NL7811861A - PROCESS FOR PREPARING HYDROCARBONS. - Google Patents

Description

K 5465 NET

Applicant: Shell Internationale Research Maatschappij B.V.

Carel van Bylandtlaan 30, 1s-Gravenhage

Short designation: Process for the preparation of hydrocarbons

The invention relates to a process for the preparation of a hydrocarbon mixture boiling in the gasoline range from a mixture of carbon monoxide and hydrogen.

Hydrocarbon mixtures boiling in the gasoline range 5 can be obtained, inter alia, by direct distillation of crude oil, by conversion of heavier petroleum fractions, for example, by catalytic cracking, thermal cracking and hydrogen cracking, and by conversion of lighter petroleum fractions, for example, by alkylation.

In order to improve the octane number of the hydrocarbon mixtures thus obtained, these are often subjected to a catalytic reforming, whereby the aromatic content increases.

In view of the depletion of petroleum reserves 15, there is great interest in processes which provide the opportunity to economically convert non-petroleum based carbonaceous materials such as coal to hydrocarbon mixtures boiling in the gasoline range. It is desirable that said hydrocarbon mixtures have a sufficiently high octane number that they qualify for use as petrol without further refining.

It is known that carbonaceous materials such as coal can be converted into mixtures of carbon monoxide and hydrogen by gasification. It is also known that mixtures of carbon monoxide and hydrogen can be converted into mixtures of hydrocarbons by contacting the gas mixtures with suitable catalysts. It is further known 78 1 1 8 6 1 y -2- that paraffinic hydrocarbons can be converted to resp. By partial dehydrogenation or partial oxidation. olefinic hydrocarbon mixtures and oxygen-containing hydrocarbon mixtures. Finally, it is known that aromatic hydrocarbon mixtures can be prepared boiling in the gasoline range by contacting olefinic hydrocarbon mixtures and oxygen-containing hydrocarbon mixtures with suitable catalysts.

An investigation has been carried out by the Applicant in order to investigate to what extent the above processes can be used in the preparation of petrol from a mixture of carbon monoxide and hydrogen. It has been found that high octane gasoline can be prepared in high yield from a mixture of carbon monoxide and hydrogen by a combination of the above processes, provided the following conditions are met.

First, an aromatic hydrocarbon mixture must be prepared from the mixture of carbon monoxide and hydrogen using a catalyst containing a crystalline silicate, which silicate is characterized in that after calcining in air at 500 ° C for 1 hour it has the following properties 1) thermal stable up to a temperature above 600 ° C, 2) an X-ray powder diffraction pattern including the reflections listed in Table A, 78 1 1 8 61 9 Λ -3- ψ

Table A

Radiation: Cu-Kd_Wavelength 0.15418 nm 2 Θ relative intensity

7.8-8.2 S

8.7-9.1 M

11.8- 12.1 Z

12.4- 12.7 Z

14.6-14.9 Z

15.4- 15.7 Z

15.8-16.1 Z

17.6- 17.9 Z

19.2-19.5 Z

20.2-20.6 Z

20.7-21.1 Z

23.1-23.4 ZS

23.8-24.1 ZS

24.2- 24.8 S

29.7-30.1 M

in which the letters used have the following meaning: ZS = very strong; S “strong; M = * moderate; Z = weak; Θ - the angle according to Bragg.

3) after evacuation at 2 × 10 bar and 400 ° C for 16 hours -2 and measured at a hydrocarbon pressure of 8 × 10 bar and 100 ° C, the adsorption of n-hexane is at least 0.8 rmol / g, the adsorption of 2,2-dimethylbutane at least 0.5 mmol / g and the ratio adsorption of n-hexane adsorption of 2,2-dimethylbutane 4) the composition, expressed in moles of the oxides, is the following y (1.0 + 0.3) M2O. y (a Fe2Oy b A ^ Og). SiO 2 in which M 5 H and alkali metal, 15 a + b = 1, a £ o, b ^ o, and o ^ y ^ f0 »1 • Subsequently, from the aromatic thus obtained, 78 1 1 8 6 1 -4-

Jr, a hydrocarbon mixture to separate a propane and / or butane-containing gaseous fraction and a liquid fraction boiling in the gasoline range. The gaseous fraction then converts the olefinic or oxygen-containing product thus obtained to an aromatic hydrocarbon mixture of crystalline silicate as defined above as the catalyst. Finally, a fraction boiling in the gasoline range is separated from the latter aromatic hydrocarbon mixture.

The present patent application therefore relates to a process for the preparation of a hydrocarbon mixture boiling in the gasoline range from a mixture of carbon monoxide and hydrogen, wherein a) the mixture of carbon monoxide and hydrogen is converted into an aromatic hydrocarbon mixture using a catalyst containing a crystalline silicate as defined above, b) separating from the aromatic hydrocarbon mixture a propane and / or butane-containing gaseous fraction and a liquid fraction 2q boiling in the gasoline range, c) the gaseous fraction is subjected to partial dehydrogenation or partial oxidation, d) the olefinic or oxygen-containing product obtained according to c) is converted into an aromatic hydrocarbon mixture boiling in the gasoline range using a crystalline silicate as defined above as a catalyst, and e) from the obtained in d) aromatic ko Hydrogen mixture A fraction boiling in the gasoline range is separated.

The process according to the invention is based on a / CO mixture. Such a mixture can very suitably be prepared by steam gasification of a carbonaceous material. Examples of such materials are brown coal, anthracite, coke, crude oil and fractions thereof, as well as oils obtained from tar sand and bituminous slate. The 78 1 1 8 6 1 -5-

a

steam gasification is preferably carried out at a temperature between 1000 and 2000 ° C and a pressure between 10 and 50 bar

The process according to the invention preferably starts from a / / CO mixture whose molar ratio is between 0.25 and 1.0.

The H 2 / CO mixture is converted in step a) of the process into an aromatic hydrocarbon chicory mixture using a catalyst containing a crystalline silicate belonging to a special class.

Although in steps a) and d) of the process silicates can be used which contain both iron and aluminum • (a> o and b> o), preference is given to the use of silicates which contain either only iron (a = 1 and bso), or contain only aluminum (a = o and b = 1). Step a) 15 can be performed as a one-step or two-step process per se. In the two-step process, the ^ / CO mixture is preferably contacted in the first step with a catalyst containing one or more metal components with catalytic activity for the conversion of a ^ / CO mixture to acyclic hydrocarbons. In the second stage, the product thus obtained is converted into an aromatic hydrocarbon mixture by contacting it with the crystalline silicate under aromatization conditions.

In the one-step process, the ^ / CO mixture is contacted with a bifunctional catalyst which, in addition to the crystalline silicate, contains one or more metal components with catalytic activity for the conversion of an H2 / CO mixture to acyclic hydrocarbons and / or oxygen-containing hydrocarbons. Step a) of the method according to the invention is preferably carried out as one-step processes.

The process according to the invention starts from a ^ / CO mixture, the ^ / CO mol ratio of which can vary within wide limits. Before this mixture is converted according to step a), its ^ / CO molar ratio can be changed by adding hydrogen or 7811861

a

-6- carbon monoxide.

The hydrogen content of the mixture can also be increased by applying the known water gas shift reaction to it. If the H2 / CO2 mixture used in the process 5 as feed for step a) has an H2 / CO2 molar ratio of less than 1.0, step a) is preferably carried out using a catalyst containing one or more metal components with catalytic activity for the water gas shift reaction. When performing step a) as a two-step process, the H2 / CO mixture with H2 / CO molar ratio of less than 1.0 is preferably contacted in the first step with a bifunctional catalyst containing one or more metal components with catalytic activity for the conversion of an H 2 / CO mixture into acyclic hydrocarbons and one or more metal components with catalytic activity for the water gas shift reaction and the product thus obtained is converted in the second stage to an aromatic hydrocarbon mixture by contacting under aromatization conditions with the crystalline silicate.

When performing step a) as a one-step process, the H 2 / CO mixture with H 2 / CO molar ratio of less than 1.0 is preferably contacted with a tri-functional catalyst containing one or more metal components with catalytic activity for the conversion of an H2 / CO mixture to acyclic hydrocarbons and / or oxygenated hydrocarbons, one or more metal components with catalytic activity for the water gas shift reaction and the crystalline silicate.

Although the trifunctional catalysts usable in step a) of the process in this patent application are described as catalysts containing one or more metal components with catalytic activity for the conversion of an H 2 / CO mixture to acyclic hydrocarbon- 78 1 1 8 6 1 -7- substances and / or oxygen-containing hydrocarbons and one or more metal components with catalytic activity for the water gas shift reaction, this does not mean in any way that separate metal components, each of which has one of the two catalytic functions, must always be present in the catalysts. Namely, it has been found that metal components and combinations of metal components with catalytic activity for the conversion of an HL, / CO mixture into mainly oxygen-containing hydrocarbons, as a rule, also have sufficient catalytic activity for the water gas shift reaction, so that in that case with the inclusion of one metal component or one combination of metal components in the catalysts can be sufficient. Examples of such metal components are the metalen5 metals selected from the group consisting of zinc, copper and chromium. When using trifunctional catalysts in step a) of the process containing these metals, preference is given to a trifunctional catalyst which, in addition to the crystalline silicate, contains the metal combination 2q zinc-chromium. Metal components and metal combinations of metal components with catalytic activity for the conversion of an I / CO mixture to mainly hydrocarbons generally have no or insufficient activity for the water gas shift reaction. Thus, when using such metal components or combinations of metal components in the catalyst for the first step of the two-step process or in the catalyst for the one-step process, when using feeds with an H 2 / CO molar ratio of less than 1, 0, preferably one or more separate metal components with catalytic activity for the water gas shift reaction in the catalyst.

When using a ^ / CO mixture with an I ^ / CO molar ratio of less than 1.0 as feed for step a) of the process, this step is preferably performed as a one-step process using a tri - 75 1 1 8 61 c - «», -8- functional catalyst which is composed of two or three separate catalysts, which will be conveniently referred to as catalysts X, Y and Z. Catalyst X is the catalyst containing the metal components with catalytic activity for the conversion of an H 2 / CO mixture into acyclic hydrocarbons and / or oxygen-containing hydrocarbons. Catalyst Y is the crystalline silicate. Catalyst Z is the catalyst containing the metal components with catalytic activity for the water gas shift reaction. As explained above, the use of a catalyst Z may in some cases be omitted.

If as catalyst X a catalyst is used which is capable of converting a KL 2 / CO mixture into mainly oxygen-containing hydrocarbons, a catalyst is preferably chosen which is capable of converting the I 2 / CO mixture into in mainly methanol and / or dimethyl ether. Catalysts containing the above-mentioned metal combinations (selected from Cu, Zn and Cr) are very suitable for the conversion of an H2 / CO mixture into mainly methanol.

Catalysts X capable of converting an I / CO mixture into predominantly acyclic hydrocarbons are known in the literature as Fischer-Tropsch catalysts. Such catalysts often contain one or more iron group or ruthenium metals together with one or more promoters to enhance activity and / or selectivity. If, in step a) of the process according to the invention, a catalyst-1 combination is used in which catalyst X is a Fischer-Trops catalyst, an iron or cobalt catalyst, in particular such a catalyst, is preferably chosen for this purpose. catalyst prepared by impregnation. If desired, in step a) of the process according to the invention, it is also possible to use catalyst combinations containing a catalyst X., which is capable of converting an H2 / CO mixture to a mixture which contains both hydrocarbons and oxygen-containing hydrocarbons in comparable amounts. As a rule, such a catalyst also has sufficient catalytic activity for the water-gas shift reaction, so that the use of a catalyst Z in the combination can be dispensed with. An example of a catalyst X of this type is an iron-chromium oxide catalyst.

Catalysts Z which are capable of converting a ^ O / CO10 mixture to a ^ / CO2 mixture are known in the literature as CO shift catalysts. If, in step a) of the process according to the invention, use is made of a catalyst Z, a catalyst is preferably chosen for this purpose which contains the metal combination of copper-zinc.

The trifunctional catalysts are preferably used as a mixture. This mixture can be a macro mixture or a micro mixture. In the first case, the trifunctional catalyst consists of two or three kinds of macro-particles, one kind consisting entirely of catalyst X, a second kind consisting entirely of catalyst Y and optionally a third kind consisting entirely of catalyst Z. In the second case, the trifunctional catalyst of one kind of microparticles, each macroparticle being made up of a large number of microparticles of each of the catalysts X, Y and optionally Z. In step a) of the process, trifunctional catalysts in the form of micro mixtures are preferably used.

The crystalline silicate used in steps a) and d) of the process is defined inter alia by the powder X-ray diffraction pattern that the silicate shows after 1 hour of calcination in air at 500 ° C.

This X-ray powder diffraction pattern should include the reflection listed in Table A. The complete rb'ntgen-35 powder diffraction pattern of a typical example of a silicate suitable for use according to the invention is shown in Table B (Radiation: Cu-KoCj wavelength: 0, 15418 ma).

Table B

2 Θ relative intensity description ÜOO. I / Io)

8.00 55 SP

8.90 36 SP

9.10 20 SR

11.95 7 NL

12.55 3 NL

13.25 4 NL

13.95 10 NL

14.75 9 BD

15.55 7 BD

15.95 9 BD

17.75 5 'BD

19.35 δ NL

20.40 9 NL

20.90 10 NL

21.80 4 NL

22.25 8 NL

23.25 1001 SP

23.95 45 SP

24.40 27 SP

25.90 11 BD

26.70 9 BD

27.50 4 NL

29.30 7 NL

29.90 11 BD

31.25 2 NL

32.75 4 NL

34.40 = 4 NL

36.05 5 BD

37.50 4 BD

45.30 9 BD

78 1 1 8 6 1 I - intensity of the strength separated reflection that occurs in the pattern.

-11-

The letters used in table B to describe the reflections have the following meanings: SP = sharp; SR = shoulder; NL = normal; BD = wide; Θ is the angle according to Bragg.

The crystalline silicates can be prepared from an aqueous mixture containing the following compounds in a given ratio: one or more compounds of an alkali metal (M), one or more compounds containing an organic cation (R) from which such cation is formed during the preparation of the silicate, one or more silicon compounds and one or more aluminum and / or iron compounds. The preparation is carried out by keeping the mixture at an elevated temperature until the silicate is formed and then separating the crystals of the silicate from the mother liquor. The silicates are preferably prepared from a base mixture in which M is present in a sodium compound and R in a tetrapropylammonium compound.

The silicates prepared as described above contain alkali metal ions as well as organic cations. Using suitable exchange methods, the alkali metal ions can be replaced by other cations such as hydrogen ions or ammonium ions. Organic cations can very suitably be converted to hydrogen ions by calcining the silicates. The crystalline silicates which are used in the catalysts preferably have an alkali metal content of less than 1% by weight and in particular less than 0.05% by weight.

3q Step a) of the process is preferably carried out at a temperature of 200-500 ° C and in particular of 300-450 ° C, a pressure of 1-150 bar and in particular of 5-100 bar and a spatial throughput of 50-5000 and in particular of 300-3000 NI gas / 1 catalyst / hour.

Step a) of the process can very suitably be carried out by passing the feed in an upward or downward direction through a vertically arranged reactor containing a fixed or moving catalyst bed. For example, step a) of the process can be carried out by passing the feed upwardly through a vertically disposed catalyst bed using a gas velocity such that expansion of the catalyst bed occurs. If desired, step a) of the process can also be carried out using a suspension of the catalyst in a hydrocarbon oil. Depending on whether step a) of the process is carried out using a fixed catalyst bed, an expanded catalyst bed or a catalyst suspension, preference is given to catalyst particles with a diameter between resp.

1 and 5 mm, 0.5 and 2.5 mm and 20 and 150/15 According to the invention, in step b), a propane and / or butane-containing gaseous fraction of the aromatic hydrocarbon mixture obtained according to step a) and a liquid fraction to be separated boiling in the gasoline range. Preferably, the reaction mixture from step a) in step b) is separated into one

Hl C2 fraction, a C 1 / C 2 fraction and a gasoline fraction. The C2 fraction can be used as fuel gas. If desired, an I / CO mixture can be separated from the C2 fraction, which can be recycled to step a). If the hydrocarbon content of the C2 fraction is sufficiently high, it may be preferable to steam reform it, whether or not after removal of an I / CO mixture therefrom, in order to prepare additional synthesis gas that can be used as a food component for step a). The steam reformation of the Cj fraction can very suitably take place by contacting it together with steam at an elevated temperature and pressure with a nickel-containing catalyst.

In the process according to the invention in step c) the propane and / or butane-containing gaseous fraction must be subjected to partial dehydrogenation or partial oxidation. Partial dehydrogenation of the gaseous fraction can take place by contacting it with an chromium-containing catalyst at elevated temperature. Partial oxidation of the gaseous fraction can be carried out by treating the fraction at elevated temperature with or without oxygen in the presence or absence of a catalyst. In the partial oxidation, CO is generally formed which, if desired, can be used as a feed component of step a).

In the process according to the invention, the olefinic or oxygen-containing product obtained in step c) must be converted in step d) to an aromatic hydrocarbon mixture by contacting it with a silicate under aromatization conditions as defined above. In the step e), a fraction boiling in the gasoline range is separated from the product prepared according to step d).

The conversion of the olefinic or oxygen-containing product obtained according to step c) over the crystalline silicate can in principle take place in two ways.

First, the product prepared according to step c) can be contacted with the crystalline silicate in a separate reactor. If step a) of the method according to the invention is carried out as a two-step process, it is also very suitable to mix the product prepared according to step c) with the product of the first step.

An attractive embodiment of the process according to the invention is that in which the reaction of the product prepared according to step c) is carried out by contacting it in step d) in a separate reactor with the crystalline silicate, from the step d). The prepared product separates a propane and / or butane-containing gaseous fraction and a liquid fraction boiling in the gasoline range and recirculates the gaseous fraction to step c).

A process diagram for the conversion of synthesis gas 781 1 8 61 J -14-.

* / * to aromatic gasoline according to the invention will be explained in more detail below with reference to the drawing.

Process diagram (See figure) 5 The process is carried out in a device which successively consists of a methanol synthesis section (1), a first aromatization section (2), a first separation section (3), a partial oxidation section (4), a second flavoring section ( 5) and a second separation section. 10 (6). An I / CO mixture (7) is converted into methanol (8).

The methanol stream is divided into two portions (9) and (10). Portion (9) is flavored. The aromatized product (10) is separated into a fraction (11), and the Cg / C fract fraction (12) and a C ^ + gasoline fraction (13). The C3 C3C4 fraction (12) is mixed with a Cg / C 1 fraction (14) and the mixture (15) is partially oxidized. The partially oxidized product (16) is mixed with methanol portion (10) and the mixture (17) is flavored.

The flavored product (18) is separated into a 20 ^ 2 fraction: * - e (19), a Cg / C ^ fraction (14) and a Cg + gasoline fraction (20)

The present patent application also includes an apparatus for carrying out a method according to the invention, as shown schematically in the figure.

The invention is now illustrated by the following example.

Example

A crystalline silicate (Silicate A) was prepared as follows.

3Q, A mixture of S1O2, Fe (NOg) g, NaOH and / TCgHy) ^ N70H in water with the molar composition 8Na20.Al20g. 12 / TCgH ^^ I ^ O. 200 SiO2.3750 ^ 0 was heated in an autoclave at 150 ° C under autogenous pressure for 48 hours. After cooling of the reaction mixture, the resulting silicate was filtered off, washed with water until the pH of the washing water was approximately 8 and dried for 7 hours at 1 8 6 1-15 at 120 ° C. After calcining in air at 500 ° C for 1 hour, silicate A had the following properties

a) thermally stable up to a temperature above 900 ° C

b) an X-ray powder diffraction pattern substantially consistent with that listed in Table B

c) after evacuation at 2x10 ^ bar and 400 ° C for 16 hours -2 and measured at a hydrocarbon pressure of 8x10 bar and 100 ° C, the adsorption of n-hexane is 1.2 mmol / g, the adsorption of 2.2- dimethylbutane 0.7 mmol / g and the ratio adsorption of n-hexane-adsorption of 2,2-dimethylbutane. d) the composition, expressed in moles of the oxides, is the following 0.0054. 0.0054 Fe2 O3 SiO2 where M = H and Na.

From silicate A having an average crystallite size of 225 nm, a silicate B was prepared by boiling the material calcined at 500 ° C with 1.0 molar N 1 N 2 NO solution, washing with water, boiling again with 1.0 molar NH 2 NO 2 solution and wash, dry at 120 ° C for 2 hours, and calcine at 500 ° C for 1 hour.

A crystalline silicate (silicate C) was prepared essentially in the same manner as silicate A, except that the preparation of silicate C C was started with an aqueous mixture containing instead of Fe (NO3) 3, Na2A102 and the following malar composition had: 16 Na 2 O. A1203. Ί2βζ ^ ίη) 400 SiO2 · 7200 H20.

After calcination in air at 500 ° C for 1 hour, silicate C in X-ray powder diffraction pattern and in adsorption behavior were completely consistent with silicate A. Silicate C was thermally stable to a temperature above 800 ° C. The composition of silicate G (after calcination), expressed in moles of oxides of oxides, was 0.0035 M 2 O as follows. 0.0035 Al2 O3 · SiO2 where M = H and Na.

From silicate C having an average crystallite size of 240 nm, a silicate D was prepared in the same manner as described above in the preparation of silicate B from silicate A 781 1 8 6 1 -16-.

Two catalyst mixtures (I and II) were prepared by mixing a ZnO-C 2 O 2 composition with silicate B, respectively. with 5 silicate D. The atomic Zn percentage of the ZnO-C 2 O 2 composition based on the sum of Zn and Cr was 70%. The catalyst mixtures both contained, per volume part of silicate, 2 parts by volume of the ZnO-C 2 O 2 composition.

The catalyst mixtures I (prepared using silicate B) and II (prepared using silicate D) were used in a process for preparing an aromatic hydrocarbon mixture boiling in the gasoline range starting from a ^ / CO mixture with a ^ / CO mol 0.5 ratio. To this end, the H 2 / CO mixture was converted in one step to an aromatic hydrocarbon mixture by passing it at a temperature of 375 ° C, a pressure of 60 bar and a spatial flow rate of 200 µl over a fixed bed with a volume of Pass 7.5 ml of the respective catalyst mixture contained in a 50 ml reactor.

The product thus obtained was separated into a C2 fraction, a C 1 / C 2 fraction and a C 1 + gasoline fraction. The C 1 / C 2 fraction was partially dehydrogenated and the product thus obtained was flavored by contacting it at a temperature of 375 ° C, a pressure of 30 bar and a spatial throughput of 25 kg / kg / h *. with silicate B or silicate D. The product thus obtained was separated into a fraction and a C 2+ gasoline fraction.

The results of these experiments are stated below 78Ί 18 61 -17-

Experiment No 1 * 2

Conversion of the H 2 / CO mixture carried out using Catalyst mixture No I II

Composition of the aromatic hydrocarbon mixture prepared from the H ^ / CO mixture (C ^ *), wt% C "10 7 C3 / C4 26 32 C5 + 64 61

Composition of the C 1 fraction prepared from the Hg / CO mixture, wt% acyclic hydrocarbons 20 18 naphthenes 18 16 aromatics 62 66

Average conversion of / ^ /, paraffins to C ^ / C, olefins,% 33 34

Aromatization of the partially dehydrogenated C 1 / C 2 fraction was carried out

using silicate No B D

Yield of C 1 fraction, calculated on C *, wt% 6 8

Aromatics of the latter C 2 fraction, wt.% 85 88 78 1 1 8 6 1

Claims (20)

Process for the preparation of a hydrocarbon mixture boiling in the gasoline range from a mixture of carbon monoxide and hydrogen, characterized in that a) the mixture of carbon monoxide and hydrogen is converted into an aromatic hydrocarbon mixture using a catalyst which contains a crystalline silicate, which silicate is characterized in that after calcining in air at 500 ° C for 1 hour, it has the following properties 10 1) thermally stable up to a temperature above 600 ° C, 2) an X-ray powder diffraction pattern which includes the table A reflections listed, Table A Radiation; Cu-KiC_Wavelength 0.15418 nm 2.relative intensity 7.8- 8.2 S 8.7- 9.1 M '11.8-12.1 Z 12.4- 12.7 Z 14.6- 14.9 Z 15.4- 15.7 Z 15.8-16.1 Z 17.6- 17.9 Z 19.2- 19.5 Z 20.2- 20.6 Z 20.7- 21.1 Z 23.1- 23.4 ZS 23.8- 24.1 ZS 9 24.2 - 24.8 S 29.7-30.1 M in which the letters used have the following meaning: 15 zs - very strong; S - strong; M = moderate; Z = weak; Θ = the angle according to Bragg. "9 o 3. after evacuation at 2x10 bar and 400 C for 16 hours -2 and measured at a hydrocarbon pressure of 8x10 bar and 781 1 8 6 1 -19-100 ° C, the adsorption of n-hexane is at least 0.8 mmol / g, the adsorption of 2,2-dimethylbutane at least 0.5 mmol / g and the ratio adsorption of n-hexane., -5-_. ~~ v "ö ~ j '· -' ί" · , ν - at least 1.5 adsorption of 2,2-dimethylbutane 5 4) the composition, expressed in moles of the oxides, is the following y (1.0 + 0.3) M 2 O. y (a Fe ^. b A1203) SiO2 in which M = H and alkali metal, 10 a + b = a ^ 0, b ^ 0, and 0 <y 4: 0 »1» b) from the aromatic hydrocarbon mixture a propane 15 and / or butane containing gaseous fraction and a liquid fraction boiling in the gasoline range are separated, c) the gaseous fraction is subjected to partial dehydrogenation or partial oxidation, d) the olefinic or oxygen-containing product obtained according to c) is converted into an aromatic hydrocarbon mixture using a crystalline silicate as defined under a) as a catalyst, and e) a fraction boiling in the gasoline range is separated from the aromatic hydrocarbon mixture obtained according to d). 1 * 18- 2. Process according to claim 1, characterized in that the molar ratio between hydrogen and carbon monoxide in the feed is between 0.25 and 1.0. 3. Process according to claim 1 or 2, characterized in that the catalyst used in steps a) and d) contains a crystalline silicate of which a is o or 1 in the formula indicating the gross composition. 4. Process according to any one of claims 1-3, characterized in that the catalyst used in steps a) and d) contains a crystalline silicate with an alkali metal content of less than 0.05% by weight. 7811861 «· <-20- 5. Process according to any one of claims 1-4, characterized in that step a) of the process is carried out as a two-step process by contacting the / / CO mixture in a first step with a catalyst containing one or more metal components with catalytic activity for the conversion of a ^ / CO mixture to acyclic hydrocarbons and converting the product thus obtained in the second step into an aromatic hydrocarbon mixture by contacting it with the crystalline silicate under aromatization conditions. Process according to any one of claims 1 to 4, characterized in that step a) of the process is carried out as a one-step process by contacting the I / CO mixture with a bifunctional catalyst which, in addition to the crystalline silicate, contains one or more contains metal components with catalytic activity for the conversion of an H2 / CO mixture into acyclic hydrocarbons and / or oxygen-containing hydrocarbons. 7. Process according to claim 6, characterized in that the mixture / CO mixture is used as feed for step. a) has an I / CO molar ratio of less than 1.0 and that step a) is performed as a one-step process by contacting the gas with a trifunctional catalyst containing one or more metal components with catalytic activity for the conversion of a 1 / CO mixture into acyclic hydrocarbons and / or oxygen-containing hydrocarbons, one or more metal components with catalytic activity for the water gas shift reaction and the crystalline silicate. Process according to claim 7, characterized in that the trifunctional catalyst is composed of two separate catalysts, one catalyst (catalyst X) containing the metal components with catalytic activity for the conversion of an I / CO mixture into 35 'substantially oxygen-containing hydrocarbons as well as having catalytic activity for the water gas shift 781 1 8 6 1 -21 reaction and the other catalyst (catalyst Y) is the crystalline silicate. 9. Process according to claim 8, characterized in that the catalyst X used is a catalyst capable of converting a ^ / CO mixture into mainly methanol and / or dimethyl ether. Process according to claim 8 or 9, characterized in that catalyst X contains the metal combination zinc-chromium. The process according to claim 7, characterized in that IQ the trifunctional catalyst is composed of three separate catalysts, the first catalyst (catalyst X) of which contains the metal components with catalytic activity for the conversion of an I / CO mixture into mainly hydrocarbons the second catalyst (catalyst Y) is the crystalline silicate and the third catalyst (catalyst Z) contains the metal components with catalytic activity for the water gas shift reaction. 12. Process according to claim 11, characterized in that as catalyst X an iron or cobalt catalyst is used and as catalyst Z a catalyst containing the metal combination copper-zinc. 13. A method according to any one of claims 7-12, characterized in that a trifunctional catalyst is used which consists of one kind of macroparticles, each macroparticle consisting of a large number of microparticles of each of the catalysts X, Y and possibly Z. 14. A method according to any one of claims 1-13, characterized in that step a) is carried out at a temperature of 200-500 ° C, a pressure of 1-150 bar and a spatial throughput of 50-5000 µl / l. catalyst / hour. 15. Process according to claim 14, characterized in that step a) is carried out at a temperature of 300-450 ° C, a pressure of 5-100 bar and a spatial flow rate of 300-3000 NI gas / 1 catalyst. /hour. 781 1 8 6 1 -22- 16. A process according to any one of claims 1-15, characterized in that the aromatic hydrocarbon mixture from step a) is separated in step b) into a C 2 -C fraction, a C 1 / C 1 fraction and a Cg + gasoline fraction, and the C ^ / C ^ fraction is used as feed for step e). Process according to any one of claims 1 to 16, characterized in that the product prepared according to step c) is brought into contact with the crystalline silicate in step d) in a separate reactor, from the product prepared according to step d). product a propane or butane-containing gaseous fraction and a liquid fraction boiling in the gasoline range are separated and the gaseous fraction is recycled to step c). 18. Process for the preparation of a hydrocarbon mixture boiling in the gasoline range, substantially as described above and in particular with reference to the example. 19. Gasoline boiling range hydrocarbon mixtures, prepared according to an x process as described in claim 18. Device for carrying out the method according to claim 18, characterized in that this device substantially corresponds to the device as schematically shown in the figure. 781 1 8 61