NZ202023A - Catalytic production of hydrocarbons from hydrogen/carbon monoxide mixtures and ferrierite - Google Patents

Description

New Zealand Paient Spedficaiion for Paient Number £02023 2020 23 ro'-i'.2i ■aj-Oii/.y <^*1.

Cor/ipicto Cpi-ciflcstion Filed: 4?.'%• r-jc*.— CO~]C- I ^ jjV JAN 1985"] I 5 (o (o WiV Ps£? yuliHQiltiZn Liiits: P.O. Journs?, &5o: mm§! NEW ZEALAND No.: Date: PATENTS ACT, 1953 COMPLETE SPECIFICATION PROCESS FOR THE PRODUCTION OF HYDROCARBONS XI/We, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. Carel van Bylandtlaan 30, The Hague, the Netherlands, a Netherlands Company hereby declare the invention for which^QC/ we pray that a patent may be granted to xqe/us, and the method by which it is to be performed, to be particularly described in and by the following statement:- - 1 - (followed by page la) PROCESS FOR THE PRODUCTION OF HYDROCARBONS The invention 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 5 catalytic activity for the conversion of an H2/CO mixture into hydrocarbons and a carrier consisting of a crystalline silicate.

In an investigation by the Applicant concerning this process it was found that it has two drawbacks. 10 in the first place, when using space velocities acceptable in actual practice, the conversion of the H2/CO mixture is unsatisfactory. Further, the process yields a product substantially consisting of hydrocarbons with less than 5 carbon atoms in 15 the molecule and too few hydrocarbons with 5-12 carbon atoms in the molecule.

Further investigation by the Applicant concerning this process has shown that the two above-mentioned drawbacks can be obviated by using 20 ferrierite as a carrier i.e. by contacting the feed with a catalyst containing one or more metal components with catalytic activity for the conversion of an ^/CO mixture into acyclic hydro- carbons, which metal components are preferably chosen from the group formed by Fe, Co, and Ru, and which component(s) is/are deposited on ferrierite. In this manner it is not only achieved that, when 5 using space velocities acceptable in actual practice, a high conversion of the I^/CO mixture is obtained, but moreover that the reaction product consists predominantly of hydrocarbons with 5-12 carbon atoms in the 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 15 conversion of an I^/CO mixture into hydrocarbons and a carrier, consisting of a crystalline silicate zeolite, characterized in that, the metal component(s) has (have) been combined with ferrierite. In the process according to the invention the 20 starting material is an I^/CO mixture. Such I^/CO mixtures can very suitably be prepared by steam gasification or partial combustion of a carbon-containing material. Examples of such materials are wood, peat, brown coal, bituminous coal, anthracite, 25 coke, crude mineral oil and fractions thereof as well as tars and oils extracted from tar and sand and bituminous shale. 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 5 is preferred to start from an t^/CO mixture with an I^/CO molar ratio of more than 0.25 and less than 6.

The catalyst combinations used in the process according to the invention contain, in addition to 10 metal components with catalytic activity for hydrocarbon synthesis, ferrierite. This crystalline aluminosilicate is described in the "Atlas of zeolite structure types" by W.M. Meier and D.H. Olson (1978), Polycrystal Book Service, 15 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 I^/CO mixture into hydrocarbons. 20 Catalyst components capable of converting an H2/CO mixture into mainly hydrocarbons are known in the literature as Fischer-Tropsch catalysts such catalyst components comprise one or more metals of the iron group or ruthenium together, optionally 25 with one or more promoters to increase the activity and/or selectivity. Suitable catalysts contain 0 0.1-10% by weight of ruthenium and/or 0.05-10% by weight of one or more metals of the iron group together with one or more promoters in a quantity of 1-50% of the quantity of the iron group metals 5 present on the catalyst. As promoters for the catalysts according to the invention a large number of elements are suitable. The following may be mentioned as examples: alkali metals, alkaline earth metals, metals of group VIB (W, Mo, Cr), Ti, 10 Zr, Al, Si, As, V, Mn, Cu, Ag, Zn, Cd, Bi, Pb, Sn, Ce, Th and U. One or more of these promoters are preferably introduced into the carrier by ion-exchange. Very suitable promoter combinations for the iron catalyst component used according to the 15 invention consist of an alkali metal such as K, a readily reducible metal such as Cu or Ag and optionally a metal difficult to reduce, such as Al or Zn. An example of a very suitable iron catalyst component to be used according to the invention is 20 a catalyst component containing iron, potassium and copper in the crystalline silicate as carrier. If in the process according to the invention use is made of an iron catalyst component containing K as selectivity promoter, a catalyst containing not 25 more than 0.15 g of K per g of Fe is preferred, since it has been found that if higher K concen trations are applied the selectivity does not rise further while the stability substantially decreases as a result of carbon deposition on the catalyst.

Very suitable promoter combinations for cobalt 5 catalyst components to be 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 to be used according to the invention is a catalyst containing cobalt, 10 magnesium and thorium in the crystalline silicate as carrier. Other very suitable cobalt catalyst components to be used according to the invention are catalysts containing Co/Cr, Co/Zr, Co/Zn or Co/Mg in the crystalline silicate as carrier. 15 if in the process according to the invention it is intended to use a catalyst combination of which the catalyst component having Fischer-Tropsch activity is iron, an iron catalyst component is preferably chosen containing a promoter consisting 20 of an alkali metal, a readily reducible metal such as copper or silver and optionally a metal difficult to reduce, such as aluminium or zinc. A very suitable iron catalyst component for the present purpose is a catalyst prepared by ion-exchange containing 25 iron, potassium and copper into the crystalline silicate as carrier. If in the catalyst combination iron is used as catalyst component having 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 5 20-100 bar.

If in the process according to the invention it is intended to use a catalyst combination of which the catalyst component having the required Fischer-Tropsch activity is cobalt, a cobalt 10 catalyst component is preferred containing a promoter combination consisting of an alkaline earth metal and chromium, thorium, uranium or cerium.

A very suitable cobalt catalyst for the present 15 purpose is a catalyst prepared by ion-exchange and containing cobalt, magnesium and thorium in the crystalline silicate as carrier. Other very suitable cobalt catalysts prepared by ion-exchange are catalysts containing, in addition to cobalt, one of 20 the elements chromium, titanium, zirconium and zinc in the crystalline silicate as carrier.

If in the catalyst combination cobalt is used as catalyst having the required Fischer-Tropsch activity, the process according to the invention is 25 preferably carried out at a temperature of 220-300°C and a pressure of 10-100 bar. 2Pj?023 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 carrier and prepared by impregnation or preferably by ion-exchange of the carrier with one or more solutions of salts of iron and of magnesium followed by washing and drying the composition, calcining it at 10 a temperature of 300-600°C and reducing it. Special preference is given to such catalysts containing, 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 promoter and 15 0.1-1.5 parts by weight of potassium as selectivity promoter per 100 parts by weight of carrier and 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 carrier and prepared by impregnation or preferably by ion-exchange of the carrier with one or more solutions of salts of cobalt and of chromium followed by washing and drying the composition, 25 calcining it and reducing it at a temperature of 300-750°C. Particular preference is given to such 207.0 catalysts containing, in addition to 0.1-5 parts by weight of cobalt and 0.05-1 parts by weight of chromium per 100 parts by weight of ferrierite 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 carrier and prepared by impregnation or preferably by ion-exchange of a 10 silicate carrier with one or more solutions of salts of cobalt and zirconium, titanium or chromium, followed by washing and drying the composition, calcining at 350-700°C and reducing it at 200-700°C.

In the process according to the invention catalysts are used that are preferably prepared by ion-exchange of the carrier, advantageously with one or more aqueous solutions of salts of ruthenium or of metals of the iron group and salts of 20 promoters, followed by washing with water, drying and calcining the composition.

The ion-exchange Ability of ferrierite is well known. In ferrierite the electrovalence of the aluminium in the crystalline structure is balanced 25 by the presence of cations on the anionic latice position in the crystal. The cation is most commonly ?€>l>0 23 an alkali metal, such as sodium or potassium. The cations of aluminosilicate ferrierite can be exchanged for the mono- or polyvalent cations which are of a suitable physical size and configuration 5 to diffuse into the intracrystalline passages in the silicate structure. The original cation can be replaced by another cation e.g. by a hydrogen ion or by an ammonium ion. In general, any suitable acid or salt solution such as a sulphate or nitrate 10 can be used as a source of cations to be exchanged into the silicate.

The theoretical exchange capacity of the ferrierite is represented by the number of equivalents of cations., e.g. sodium ions, which balance 15 the electroneutrality of this crystalline aluminosilicate. The exchange capacity varies according to the particular type of sieve involved. In practice, not all of the cations in the silicate are readily replaced with the desired cations, so that the 20 effective exchange capacity is often somewhat less than the theoretical exchange capacity. The extent of the exchange depends on such factors as the type of sieves, cations in the sieve, cations to be exchanged, type of solvent (water, alcohol) and 25 temperature of exchange. Clearly, there is a limit to the amount of catalytically active metal which can be ion-exchanged into the crystalline alumino-silicate ferrierite.

The ion-exchange is preferably carried out at a temperature in the range from 20 to 200°C.

Following the ion-exchange step, the ion- exchange solution is removed from the ferrierite containing the catalytically active metal exchanged therein, for example by filtration. The ferrierite is then washed preferably with the ion-exchange 10 solvent to remove any unreacted metal and the wash liquid is removed, for example by filtration. The zeolite cake from which the wash liquid has been removed usually contains about 50% solids. Either with or without further adjustment of the solvent 15 content, the zeolite can be shaped to desired size. If desired one or more binders and/or extrusion aids can be added. The zeolite may then be dried, and the shaped catalyst is calcined, at a temperature of from about 300 to about 600°C, to 20 form the finished catalyst.

In the preparation of the catalysts the metals can be deposited on the carrier in one or more steps. Between the separate steps the material may be dried. For the preparation of catalysts with a 25 high metal content the use of a multi-step technique may be necessary. The salts of the iron group metals and the salts of the promoters can be deposited on the carrier separately from different solutions or together from one solution.

In the process according to the invention the 5 intention is to convert the largest possible quantity of the CO present in the feed into hydrocarbons over a catalyst containing one or more metal components with catalytic activity for the conversion of an f^/CO mixture into hydrocarbons, which metal components are chosen from the group formed by iron, cobalt, and ruthenium. To this end the I^/CO molar ratio in the feed is suitably at least 1.0 and preferably 1.25-2.25.

The process according to the invention can 15 very suitably be carried out by conducting the feed in upward or downward direction through a vertically mounted reactor containing a fixed bed of the catalyst or by passing the gaseous feeds upwardly through a fluid catalyst bed. The process 20 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 25 of 1-150 bar and in particular of 5-100 bar. 2 020 The invention will now be explained with reference to the following Examples.

Example I Ferrierite was first transferred into the 5 ammonium form by ion-exchange with a 2 Normal NH^NO^ solution. The ammonium form of the ferrierite was ion-exchanged with an aqueous solution of RuC13(5% wt.) during 48 hours. The catalyst was then washed with water, dried and 10 subjected to a 2-hour calcination at 300°C with nitrogen at atmospheric pressure and reduced for two hours at 280°C with H2 at 4 bars. The resulting catalyst had the following composition: 1.5 Ru/ 49 SiC^/l Al^^ (parts by weight). A gas 15 mixture consisting of H2 and CO (H2/CO = 1) was passed over this catalyst applying the following conditions: gas hourly space velocity: 1000 1 (NTP)/lh pressure: 20 bar 20 temperature: 260°C The conversion of H2 + CO into hydrocarbons was 46.4% wt. The space-time yield was 106 grams of hydrocarbons per litre of catalyst volume per hour. The selectivity is given in the following table: C1+ C2 : 17% wt.

C3 + C4 : 10% wt.

C5 " C12 : 59% wt.

C13" C19 : 10% wt.

C20+ : 4% wt.

From this table it can be seen that the yield of desired hydrocarbons boiling in the gasoline boiling range (C^-C.^) "*"s ver¥ high compared with those boiling below and above the preferred range. 10 The condensed hydrocarbon liquid phase contained 99% wt. paraffins.

Example II Ferrierite was first transferred into the ammonium form by ion-exchange with a 2 Normal 15 NH^NO^ solution and then washed with water, dried and subjected to a 2-hour calcination at 500°C with air at atmospheric pressure whereupon it was impregnated with an aqueous solution of cobalt nitrate, dried, calcined during 2 hours at 500°C in 20 air and reduced for 2 hours at 280°C with hydrogen at 4 bar pressure in order to obtain a catalyst having the composition: Co/49 SiC^/l (parts by weight) . Using this catalyst under the conditions described in Example 25 I hydrocarbons were formed from an I^/CO gas mixture H2/CO = 1). The conversion was 66% wt. The space-time yield was 120 grams of hydrocarbons per litre of catalyst per hour.

The selectivity was: C1 + C2 : 17% wt.

C3 + C4 : 7% wt.

C5 " C 12" 47% wt.

C13~ c <~19* % wt.

C20 • 13% wt.

A good result as regards the yield of gasoline components (Ccj-C^) was t*1113 obtained. No aromatics were present in the product. The metal weight time yield was 1300 grams of hydrocarbons per kg cobalt on the catalyst per hour.

Example III Ferrierite was first transferred to ammonium form by ion-exchange with a 2N NH^NO^ solution. The ammomium form was ion-exchanged with an aqueous solution of ^Co (NH^)^(NO^)2 (15% wt.) during 24 hours.

The catalyst was then washed with water, dried, calcined two hours at 500°C and subjected to a 24 hours1 reduction with hydrogen at 575°C and 1 bar abs.

This catalyst had the following composition: 3.1 Co.49 SiC^.lA^O^ (parts by weight).

Claims (9)

- 15 - An H^/CO mixture (I^/CO = 1) was passed over this catalyst applying the following conditions, gas hourly space velocity: -1000 1 (NTP/1 h) pressure: 20 bar 5 temperature: 260°C The conversion of H2 + CO into hydrocarbons was 43% wt. The space-time yield was 99 grams of hydrocarbons per litre of catalyst per hour. 10 The selectivity is given in the following table: C1+ C2 : 20% wt C3 + C4 5 9% wt C5 " C12: 55% wt C13" C19: 10% wt C20 + 5% wt The metal weight time yield was 2500 grams of hydrocarbons per kg cobalt on the catalyst per hour. No aromatics were present in the product. 202023 ; *v Jhl •-V 3 16 WHAT f/Vv'E CLAIM IS;

1. 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 I^/CO mixture into hydrocarbons and a carrier, consisting of a crystalline silicate characterized in that, the metal component(s) has (have) been combined with ferrierite.

2. A process as claimed in claim 1, characterized in that it is carried out at a temperature of 125-350°C and a pressure of 1-150 bar.

3. A process as claimed in claim 1 or 2, characterized in that the catalyst contains iron, cobalt, and/or ruthenium as the metal component(s).

4. A process as claimed in any one or more of the preceding claims, characterized in that the metal component(s) has (have) been combined with the ferrierite by ion-exchange followed by washing, drying and calcining.

5. A process as claimed in any one or more of the preceding claims, characterized in that the catalyst contains from 0.05 up to 10% by weight of one or more metals chosen from the group consisting of iron and cobalt. 17

6. A process as claimed in claim 5, characterized in that the catalyst contains one or more promoters in a quantity of 1-50% by weight of the quantity Of the metals chosen from the group consisting of iron and cobalt.

7. A process as claimed in any one or more of the preceding claims, characterized in that the catalyst contains from 0.1 up to 10% by weight of ruthenium.

8. A process as claimed in claim 1, as described hereinbefore with special reference to the Examples.

9. Hydrocarbons, in so far as obtained by means of the process as claimed in any one or more of the preceding claims. DATED THIS I^DAYOF OcWl 19SKf A. J. PARK & SON PER •\GF\TS FO"' TMP APPLICANTS 18 OCT I984