JPS5839131B2 - gouseigasuotankasuisokongobutsuhetenkasurhouhou - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to an improved process for converting synthesis gas, a mixture of gaseous carbon oxides and hydrogen or a hydrogen donor, to a hydrocarbon mixture.

Methods of converting coal and other hydrocarbons such as natural gas into gas mixtures consisting essentially of hydrogen and carbon monoxide and/or carbon dioxide are well known.

The principal of these methods rely on partial combustion of the fuel with an oxygen-containing gas, or on the high temperature reaction of the fuel with steam, or on a combination of these two reactions.

An excellent overview of gas production technology, including synthesis gas from solid and liquid fuels, is available at Interscience Publishers, New York City, New York.
Published by Kirk Othmer.
r) “Encyclopedia of Chemicals”
Technology
Chemical Technology) 2nd edition,
10, pp. 353-433 (1966).

It is also well known that synthesis gas undergoes conversion over a wide variety of catalysts at pressures from about 300 below to about 850 below and from about 1 to 1000 atmospheres to produce carbon monoxide reduction products such as hydrocarbons. .

For example, the most widely studied Fischer-Trobzu process produces a range of liquid hydrocarbons, some of which are used as low-octane gasoline.

The catalysts used in this and related processes are based on iron, cobalt, nickel, ruthenium, thorium, rhodium, and osmium, or their oxides.

However, the catalyst and conversion operating conditions yield liquid hydrocarbons in the gasoline boiling range containing highly branched paraffins and significant amounts of aromatic hydrocarbons, both of which are necessary for high-grade gasoline. It has not been found possible to determine the combination or to selectively produce liquid-rich aromatic hydrocarbons in the benzene to xylene range.

An overview of the current state of this technology can be found in Kirk Othmer, Encyclopedia of Chemical Technology, 2nd Edition, Volume 4, 446-488, published by Interscience Publishers, New York City, New York.
It is described in "Carbon dioxide-hydrogen reaction" on the page.

The synthesis gas was recently converted to oxygen-containing organic compounds by contacting the synthesis gas with a carbon monoxide reduction catalyst and then contacting the resulting conversion product with a special type of zeolite catalyst in a separate reaction zone, and then It has been found that the resulting compounds can be converted into higher hydrocarbons, especially high octane gasolines.

This two-stage conversion process is described in DT-O82438252.

Now synthesis gas i.e. hydrogen and carbon monoxide, optionally mixtures of other carbon oxides or equivalents of such mixtures, in the presence of certain heterogeneous catalysts consisting of intimate mixtures of two or more components. It has been found that valuable hydrocarbon mixtures can be produced directly by reaction.

Accordingly, the method for producing hydrocarbons from synthesis gas according to the present invention comprises converting synthesis gas, at a temperature within the range of 450 to 1000'F, to - thorium, zinc, copper, chromium, titanium, characterized by carbon oxide reduction catalytic activity; a metal or metals or combinations thereof selected from iron, ruthenium, a pore diameter greater than about 5 angstroms, a silica to alumina ratio of at least 120 and a constraint index within the range of 1 to 12; It consists of recovering hydrocarbons in the gasoline boiling range by contacting them with a catalyst containing a mixture of crystalline aluminone silica.

The metal or metal compound accounts for 0.1 to 99% of the mixture.
Preferably it comprises from about 1% to about 80% by weight.

The carbon monoxide reducing component selected from a metal selected from thorium, zinc, copper, chromium, titanium, iron, and ruthenium or multiple metals or a compound thereof and the crystalline aluminosilicate may be present in the same particle or in separate particles. It may be in particles.

Suitable crystalline aluminosilicate is ZSM-5, ZSM
-11, ZSM -12, ZSM-35 and ZSM
-38.

Preferred metals are iron and ruthenium, but metals or metals selected from copper, zinc, thorium, titanium and their compounds also produce excellent effects.

Mixtures of all of these with promoters such as chromia are of value.

The ratio of carbon monoxide reducing components to crystalline aluminosilicate is adjusted to control the character of the product, i.e. whether gasoline boiling range components predominate, paraffins/aromatics predominate or internal Adjustments are made to determine whether the olefin is predominant.

Advantageously, the hydrogen to carbon oxide volume ratio is maintained within the range 0.2 to 6.0.

Depending on the selection of components and reaction conditions used, significant liquid mixtures rich in one or more olefins, branched paraffins and aromatic hydrocarbons can be obtained for high octane gasoline production or for petroleum production. Very suitable for chemical applications.

The catalyst and operating conditions can thus be selected to produce as the main product a normally gaseous hydrocarbon having at least one carbon-to-carbon bond or a hydrocarbon stream rich in internal olefins.

Such products are valuable as petrochemical feedstocks and for the production of easily liquefied petroleum fuels.

The catalysts used not only produce highly desirable products with good selectivity, but also often produce them at very high conversions per stream or under mild conditions. or both.

- Using doria as the carbon oxide reducing component converts synthesis gas at surprisingly low temperatures and pressures.

Using a zinc-copper-chromite type methanol synthesis catalyst as the reducing component increases the synthesis gas conversion and provides a high proportion of hydrocarbons having at least one carbon-to-carbon bond instead of methanol.

The amount of aromatic hydrocarbons is increased by using Fischer-Tropsch type catalysts.

Furthermore, with the use of suitable crystalline aluminosilicate components, catalyst activity is usually sustained over long periods of time, and when aromatic hydrocarbons are produced, they are highly enriched in toluene and xylene.

A typical purified synthesis gas has a volumetric composition and on a water-free basis of 51.5% hydrogen. - Consisting of 40 carbon oxides, 4 carbon dioxide, 1 methane and 4 nitrogen.

Synthesis gas encompasses in-situ gasification methods such as underground partial combustion of coal and oil reserves.

Can be made from fossil fuels by any known method.

Fossil fuels as used herein include anthracite and bituminous coal, lignite, crude oil, shale oil, oil from tar sands, natural gas as well as coked coal, petroleum coke, gas oil, residues from petroleum distillation and It is intended to include fuels derived from simple physical separations of these materials or further conversions of these materials, including combinations of two or more.

Other carbonaceous fuels such as peat, wood and cellulosic waste can also be used.

Crude synthesis gas produced from fossil fuels contains various impurities such as particulates, sulfur, and metal carbonyl compounds, and is characterized by a hydrogen to carbon oxide ratio that depends on the fossil fuel and gasification technology used.

It is generally desirable to purify the crude synthesis gas by removing impurities for efficiency of subsequent conversion steps.

Techniques for such purification are known and are not part of this invention.

When thoria is used as the carbon reducing component, it is not necessary to remove substantially all sulfur impurities since thoria is not irreversibly poisoned by sulfur compounds.

Furthermore, if necessary, it is preferred to adjust the hydrogen to carbon oxide volume ratio to be within the range of 0.2 to 6.0 prior to use in this invention.

If the purified syngas is too rich in carbon oxides, well-known water-gas shift reactions can be used to bring the ratio within the preferred range.

If, on the other hand, the synthesis gas contains too much hydrogen, the ratio is adjusted within the preferred range by addition of carbon dioxide or carbon monoxide.

Purified synthesis gas conditioned to contain a hydrogen to carbon oxide volume ratio of 0.2 to 6.0 shall be referred to as "conditioned" synthesis gas.

Industry recognized syngas equivalents may also be used.

For example - mixtures of carbon oxide and steam, or mixtures of carbon dioxide and hydrogen are also intended to be used to obtain the synthesis gas prepared by in-situ reactions.

Additionally, when the process of this invention is used to produce a hydrocarbon mixture rich in aromatic hydrocarbons, a hydrogen donor such as methane, methanol or a higher alcohol is added to the feedstock as described in more detail below. It is advantageous to prepare them together.

The components characterized by carbon dioxide reduction catalytic activity can be selected from any of the art-recognized catalysts for producing hydrocarbons, oxygen-containing products, or mixtures thereof from synthesis gas, and include 0.1 of active ingredient
~99% by weight, preferably 1-80% by weight.

In a broad sense, these components are recognized as methanol synthesis catalysts, Fischer-Tropsch synthesis catalysts, and variations thereof containing the aforementioned metals or their compounds.

Commercially available methanol synthesis catalysts include those containing metallic zinc or zinc oxide together with chromia, those containing metallic zinc and copper or zinc oxide and copper oxide together with chromia or alumina, or known modifications thereof.

In fact, synthetic gas is about 300 below to about 850 below, about 1 to 100
It undergoes conversion over a fairly wide range of catalysts under pressures of 0 atmospheres to produce reduction products of carbon monoxide such as alcohols and hydrocarbons.

Prominent types of catalysts to induce conversion include zinc, iron, ruthenium, thorium, metals or their oxides alone or in combination.

In particular, iron-based Fischer-Tropsch type catalysts are particularly suitable for the production of oxygenated and hydrocarbon products having at least one carbon-to-carbon bond in their structure.

With the exception of ruthenium, all industry-accepted practical synthesis catalysts contain chemical and structural promoters.

These promoters include copper, chromia, alumina, alkaline earth metals, rare earth metals and alkalis.

Alkali, such as carbonates of group IA of the periodic table, especially potassium carbonate, are of particular importance in the case of iron catalysts, since they greatly increase the product distribution.

A carrier such as quartz earth may sometimes be advantageous.

- It should be recognized that the carbon oxide reducing component should be provided as a metal element or as a corresponding metal compound.

The production and use of such catalytic materials often involve one or more partial or complete conversions of metal elements into compounds.

As an example pure iron roasted in an oxygen atmosphere in the presence of added aluminum nitrate and potassium nitrate is Fe3O49
7%, A12032.4% and 20%, giving a composition containing 0.6% and a total amount of sulfur and carbon.

This composition after reduction with hydrogen under about 850
promotes the conversion of synthesis gas at temperatures in the range below 30°F and elevated pressures up to about 20 atmospheres, and - hydrocarbons in which 65% of the carbon oxide boils in the range of 200″F to about 680″F. is reduced to a mixture consisting of approximately 100% of oxygenated compounds, the majority of which are alcohols, of the same boiling range.

Manganese ore blocks can also be used as catalysts.

The crystalline aluminosilicate component of the heterogeneous catalyst according to this invention is characterized by a pore size greater than about 5 angstroms.

That is, it can sorb paraffins with one methyl branch and normal paraffins and has a silica to alumina ratio of at least 120.

For example, zeolite A with a silica to alumina ratio of 2 cannot be used in this invention.

This is because there are no pores larger than about 5 angstroms in size.

The crystalline aluminosilicates described herein, also known as zeolites, are characterized by a rigid crystalline skeletal structure consisting of SiO4 and AlO4 tetrahedra bonded by intersecting covalent oxygen atoms.

Such a structure produces precisely regulated pores.

There are exchangeable cations to balance the negative charge on the AlO4 tetrahedron.

Preferred zeolites useful in this invention are selected from a recently identified class of zeolites that have exceptional properties and are themselves capable of converting aliphatic hydrocarbons to aromatic hydrocarbons in industrially desirable yields. It is something.

They are also generally very effective in alkylation, isomerization, disproportionation and other reactions involving aromatic hydrocarbons.

In many cases, they usually have low alumina content, ie high silica to alumina ratios, and are very active even with silica to alumina ratios greater than 30.

Moreover, they retain their crystallinity for long periods despite the presence of steam, even at such high temperatures that the crystalline framework of other zeolites, such as zeolites of type X and A, undergoes irreversible collapse.

When carbonaceous precipitates form, they can be removed from the zeolite and preserved in activity by combustion at higher than normal temperatures, but in many environments they exhibit very low coke-forming potential. Therefore, the operating period between combustion regeneration processes can be made very long.

The silica to alumina ratios mentioned herein, of course, relate only to silicon and aluminum arranged in a tetrahedral structure.

Although zeolites with a silica to alumina ratio of at least 120 are useful, it is preferred to use zeolites with a silica to alumina ratio of at least 30.

Such zeolites have a greater sorption capacity for normal hexane within their crystal structure than for activated water withdrawal and are therefore called hydrophobic, and such zeolites are advantageously used in this invention. .

The zeolites useful as catalysts in this invention freely sorb normal hexane and have a dog hole size of less than about 5 angstroms.

In addition, their structure must restrain some larger molecules from entering the pores.

It is often possible to judge from the known crystal structure whether access to and exit from such restricted pores exists.

For example, if only the pore openings in the crystal are formed from eight-membered rings of oxygen atoms, molecules with a cross section larger than normal hexane are virtually prevented from entering the pores, and the zeolite is not of the desired type. do not have.

Zeolites with 10-membered ring openings are preferred.

However, excessive constriction of the openings or pore blockage renders these zeolites virtually ineffective.

Zeolites with 12-membered ring openings generally do not appear to provide sufficient restraint to produce the advantageous conversions desired in this invention.

However, it is assumed that this is due to blockage of the opening or other causes, and that this structure can be used.

As an alternative to attempting to determine from the crystal structure whether a zeolite has the necessary constrained entry, an equal weight mixture of normal hexane and 3-methylpentane may be applied at atmospheric pressure to a small sample of the zeolite, about 1 y or less. A simple determination of the constraint index can be made by successive passes according to the procedure described below.

A sample of zeolite in the form of pellets or extrudates is ground to coarse sand-sized particles and placed in a glass tube.

Before testing, treat the zeolite with an air flow of 10,001' for at least 15 minutes, then wash the zeolite with helium and heat at 550'F to give a total conversion of 10% to 60%.
-Adjust temperature to ~950'F.

The mixture of hydrocarbons is diluted with helium to a helium to total hydrocarbon molar ratio of 4:1 and passed over the zeolite at 1 liquid hourly space velocity (ie, 1 volume of liquid hydrocarbon/catalyst volume/hour).

taking a sample of the effluent after running the hydrocarbon stream for 20 minutes;
analyse.

Analysis is most conveniently performed by gas chromatography to determine the proportion remaining unchanged for each of the two hydrocarbons.

The constraint index is calculated as follows.

This constraint index approximates the cracking rate constants of the two types of hydrocarbons.

Catalysts suitable for this invention are those using zeolites with a constraint index of 1.0 to 12.0.

The constraint index (CI) of some representative zeolites, including some zeolites outside the scope of this invention, are as follows.

It should be noted that the actual nature of this index and the techniques for determining it allow for the possibility that a given zeolite can be tested under somewhat different conditions and therefore have a different constraint index. .

The restraint index appears to vary slightly depending on the severity of the operation (conversion rate).

It is therefore possible to select test conditions to establish multiple restraint indices, both within and outside the ranges defined above, from 1 to 12 for individual zeolites.

The present invention is capable of producing a zeolite that exhibits a constraint index in the range of 1 to 12 under a combination of conditions within the scope of the measurement operation described above, even if it exhibits a constraint index outside the said range under other combinations of conditions. However, it is included within the scope of this invention.

This category of zeolite is Zeolite ZSM-5, ZSM
-11, ZSM-12, ZSM-35 and ZSM
-38 is particularly well exemplified.

ZSM-5 is U.S. Patent No. 3,702,886, ZSM-1
No. 1 is described in U.S. Pat. No. 3,709,979, ZSM-12 is described in U.S. Pat.

The above-mentioned zeolites are virtually catalytically inactive when produced in the presence of organic cations, presumably because the free space within the crystals is occupied by the organic cations from the product solution.

They are heated, for example, at 1000'F for 1 hour in an inert atmosphere, then base exchanged with an ammonium salt, then 1
Activate by baking in air at 000'F for 15 minutes to 24 hours.

Although the presence of organic cations in the product solution is not absolutely necessary for making the particular classes of zeolites mentioned above, it appears to be advantageous.

Naturally occurring zeolites can sometimes be converted to this class of zeolites by various activation operations and by using other treatments such as base exchange, steam treatment, alumina extraction and calcination, alone or in combination.

Natural ores processed in this way include ferrierite,
Includes briustellite, stilbite, dachialdite, epistilbite, hyurandite and chiptyrolite.

Zeolites are used in hydrogen, metal-exchanged or ammonium form.

The metal cations that may be present include any of the metals from Groups I to II of the Periodic Table, although Group IA metal cations should not be present in large quantities.

The most preferred zeolites are those having a crystalline skeletal density not substantially lower than about 1.6 t/crt in dry hydrogen form.

Dry densities for known structures are determined, for example, by the Society on Chemical Industry (London) in 196
Published in 1967, ``Proceedings on the Conference on Molecular Thieves, London, April 1967.
theConference on Molec
ular 5ieves 1London, Ap
It can be calculated from the sum of the numbers of silicon atoms and aluminum atoms per 1000 cubic angstroms, as described on page 19 of the paper on zeolite structure by W. M. Meier in J. Rie, 1967).

When the crystal structure is unknown, the crystal skeleton density is determined by the classical pycnometer method.

For example, it is measured by soaking the dry hydrogen form of the zeolite in an organic solvent that is not sorbed by the crystals.

The persistent extraordinary activity and stability of this class of zeolites can be associated with a high crystalline anion framework density of no less than about 1.61 per crt.

This high density is of course related to the relatively little free space within the crystal, which is expected to result in a more stable structure.

However, this free space appears to be important as a catalytic active site.

The crystalline structure densities of some representative zeolites are listed, including some zeolites that are not within the scope of this invention.

The heterogeneous catalyst of this invention can be made in a variety of ways.

For example, the two components may be formed separately in the form of catalyst particles, such as pellets or extrudates, and simply mixed together in the required proportions.

The particle size of each individual component may be very small, for example from about 20 to about 150 microns, if intended for use in fluidized bed operations, but may be as large as up to about 1 inch for fixed bed operations.

The two components may be mixed as powders and formed into pellets or extrudates containing both components in substantially the required proportions.

A binder such as clay can be added during the mixing.

Alternatively, the component having carbon monoxide reduction catalytic activity may be bound to the zeolite by such means as impregnating the crystalline aluminosilicate zeolite with a solution of the desired metal salt, followed by drying and calcining.

Base exchange of the crystalline aluminosilicate component can also optionally be used to introduce some or all of the carbon monoxide reducing component.

Other means of achieving intimate mixing include precipitating the carbon monoxide reducing component in the presence of crystalline aluminosilicate;
There are electroless deposition of metals onto zeolites and vapor deposition of metals from the vapor phase.

Various combinations of the above-mentioned manufacturing methods will be readily envisaged by the catalyst manufacturer with the need to avoid techniques likely to reduce the crystallinity of the crystalline aluminosilicate.

It will be apparent from the foregoing that the mixtures used in the process of this invention have varying degrees of consistency.

In one extreme, using + inch pellets of carbon monoxide reducing component mixed with 1 inch pellets of crystalline aluminosilicate, substantially all positions within at least one of said components are Regardless of the proportions in which the two components are used, they are within about a thousand inches of each other.

If different sized pellets are used, such as 10 inch and 10 inch pellets, virtually all locations within one component will be within a ladle inch of the other component.

These examples illustrate the lower limits of tightness required for practicing this invention.

At the other extreme, crystalline aluminosilicate particles of about 0.1 micron particle size are ball milled with colloidal iron oxide of similar particle size and then pelletized.

In this case, substantially all positions within at least one of the components are within about 0.05 microns of the other component.

This example illustrates the closest degree in practice.

In the method of this invention, the synthesis gas is
Temperature below 00, preferably 500T to 850T, 1 to 1o
oo atmospheres, preferably 3 to 200 atmospheres, a volumetric hourly space velocity of about 500 to 500,000 volumes of gas per volume of catalyst [standard temperature and pressure (STP)] or equivalent contact if a fluidized bed is used. contact with the heterogeneous catalyst for an hour.

The product stream containing carbon hydrogen, unreacted gases and water vapor is cooled and the hydrocarbons are recovered by any technique known in the art.

The recovered hydrocarbons can be used as high-octane gasoline, propane fuel,
Further separation by distillation or other means into one or more products such as benzene, toluene, xylene or other aromatic hydrocarbons.

Some embodiments of this invention are described in the following examples for purposes of illustration.

Example 1 Doria was treated with Th(NO) essentially by Na2CO3 solution.
3) Precipitation of 4 solutions, then separating the precipitate, washing and 10
U.S. Bureau of Mines Regulation 488, which consists of drying at 0°C (
1950)'s "The IsoSynthesis"
5osynthesis) Pickler described in J.
(P 1chler) and Siesenke (S 1es
ecke) method.

A composite catalyst was prepared by ball milling equal weights of NH428M-5 and dry triagel, pelletizing, and calcining at 10001F for 10 hours.

800 respectively, H2/CO ratio 1 at 1215 psia
．． Three experiments were performed using a mixture of 0 hydrogen and carbon monoxide.

The first and second experiments used thorium oxide and H2SM-5 each separately, and the third experiment used a heterogeneous catalyst containing both thorium oxide and H2SM-5.

The results are summarized in Table 1.

Example 2 ZnO supported on A1203 was made from commercially available source materials and used as the -carbon oxide reducing component.

It contained 24% by weight of Zn0.

H2SM-5 was used as the acidic crystalline aluminosilicate component.

By ball milling 54 parts of H2SM-1 part of Z no /A I20s and then pelletizing*
*We created a heterogeneous composite catalyst.

Both experiments were carried out at 600'F and 750 psia.
It was carried out using a mixture of hydrogen and carbon monoxide in a ratio of 2 to CO of 4.

The first experiment used ZnO/Al2O3 catalyst alone, and the second experiment used ZnO/Al2O3 and H2SM-5.
A composite catalyst containing both a catalyst and a catalyst was used.

The results are shown in Table 2.

Example 3 A methanol synthesis catalyst was made containing 54.55% by weight copper, 27.27% by weight zinc, 9.09% by weight chromium and 9.09% by weight lanthanum on an oxygen-free basis.

A composite catalyst was then made from equal weights of this component and H2SM5 using 5% graphite as a binder.

Two experiments were conducted at 600 psia and 750 psia using a mixture of hydrogen and carbon monoxide with a H2 to CO2 ratio of 2 as the feedstock.

The results are summarized in Table 3.

As shown in the table above, the contact time (inverse space velocity) for the methanol catalyst component is very similar in the two experiments, although it is slightly lower for the composite catalyst.

* * The composite catalyst exhibits the production of far more hydrocarbons than the carbon monoxide reducing component itself, especially hydrocarbons with a higher carbon number than methane.

Example 4 The carbon monoxide reducing component was a commercially available iron oxide type ammonia synthesis catalyst containing small amounts of Ca and Al promoters.

The zeolite component contained 65% H2SM-5 and 35% alumina binder.

The heterogeneous composite catalyst contains 75% iron and 25% zeolite.
were prepared by ball milling the ingredients and then pelletizing the resulting powder.

3 experiments under 700, 265 psia, H2 vs. C
It was carried out using a mixture of hydrogen and carbon monoxide with an O ratio of 1.0.

The results are summarized in Table 4. Experiment 1 illustrates the selectivity of iron components in the absence of H2SM-5.

C5+ hydrocarbons contain only 1.9% aromatics.

In experiment 0) the H2SM-5 containing reaction zone was placed after the iron catalyst containing reaction zone.

It can be seen that the aromatic selectivity did not change significantly.

However, in experiments, an intimate mixture of the iron component and HzSM-5 increased the aromatics selectivity by about 7 times.

Example 5 The catalyst in this example is NH4 containing 35% alumina binder.
ZSM-5 was made by impregnating with a solution of Fe(NOs)3, drying the catalyst, and calcining at 1000″F for 10 hours.

The final catalyst contained 3% iron.

Synthesis gas (H2/Co = 1) was heated at 70% over this catalyst.
The following conversions and products were obtained when the reaction was run at 0"F, 515 psia, and a contact time of 30 seconds.

The example catalyst is titanium iron ore sand (FeO-TiO2)54.
7%, H2SM-521, 3% and alumina binder 2
It was an intimate mixture of 1.3%.

Synthesis gas (H2/Co = 1) was poured onto the above catalyst at 70°C.
When reacted at 0″F, 265 psia, and a contact time of 10 seconds, the following conversions and products were obtained.

Example 7 The catalyst in this example was 41.2% magnetite (Fe304), H2
It was an intimate mixture of 4% SM-529 and 29.4% alumina binder.

Synthesis gas (H2/C0=1) was poured onto the above catalyst for 700'
F, 265 psia, and 10 seconds contact time, the following conversions and products were obtained.

Example 8 The catalyst in this example was 41.2% iron carbide, H2SM-529,
4% and 29.4% alumina binder.

Synthesis gas (H2/C0-1) was heated over the above catalyst under 700℃,
The reaction was carried out at 265 psia and a contact time of 10 seconds and the following conversions and products were obtained.

Example 9 The catalyst of this example is an extrudate consisting of ZSM-5 crystalline zeolite containing about 35% alumina as a binder.
impregnated with e(NOs)a) solution, dried and ca.
Made by reduction with hydrogen at 0'F.

The iron impregnation rates were determined to have three different iron concentrations as shown in Table 10.

Synthesis gas (H2/C0=2) at 600'F, 200
It was brought into contact with the catalyst at a pressure of s Ig .

The results obtained were as follows. Example 10 The catalyst used in this example consists of a mixture of ZSM-5/alumina extrudates (65/35 ratio) and copper methanol synthesis catalyst.

In the experiments of 912-1 and -2, the volume ratio of ZSM-5 to Cu combined catalyst was 2.9:2, and 913-3 to 5
In the experiment, the volume ratio of ZSM5 to Cu synthesis catalyst was 4:1.

ZSM-5/alumina extrudates were mixed with iron ammonia synthesis catalyst in a 4:1 ratio and used as catalyst in the 903-1, -2 and -6 experiments.

The operating conditions used and the results obtained in each experiment are summarized in Table 10 below.

Example 11 Tria-ZSM-5 made as fixed in Example 1
The catalyst (without alumina) was used in two separate experiments for comparison with similar alumina-containing catalysts as described below.

In these examples, syngas (H2/CO=1) was passed under 800 psi at a pressure of 1200 psig to contact the catalyst.

The results obtained are listed in Table 11.

Example 12 Ruthenium dioxide was used as a Fischer-Tropsch catalyst to convert syngas to paraffin wax under high pressure and low temperature (248-428''F).

However, at higher temperature (572'F) only methane was produced.

Ruthenium supported on aluminum was used in syngas conversion to produce gaseous, liquid, and solid hydrocarbons.

However, at higher temperatures above 482''F, methane again became the predominant product.

No aromatic compounds were produced using these catalysts.

Ruthenium in combination with H2SM-5 produced aromatic-containing gasoline in high yield from syngas over a wide range of temperatures.

Example A NH, -ZSM -510f? RuCl3・3H20
A 5% ruthenium catalyst on ZsM-5 catalyst was prepared by vacuum impregnation with 18d of 1,25P-containing aqueous solution.

After drying in vacuo, the catalyst was air calcined at 1000'F for 2 hours.

This changed the ammonium type of ZSM-5 to the hydrogen type.

Example B RuC13・3H200,5 containing aqueous solution 36 vertically※※
A 1% Ru/zSM-5 catalyst was made using the procedure of Example A except that impregnated NH4-ZSM-520P was used.

Example C Synthesis gas (H2/Co) conversion was carried out in a fixed bed continuous flow reactor.

A rustless copper reactor was charged with 5.5 l of the 5% Ru/ZSM-5 catalyst prepared in Example A.

The catalyst was prereduced with flowing hydrogen at 750'F and 750 psig pressure for 3 hours.

Syngas (H2/Co) conversion at 750 psig,
580'F, WH8V=0.32 and H2/C
I went 0-2/1.

The obtained results and detailed hydrocarbon distribution are listed in Table 13.

High conversions with good selectivity to liquid (C3+) products were obtained.

The liquid product contains 25% aromatics and has an octane number R+0=771. R+3=92.

For example, the conversion of syngas to 1% RV'ZSM-55 made in Example B
, 5f was used, but the conditions were substantially the same as in Example C.

The results are listed in Table 13. Rich in C2+ hydrocarbons, 13
．． A high conversion to hydrocarbons containing 8% hydrocarbons was obtained.

*(Total amount of carbon converted - total amount of carbon in CO2)/Total amount of carbon converted

Claims (1)

[Scope of Claims] 1- A metal or metals or metal compounds thereof selected from thorium, zinc, copper, chromium, titanium, iron, ruthenium, having a catalytic activity to reduce carbon oxide, and a diameter larger than 5 angstroms. pores, a silica-to-alumina ratio of at least 12, and a crystalline aluminosilicate having a constraint indication ranging from 1 to 12, is contacted with synthesis gas at a temperature of 450 to 1000'F'' and elevated pressure. A method of producing hydrocarbons.