# Patent

## Title
Skinless porous particle PVC resin and process for producing same

## Abstract

Also a process for the conversion of synthesis gas using the catalyst produced as aforsaid, optionally in combination with a zeolite.

## Background
This is a division of application Ser. No. 848,401, filed Mar. 4, 1986, as PCT GB85/00330 on Jul. 25, 1985, published as WO86/00885 on Feb. 13, 1986, now U.S. Pat. No. 4,683,219.

The present invention relates to a process for the production of a catalyst for use in the conversion of gaseous mixtures principally comprising carbon monoxide and hydrogen, hereinafter referred to as synthesis gas, to hydrocarbons of carbon number greater than one, in particular to aliphatic hydrocarbons in the gasoline boiling range, and to the use of the catalyst so-produced in the conversion of synthesis gas to the aforesaid hydrocarbons.

The conversion of synthesis gas to hydrocarbons by the Fischer-Tropsch process has been known for many years but the process has only achieved commercial significance in countries such as South Africa where unique economic factors prevail. The growing importance of alternative energy sources such as coal and natural gas has focussed renewed interest in the Fischer-Tropsch process as one of the more attractive direct and environmentally acceptable routes to high quality transportation fuels.

Of the Group VIII metals, ruthenium has long been known to be one of the most active catalysts in the conversion of synthesis gas, the product, at moderate pressures and above, being high molecular weight paraffin waxes and, at low pressures, principally methane. Several recent patent publications, for example U.S. Pat. Nos. 4,042,614; 4,171,320; 4,206,134; 4,413,064 and 4,410,637 and GB-A-22119277, describe and claim the formation of different products from synthesis gas using catalysts containing ruthenium as an active component.

U.S. Pat. No. 4,042,614 described a process for the selective synthesis of olefins from C.sub.2 to C.sub.10 chain length inclusive from synthesis gas using as catalyst ruthenium on a titanium-containing oxide support, wherein said titanium-containing oxide support is selected from the group consisting of TiO.sub.2, ZrTiO.sub.4, TiO.sub.2 -carbon, titanates and mixtures thereof.

U.S. Pat. No. 4,171,320 describes a process for the synthesis of olefins of from C.sub.2 to C.sub.5 chain length inclusive from synthesis gas using as catalyst ruthenium on a support selected from the group consisting of V.sub.2 O.sub.3, Nb.sub.2 O.sub.5, Ta.sub.2 O.sub.5, Al.sub.2 O.sub.3 -V.sub.2 O.sub.3 -V.sub.2 O.sub.3, Al.sub.2 O.sub.3 -Nb.sub.2 O.sub.5, Al.sub.2 O.sub.3 -Ta.sub.2 O.sub.5, SiO.sub.2 -V.sub.2 O.sub.3, SiO.sub.2 -Nb.sub.2 O.sub.5, SiO.sub.2 -Ta.sub.2 O.sub.5, V.sub.2 O.sub.3 -carbon, Nb.sub.2 O.sub.5 -carbon, Ta.sub.2 O.sub.5 -carbon, alkaline earth-group VB oxides, alkali metal-Group VB oxides, Group IVB-Group VB oxides and mixtures thereof.

U.S. Pat. No. 4,206,134 describes a process for the enhanced synthesis of C.sub.2 -C.varies.olefins with reduced production of methane from synthesis gas using as catalyst ruthenium on a manganese-containing oxide support, wherein said manganese-containing oxide support is selected from the group consisting of MnO, Al.sub.2 O.sub.3 -MnO, SiO.sub.2 -MnO, MnO-carbon, Group IVB-manganese oxide, Group VB-manganese oxides, rare earth-manganese oxides and mixtures thereof.

U.S. Pat. No. 4,413,064 describes a process for the conversion of synthesis gas to a product high in straight chain paraffins in the diesel fuel boiling range from synthesis gas utilising a catalyst consisting essentially of cobalt, thoria or lanthana and ruthenium on an alumina support wherein said alumina is gamma-alumina, etaalumina or a mixture thereof, said catalyst being prepared by contacting finely divided alumina with salt of thorium or lanthanum.

U.S. Pat. No. 4,410,637 describes a process for the preparation of a hydrocarbon mixture consisting substantially of C.sub.5 -C.sub.12 hydrocarbons from synthesis gas using a catalyst containing one or more of iron, nickel, cobalt, chromium and/or ruthenium and, as a carrier, magadite, a laminar crystalline silicate compound capable of absorbing metal ions or metal salts by intercalation.

The reaction of carbon monoxide and hydrogen on rare earth metal oxide catalysts is described in Chemical Communications, 1983, page 763/764 by Kieffer et al. Catalysts studied were Pd - La.sub.2 O.sub.3 and Pd - Dy.sub.2 O .sub.3, both of which were prepared by impregnation.

Finally, GB-A-2,119,277 describes a catalyst for the selective synthesis of olefins from a mixture of hydrogen and carbon monoxide or hydrogen and carbon dioxide comprising a ruthenium carbonyl compound deposited on a ceric oxide-containing support. In Example 3 there is disclosed a catalyst prepared by impregnating ceric oxide with an aqueous solution of RuCl.sub.3.3H.sub.2 O (ruthenium content 0.62% w/w). The impregnated catalyst when used in the conversion of synthesis gas (Run 9) produces an undesirably high methane yield (35.7%) and a low selectivity (1.6%) to desirable olefins.

We have found that ruthenium-containing catalysts produced by coprecipitation can substantially overcome the disadvantages in terms of high methane yield and low selectivity to olefins associated with the prior art impregnated catalysts.

Accordingly the present invention provides a process for the production of a composition for use after reductive activation as a catalyst in the conversion of synthesis gas to hydrocarbons of carbon number greater than one, which composition has the formula:

wherein oxygen is satisfied, the composition, composition, and

which process comprises the steps of: cerium and a precipitant comprising a carbonate and/or a bicarbonate and/or a hydroxide of an alkali metal or ammonium under conditions whereby there is formed a precipitate comprising ruthenium and cerium in the form of compounds thermally decomposable to their oxides, and

It has been found that catalysts differing from catalysts of the invention in the respect that their ruthenium content is greater than 1% w/w tend to produce large quantities of methane, the actual proportion of methane increasing with increasing ruthenium content, whereas catalysts according to the present invention in which the ruthenium content is less than 1% w/w, preferably less than 0.5% w/w, are at the same time both active and selective to hydrocarbons other than methane, and in particular to aliphatic hydrocarbons of carbon number greater than 2, of which C.sub.5.sup.+  hydrocarbons form a major proportion. Moreover the selectivity to unwanted carbon dioxide can be maintained within acceptable limits, unlike catalysts containing higher ruthenium loadings.

In the formula (I) A is an alkali metal, which is preferably potassium. Preferably the amount b of alkali metal is greater than zero and up to 5% w/w, even more preferably up to 2% w/w.

As regards step (A) of the process, the salts of ruthenium and cerium may suitably be brought together in aqueous solution. Suitably an aqueous solution of the precipitant may be added to an aqueous solution of water soluble salts of the metals, though other variations in the order of addition will be readily apparent to those skilled in the art and may be used if desired. Whilst any soluble salt of ruthenium and cerium may be employed, it will usually be found convenient to use ruthenium in the form of the chloride because this is a commercially available form and cerium in the form of the nitrate, for example cerrous nitrate. Commercially available cerrous nitrate, which contains rare earth metals other than cerium, may be employed if desired.

The precipitant in step (A) is a carbonate and/or a bicarbonate and/or a hydroxide of an alkali metal. Instead of using a pre-formed carbonate or bicarbonate it is possible to use the precursors of these salts, for example a water soluble salt and carbon dioxide. Alternatively, urea, which is thermally decomposable to carbon dioxide and ammonia, may be used. In any event, b in the aforesaid formula (I) will have a value greater than zero, which value may be adjusted if desired by washing or addition of further alkali metal compound. Alternatively, ammonium carbonate and/or bicarbonate and/or hydroxide may be employed as the precipitant, in which case the value of b in the catalyst as initially produced will be zero, though this value may subsequently be adjusted if desired by addition of alkali metal.

Suitably the soluble salts of the metals ruthenium and cerium may be brought together at a temperature in the range from 0.degree. to 100.degree. C. In one preferred embodiment of the invention the temperature is suitably in the range from 60.degree. to 100.degree. C., preferably from 80.degree. to 100.degree. C. In another preferred embodiment the temperature is suitably below 50.degree. C., preferably below 30.degree. C., for example ambient temperature.

Addition of the precipitant to the solution of metal salts causes the intitially low pH of the mixture to rise. It is desirable in the preparation of catalysts according to the invention that the final pH of the mixture is greater than 6, preferably in the range from 6 to 10, even more preferably in the range from 8 to 10. The precipitant may be added until a pH in the aforesaid range is achieved, whereupon the addition of further precipitant may be discontinued, thereby arresting the rise in the pH. In order to improve the homogeneity of the catalyst it is preferred to agitate the mixture during precipitation, suitably by mechanical stirring. After precipitation, it is preferred to maintain the mixture at a temperature close to boiling for a period of at least 15 minutes, preferably whilst stirring, for the purpose of completing the precipitation.

The amounts of the ruthenium and cerium salts and precipitant employed should be such as to satisfy the stoichiometric relationships in the formula (I). Alternatively, the alkali metal content of the composition may be supplemented by further addition thereof, or reduced, for example by washing, at any subsequent point in the preparative process.

In step (B) the precipitate obtained in step (A) is recovered. This may suitably be accomplished by filtration but other methods for separating solids from liquids, for example centrifugation, may be employed. After recovery it is preferred to wash the precipitate, suitably with water, so as to remove unwanted residual soluble matter. It is also preferred to dry the precipitate, suitably at an elevated temperature below 180.degree. C., for example about 120.degree. to 150.degree. C.

Thermally decomposable compounds comprised in the precipitate recovered in step (B) are preferably thermally decomposed in a discrete step (C). This may suitably be accomplished by heating the precipitate, suitably in a non-reducing atmosphere, for example a stream of inert gas, such as nitrogen, or an oxygen-containing gas such as air, at a temperature suitably in the range from 250.degree. to 600.degree. C.

In order to convert the composition of formula (I) into a catalyst for use in the conversion of syngas to hydrocarbons having a carbon number greater than 1, it is generally necessary to reductively activate the composition, suitably by contact at elevated temperature with a reducing gas, for example hydrogen, carbon monoxide or mixtures thereof. A suitable reducing gas is for example hydrogen which may be diluted with an inert gas such as nitrogen. Typically, the conditions employed may suitably be a pressure in the range from 1 to 100 bar and a temperature in the range from 150.degree. to 350.degree. C. for a period of up to 24 hours or longer. Reductive activation may be effected as a discrete step prior to use as a catalyst for the conversion of synthesis gas or it may be incorporated into the synthesis gas conversion process.

Those skilled in the art will readily appreciate that it may be possible to combine the thermal decomposition step and the reductive activation step into a single step under certain circumstances.

It is believed that coprecipitated catalysts differ fundamentally from impregnated catalysts and that this difference is reflected in their catalytic performance.

The present invention also provides a process for the production of hydrocarbons having a carbon number greater than one from synthesis gas which process comprises contacting synthesis gas with a catalyst comprising the reductively activated composition having the formula (I) at a temperature in the range from 190.degree. to 400.degree. C. and a pressure in the range from 0 to 100 bar.

Reductive activation of the composition of formula (I) may be conducted either as a separate step outside the syngas conversion reactor, as a discrete step within the syngas conversion reactor prior to syngas conversion or within the syngas conversion reactor under syngas conversion conditions.

As is well known in the art synthesis gas principally comprises carbon monoxide and hydrogen and possibly also minor amounts of carbon dioxide nitrogen and other inert gases depending upon its origin and degree of purity. Methods for preparing synthesis gas are established in the art and usually involve the partial oxidation of a carbonaceous substance, e.g. coal. Alternatively, synthesis gas may be prepared, for example by the catalytic stream reforming of methane. For the purpose of the present invention the carbon monoxide to hydrogen ratio may suitably be in the range from 2:1 to 1:6. Whilst the ratio of the carbon monoxide to hydrogen in the synthesis gas produced by the aforesaid process may differ from these ranges, it may be altered appropriately by the addition of either carbon monoxide or hydrogen, or may be adjusted by the so-called shift reaction well known to those skilled in the art.

In a modification of the process for the production of hydrocarbons, there may be combined with the catalyst an inert material, for example silica. It is preferred, however, to combine the catalyst with a zeolite.

The zeolite may be either physically admixed with the composition to form an intimately mixed bed or may be separate therefrom, for example in the form of a split bed, the zeolite forming one portion of the bed and the catalyst another. In the case of a physical admixture, the zeolite may be mixed with the composition either before or after reductive activation. Alternatively, the coprecipitation (step A) in the process for producing the composition of formula (I) may be performed in the presence of the zeolite, particularly when the precipitant is ammonium carbonate and/or bicarbonate and/or hydroxide.

A suitable zeolite is an MFI-type zeolite, for example ZSM-5 as described in U.S. Pat. No. 3,702,886. It is preferred to use the hydrogen form of the zeolite which may be obtained by acid exchange or by thermal decomposition of the ammonium-exchanged form of the zeolite. Preferably the alkali metal-free composition (b in the formula (I)=0) is modified by combination with the zeolite. Suitably the ratio of the number of parts by volume of catalyst composition to the number of parts by volume of the zeolite may be in the range from 5:1 to 1:5, preferably about 2:1. Combination with a zeolite can improve the selectivity to gasoline range paraffinic hydrocarbons.

The temperature is preferably in the range from 250.degree. to 350.degree. C. and the pressure is preferably in the range from 10 to 50 bars. The GHSV may suitably be in the range from 100 to 5000h.sup.-1.

The process may be carried out batchwise or continously in a fixed bed, fluidised bed or slurry phase reactor.

The invention will now be further illustrated by the following Examples.

Cerous nitrate (68.8 g: 0.16 mol) was dissolved in deionised water (300 ml). To this was added a solution of ruthenium (III) chloride (0.31 g: 0.001 mol) dissolved in hot deioinised water (30 ml). The solution was heated to 80.degree. C. with stirring and then a solution of potassium carbonate (160 g) in deionised water (200 ml) was added dropwise until pH 8.3 was attained (ca 60 ml). The mixture was heated at ca. 90.degree. C. with stirring for 0.5 h. The grey precipitate was filtered, washed twice by slurrying with deionised water (2.times.500 ml) and dried in air at 125.degree. C. for 17.0 h.

The procedure of Example 1 was repeated.

A 0.5% Ru/Kx/CeO.sub.2 catalyst was prepared by the procedure of Example 1 and a further 1% w/w potassium added thereto.

Cerous nitrate (68.8 g; 0.16 mol) was dissolved in deionised water (200 ml). To this was added a solution of ruthenium (III) chloride (0.31 g; 0.001 mol) dissolved in hot deionised water (30 ml). The solution was heated to ca 80.degree.-85.degree. C. with rapid stirring and then a solution of potassium carbonate (150 g) in deionised water (1000 ml) was added at a rate of 25 ml/min until pH 8.5-9.5 was attained (ca 225 ml). The mixtrue was heated to boiling point and boiled for 12 minutes. The heat was then removed and stirring was continued for a further 20 minutes. The precipitate was left to stand in solution overnight and then filtered, washed by slurrying twice with deionised water (2.times.300 ml) and then dried in air at 150.degree. C. overnight (17.0 h).

Cerous nitrate (68.8 g; 0.16 mol) was dissolved in deionised water (300 ml). To this was added a solution of ruthenium (III) chloride (0.34 g; 0.0011 mol) dissolved in hot deioinised water (30 ml). A solution of potassium carbonate (75 g) in deionised water (500 ml) was added at room temperature dropwise with vigorous stirring until pH 9.5 was attained. The mixture was stirred for a further 15 minutes to ensure complete reaction. The resulting grey precipitate was filtered, washed twice by slurrying with deionised water (2.times.300 ml) and dried in air at 120.degree. C. for 17 hours.

The compositions were pretreated as follows: ##STR1##

Catalyst A was sieved to BSS 8-20 mesh and loaded into a fixed bed reactor. The catalyst was reduced in the reactor under a slow stream of hydrogen at 225.degree. C. for 17 hours. Synthesis gas was then introduced into the reactor, the pressure adjusted to 20 bar and the run started.

The reaction conditions employed and the results obtained are shown in the Table.

Example 8 was repeated except that Catalyst A was replaced by Catalyst B.

Example 8 was repeated except that Catalyst A was replaced by Catalyst C.

Example 8 was repeated except that Catalyst A was replaced by Catalyst D.

Example 8 was repeated except that Catalyst A was replaced by Catalyst E.

Example 8 was repeated except that Catalyst A was replaced by Catalyst F.

Example 8 was repeated except that Catalyst A was replaced by Catalyst G.

Example 18 was repeated except that Catalyst A was replaced by a split bed consisting of a catalyst prepared in the manner of Catalyst A (6.0 ml) forming the top portion thereof and an H-MFI zeolite (4.0 ml) forming the bottom portion thereof.

Example 15 was repeated except that the temperature was increased.

The reaction conditions employed in the results obtained for Examples 8 to 16 are shown in the Table. __________________________________________________________________________ CO:H.sub.2 molar ratio = 1:2 Pressure = 20 bar CO Temp. GHSV conversion Molar Selectivity (%) C.sub.5.sup.+  Productivity Example Catalyst (.degree.C.) (h.sup.-1) (%)   CO.sub.2 CH.sub.4 C.sub.2 -C.sub.4 C.sub.5.sup.+ (g/liter catalyst/h) __________________________________________________________________________ 8    A    357 1250 71    18 8  15  58   90 9    B    385 5002 38    25 16 24  35  124 10   C    323 2501 36    17 12 20  51   81 347 2501 59    19 15 22  43  145 11   D    349 2500 80    17 9  22  52  216 12   E    345 2500 68    16 8  18  57  202 13   F    335 2500 63    14 8  21  58  190 14   G    345 2520 90.9  12 8  19  61  272 15        330 1500 43    20 5  19   56** 75 16        340 1500 53    17 11 23   49** 81 __________________________________________________________________________ *Oxygenates not included in molar selectivity **C.sub.5 to C.sub.11 + light aromatics (BTX)

## Claims

1. A process for the production of hydrocarbons having a carbon number greater than one from a synthesis gas principally comprising carbon monoxide and hydrogen which process comprises contacting the synthesis gas at a temperature in the range from 190.degree. to 400.degree. C. and a pressure in the range from atmospheric pressure to 100 bar with a catalyst comprising a reductively activated composition having the formula: wherein oxygen is satisfied, the composition, composition, and said composition of the formula (I) having been prepared by the steps comprising: cerium and a precipitant selected from the carbonate, bicarbonate, hydroxide and mixtures of same of an alkali metal or ammonium under conditions whereby there is formed a precipitate comprising ruthenium and cerium in the form of compounds thermally decomposable to their oxides, and

2. A process according to claim 1 wherein the ruthenium content of the composition of formula (I) is less than 0.5% w/w.

3. A process according to claim 1 wherein the amount (b) of alkali metal (A) in the composition of formula (I) is greater than zero and up to 5% w/w.

4. A process according to claim 3 wherein the alkali metal is potassium.

5. A process according to claim 2 wherein the salts of ruthenium and cerium are brought together in step (A) in aqueous solution.

6. A process according to claim 1 wherein the salts of ruthenium and cerium are brought together in step (A) at a temperature below 30.degree. C.

7. A process according to claim 1 wherein in step (A) the final pH is in the range from 6 to 10.

8. A process according to claim 1 wherein the composition of formula (I) is reductively activated by contact at a pressure in the range from 1 to 100 bar and a temperature in the range from 150.degree. to 350.degree. C. for a period of up to 24 hours with a reducing gas.

9. A process for the production of hydrocarbons having a carbon number greater than one from a synthesis gas principally comprising carbon monoxide and hydrogen which process comprises contacting the synthesis gas at a temperature in the range from 190.degree. to 400.degree. C. and a pressure in the range from atmospheric pressure to 100 bar with a catalyst comprising (i) a reductively activated composition having the formula: wherein oxygen is satisfied, the composition, composition, and and (ii) a zeolite.

10. A process according to claim 9 wherein the zeolite is of the MFI-type.

11. A process according to claim 10 wherein the zeolite is in hydrogen form.

12. A process according to claim 9 wherein b in the formula (I) is zero.

13. A process according to claim 9 wherein the composition of formula (I) and the zeolite are physically admixed to form an intimately mixed bed.

14. A process according to claim 9 wherein the composition of formula (I) and the zeolite are in the form of separate beds.

15. A process according to claim 9 wherein the composition of formula (I) and the zeolite are in the form of a physical admixture and the composition of formula (I) is reductively activated before mixing with the zeolite.

16. A process according to claim 9 wherein the composition of formula (I) and the zeolite are in the form of a physical admixture and the compositon of formula (I) is reductively activated in the presence of the zeolite.

17. A process according to claim 9 wherein the ratio of the number of parts by volume of the composition of formula (I) to the number of parts by volume of zeolite is in the range from 5:1 to 1:5.

18. A process according to claim 9 wherein the composition of formula (I) is obtained by the steps comprising: cerium and a precipitant selected from the carbonate, bicarbonate, hydroxide and mixtures of same of an alkali metal or ammonium under conditions whereby there is formed a precipitate comprising ruthenium and cerium in the form of compounds thermally decomposable to their oxides, and

19. A process according to claim 9 wherein the composition of formula (I) is reductively activated by contact at a pressure in the range from 1 to 100 bar and a temperature in the range from 150.degree. to 350.degree. C. for a period of up to 24 hours with a reducing gas.

20. A process according to claim 1 wherein the temperature is in the range from 250.degree. to 350.degree. C. and the pressure is in the range from 10 to 50 bars.

21. A process according to claim 1 wherein thermally decomposable compunds comprised in the precipitate recovered in step (B) are thermally decomposed in a discrete step (C) comprising heating the precipitate at a temperature in the range from 250.degree. to 600.degree. C.

22. A process according to claim 21 wherein the precipitate is heated in a stream of nitrogen or air.