DE3235848A1 - Process for the preparation of hydrocarbons - Google Patents

Description

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ELISABETH JUNG dr. phil, diplWmj '* · '] '. · ..: ".". .6000 MÖNCHEN 40, 323584ε JÜRGEN SCHIRDEWAHN dr. 4 phone: (089) 34so67

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() GERHARD B. HAGEN dr.phil. t * telegram / cable: invent Munich

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PETER HIRSCH dipl-inq. PATENT LAWYERS EUROPEAN PATENT ATTORNEYS

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K 5959 GEW (J / kö) September 28, 1982

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

"Process for the production of hydrocarbons."

Claimed

Priority: September 30, 1981, France, No. 8118471

The invention relates to a method for the production of hydrocarbons from a mixture of carbon monoxide and Hydrogen using a catalyst combination that one or more metal components with catalytic activity for the conversion of an H ^ / CO mixture into hydrocarbons as well as a carrier consisting of a crystalline silicate.

Investigations by the applicant on this process have now shown that it has two disadvantages. On the one hand is when using space velocities that are acceptable in practice the converted amount of the H ^ / CO mixture is unsatisfactory. On the other hand, the process produces a product which essentially consists of hydrocarbons with less than 5 carbon atoms in the molecule and too few hydrocarbons with 5 to 12 carbon atoms in the molecule.

The applicant has further investigations into this process show that the two disadvantages mentioned above thereby

it can be countered that ferrierite is used as a carrier, ie that the feedstock is brought into contact with a catalyst which has one or more metal components: (n) 'ittite catalytic activity for the conversion of a H ^ / CO mixture into acyclic hydrocarbons , wherein the metal components are preferably iron, cobalt and ruthenium and the metal component (s) is / are applied to ferrierite. This not only ensures that a high conversion of the H ₂ / CO mixture is obtained when using space velocities which are acceptable in practice, but also that the reaction product consists essentially of hydrocarbons with 5 to 12 carbon atoms in the molecule.

The present application therefore relates to a process for the production of γοη hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst combination which has one or more metal component (s) with ka-. Has analytical activity for the conversion of an H ₂ / CO mixture into hydrocarbons and a carrier consisting of a crystalline silicate zeolite. The method is characterized in that the metal component (s) has (have) been combined with ferrierite. In the process according to the invention, the starting material is an H ₂ / CO mixture. Such H ₂ / CO mixtures can very suitably be produced either by steam gasification or by partial combustion of a carbonaceous material. Examples of this are wood, peat, lignite, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof, as well as tars and oils extracted from tar sand and bituminous shale. The vapor gasification or partial combustion takes place preferably at a temperature of 900 to 1600 ° C. and a pressure of 10 to 100 bar. The process according to the invention is preferably based on an H ₂ / CO mixture with a molar ratio of H ₂ : CO of more than 0.25 and less than 6.

The catalyst combinations used in the process according to the invention contain ferrierite in addition to metal components with catalytic activity for hydrocarbon synthesis.

This crystalline aluminum silicate is in "Atlas of zeolite structure types "by W.M. Meier and D.H. Olson (1978), Polycrystal Book Service, Pittsburgh, Pa.

The catalyst combinations used in the process according to the invention contain one or more metal components with catalytic activity for the conversion of an H_ / CO mixture in hydrocarbons.

Catalyst components which have the ability _{to convert an H 2} / CO mixture into essentially hydrocarbons are known in the relevant literature as Fischer-Tropsch catalysts. Such catalyst components have one or more metal (s) of the iron group or ruthenium and, if appropriate, one or more promoter (s) in order to increase the activity and / or selectivity. Suitable catalysts contain 0.1 to 10 percent by weight ruthenium and / or 0.05 to 10 percent by weight of one or more metals (metals) of the iron group together with one or more promoter (s) in an amount which is 1 to 50% of the amount of the metals corresponds to the iron group present in the catalyst. Many elements are suitable as promoters for the catalysts of the invention. The following elements may be mentioned as examples: alkali metals, alkaline earth metals, metals from group VIB (W, Mo, Cr), Ti, Zr, Al, Si, As, V, Mn, Cu, Ag, Zn, Cd, Bi, Pb, Sn , Ce, Th and U. One or more of these promoters is / are incorporated into the carrier, preferably by ion exchange. Very suitable promoter combinations for the iron catalyst component used in the process according to the invention consist of an alkali metal such as potassium, an easily reducible metal such as copper or silver, and optionally a difficult to reducible metal such as aluminum or zinc. A very suitable iron catalyst component to be used according to the process according to the invention is, for example, a catalyst component which contains iron, potassium and copper in the crystalline silicate as a carrier. If an iron catalyst component is used in the process according to the invention, the selectivity promoter potassium

contains / so preference is given to a catalyst which contains no more than 0.15 g of potassium per g of iron, as has been determined is that when using higher potassium concentrations the Selectivity does not increase any further, while the stability is essentially due to the carbon deposits on the catalyst decreases. There are very suitable promoter combinations for cobalt catalyst components to be used according to the invention from an alkaline earth metal and thorium, uranium or cerium.

very suitable

An example of a cobalt catalyst component to be used in accordance with the invention is a catalyst which contains cobalt, magnesium and thorium in the crystalline silicate as carriers. Further very suitable cobalt catalyst components to be used according to the invention are catalysts that contain Co / Cr, Co / Zr, Co / Zn or Co / Mg in the crystalline silicate support.

If the process according to the invention is intended to be a catalyst combination to use in which the catalyst component with Fischer-Tropsch activity is iron, one chooses preferably an iron catalyst component containing a promoter composed of an alkali metal, an easily reducible one Metal-like copper or silver, and optionally one difficult to reducible metal, such as aluminum or zinc. A very suitable iron catalyst component for the present The purpose is a catalyst, which has been produced by ion exchange and iron, potassium and copper in the from Contains the crystalline silicate existing carrier. Used in the catalyst combination with iron as a catalyst component the required Fischer-Tropsch activity is used, the inventive method is preferably carried out at one temperature carried out from 150 to 325 ° C and a pressure of 20 to 100 bar.

If the use of a catalyst combination is intended in the process according to the invention, in which the catalyst component with the required Fischer-Tropsch activity is cobalt, preference is given to a cobalt catalyst component given, which contains a promoter combination that consists of

an alkaline earth metal and chromium, thorium, uranium or cerium.

A cobalt catalyst very suitable for the present purpose is an ion exchange catalyst that contains cobalt, magnesium and thorium in the carrier consisting of the crystalline silicate. More very suitable, through Cobalt catalysts produced by ion exchange are catalysts that, in addition to cobalt, contain one of the elements chromium, titanium, Zirconium and zinc contained in the carrier consisting of the crystalline silicate.

If cobalt is used as a catalyst with the required Fischer-Tropsch activity in the catalyst combination, see above the inventive method is preferably at one temperature from 220 to 300 ° C and a pressure of 10 to 100 bar.

Very suitable catalysts for the process according to the invention

a) Catalysts which contain 0.05 to 10 parts by weight of iron and 0.025 to 5 parts by weight of magnesium per 100 parts by weight of crystalline silicate support and are made by impregnating or preferably ion-exchanging the support with one or more solutions of iron and magnesium salts, then washing and drying the composition, Calcining at a temperature of 300 to 600 ° C and reducing. Particular preference is given to those catalysts which, in addition to 0.1 to 5 parts by weight of iron and 0.05 to 2.5 parts by weight of magnesium, 0.05 to 2.5 parts by weight of copper as a reduction promoter and 0.1 to 1.5 parts by weight of potassium as Selectivity promoter contain per 100 parts by weight of carrier, calcined at 400 to 500 ° C and reduced ^{at 250 to 450 0 C.}

b) Catalysts which contain 0.05 to 10 parts by weight of cobalt and 0.01 to 2.5 parts by weight of chromium per 100 parts by weight of crystalline Contain silicate carriers and - by impregnation or pre-

preferably ion exchange of the support with one or more solutions of cobalt and chromium salts, subsequent washing and drying of the composition, calcining and reducing at a temperature of 300 to 750 ⁰ C have been produced. Particular preference is given to those catalysts which contain 0.1 to 5 parts by weight of cobalt and 0.05 to 1 part by weight of chromium

per 100 parts by weight of ferrierite contained, have been calcined at 300 to 700 ⁰ C is reduced at 300 to 700 ° C.

c) catalysts containing 0.05 to 10 parts by weight of cobalt and 0.01 to 2.5 parts by weight of zirconium, titanium or chromium per 100 parts by weight Contain crystalline silicate carrier and by impregnation or preferably ion exchange of a silicate carrier with one or more solutions of cobalt and zirconium, titanium or chromium salts, subsequent washing and Drying the composition, calcining at 350 to 700 ° C and reducing at 200 to 700 ° C.

In the process according to the invention, catalysts are used preferably by ion exchange of the support, advantageously with one or more aqueous solutions of ruthenium salts or salts of metals of the iron group and salts of promoters, then washing with water, drying and calcining the composition.

The ion exchange ability of ferrierite is well known. In the ferrierite, the electrovalence of aluminum is in the crystalline structure is kept in equilibrium by the presence of cations at the anionic lattice site in the crystal. The cation is generally an alkali metal such as sodium or potassium. The cations of aluminum silicate ferrierite can be exchanged for mono- or divalent cations that have a suitable physical "size" and Have configuration to diffuse into the intergranular channels of the silicate structure. The original cation can be replaced by another cation, for example a hydrogen ion or an ammonium ion. In general, can

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any suitable acid or salt solution, for example a sulphate or nitrate, as a source of cations to be exchanged in the silicate be used.

The theoretical interchangeability of ferrierite is given by represents the number of cation equivalents, for example sodium ions, that the electroneutral! did this crystalline Keep aluminum silicate in balance. The interchangeability varies depending on the type of screen used. In practice, not all of the cations in the silicate will pass through easily replaces the desired cations, so that the effective exchange capacity is often somewhat below the value for the theoretical exchange capacity lies. The extent of the exchange depends on factors such as the sieves, the cations in the sieve, the ones to be exchanged Cations, the type of solvent (water, alcohol) and the exchange temperature. Of course they are Amount of catalytically active metal, which is the crystalline aluminosilicate ferrierite can be incorporated by ion exchange, limits are set.

Following the ion exchange step, the ion exchange solution is removed from the ferrierite containing the exchanged catalytically active metal, for example by filtration. The ferrierite is then preferably washed with the solvent V-- of the ion exchange solution in order to remove any unreacted metal, and the washing liquid is separated off, for example by filtration. The zeolite cake from which the wash liquor has been separated generally contains about 50% solids. Either with or without further adjustment of the solvent content, the zeolite can be shaped to the desired size. If necessary, one or more binders and / or extrusion aids can be added. The zeolite may then be dried, and the molded catalyst is used to produce the finished catalyst at a temperature of about 300 to about 600 ⁰ C.

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To prepare the catalysts, the metals can be deposited on the support in one or more step (s) will. The material can be dried between the individual steps. For the production of catalysts with a high metal content, a multi-step process may be required. The salts the metals of the iron group and the salts of the promoters can be on the support either individually from different solutions or get knocked out of a solution together.

According to the process according to the invention, the largest possible proportion of the carbon monoxide present in the feedstock is to be converted into hydrocarbons over a catalyst which has one or more metal components with catalytic activity for converting an H ₂ / CO mixture into hydrocarbons, the Metal components are iron, cobalt and ruthenium. For this purpose the molar ratio of H2: CO in the feed is suitably at least 1.0 and preferably 1.25 to 2.25.

The process of the invention can very suitably be carried out by passing the feed up or down through a vertically arranged reactor containing the catalyst as a fixed bed, or by passing the gaseous feed up through a fluidized catalyst bed. The process can also be carried out using a suspension of the catalyst or the catalyst combination in a hydrocarbon oil. The process is preferably carried out under the following conditions: at a temperature of 125 to 400 ° C, in particular 175-275 ⁰ C, and a pressure of from 1 to 150 bar and particularly from 5 to 100th

The invention will now be explained in detail with the aid of the following examples.

example

First, ferrierite was converted into the ammonium form by ion exchange with a 2n ΝΗ.ΝΟ, solution. The ammonium form of the ferrierite was then _{ion-exchanged for 48 hours with an aqueous RuCl 3} solution (5% by weight). The catalyst was washed / dried with water and ^{calcined at 300 °} C. for 2 hours with nitrogen under atmospheric pressure and reduced with hydrogen at 280 ^° C. and a pressure of 4 bar for 2 hours. The resulting catalyst had the following composition: 1.5 Ru / 49 SiO_ / 1 Al ₀ O, (parts by weight), a _{gas mixture consisting of H 2} and CO (H ₂ / CO = 1) was passed over this catalyst under the following conditions directed:

Space velocity of the gas / h: 1000 1 (NTD) / lh pressure: 20 bar
Temperature: 260 ⁰ C.

The amount of H _{2 and} CO converted into hydrocarbons was 46.4% by weight. The Raura time yield was 106 g of hydrocarbons per liter of catalyst volume / h. The selectivity is shown in the table below.

C ₁ + C ₂ : 17% by weight

C ₃ + C ₄ : 10% by weight

C ₅ to C ₁₂ : 59% by weight

C ₁₃ to C ₁₉ : 10% by weight
C ₂₀ ⁺ : 4% by weight.

It can be seen from this table that the yield of the desired _{hydrocarbons boiling in the gasoline boiling range (C g} to C ₁₂ ) is very high compared to those boiling below or above the preferred range.

The liquid phase of the condensed hydrocarbons contained 99% by weight of paraffins.

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Example 2

Ferrierite was first converted into the ammonium form by ion exchange with a 2N-NH.NO_ solution and then washed with water, dried and subjected to a 2-hour calcination with air at 500 C and atmospheric pressure, after which it was impregnated with an aqueous cobalt nitrate solution and dried , Calcined for 2 hours at 500 ^° C. in air and ^{reduced with hydrogen for 2 hours at 280 °} C. and under a pressure of 4 bar in order to obtain a catalyst with the following composition:

10 Co / 49 SiO ₂ / l Al ₃ O ₃ (parts by weight). Using this catalyst under the conditions described in Example 1, _{hydrocarbons were prepared from an H 2} / CO gas mixture (H ₂ / CO = 1). The amount converted was 66% by weight. The space-time yield was 120 g of hydrocarbons per liter of catalyst / h.

The selectivity was:
C ₁ + C ₂ : 17% by weight
C ₃ + C ₄ : 7% by weight
C ₅ to C ₁₂ : 47% by weight
C ₁₃ to C ₁₉ : 15% by weight
C ₂₀ +: 13% by weight

In this way, a good result was obtained as to the yield of gasoline components (Cg to Cj _2). There were no aromatics in the product. The yield, based on metal weight and time, was 1300 g of hydrocarbon per kg of cobalt on the catalyst / h.

Example 3

First, ferrierite was converted into the ammonium form by ion exchange with a 2n-NH.NO-j solution. The ammonia uniform was ion exchanged with an aqueous solution of Co (NH ₃ ) 1 (NO ₃ ) ₂ (15% by weight) for 24 hours.

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The catalyst was then washed with water, dried, ^{calcined for 2 hours at 500 °} C. and for 24 hours at a temperature of 575 ^° C. and a pressure of 1 bar abs. reduced with hydrogen.

The catalyst had the following composition: 3.1 Co.49 SiO ₂ . IAl ₂ O ₃ (weight cfcts parts).

_{An H 2} / CO mixture (H ₂ / CO = 1) was passed over this catalyst under the following conditions:

Space velocity of the gas: 1000 1 (NTEj) / lh Pressure: 20 bar Temperature: 260 ⁰ C.

The amount of H2 and CO converted into hydrocarbons was 43 wt%.

The space-time yield was 99 g of hydrocarbons per liter Catalyst / h.

The selectivity is shown in the table below.

^C 1 ^{+ C} 2 : 20 Weight -% ^C 3 ^{+ C} 4 : 9 Weight - ■ & ^C 5 to C ₁₂ : 55 Weight -% , to C _1c ) - ¹⁰ Weight -% +
■ ν : 5 Weight -%

The yield based on metal weight and time was 2500 g Hydrocarbons per kg of cobalt on the catalyst / h. There were no aromatics in the product.

Claims (7)

Patent claims iy Process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen using a catalyst combination which has one or more metal components with catalytic activity for converting an H ₂ / CO mixture into hydrocarbons and a carrier consisting of a crystalline silicate , characterized in that the metal component (s) has (are) combined with ferrierite, 2. The method according to claim 1, characterized in that this is carried out at a temperature of 125 to 400 ⁰ C and a pressure of 1 to 150 bar, preferably at a temperature of 175 to 275 C and a pressure of 5 to 100 bar . 3. The method according to claim 1 or 2, characterized in that the catalyst is iron, cobalt and / or ruthenium as the metal component (n) contains. or more 4. The method according to any one of the preceding claims, characterized in that that the metal component (s) with the ferrierite by ion exchange, subsequent washing, drying and calcining has been combined. or more 5. The method according to one / the preceding claims, characterized in, that the catalyst contains 0.05 to 10 percent by weight of one or more of the metals of the iron group. 6. The method according to claim 5, characterized in that the catalyst has one or more promoter (s) in an amount of Contains 1 to 50% by weight of the amount of the iron group metals. 7. The method according to one or more of the preceding claims, characterized in that the catalyst contains 0.1 to 10% by weight of ruthenium.