in contrast to that observed in the protonic forms of the zeolites A _{ X and Y. (except the mordenites), which become more stable as they are easily converted to more stable silicoaluminates.

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As such, the silicoaluminates have an acidity that is slightly lower; for example, it is in the range of 1 χ ίο "meq / gH ⁺ with a commercial Silicoaluminat containing 25 wt .-% A1 ~ O_.

It has surprisingly been found that by appropriate dimensioning of the amount of aluminum it is possible to adjust the acidity with regard to the application of the products. ", '" "

The object of the invention is now to show an aluminum-modified silica with adjustable acidity and catalytic activity 'for certain reactions. The new aluminum-modified silicic acids can be represented by the following formula:

Si. (0.0012 to 0, OO5) A1.O, where y is 2, is from 0018 to 2.0075.

Depending on the firing temperature, larger or smaller amounts of water of crystallization are additionally present.

The process for the preparation of the new products can be varied with regard to their special properties.

To prepare the novel aluminum-modified silica, a silicon and an aluminum compound in an aqueous, alcoholic or aqueous-alcoholic solution is reacted with a clath-rating or archivolt, optionally in the presence of one or more crystallization facilitators. where appropriate

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if an inorganic base can also be present. The reaction mass is then crystallized within a few hours to a few days at 100 to 220 ⁰ C. Preferably, the crystallization takes place at 150 to 200 C within a week. The crystal slurry is cooled, filtered, the crystals are dried and fired at a temperature of 300-700 ^° C., preferably at about 550 ^° C. for 2-24 hours, after which the product is washed to remove possibly exchangeable cationic impurities. namely with boiling distilled water in which an ammonium salt is dissolved, preferably the nitrate or acetate, whereupon it may optionally be fired again.

Suitable silicon compounds are, for example, silica gel (regardless of how this has been obtained) or tetraalkyl orthosilicates, such as tetraethyl or tetramethyl orthosilicates.

As the aluminum compound, salts such as the nitrates or acetates are preferred.

Suitable reactants include tertiary amines, amino alcohols, amino acids, polyhydric alcohols, and quaternary ammonium bases such as tetraalkylammonium, NR.QH, wherein R is an alkyl group of 1 to 5 carbon atoms, or tetraarylammonium, NR ¹ OH, where R 'is a phenyl - or alkylphenyl group.

These reaction components have the task of producing a crystal structure with pore-predetermined size, and are therefore correspondingly large molecules.

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Suitable mineralizers are the alkali metal or alkaline earth metal hydroxides and halides, such as LiOH, NaOH, KOH, Ca (OH) ", KBr, NaBr, NaO, CaD ₉ , CaBr".

The inorganic base used may be the alkali metal or alkaline earth metal hydroxides (NaOH ₁ KOH, Ca (OH) ₂ ) or ammonia.

As far as the amounts of inorganic base and / or reaction component are concerned, these are generally below the stoichiometric amount of the table, based on silica, with 0.05 to 0.5 mol / mol of SiO _{2 being} preferred.

The new products can be characterized by a protonic acidity, which can be influenced by the variation of the silicon-replacing cation. For pure SiO 2 the acidity is 1. 10 meq / gH ⁺ , but this can be increased to about 1 »10" by introducing aluminum.

The new materials are characterized by a well-defined crystal structure, as can be seen from the X-ray diffraction spectra of FIGS. 1 and 2.

They have a high specific surface of y 150 m / g,

in particular 300 to 500 m / g.

The presence of aluminum, which is so fundamentally capable of modifying the acidity of silica or silica, results in the formation of a crystalline material which is either substantially similar to the crystalline silicas known from the literature "silicates" (Nature, 271, 512 of 1978), or significantly different from them.

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The new aluminum-modified silicas are useful for catalysis or adsorption, either as such or dispersed in a more or less Erten * in carrier having a high or a low specific surface area and porosity.

The carrier has the task to improve the physical and mechanical stability and possibly also to influence the catalytic properties of the material. The preparation of such substances on carrier is done in the usual way.

The amount of carrier can be between 1 and 90 % , but 5 to 60 % is preferred.

The preferred carriers are clays, silicates or silicas, alumina, diatomaceous earth, silicoaluminates and the like.

The new aluminum-modified silicas are used for a wide variety of reactions as a catalyst, as for the alkylation of benzene, especially with ethylene or ethanol.

Further possible applications are the alkylation of toluene with methanol to produce xylene, especially p-xylene, disproportionation of toluene to p-xylene, reaction of dimethyl ether and / or methanol or other lower alcohols to hydrocarbons (olefins and aromatics), cracking and hydrocracking and isomerization of n-paraffins and naphthenes, polymerizing olefinisch- or ethylenically-unsaturated compounds, reforming, isomerizing polyalkyl substituted aromatics such as _t

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o-xylene, disproportionation of aromatics, especially toluene, reaction of aliphatic carbonyl compounds in at least partially aromatic hydrocarbons, separation of ethylbenzene from other C _ß aromatics, 'hydrogenation and dehydrogenation of hydrocarbons and finally for the methanation.

The invention will be further illustrated by the following examples.

example 1

Production of porous crystalline silicic acid TRS-22, in which aluminum has entered silicon lattice sites.

In a Pyrex glass vessel 80 g under nitrogen atmosphere tetraethyl-o-silicate (TEOS) was fed at 80 ⁰ C, whereafter a solution von.20 g of tetrapropylammonium hydroxide (obtained from tetrapropylammonium and moist silver oxide, that is free of inorganic alkali bases) in 80 cm ^J distilled water was introduced and stirred at 80 ⁰ C to homogeneity and clarity, which took about an hour *

Subsequently, 80 mg of Al (NO) -, -. 9HpO in 50 cm of absolute ethanol was added

It immediately formed a compact gel, the distilled water was added to a total volume of 200 cm; if necessary, was stirred. Finally, the mass was boiled to complete the hydrolysis and drive off ethanol, the added ethanol and also that released during the hydrolysis.

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These measures took 2 to 3 hours. The gel was then slowly and gradually converted to a white powder, which was the precursor of the modified crystalline silica.

This was added up to 150 cm of distilled water and the glass vessel is now placed in an autoclave and held at 155 ⁰ C for 7 days. After cooling, the solid was centrifuged at 10,000 rpm in 15 minutes, re-slurried in distilled water, the crystal pulp again centrifuged, and finally the crystals were washed four times with water. Then it was dried at 120.degree. X-ray diffraction analysis confirmed the crystallinity.

Chemical analysis of the dried at 120 ⁰ C Probet

SiO ₂ 83.0% by weight

Al ₂ O ₃ 0.2% by weight

Na ₀ O 0.18 wt%

ICO 0.02% by weight

Loss on ignition (1100 ^° C.) 16.6 %, molar ratio 704,

The alkalis contained in the product originate from the starting materials and from the glass; to these contaminants as a result of alkalis to be removed, the product was held for 16 hours in an air stream at .550 ⁰ C and then repeatedly with boiling distilled water, corresponds. holding Aromoniumacetat, washed and finally fired again at 550 ⁰ C for 6 hours.

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The product obtained had a specific surface area

(BET) of 444 m ~ / g, and the protonic acidity was

- 1 1.5. 10 meq / g.

B ei s ρ i e 1 2

Preparation of a porous crystalline silica TRS-O.

40 g of tetraethyl silicate and 120 cm of a 20% strength aqueous solution of tetrapropylammonium hydroxide (% by weight) were introduced into a Pyrex flask with reflux condenser and a nitrogen atmosphere and the whole was heated to boiling. A clear colorless solution was obtained, which remained clear even after long refluxing boiling. Now, 30 mg of A1 (NO _) _, .9H _? 0, whereby the mass became opalescent. Upon further heating, a white powder separated.

It was cooked for 6 days, after which the reaction mass was allowed to cool. The crystals were filtered off and washed with distilled water and finally dried at 100 ⁰ C. This product was X-ray crystal.

It was fired at 550 ^° C. for 16 hours in a stream of air and then washed repeatedly with boiling distilled water containing ammonium acetate. Finally, another 6 hours at 550 C was fired.

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Chemical Analysis:

SiO ₂ 96.2% by weight

Al ₂ O ₃ ' 0.2 wt.% Na ₂ O ₂ K ₂ O 0.02 wt

Loss on ignition (llOO ⁰ C) 3.58 % _t molar ratio SiO ₂ JAl ₂ O ₃ 816.

The traces of ¹ alkali metals are derived from the starting

and glass, specific surface area (BET) 420 m / g,

~ 1 protonic acidity 1.9. 10 meq / g.

B ₁ ice ρ ie 1 3.

Preparation of Porous Crystalline Silica TRS-23.

In a modification of Example 1, an organic base was used, namely tetraethylammonium hydroxide.

According to Example 1, 80 g of tetraethyl o-silicate, 68 cm of a 25 wt .-% aqueous solution of tetraethylammonium hydroxide, 80 mg of aluminum nitrate in 50 cm of absolute ethanol and 2 g of NaOH in 10 cm of distilled water for 18 days at 155 C. The resulting crystals were dried at 120 ⁰ C and was X-ray crystal. The protonic acidity was 1.1. 10 fiiAq / g of calcined at 550 ⁰ C sample. Chemical analysis after thorough washing and firing at 550 ^° C.:

SiO ₂ 96.3% by weight

.Al ₂ O ₃ . 0.2% by weight of Na ₂ O 0.03

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Ignition loss (1100 ^° C.) 3.47 %, molar ratio 816, specific surface area (BET) 470 m ² / g »protonic acidity 4.3. 10 niq / g _e

B e J ₁ game 4

Preparation of the porous, crystalline silicic acid TRS-19.

In this case, an organic base was used, namely Tet rabutylammonium hydroxide.

In a modification of Example 1, 50 g of tetraethyl oellicat, a solution of 100 mg of aluminum nitrate in 50 cm of absolute alcohol, a solution of 29 g of tetrabutylammonium hydroxide (obtained from tetrabutylammonium bromide and humid

3 silver oxide) in 120 cm of distilled water and 2 g of NaOH in

20 cm of distilled water in an autoclave for 16 days at 155 C. The product dried at 120 ° C was X-ray crystalline. Protonic acidity of at 550 "fired ⁰ C product 4,5 10". Meq / g, chemical analysis after thoroughly washing:

96 _f 0 wt .-%

₃ 0.3 GeWo-%

Na ₂ O 0.03 wt%

Ignition loss (1100 ^° C.) 3.67 %, molar ratio SiD ₂ : Al ₂ O Specific surface area (BET) 380 m ² / g _f 2.5 * ΙΟ "" ¹ meq / g.

The X-ray diffraction spectrum of this sample is shown in FIG.

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B e i spie 1 5

Production of Porous Crystalline Silica TRS-20 «

In this case, no inorganic base was used. The only alkali cations are trace impurities from the starting materials.

According to Example 1, 40 g of tetraethyl ~ o-silicate, a

3 solution of 100 mg of aluminum nitrate in 50 cm of absolute ethanol and 50 cm of a 40 wt .-% aqueous solution of tetrapropylammonium for 10 days at 155 C. The dried at 120 ⁰ C sample was X-ray crystal.

In order to use this product as a catalyst, it was calcined 16 hours in air at 550 C and then washed repeatedly with boiling distilled water which contained ammonium acetate. Finally, the crystals were fired again at 550 ^° C. for 6 hours. "

Chemical analysis: 96.1 wt _e -% SiO _2, 0.3 wt .-% Al ₂ O _3,

0.01% by weight of Na "O. Ignition loss (1100 ⁰ C) 3.59 %, molar ratio

- o

Si0 ₂ : Al ₂ 0 ₃ 544, specific surface area 500 m / g, acidity

4.7. 10 "l meq / g _e

B e i s ρ i e 1 6

Preparation of Porous Crystalline Silica TRS-57.

There were 80 g of tetraethyl-o-silicate, 80 mg'Aluminiumnitrat

in 50 cm of absolute ethanol and a solution of 27 g of tri-

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ethanolamine in 50 cm of distilled water according to Example 1 implemented.

Then, 7 g of sodium hydroxide was added and the glass jar was placed in an autoclave and held therein at 194 ^° C. for 7 days.

The dried at 120 ⁰ C product was X-ray crystal.

The X-ray diffraction pattern of this product is shown in FIG. 2,

Chemical analysis of the sample fired at 550 C: 96.2% by weight of SiO ₂ , 0.2% by weight of Al ₂ O ₃ , 0.05% by weight of Na ₂ O; Weight loss (1100 ^° C.) 3.55 %, molar ratio. SiO ₂ : Al ₂ O ₃

816. Specific surface area (BET) 344 m ² / g, acidity 1.5

- 1 . 10 meq / g.

Ba i s ρ i e 1 7 (comparison)

In this example, the absence of catalytic! Proportional dehydration of modified crystalline silicic acid TRS-22, corresponding to Example 1, containing sodium ions, exhibiting an acidity

-4 of only 4.1 x 10 meq / g.

As an example of a dehydration reaction, the formation of dimethyl ether from methanol was chosen.

An electrically heated tube reactor - inside diameter 8 m -

3 was filled with 4 cm (2 g) of catalyst according to Example 1 - grain size 0.177 to 0.59 mm - and in dry Stickstoffst rom

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Heated to 500 ⁰ C for 2 hours.

Methanol was fed at 240, 300 and 400 ^° C, with a throughput rate (WHSV) of 1.75 g / g. H.

In all three Verfahronsvarianten no dimethyl ether could be found in the process, but one received only unchanged methanol.

Catalytic activity on the dehydration of the modified crystalline silica catalyst TRS-22 according to Example 1 with an acidity of 1.5. 10

Under the process conditions of Example 7 (8), 5 cm (3.5 g) of the same granular catalyst was introduced into the reactor. It was fired in dry nitrogen stream for 2 hours to remove adsorbed water. Then, methanol was fed at 250 and 265 ° C and at a flow rate of 1.5 g / g · hr.

The analysis of the Reaktionsg'ase yielded dimethyl ether, unreacted methanol and water, without gas chromatographically detectable by-products. The results are summarized in Table. ·

As a result, the modified crystalline silica of the present invention has excellent dehydrating activity, and the conversion is better than another proposal in which active clay has been modified with silicon compounds (DD-PS 122 068).

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It can be stated that with the TRS-22 according to the invention at 250 and 265 ⁰ C and a throughput rate of 1.5 g / g. the methanol conversion is at least equal to that treated with active compounds using silicon compounds at 300 C and a throughput rate of 1 g / g. h receives.

Ta b 'e 1 1 e I

methanol to dimethyl ether 265 ⁰ C Catalyst TRS-22 1 Temperature, ⁰ C 250 ⁰ C * · ' 5 Pressure bar 1 88 1 Throughput g / g. H 1.5 Degree of conversion mol% 82.4 methanol Example 10 Same as ^

Reaction of dimethyl ether to hydrocarbons, especially light olefins, using modified crystalline TRS-22 of Example 1 containing sodium, having an acidity of 4.1. 10 ° "'meq / g as a catalyst:

Into an electrically heated tube reactor 8 mm in width, 2 cm (1 g) 0.177 to 0.59 mm catalyst was charged and purged with dry nitrogen for 2 h at 550 C to remove adsorbed water. Then dimethyl ether was fed in gaseous form, for which purpose

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Prevention of condensation all pipes u. Like. Were heated. The gases leaving the reactor were subjected to gas chromatographic analysis.

In calculating the degree of conversion is to be considered that the methanol formed during the partial hydrolysis of dimethyl ether is regarded as not responding, so that the molar conversion refers to dimethyl ether, which was converted to hydrocarbons, CO and COP.

The molar selectivities with respect to the products refer to the number of moles of dimethyl ether converted to the corresponding product based on the total number of moles that has reacted.

The results are summarized in Table II. It follows that the catalyst is not very active and not very selective, since considerable amounts of CO, C0 _? and CH. were formed.

T a_b. II

Dimethyl ether to hydrocarbon furnace catalyst TRS-22

Trial No. Jemp. Pressure by-conversion selectivity for C bar set per mol-f

/O

mol%

1 375 1 0.65 2.3 5.0 14.9 30.1 50.0

2 475 1 0,20 97,0 10,9 6,5 26,1 56,5

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B e i s ρ i e 1 11

Conversion of dimethyl ether into hydrocarbon, in particular light: olefins, with TRS-22 according to Example 1, acidity 1.5. M " ¹ meq / g: ·

According to Example 9, the reactor was filled with 3 cm (1.5 g) of catalyst above grain and 2 hours with dry

ο *

· Purge nitrogen at 550 C to remove any water.

The results are summarized in Table III. Comparing these with Table II, it follows that with a change in acidity, the behavior of the catalyst improves.

table

III

Ternp. ⁰ C Dimethylä Through sentence ther in hydrocarbons Selektiviti C0 + C0 "+ CH.-a d. Hi 30.1 ät fü r mol% 3 ^H 6 ~ ^C 4 ~ 305 TRS-22 2.7 0.5 23.0 24.3 45.1 catalyst 335 Pressure bar 2.7 Conversion per each molar% 0.5 19.0 19.9 56.6 Test no. 365 1 4.7 38.8 0.5 23.2 18.8 61.7 1 365 1 6.7 87.9 0.5 18.3 19.7 56.6 2 485 1 6.7 97.3 0.5 20.1 18.7 61.9 3 485 1 8.7 87.4 0.5 16.5 18.2 61.2 4 440 1 9.0 97.1 0.5 15.2 67.8 5 1 87.1 6 1 92.1. 7

- "18 -

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Example 12

Alkylation of benzene with ethylene:

1.2 cm (0.8 g) of catalyst TRS-22 (1.5 × ¹ ** ¹ meq / g, grain size 0.297 to 0.59 mm) were introduced into an electrically heated tube reactor (inside diameter 8 mm); Through a metering pump benzene was first passed through a preheater, in this mixed with a predetermined amount of ethylene and the mixture then fed with the appropriate flow rate to the reactor. The reaction products were analyzed by gas chromatography. The results are summarized in Table IV,

T a b e 1 1 e IV

Alkylation of TRS-22 Jemp. : C ₂ H ₄ Benzene with ethylene mol% diethylbenzene Implementation of ethylene % catalyst 440 mol% of ethylbenzene 1.50 100.0 Pressure 20 bar 440 13.8 1.55 100.0 Throughput 14 Molar ratio C, H- Jb 6 440 13.7 1.45 100.0 Verse time h 440 13.9 7 1.45 100.0 10 440 13.9 1.50 100.0 50 440 13.8 0.80 80.8 100 440 11.9 0.25 51.8 150 470 • 8.2 0.70 76.7 , 200 470 11.5 0.65 72.6 250 470 10.9 0.60 68.2 300 10.3 320 350 400

22 1479

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B _m e I ₁ s ρ J ₁ el 13

Regeneration of the catalysts:

The catalyst from Example 12 was regenerated after 400 hours of operation at 550 ⁰ C with a corresponding air flow in 5 hours. Thereafter, the whole system was purged with nitrogen at 550 ^° C. for 1 hour, after which the reaction could be continued under the above conditions. The results with the regenerated catalyst are summarized in Table V.

Table V

Al ky 1 ieru η c | yon Be η ζ oil w ith h ät ι y Ί e η

Catalyst TRS-22

Pressure 20 bar

Throughput 14

Molar ratio C _C H, -: C _O H. 7

Verse time h Jemp. raol-% ethyl benzene mol% diethylbenzene Implementation of ethylene % 10 440 13.7 1.55 100.0. 50 440 13.6 1.40 97.6 100 440 13.8 1.50 100.0 150 440 13.9 1.45 100.0 200 440 13.7 1.55 100.0 250 440 12.2 0.95 83.9 300 440 10.3 0.60 68.45 350 440 9.8. 0.38 62.85

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i p

J ₁₁ Θ 1 14

Alkylation of benzene with ethanol using the catalyst TRS-O from Example 2:

1.2 cm (0.8 g) of catalyst with a grain size of 0.297 to 0.59 mm were filled into an electrically heated tubular reactor - inside diameter 8 ml - and a reaction mixture of benzene and ethanol in a molar ratio of 5: 1 via a metering pump fed after preheating. The reaction took place at 440 C, the reaction products were analyzed by gas chromatography. The results are summarized in Table VI «

yl

alkylation ⁰ C of benzene with ethanol Catalyst TRS-O Temperature 440 Pressure 20 bar ^C 6 ^H 6 ^{: C} 2 ^H i Throughput 10 mol% of ethylbenzene molar ratio 19.0 -OH. = 4 > Time "h 19.0 mol% diethylbenzene Reaction of C ₉ H ₁ -OH 2 5 _{C /} 50 19.0 1.2 100 100 19.0 1.2 100 150 19.0 1,2. 100 200 19.0 1.2 100 300 1.2 100 400 1.2 100

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To play 1 15

5 cm alurninium-modified silica TRS-20 according to Example

¹ OSi :

5 were impregnated with an aqueous solution of platinum hydrochloric acid, so that the catalyst platinum content of 0.2 wt .-% aufwfes. The catalyst thus impregnated was heated to 600 ^° C. in a stream of hydrogen in order to reduce the platinum compound to platinum, and this catalyst was then introduced into a tubular reactor 20 ram.

Two series of tests were carried out on a possible exhaust gas detoxification of internal combustion engines, which were based on two reactions, namely oxidation of propylene to COp and oxidation of CO to CO ".

Gases containing 800 ppm of propylene, 8 % O _p , balance t \ L · were

preheated to 120 C and over the catalyst with a

- 1

• Space velocity GHSV of 50 000 h. The conversion of propylene was 99%. Was the same gas mixture preheated to 90 C, it was also obtained in a

·· 1 gas flow rate of 20,000 hours or 99 % propylene conversion .

Trial B

A gas containing 2.5 % CO, 8 % O _p , balance N _pf preheated

to 80 C, was passed over the catalyst with a space

- 1 speed of 20 000 hours. The CO conversion was 59 %.

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- 1 At a throughput rate of 50 000 h, the CO conversion was 99 %, The above-mentioned temperatures, namely 80 and 120 ⁰ C, actually must be considered special * because the best commercially available catalyst for mufflers the same conversion rates for propylene and C0 "At the same space velocities, but at a temperature of at least 150 ⁰ C results.

jB_e isp, ie _n l 16

Alkylation of benzene with ethylene:

In an electrically heated tubular reactor - clear width 8 mm · - was the catalyst TRS-57 from Example 6 in a

Amount of 1.2 cm (0.85 g) and a grain size of 0.297 to 0.59 mm filled. After preheating, benzene with a predetermined amount of ethylene and the corresponding flow rate passed through a metering pump into the reactor. The reaction gases were analyzed by gas chromatography and the results summarized in Table VII

Abe T 1 l e _m _ alkylation of VII with ethylene Βθπζο1_

Catalyst TRS-57 pressure 20 bar temperature 440 ⁰ C throughput rate 14 molar ratio C _c H _r : C "H, = 7

22 147

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Verse time h mol% of ethylbenzene raol-% diethyl benzene 10  * 13.9 1.35 50 13.9 1.35 100 14.0 1.30 150 13.8 1.30 200 13.9 1.35 250 13.7 ... 1,28 300 12.5 1.02 350 11.3 0.90 B e i ε ρ i e 1 17

Implementation of ethylene

100.0

100.0

100.0

98.8

100.0

97.9

87.6

78.9

Of catalyst TRS-57 was used for the alkylation of benzene with ethylene in the sense of Example 6, but in situ regenerated with a nitrogen diluted air stream at 500 C. After regeneration the catalyst was again used for the alkylation. The results with the regenerated catalyst are summarized in Table VIII.

Table 1 1 e VIII Alkylation of benzene with ethylene

Catalyst TRS-57 pressure 20 bar temperature 440 ⁰ C flow rate 14 molar ratio CH ^ iC ₀ H., = 7

, Ί η M Ai 1M P. Π * ft \\ 'λ

/ 7 Q 24 - , 04/14/1980 0 0% mol%. Diethylbenzene APC Ol B / 213 814 mol% of ethylbenzene 1.30 57 327/18 Verse _e ~ h time • 14.0 1.35 Implementation of ethylene % 10 ' 13.9 1:40 100.0 50 13.8 1.35 100.0 100 13.9 1.40 100.0 150 , 13 ·, 8 1.19 100.0 200 13.2 0.95 100.0 250 12.8. 93.8 300 β 1 18 88.5 B θ i ε ρ i

Alkylation of benzene with ethanol using the catalyst TRS-57 from Example 6:

In an electrically heated tubular reactor, the catalyst was arranged as a fixed bed, namely 1.2 cm (0.85 g), grain size 0.297 to 0.59 mm .. Was fed after preheating and dosing benzene and ethanol in the ratio indicated. The reaction gases were analyzed by gas chromatography and the results are summarized in Table IX.

Tab e 1 1 e IX Alkylation of benzene with ethanol

Catalyst TRS-57 pressure 20 bar temperature 440 ⁰ C throughput rate 10 molar ratio 0, .H.: CLH-OH =

I 479 - 25 - 04/14/1980 100 22 ' mol% of ethylbenzene AP C Ol B / 213 814 57 327/18 100 Verse time h 18.8 mol% conversion of diethylbenzene C ₉ H OH i. t) p / 100 50 19.0 1.3 100 100 18.8 1,2. 100 150 19.0 1.3 100 200 19.0 1.2 100 250 "19.0 1.2 300 19.0 1.2 400 1.2

The catalysts according to the invention can also be used for the alkylation of hydrocarbons, olefins and / or paraffins to give hydrocarbons having a high octane number.

have a fish surface of at least 150 m / g.

Alkylation of isobutane with n-butenes with a silica according to Example 5 :.

In a reactor according to Example 7, 3 cm (0.19 g) catalyst of grain size 0.297 to 0.59 mm were filled. The working conditions and the results are summarized in Table X.

Table X

Pressure 20 bar

Isobutene molar ratio: n-butenes = 15

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Temp. % Alkylation, or Composition C on butenes

250 l _f 3 100 ~ 90 % isoparaffins +

/ ^ 20 % aromatics

350 1.3 100 * "· 5.0 % isoparaffins +

* - 50 % aromatics

350 5.0 90 ~ 70 % isoparaffins +

% Aromatics

Another field of application of the products of the invention corresponds to the zeolites of class ZSM-5.

It is known from US-PS 37 02 886, that zeolites of the class ZSM-5 are made of silicon compounds (silica sols, Aerosil, tetra-o-silicate) or aluminum compounds (sodium aluminate, aluminum sulfate, acetate) in combination with quaternary ammonium bases ( tetrapropylammonium). ,

According to a modification of the present invention, zeolites of the type ZSM-5 can be prepared if an aminoalcohol is used to monitor (adjust) the crystallization and the compounds of silicon, germanium, aluminum and gallium are present in appropriate amounts so that the molar ratios SiO ₂ : Al ₂ O, GeO ₂ : Al ₃ O, SiO ₂ : Ga ₂ O, GeOp: Ga ₂ O _{3 are} between 5 and 100, preferably about 35.

A produced by the process according to the invention

Zeolite has an X-ray diffraction spectrum similar to that of zeolite

ZSM-5 corresponds. He can be represented by the following relationship:

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0.9 + 0.2 M ₂ / _n 0: W ₃ O ₃ + 5-100 Υ0 _£: zHgO,

wherein M is a cation in the form of H ⁺ and / or NH ₄ ⁺ and / or metal and / or cationic radical of aminoalcohols, especially ethanolamines, and η is the valency of the cation, VV is aluminum and / or gallium, Y is silicon and / or germanium and ζ can range between 0 and.

In the preferred zeolites, VV is aluminum, Y is silicon and the ratio SiO ₂ : Al ₂ O _{3 is} 10 to 60.

The preparation of the preferred zeolites by the process according to the invention is carried out by mixing the reactants in the following ratios, expressed in moles of the oxides. ,

" prefers

OH "" / SiO ₂ 0.2-0.8 0.3-0.6

amino alcohol /

Aminoalcohol + Na 0.3 - 0.8 0.4 - 0.6

H ₂ 0 / 0H ~ 10 - 100 20-40

The process according to the invention is carried out in the following manner:

A compound of silicon or germanium and a compound of aluminum or gallium is dissolved in aqueous, alcoholic or aqueous-alcoholic solution in the presence

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an amino alcohols - 'such as ethanolamine or in particular triethanolamine - and optionally one or more mineralizers - hydroxides and / or halides of alkali or alkaline earth metals - implemented. The reaction mixture is crystallized for several hours to several days at elevated temperature of 150 to 250 ⁰ C, preferably 170 to 210 ⁰ C, 2 to 10 days, generally one week; the crystal slurry allowed to cool and is filtered, the crystals washed with deionized water, dried in air at 300 to 700 ⁰ C, preferably about 550 ⁰ C, calcined for 2 to 24 hours, and then the cation exchange with an ammonium salt, preferably ammonium nitrate or acetate, washed out the product with distilled water and again fired as ^ above, so that the product is obtained in the desired hydrogen form.

The zeolite thus obtained may be used as such or diluted with one or more elements of catalytic activity, as is common for zeolites ZSM-5.

Example 20

Preparation of a zeolite ZSM-5 with the aid of triethanolamine:

60 g of Al (NO ₃ J ₃ .9H ₂ O in 800 cm ^{3 of} 95% ethanol were introduced into the Pyrex glass vessel in a CO ₂ -free atmosphere and 600 g of triethyl o-silicate were then stirred in. After the solution had cleared 200 g of triethanolamine were added in 400 cm of distilled water and the whole heated with stirring to 60 C. After a further 30 min was a

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Solution \ Λ> η 13 g of NaOH in 200 cm of distilled water and after a further 30 min still 22 g of NaOH (ie a total of 35 g of NaOH) in 400 cm ³ Wj strong gelation.

NaOH) in 400 cm of water. One watched one

The mixture was stirred vigorously for several hours, while at the same time the temperature was raised to 90 ° C, so that all the ethanol, both the one introduced into the reaction and that formed by hydrolysis, was expelled 3 liter autoclave made of corrosion-resistant steel and subjected to hydrothermal treatment at 195 ^° C. for 9 days.

Subsequently, the reaction product was cooled to room temperature, the crystal mass filtered, the crystals washed several times with very hot distilled water and finally dried at 120 ⁰ C. It was then fired for 16 hours at 550 C and by ion exchange in the heat (95 ° C) with ammonium acetate or nitrate. transferred to the Wasser¬ stofform and held this again for 6 hours at 550 C.

The X-ray diffraction spectrum corresponded to that indicated in Table I of US Pat. No. 3,702,886.

B ₁ e _t i spie j 21

In a modification of Example 20 were 880 g of tetramethyl-osilicate, 120 g of aluminum nitrate, 400 g of triethanolamine in

3 3

800 cm of water, 70 g of NaOH in 700 cm of water and mixed to about 9 * 1 with distilled water with vigorous stirring

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The whole was then concentrated at 80 ^° C. in about 30 hours to about 5 liters. The hydrothermal treatment was carried out at 190 ^° C. for 8 hours in a stirrer-equipped autoclave made of corrosion-resistant steel.

The X-ray diffraction pattern corresponded to a zeolite ZSM-5;

2 he had a specific surface of 380 m / g, and that

Ratio SiO 2 rAl ₀ O- was 38

BB _n J ₁ S ₁ ρ ie 1 22

9.6 g of sodium aluminate and 10 g of KOH were dissolved in 200 cm of water and introduced into the clear solution 208 g of ethanolamine in 1 1 of water. "The whole thing was then under inert gas

After stirring for 2 hours at 80 ^° C., 40 g of KBr in 150 cm of water were added as mineralizer. Finally, 345 g of colloidal silica (40 % SiO ₂ "Ludox") in 1.5 l of water were slowly added and aged.

This gel became

crystallized.

This gel was then left for 10 days at 198 C in an autoclave

The measures of Example 20 were then completed; a zeolite of class ZSM-5 was obtained.

Claims (2)

14.4.1980 AP C 01 B / 213 814 - 31 - 57 327/18 Process for the alkyliarone of hydrocarbons having 4 C atoms, olefins and / or saturated hydrocarbons for the formation of high octane hydrocarbons, characterized in that the catalyst used is aluminum-modified silicas having a porous crystal structure and having a specific surface area of at least 2
15p m / g of the general composition Si (O _f 0012 - 0.005) Al.Oy wherein y has a value of 2.0018 to 2.0075, which is prepared by reacting a silicon compound in aqueous, alcoholic or aqueous-alcoholic solution with an aluminum compound in the presence of a Reaktionskompononte, optionally in the presence of one or more mineralizers and optionally an inorganic base, whereupon the reaction mass was crystallized for several hours to several days at a temperature of 100 to 220 ⁰ C, then the Kriställbrei was cooled, filtered and the crystals dried and at 300 to 700 ⁰ C for 2 to 24 hours It was then calcined with boiling distilled water containing an ammonium salt, and fired again under the same conditions.