NL8202690A - PROCESS FOR PREPARING HYDROCARBONS. - Google Patents

Description

i * i! - l -

K 5953 NET

WEEKLY FOR PREPARING HYDROCARBONS

The present invention relates to a process for the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an E 2 / CO mixture in acyclic hydrocarbons and a support consisting of a crystalline silicate zeolite which in dehydrated form has the following total composition, expressed in moles of oxides: (1.0 ± 0.3) (R) 9yn0./a Me. ^ Qy.yW Si09 + e Ge0o), where 10 R = one or more mono- or bivalent cations

Me = at least one trivalent metal 0 ^ a ^ 1 y> 12 d> 0.1 15 e >> 0 8202680 * y - 2 - d + e = 1, and n = the dignity of R, and an X-ray powder diffraction pattern has that includes the reflections listed in Table A.

Table A

2Θ 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 SS

24.2 - 24.8 S

29.7-30.1 M

The values listed in Table A have been determined by standard methods. Radiation: Cu-Κα, wavelength 0.15418 nm. The letters used in Table A to indicate relative intensity have the following meanings: ZS = very strong; S = strong; M = moderate; Z = weak; Θ = book according to Bragg's law.

The complete X-ray powder diffraction pattern of a silicate to be used in the method of the invention is shown in Table B. (Radiation: Cu-Ka, wavelength: 0.15418 nm).

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Table B

2Θ Relative intensity Description of (100. I / Iq) reflection

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 6 NL

20.40 9 NL

20.90 10 NL

21.80 4 NL

22.25 8 NL

23.25 - 100 * SP

23.95 45 SP '

24.40 27 SP

25.90 11 BD

26.70 9 BD

27.50 4 NL

29.30 7EN

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

Ιφ = intensity of the strongest separated reflection that occurs in the pattern.

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The letters used in Table B to indicate reflections have the following meanings: SP = sharp; SR = shoulder; NL = normal; BD = wide; Θ = angle according to Bragg's law.

An investigation carried out by the Applicant concerning this method has shown that the method has two disadvantages. First, the conversion of the ikj / CO mixture is insufficient when using spatial throughput rates that are permissible in practice. Furthermore, the process yields a product consisting almost entirely of hydrocarbons with less than 5 carbon atoms per molecule and containing too few hydrocarbons with 5-12 carbon atoms per molecule.

A further investigation carried out by the Applicant concerning this process has shown that the two disadvantages mentioned can be avoided by preparing the spent catalysts by ion exchange, ie by contacting the feed with a catalyst containing edn or more metal components with catalytic activity for the conversion of an I / CO mixture into acyclic hydrocarbons, which metal components are preferably selected from the group 20 consisting of Fe, Ni, Co and Ru, and which component (s) by ion exchange are applied to the crystalline zeolite. In this way, using spatial throughput rates that are permissible in practice not only results in a higher conversion of the H 2 / CO mixture, but it also achieves that the reaction product consists predominantly of hydrocarbons with 5-12 carbon atoms per molecule.

The present application therefore relates to a process for the production of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H 2 / CO mixture into acyclic hydrocarbons , and a support consisting of a crystalline 8202690-5 silicate zeolite which, in dehydrated form, expresses the following total composition in moles of oxides, has: (1.0 + 0.3) (R) 2 / n0. / a He ^ O ^ / · Y (d SiO2 + e GeQ2), where R = den or more monovalent or divalent cations 5 Me = at least one trivalent metal 1> a> 0 y> 12 d> 0.1 e ^ 0 10 d + e = 1, and n = the value of R, and has an X-ray powder diffraction pattern which includes, inter alia, the reflections listed in Table A, characterized in that the metal component (s) is / are combined with the support by ion exchange followed by washing, drying and calcination.

In the method according to the invention, the starting material is an H2 / CO mixture. Such H2 / CO mixtures can very suitably be achieved by steam gasification or partial combustion of a carbon-containing material. Examples of such materials are wood, peat, brown coal, bituminous coal, anthracite, coke, crude mineral oil and fractions thereof, as well as tar and oil extracted from tar sand and bituminous slate. The steam gasification or partial combustion is preferably carried out at a temperature of 900-1600 ° C and a pressure of 10-100 bar. In the process according to the invention, it is preferred to start from an H 2 / CO mixture with a molar ratio of 1 / CO more than 0.25 and less than 6.

The catalyst combinations used in the process of the invention contain, in addition to metal components with catalytic activity for the preparation of hydrocarbons, at least one crystalline silicate, which preferably belongs to the "Pentasil" group of crystalline silicates. These silicates are described in 8202690-6 "Atlas of zeolite structure types" by W.M. Meier and D.H. Olson (1978), Polycrystal Book Service, Pittsburgh, Pa., And by E.M. Flaninger, J.M. Bennet, R.M. Grose, J.P. Cohen and J.V. Smith, Nature (London), 1978, 271, biz. 512, and by L.V.C. Rees, 5 "Proceedings of the Fifth International Conference on Zeolites", (Naples), June 2-6, 1980, biz. 562.

Particularly suitable silicates for the process of the invention are the crystalline "Silicalite" mentioned in U.S. Pat. No. 4,061,724, and the crystalline aluminosilicate ZSM-5 disclosed in U.S. Pat. 3,702,886 is described. Other preferred catalyst supports used in the process of the invention are crystalline iron silicate (CIS) (which is described in British Patent No. 1,555,928 and U.S. Patent No. 4,208,305). , a crystalline gallium silicate (Dutch Patent Application No. 7905643) and a crystalline cobalt silicate (Dutch Patent Application No. 7905643).

8101543).

In European patent application no. 80200495 describes a further crystalline silicate which is very suitable as a catalyst support in the process according to the invention. This silicate has the following composition expressed in moles of oxides: p (0.9 ± 0.3) M2 / n O.p (aX203.bY203).

SiO2, wherein M = H and / or alkali and / or alkaline earth metal; X = Rh, Cr and / or Sc; Y = Al, Fe and / or Ga; a · ζ0.5; b> 0; a + b = l; 0 <p ^ l; n = dignity of M.

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 H2 / CO mixture into acyclic hydrocarbons.

Catalyst components capable of converting an H 2 / CO mixture into substantially acyclic hydrocarbons are known in the literature as Fischer-Tropsch catalysts. Such catalyst components contain one or more metals from the 8202690-7 iron group or ruthenium together, optionally with one or more accelerators, to enhance activity and / or selectivity. Suitable catalysts contain 0.1-10 wt% ruthenium and / or 0.05-10 wt% of one or more iron group metals together with one or more accelerators in an amount of 1-50% of the amount of the iron group metals present on the catalyst. A large number of elements are suitable as accelerators for the catalyst according to the invention. The following can be mentioned as an example: 10 alkali metals, alkaline earth metals, metals of 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 accelerators are preferably ion-exchanged in the carrier included. Very suitable accelerator combinations for the iron catalyst component used according to the invention consist of an alkali metal such as K, an easily reducible metal such as Cu or Ag and optionally a difficult to reduce metal such as Al or Zn.

An example of a very suitable iron-containing catalyst component used according to the invention is a catalyst component which contains iron, potassium and copper as the carrier in the crystalline silicate zeolite.

If iron is used in the process according to the invention as a catalyst component containing K as a selectivity enhancer, preference is given to a catalyst containing not more than 0.15 g K per g Fe, since it has been found that when used at higher K concentrations, the selectivity does not increase further, while the stability decreases significantly due to the deposition of carbon on the catalyst. Very suitable accelerator combinations for cobalt catalyst components used according to the invention consist of an alkaline earth metal and Th, U or Ce. An example of a very suitable cobalt catalyst component used in accordance with the invention is a catalyst containing the crystalline silicate zeolite as a carrier in cobalt, magnesium and thorium in 8202690-8. Other very suitable cobalt catalyst components used in the present invention are catalysts containing Co / Cr, Co / Zr, Co / Zn or Co / Mg as catalysts in the crystalline silicate zeolite. Very suitable accelerators for nickel catalyst components used according to the invention are Al, Mn, Th, W and U.

If it is desired to use a catalyst combination in the process according to the invention whose catalyst component with Fischer-Tropsch activity is iron, an iron catalyst component is preferably chosen which contains an accelerator combination consisting of an alkali metal, an easily metal to be reduced, such as copper or silver, and possibly a metal that is difficult to reduce, such as aluminum or zinc.

A very suitable iron-containing catalyst component for the purpose of the present invention is an ion-exchanged catalyst containing iron, potassium and copper as the support in the crystalline silicate zeolite. When iron is used in the catalyst combination as a catalyst component with the required Fischer-Tropsch activity, the process according to the invention is preferably carried out at a temperature of 250-325 ° C and a pressure of 20-100 bar.

If it is desired to use a catalyst combination in the process according to the invention, the catalyst component of which has the required Fischer-Tropsch activity is cobalt, preference is given to a cobalt catalyst component containing an accelerator combination consisting of an alkaline earth metal and chromium, thorium, uranium or cerium.

A very suitable cobalt catalyst for the purpose of the invention is an ion-exchanged catalyst containing cobalt, magnesium and thorium as a carrier in the crystalline silicate zeolite. Other very suitable ion-exchanged cobalt catalysts are catalysts containing in the crystalline silicate zeolite as a support, in addition to cobalt, one of the elements chromium, titanium, zirconium and zinc.

If cobalt is used in the catalyst combination as a catalyst component with the desired Fischer-Tropsch activity, the process according to the invention is preferably carried out at a temperature of 220-300 ° C and a pressure of 10-100 bar.

Very suitable catalysts for the process according to the invention are: a) catalysts containing 0.05-10 parts by weight of iron and 0.025-5 parts by weight of magnesium, per 100 parts by weight of crystalline silicate zeolite support, prepared by ion exchange of the support with one or more solutions of salt of iron and magnesium, followed by washing and drying the composition, after which it is calcined at a temperature of 300-600 ° C and reduced. Particular preference is given to such catalysts which, in addition to 0.1-5 parts by weight of iron and 0.05-2.5 parts by weight of magnesium, 0.05-2.5 parts by weight of copper as reduction accelerators, and 0.1-1.5 parts by weight potassium as selectivity enhancer per 100 parts by weight of carrier, and are calcined at 400-500 ° C and reduced at 250-450 ° C; b) catalysts containing 0.05-10 parts by weight of cobalt and 0.01-2.5 parts by weight of chromium per 100 parts by weight of crystalline silicate zeolite support, and prepared by ion exchange of the support with one or more solutions of salts of cobalt and chromium, followed by washing and drying the composition, after which it is calcined and reduced at a temperature of 300-750 ° C. Particular preference is given to these catalysts if they contain 0.1-5 parts by weight of cobalt and 0.05-1 parts by weight of chromium and are calcined at 300-700 ° C and reduced at 300-700 ° C; c) Catalysts containing 0.05-10 parts by weight of cobalt and 0.01-2.5 parts by weight of zirconium, titanium or chromium per 100 parts by weight of crystalline silicate zeolite support and prepared by ion exchange of a silicate support with one or more solutions 8202690-10 of cobalt and zirconium, titanium or chromium salts, after which the composition is washed and dried, calcined at 350-700 ° C and reduced at 200-700 ° C.

In the process of the invention, catalysts prepared by ion exchange of the support, preferably with one or more aqueous solutions of salts of ruthenium or of iron group metals and salts of accelerators, are used, after which the composition is washed with wash water, dried and calcined.

The ion-exchange capacity of crystalline metal silicates is known. With crystalline metal silicates, the electro-valence of the metal in the structure is balanced by incorporating a cation in the crystal. The cation is usually an alkali metal, such as sodium or potassium. The cations of the synthetic or naturally occurring aluminosilicates can be exchanged for the terminal or polyvalent cations whose physical size and configuration are such that they can diffuse into the silicate structure in the intracrystalline corridors. The original cation can be replaced by another cation, for example by a hydrogen ion or by an ammonium ion. Generally, any suitable acid or salt solution, such as a sulfate or nitrate, can be used as a source of cations that can be incorporated into the silicate by exchange.

The theoretical exchange power of the crystalline silicate is represented by the number of equivalents of cations, eg sodium ions, that balance the electron neutrality of the crystalline silicate. The exchange power varies with the type of screen used. In practice, not all cations in the silicate are easily replaced by the desired cations, so that the effective exchange power is often slightly less than the theoretical exchange power. The degree of exchange depends on factors such as the type of screen, cations in the screen, exchangeable cations, 8202690 - - - type of solvent (water, alcohol) and the exchange temperature.

There is, of course, a maximum for the amount of catalytically active material that can be incorporated into the crystalline silicate by ion exchange.

The ion exchange is preferably carried out at a temperature of 20-200 ° C.

After the ion exchange, the ion exchange solution is removed, for example by filtration, from the zeolite in which the catalytically active metal is exchanged. The zeolite is then preferably washed with the ion exchange solvent to remove any unreacted metal, after which the washing liquid is removed, for example, by filtration. The zeolite cake from which the washings have been removed usually contains about 50% solids. The zeolite can be formed to the desired size, with or without further deterioration of the solvent content. If desired, one or more binders and / or extrusion aids can be added. The zeolite can then be dried and the formed catalyst is calcined at a temperature from about 300 to about 600 ° C to obtain the finished catalyst.

In the preparation of the catalysts, the metals can be applied to the support in one or more steps. The material can be dried between the individual ion exchanges. For the preparation of high metal content catalysts, the use of a multi-step technique may be necessary. The salts of the iron group metals and the salts of the accelerators can be applied to the support separately from different solutions or together from a solution.

In the process according to the invention it is the intention to convert the largest possible amount of the CO present in the feed into hydrocarbons over a catalyst containing one or more metal components with catalytic activity 8202690-12 - for the conversion of a ^ / CO mixture in hydrocarbons, which metal components are selected from the group consisting of iron, cobalt, nickel and ruthenium. For this purpose, the molar ratio in the feed of I / CO is suitably at least 1.0 and preferably 1.25-2.25.

The process of the invention can be very suitably carried out by passing the feed upwards or downwards through a vertically arranged reactor containing a fixed bed of the catalyst or by passing the gaseous feeds up through IQ a fluidized catalyst bed. The process can also be carried out using a suspension of the catalyst or catalyst combination in a hydrocarbon oil. The process is preferably carried out under the following conditions: a temperature of 125-350 ° C and in particular of 175-275 ° C, and a pressure of 1-150 bar and in particular of 5-100 bar.

The invention will now be elucidated by means of the following examples.

EXAMPLE 1 The crystalline aluminosilicate ZSM-5 was prepared as described in U.S. Pat. 3,702,886. The resulting silicate was first converted to ammonium form by ion exchange with a 2-normal NH 2 NO 2 solution. The ammonium form of the ZSM-5 was ion-exchanged for 48 hours with an aqueous solution of RuCl 2 (5 wt%). The catalyst became

then washed with water, dried and calcined with air for 2 hours at 500 ° C and at atmospheric pressure and reduced for 2 hours at 280 ° C at 4 bar. The resulting catalyst had the following composition: 1.7 Ru / 66 SiO2 / 1 A2 O2 (parts by weight). A gas mixture consisting of H ^ and GO (H ^ / CO = 1) was passed over this catalyst under the following conditions: Spatial flow rate: 1000 l (NTP) / lh pressure: 20 bar temperature: 260 ° C

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The conversion of + CO to hydrocarbons was 20.0 wt%,

The space-time yield was 67 g of hydrocarbons per liter of catalyst volume per hour.

The selectivity is stated in the following table: 5 Cj + C2: 4 wt% +: 16 wt% C5 - C12: 78 wt% C13 ”C19: 1.5 wt * ^

C20 +: 0.5 sew, X

This table shows that the yield of desired hydrocarbons with a boiling point in the boiling range of gasoline (C 1 -C 2) is very high compared to that whose boiling point is below and above the preferred range.

The condensed liquid phase contained 40% by weight aromatics, while only traces of dureen were present.

Comparative test 1

The ZSM-5 was prepared as described in Example 1. It was impregnated with an aqueous solution of ruthenium chloride, dried, calcined in air for 2 hours at 500 ° C and 2 hours at 280 ° C at 4 bar pressure with hydrogen to give a catalyst of the following composition: 1.7 Ru / 66 SiO2 / 1 Al 2 O 2 (parts by weight).

By using this catalyst under the conditions described in Example 1, hydrocarbons were obtained from an H 2 / CO gas mixture (1 / CO = 1). The conversion was 13% by weight. The space-time yield was 26 g of hydrocarbons per liter of catalyst per hour.

The selectivity was:

C 1 + C 2: 25 wt% C 30 + C 3: 40 wt% C 5 - C 3: 35 wt% C 13 - -C 19: 0 wt% C 2Q +: 0 wt% 8202690 - 14 -

Thus, a lower yield of gasoline components (C 1 -C 2) was obtained. In addition, no aromatics were present in the product. EXAMPLE 2

Crystalline silica was prepared with the composition of silicalite as described in column 6 of this U.S. Pat. 4,061,724.

The crystalline silica obtained was first converted to ammonium form by ion exchange with a 2N NH 2 NO 2 solution. The ammonium form was ion-exchanged for 24 hours with an aqueous solution of Co (NH4) g (NO3) 2 (15 wt%).

The catalyst was then washed with water, dried, calcined at 500 ° C for 2 hours and reduced at 1 bar abs. For 24 hours at 575 ° C with hydrogen.

This catalyst had the following composition: 100 SiO 2 * 2.5 Co 15 (parts by weight).

A H 2 / CO mixture (H 2 / CO = 1) was passed over this catalyst under the following conditions: Spatial flow rate: 1000 L (NTP / 1 h). pressure: 20 bar * 20 temperature: 260 ° C.

The conversion of H 2 + CO to hydrocarbons was 51% by weight.

The space-time yield was 112 g of hydrocarbons per liter of catalyst per hour.

The selectivity is indicated in the following table: 25 C + C2: 16% C3 + C4: 15% C5 - C12: 58% C13 ~ ° 19: 8% C2Q +: 3% 8202690

Claims (10)

A process for the preparation of hydrocarbons from a mixture of carbon monoxide and hydrogen, using a catalyst combination containing one or more metal components with catalytic activity for the conversion of an H 2 / CO 5 mixture into acyclic hydrocarbons and a carrier, consisting of a crystalline silicate zeolite which in dehydrated form has the following total composition, expressed in moles of oxides (1.0 ± 0.3) (^ -) 2 / n * ^ * / a SiO2 + e ^ eO2 ^ 'where R = edn or more monovalent or divalent cations 10 Me - at least one trivalent metal 0 <a <1 y $, 12 d>. 0,1 e 0 15 d + e * 1, and n * has the dignity of R, and has an X-ray powder diffraction pattern which includes, inter alia, the reflections listed in Table A, characterized in that the metal component (s) are ion-exchanged with the support is / are combined, after which the catalyst is washed, dried and calcined. Method according to claim 1, characterized in that the method is carried out at a temperature of 125-400 ° C and a pressure of 1-150 bar. Process according to claim 1 or 2, characterized in that the catalyst contains iron, nickel, cobalt and / or ruthenium as metal component (s). 4. Process according to one or more of the preceding claims, characterized in that the catalyst contains one or more members of the "Pentasil" group of crystalline silicates. 8202690 _ 16 _ ν »-x 4 .1 - 15 - Process according to one or more of the preceding claims, characterized in that the catalyst contains ZSM-5 and / or silicalite. Process according to one or more of the preceding claims, characterized in that the catalyst contains 0.05-10 wt.% Of one or more iron group metals, which have been ion-exchanged. 7. Process according to one or more of the preceding claims, characterized in that the catalyst contains one or more accelerators in an amount of 1-50% by weight of the amount of the metals of the iron group. Process according to one or more of the preceding claims, characterized in that the catalyst contains 0.1-10 wt.% Ruthenium. The method of claim 1, as described above with special reference to the examples. Hydrocarbons obtained by means of the method according to one or more of the preceding claims. 8202690