DK145460B - PROCEDURE FOR CONVERSION OF SYNTHESIC GAS TO CARBON HYDRADE MIXTURES - Google Patents

Description

(19) DENMARK

| P (12) PUBLICATION MANUAL od 145460 B

DIRECTORATE OF THE PATENT AND TRADEMARKET SYSTEM

(21) Application No. 1751/75 (5U IntCt, * C 07 C 1/04 (22) Filing date 23 · Apr 1975 (24) Running day 23 Apr 1975 (41) Aim available 25 Oct 1975 ( 44) Submitted Nov. 22, 1982 (86) International Application No. - (86) International Filing Day (85) Continuation Day (62) Stock Application No. -

(30) Priority Apr 24 1974, 463711, US

(71) Applicant MOBILE OIL CORPORATION, New York, US.

(72) Inventor clarence Layton Chang, US: William Harry Lang, US:

Anthony John Sllvestri, US.

(74) Full-time engineering firm Hoftnan-Bang & Bout ard.

Process for converting synthesis gas into hydrocarbon mixtures.

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The invention relates to a process for the production of hydrocarbons from synthesis gas of the kind specified in the preamble of claim 1.

The invention relates to contacting a mixture of carbon monoxide and hydrogen with a mixture of a catalyst which catalyzes the reduction of carbon monoxide, such as a Fischer-Tropsch.

QQ catalyst or a methanol synthesis catalyst, and a crystalline aluminosilicate for the production of hydrocarbon mixtures useful in the production of fuel oils, high octane gasoline, aromatic hydrocarbons therein and chemical intermediates.

The invention relates to an improved method for converting synthesis gas, i.e. mixtures of gaseous carbon oxides and hydrogen or hydrogen donors for mixtures of hydrocarbons.

Methods for converting coal and hydrocarbons, such as natural gas, into a gaseous mixture consisting essentially of hydrogen and carbon monoxide and / or dioxide are known.

Those of greater importance either make use of the partial combustion of fuel with an oxygen-containing gas or of the reaction of the fuel with high temperature steam or of a combination of these two reactions. An excellent summary of the area of gas production, including synthesis gas, from solid and liquid fuels is given in the Encyclophedia of Chemical Technology, published by Kirk-Othmer, second edition, Vol. 10, pp. 353-433, (1966), Interscience Publishers, New York, New York.

It is also known that synthesis gas will undergo conversion to carbon monoxide reduction products, such as hydrocarbons, at temperatures ranging from approx. 149 ° C to approx. 454 ° C, under pressure from approx. 1 to 1000 atm. pressure, over quite a variety of catalysts.

Eg. the Fischer-Tropsch process, which has been studied in detail, gives rise to the formation of many different liquid hydrocarbons, some of which have been used as low octane gasoline. Catalysts studied for this purpose and related processes include those based on iron, cobalt, nickel, ruthenium, thorium, rhodium and osmium, or the oxides thereof.

To date, it has not been possible to identify any combination of catalysts and treatment conditions that will give rise to the formation of liquid hydrocarbons in the gasoline boiling region containing highly branched paraffins and substantial amounts of aromatic hydrocarbons, both of which are required for high quality gasoline. , or selectively preparing aromatic hydrocarbons having a particularly high content in the benzene to xylene ranges. An overview of the state of the art in this field is given in "Carbon Monoxide-Hydrogen Reactions", Encyclopedia of Chemical Technology, published by Kirk-Othmer, second edition, Vol. 4, pages 446-488, Interscience Publishers, New York, N.Y.

It has recently been demonstrated that synthesis gas can be converted to oxygenated organic compounds and that these compounds can then be converted to higher hydrocarbons, especially high octane gasoline, by catalytic contact between the synthesis gas and a catalyst catalyzing the reduction of carbon monoxide. followed by contacting the conversion products thus produced with a particular type of zeolite catalyst in a separate reaction zone. This two-step conversion is described in German Patent Application No. 2,438,252.

It has now been found that valuable carbd & hydride mixtures can be prepared directly by reacting synthesis gas, i.e. mixtures' of hydrogen and carbon monoxide, optionally with other carbon oxides, or equivalents of such mixtures, in the presence of certain heterogeneous catalysts comprising thorough mixtures of two or more constituents.

According to the invention, a process for producing earbohydrates from synthesis gas, whereby at a temperature between 232 and 538 ° C, contact such a gas with a catalyst is therefore characterized in that the catalyst comprises a mixture of a metal or a metal compound. with catalytic activity associated with the reduction of carbon monoxide, any metal or metal compound optionally present on an A 2 O 2 support, and also a crystalline aluminosilicate having a pore diameter greater than 5 Å, a molar ratio of ; limes of silica and alumina of at least 12, and a narrowing index that is within the range of 1 to 12. In this way, hydrocarbons boiling within the boiling point range of the bone can be recovered. The metal or metal compound comprises between 0.1 and 99 wt.%, preferably between about 1 and about 80 wt.% of the mixture. The carbon monoxide reducing component and crystalline aluminosilicate may be present in the same or in separate particles.

The preferred crystalline aluminosilicates are ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38. The preferred metals are from Group 8, but metals from Group IB (eg copper), IIB (eg zinc) and / or HIB (eg thorium), and compounds thereof can produce excellent results. Mixtures of all these materials, Bam-men with promoters, such as are valuable. '' *

The ratio of the component used to reduce carbon monoxide to crystalline aluminosilicate can be adjusted to control the nature of the product, i.e. to determine whether components whose boiling points are within the boiling point of gasoline should dominate, paraffins / aromatics or internal alkenes.

Advantageously, the volume ratio of hydrogen to carbon oxides is kept within the range of 0.2 to 6.0.

Depending on the choice of constituents and the particular reaction conditions used, substantial quantities of liquid mixtures rich in one or more olefins, branched paraffins and aromatic hydrocarbons, and which are particularly suitable for the production of gasoline with high octane or petrochemicals, can be obtained. . Thus, one can select catalyst and operating conditions to produce normally gaseous hydrocarbons having at least one carbon-to-carbon bond, as the predominant product, or hydrocarbon streams rich in alkenes with an internal double bond. Such products are of value as petrochemical starting materials and for the production of condensable petroleum fuel.

The catalysts used not only produce highly desirable products with good selectivity, but in many cases produce them either with exceptionally high conversion per passage or under mild conditions, or sometimes in either way. With ThO 2 as the carbon monoxide-reducing component, synthesis gas is converted at astonishingly low temperature and astonishingly low t-smoke. With a zinc-copper-chromite-type methanol synthesis catalyst as the reducing component, the rate of conversion of the synthesis gas is increased, and large proportions of hydrocarbons having at least one carbon-to-carbon bond are substituted for methanol. With Fischer-Tropsch type catalysts, increased amounts of aromatic hydrocarbons are obtained. When the preferred crystalline aluminosilicate component is used, the catalytic activity is further maintained for an unusually long period of time and aromatic hydrocarbons, when prepared, are very rich in toluene and xylenes.

A typical purified synthesis gas will have the following volume composition on anhydrous basis: hydrogen, 51; carbon oxide, 40; carbon dioxide, 4; methane, 1; and nitrogen, 4.

The synthesis gas can be produced from fossil fuels under any known method, including such in situ gasification processes as the partial combustion in the subsurface of coal and petroleum deposits. In this context, the term fossil fuel shall include anthracite and bituminous coal, lignite, crude oil, shale oil, tar sands oil, natural gas, and fuels resulting from simple physical separations or more profound conversions of these materials, including coking coal, petroleum coke, gas oil. , the residuals from petroleum distillation, and two or more of any of the foregoing materials in combination. Other carbon-containing fuels such as peat, wood and cellulosic waste can also be used.

The crude synthesis gas produced from fossil fuels will contain various impurities such as particulate materials, sulfur and metal-carbonyl compounds, and they will be characterized by a hydrogen-to-carbon ratio which will depend on the fossil fuel. and the particular gasification technique used. It is generally desirable for the efficiency of subsequent conversion steps to purify the crude synthesis gas by removing the impurities. Methods of such purifications are known and are not part of this invention. However, it is not necessary to remove substantially all the sulfur-containing impurities when using ThO2 as the carbon monoxide-reducing component because ThO2 is not irreversibly poisoned by sulfur compounds. If necessary, it is further preferred to adjust the volume ratio of hydrogen to carbon oxide within the range of 0.2 to 6.0 prior to use according to the invention. If the purified synthesis gas is to be woven excessively rich in carbon oxides, it can be brought within the preferred range using the known water gas exchange reaction.

On the other hand, if the synthesis gas should be very rich in hydrogen, it can be adjusted to the preferred range by the addition of carbon dioxide or carbon monoxide. Purified synthesis gas, adjusted to have a volume ratio of hydrogen to carbon oxides of between 0.2 and 6.0, will be referred to as "adapted" sy'nté ^ segas.

6145460 Recognized equivalents for synthesis gas may also be used. Mixtures of e.g. carbon monoxide and steam or carbon dioxide and hydrogen may be considered in order to provide adapted synthesis gas by in situ reaction. When the process of the invention is further used in the preparation of carbohydride hydrate mixtures rich in aromatic hydrocarbons, as will be described in more detail below, advantageously, along with the starting materials, a hydrogen donor such as methane, methanol or higher alcohols may be added.

The component characterized by catalytic activity for the reduction of carbon monoxide can be selected from any catalysts recognized in the art for the production of hydrocarbons, oxygenated products or mixtures thereof, from synthesis gas, and it is between 0.1 and 99% by weight. %, preferably between 1 and 80% by weight of the active ingredient of the catalyst. Mostly, these components include those recognized as methanol synthesis catalysts, Fischer-Tropsch synthesis catalysts and variants thereof. Commercial methanol synthesis catalysts include metals or oxides of zinc together with Cr 2 O 2, or of zinc and copper together with Cr 2® 3 or alumina, or known modifications thereof. In fact, synthesis gas will undergo conversion to form carbon monoxide reduction products, such as alcohols and hydrocarbons, at from ca. 149 ° C τϋ ca. 454 ° C and under a pressure of approx. 1 to 1000 atm. to be led over a fairly wide range of catalysts. The most prevalent types of catalysts that produce conversion include the metals or oxides selected from groups IB, IIB, HIB, IVB, VIB and VIII, taken alone or in combination. In particular, they include the metals or oxides of zinc, iron, cobalt, nickel, ruthenium, thorium, rhodium and osmium. Fischer-Tropsch type catalysts based on iron, cobalt or nickel, and especially iron, are particularly suitable for the production of oxygenated products and hydrocarbon products having at least one carbon-to-carbon bond in the structure. With the exception of ruthenium, all known synthetic catalysts used include chemical and structural promoters. These promoters include copper, Cr2 O3, alumina, alkaline earth metals, rare earth metals, and alkali. Alkali, e.g. the carbonates of group IA in the periodic table, and especially potassium, are of particular importance in connection with iron catalysts because the product distribution is thereby greatly improved. Carriers such as diatomaceous earth are sometimes advantageous.

It should be noted that the carbon monoxide reducing component can be provided as elemental metal or as corresponding metal compounds. Frequently, in the manufacture and use of such catalytic agents, one or more partial or complete transformations from elemental metal to compounds or vice versa will occur. By way of illustration, it can be argued that pure iron shaken in an oxygen atmosphere in the presence of added aluminum and potassium nitrates provides a mixture containing 97% Fe 2 O 2, 2.4% A 2 O 2, and 0 , 6% I ^ O with trace amounts of sulfur and carbon. This mixture catalyzes after reduction with hydrogen at ca. 454 ° C the conversion of synthesis gas at a temperature in the range of 182 to 221 ° C, and at elevated pressures up to approx. 20 atm., Reducing 65% of the carbon monoxide to a mixture consisting of approx. 1/3 weight hydrocarbons boiling in the range of 93 to approx. 360 ° C, and approx. 2/3 .oxygenating products, mostly alcohols, with the same boiling range. Manganese modules can be used as catalysts.

The crystalline aluminum silicate component of the heterogeneous catalyst is characterized by a pore size greater than 5 Å, i.e. it is capable of absorbing paraffins having a single methyl branch as well as normal paraffins, and having a ratio of silica to alumina which is reduced to 12, e.g. For example, zeolite A having a silica to aluminum oxide ratio of 2.0 is not usable according to the invention, and it has no pore dimension greater than ca. 5 Å.

The crystalline aluminum silicates referred to herein, which are also known as zeolites, are characterized by a rigid, crystalline lattice structure consisting of SiO 2 and A 10 3 tetrahedrons crosslinked by sharing oxygen atoms; such a structure gives rise to the emergence of precisely defined pores. Exchangeable cations exist which compensate for the negative charge on the A10 tetrahedron.

8 145460

The preferred zeolites useful according to the invention are selected from a recently identified category of zeolites with unusual properties, in themselves capable of catalyzing the conversion of aliphatic hydrocarbons into aromatic hydrocarbons in commercially desirable yields.

They are also generally highly effective in alkylation, isomerization, disproportionation and other reactions involving aromatic hydrocarbons. In many cases, they have exceptionally low alumina content, i.e. high silica-alumina ratios, and they are very active even with silica-alumina ratios exceeding 30. Furthermore, they maintain their crystallinity for long periods of time despite the presence of steam, even at such high temperatures that induce irreversible degradation of the crystal lattice of other zeolites, e.g. those of the X and A type. When carbonaceous precipitates are formed, they can be removed therefrom by burning at temperatures higher than the temperatures usually required to restore activity, although in many environments they exhibit very low coke-forming ability, which is very long operating times between regenerations by burning.

Of course, the ratios of silica to alumina referred to relate only to the tetrahedrally coordinated silicon to aluminum. Although zeolites with a silica to alumina ratio of at least 12 are useful, it is preferred to use zeolites with ratios of at least 30.

Such zeolites, upon activation, acquire an intracrystalline adsorption capacity for normal hexane greater than the water capacity and are referred to as "hydrophobic": such zeolites are advantageously used in accordance with the invention.

The zeolites useful as catalysts in the process of the invention freely adsorb normally hexane and have a pore dimension greater than 5Å. In addition, their structure must provide limited access for some larger molecules. It is sometimes possible, on the basis of a known crystal structure, to judge whether such limited access exists. For example, the only pore windows in a crystal are formed by 8-membered rings of oxygen atoms, essentially the access of molecules of greater cross-section than normal hexane is prevented, and the zeolite is not of the desired type. Zeolites with windows of 10-membered rings are preferred, although excessive constipation or pore blocking may render these zeolites substantially ineffective. Zeolites with windows of twelve-membered rings generally do not appear to provide sufficient constriction to produce the advantageous conversions desired by the invention, although structures which may be operative due to pore blocking or other reasons may be devised.

Instead of trying to judge from the crystal structure whether a zeolite possesses the necessary limited access or not, one can simply determine "narrowing index" by continuously passing a mixture of equal parts by weight of normal hexane and 3-methyl-pentane over a small sample, approximately 1 g or less, of zeolite under atmospheric pressure according to the method set forth below. A sample of the zeolite, in the form of pellets or extrudate, is crushed to a particle size approximately equal to the particle size of coarse sand and mounted in a glass tube. Prior to the test, the zeolite is treated with an air stream at 538 ° C for at least 15 minutes. The zeolite is then rinsed with helium and the temperature is set to a value between 288 ° C and 510 ° C to produce a total conversion between 10 and 60%. The hydrocarbon mixture is passed at a space velocity of the liquid material of 1 (i.e., 1 volume of liquid hydrocarbon per volume of catalyst per hour) over the zeolite with a helium dilution to produce a molar ratio of helium to the total hydrocarbons of 4: 1. After 20 minutes of operation, a sample of the discontinued material is taken, which is analyzed, most conveniently by gas chromatography, to determine the fraction of each of the two hydrocarbons remaining unchanged.

"Narrowing index" is defined as follows: - log10 (fraction of n-hexane remaining) g log ^ -. (fraction of 3-methylpentane remaining 10)

"The hydrocarbon fraction remaining" means the hydrocarbon fraction which has not yet reacted at the end of the test.

10 145460

The narrowing index approximates the ratio of the cracking rate constant of the two hydrocarbons. Crystals suitable for the invention are those using zeolite having a narrowing index between 1.0 and 12.0. Values of narrowing index (Cl) for some typical zeolites, including some that cannot be used according to the invention, are:

Zeolite C.I.

ZSM-5 8.3 ZSM-11 8.7 TMA Offretit 3.7 ZSM-12 2

Beta 0.6 ZSM-4 0.5 H-Zeolone 0.5 REY 0.4

Amorphous silica-alumina 0.6

Erionite 38

It should, of course, be borne in mind that the very nature of the index and the method by which it is determined allow it the possibility that a given zeolite may be examined under somewhat divergent conditions and thereby have different narrowing indices. The narrowing index seems to vary to some extent with the intensity of the operation (conversion). Therefore, it may be possible to select sample conditions to establish multiple narrowing indices for a particular zeolite, which may be both within and outside the range defined above between 1 and 12. Anyone can be used '. zeolite exhibiting a narrowing index in the range of 1 to 12 for a combination of conditions that is within the scope of the above procedure, regardless of whether it exhibits an index outside this range for other combinations of conditions of this kind.

This category of zeolites is particularly well exemplified by the zeolites ZSM-5, ZSM-11, ZSM-12, ZSM-35 and ZSM-38. ZSM-5 is described in U.S.A. Patent No. 3,702,886; ZSM-11 of U.S.A. Patent No. 3,709,979; ZSM-12 in U.S.A. U.S. Patent Nos. 3,832,449 and ZSM-35 and 38 respectively. U.S.A. patents 4,016,245 and 4,046,859.

145460 11

The zeolites specifically described, in the case where they are prepared in the presence of organic cations, are essentially catalytically inactive, possibly because the intracrystalline free space is occupied by organic cations from the solution formed. They can be activated by heating in an inert atmosphere at 538 ° C for one hour, e.g. followed by base exchange with ammonium salts followed by calcination at 538 ° C in air for between 15 minutes and 24 hours. The presence of organic cations in the formed solution need not be absolutely essential for the formation of this particular type of zeolite, but it does seem to favor it. Natural zeolites can sometimes be converted to this type of zeolite by various activation methods and other treatments, such as base exchange, steam treatment, alumina extraction and calcination, alone or in combination. Natural minerals that can be treated in this way include ferrierite, brewsterite, stilbit, dachiardite, epistilite, heaandandite and quinoptilolite.

The zeolites can be used in the hydrogen form, the metal exchanged form or the ammonium form. The metallic cations that may be present include any of the cations of the metals in groups I through VIII of the periodic system, although metallic cations from grt Ipe should not be present in larger quantities.

The most preferred zeolites are those whose density of the crystal lattice in the dry hydrogen form has a value which is not substantially less than ca. 1.6 g / cm 2 The dry density of the known structures can be calculated from the number of silicon plus aluminum atoms per 1000 Å ^, such as e.g. is listed on page 19 of the article on zeolite structure by W.M «· Meier i. "Proceedings of Conference on Molecular Sieves, London, April, 1967", published by the Society of Chemical Industry, London, 1968. When the crystal structure is unknown, the density of the crystal lattice can be determined using classical pycnometer methods. Eg. it can be determined by immersing the dry hydrogen form of the zeolite in an organic solvent not absorbed by the crystal.

It is possible that the unusually retained activity and stability of this category of zeolites is associated with the high 3 density of the anionic crystal lattice of not less than ca. 1.6 g / am. Of course, this density must be associated with a relatively small amount of free run within the crystal, which can be expected to result in more stable structures. However, this free space seems to be important as the site of catalytic activity.

Density of crystal lattices of some typical zeolites, including some that cannot be used according to the invention, are

Zeolite Empty volume Grid mass field

Ferrierite 0.28 cm 2 / cm 2 1.76 g / cm 2

Mordenite 0.28 1.7 'ZSM-5, -11 0.29 1.79

Dachiardite 0.32 1.72 L 0.32 1.62

Clinoptilolite 0.34 1.71

Laumontite 0.34 1.77 ZSM-4 (omega) 0.38 1.65

Heulandite 0.39 1.69 P 0.41 1.57

Offset 0.40 1.55

Levynite 0.40 1.54

Erionite 0.35 1.51

Gmelinite 0.44 1.46

Chabazite 0.47 1.45 A 0.5 1.3 Y 0.48 1.27

The heterogeneous catalysts used in the process of the invention can be prepared in various ways. The two components can be prepared separately in the form of catalyst particles such as e.g. tablets or extruders, and simply mix in the required conditions. The particle size of the individual particles of the constituents can be quite small, e.g. between 20 and approx. 150 µU when intended to be used in operating fluidized mass; or they can be as large as up to approx. 1.27 cm for operating a fixed mass. The two constituents can be mixed as powders and formed into tablets or extrudate, each tablet containing both constituents in substantially the required ratio. Binders, such as clays, can be added to the mixture. Alternatively, the component having catalytic activity for the reduction of the carbon monoxide may be associated with the crystalline'-aluminum silicate component by e.g. impregnating the zeolite with a brine of the desired metal, followed by drying and calcination. Booth exchange of the crystalline aluminosilicate component may also be used in certain selected cases to provide the introduction of SS part or all of the amount of the carbon monoxide reducing agent. Other agents for forming the thorough mixture include precipitation of the carbon monoxide reducing agent in the presence of crystalline aluminum silicate, electricity-free precipitation of metal on the zeolite, and precipitation of vapor-phase metal. Various combinations of the above preparations will be apparent to those skilled in the art which "include catalyst preparation, as well as the need to avoid methods which tend to reduce the crystallinity of the crystalline aluminum silicate.

It is clear from the foregoing that the blends used in the process of the invention may have varying degrees of blending. ^ '

From a lower value for the degree of mixing, this can vary up to an upper value corresponding to the treatment of crystalline aluminosilicate crystalline particles with a particle size of approx. 0, lyU with colloidal iron oxide having a similar particle size followed by tabletting. In this case, substantially all positions within at least one of the components may be within not more than about. 0.05 ^ u of any of the other constituent. This exemplifies the highest degree of mixing which is theoretically possible.

In the process according to the invention, synthesis gas is contacted with the heterogeneous catalyst at a temperature of from ca. 232 to 538 ° C, preferably between 260 and 454 ° C, under a pressure of from 1 to 1000 atm., Preferably from 3 to 200 atm., And at a volume rate of volume of about 500 to 50,000 volumes of gas (STP) per catalyst volume per using an equivalent contact time if using a fluidized mass. The product stream containing hydrocarbons, unreacted gases and vapors can be cooled and the hydrocarbons can be recovered using any known method. The recovered hydrocarbons can be further separated by distillation or other means for the extraction of one or more products, such as high octane gasoline, propane fuel, benzene, toluene, xylenes or other aromatic hydrocarbons.

The invention is illustrated by the embodiments shown in the following examples.

EXAMPLE 1

Thorium dioxide was prepared according to the method prepared by Pichler and Ziesecke and described in "The Isosynthesis", U.S. Bureau of Mines Bulletin, 488 (1950), substantially involving the precipitate of Th (NO 2) 3 solutions with NagCO 2 solutions followed by filtration, washing and drying at 100 ° C.

A composite catalyst was prepared by treating, in a ball mill, equal parts by weight of NH4 ZSM-5 and dried gel of thorium dioxide, tablets and calcining at 538 ° C for 10 hours. Three tests were carried out, each at 427 ° C, 85.41 kg / cm 2 absolute, and with a mixture of hydrogen and carbon monoxide having a ratio E 2 / CO of 1.0. The first and second experiments included thorium oxide and hzsm-5, each used separately, while the third experiment used a heterogeneous catalyst containing both thorium oxide and HZSM-5.

The results are summarized in Table 1.

TABLE 1 165460 (A) (B) (C)

Catalyst ThOp HZSM-5 Th02 Plus ΑΙθπθ Alone hzsm ~ 5

Contact time - seconds (relieves reaction conditions) 15 15 15

Conversion, weight # CO 5.3 1 22.4 '- H2 2.6 1 15.2 Total weight # carbon dioxide from the reaction materials 0.6 0.2 5.5 • ···' * ·: ^ R!

Hydrocarbon distribution (weight #) '

Methane 41.0 39.6 17.3.

C2-C4 hydrocarbons 58.6 60.4 73.8 C5 + -, .. Q * 4 ___ 8 * 2 100.0 100.0 100.0

Aromatics 1 C, - +. weight # trace track 41.6 EXAMPLE 2

A ZnO supported on Al 2 O 3 was prepared from a commercial source and used as the component which reduced the carbon monoxide. It contained 24% by weight of HZSM-5 as the acidic crystalline aluminosilicate ingredient.

The heterogeneous composite catalyst was prepared at i. a ball mill simultaneously treating four parts of HZSM-5 and one part of the catalyst Zn0 / Al2O3, followed by tabletting. Two experiments were carried out, both at 516 ° C, 52.7 kg / cm 2 absolute and with a mixture of hydrogen and carbon monoxide having a ratio H2 / C0 of 4. The first experiment used the catalyst Zn0 / Al2O4 alone , while the second experiment used a composite catalyst containing both the ZnO / Al2O3 and the HZSM-5 catalysts.

The results are shown in Table 2.

TABLE 2 145460 16 (D) (E)

Catalyst Zn0 / Alo0, 20% Zn0 / Alo0 ^ plus

Alone2 “5 ™ *

Contact time - seconds (under reaction conditions) 25

Conversion,% by weight

Co 32.0 6.7 H2 5.4 3.4% by weight of total hydrocarbons derived from the reaction 0.2 1.0

Hydrocarbon distribution (weight-90

Methane 100.0 11.4 C2-C4 hydrocarbons - 42.9 C5 + I_ * 5.7 100.0 100.0

Aromatics in Cr- + (wt%) None 71.8 EXAMPLE 3

A methanol synthesis catalyst was prepared containing the following components in the following weight percentages: copper - 54.55, zinc -27.27, chromium - 9.09, and lanthanum - 9.09 on an oxygen free basis. A composite catalyst was then prepared from equal parts of this component and HZSM-5, using 5% graphite as a p binder. Two experiments were performed, each at 316 ° C, 52.7 kg / cm absolute, using as a starting material a mixture of hydrogen and carbon monoxide with a ratio of H 2 / CO of 2, and a summary thereof is shown in Table 3.

TABLE 3 (F) (G)

Catalyst Methanol-type Methanol-type plus HZSM-5 mixture 17 U5A60 alone

V

Space velocity of methanol catalyst component 5825 6764 (cm 2 synthesis gas / g of methanol catalyst / hour) CO conversion, weight # 24 34% by weight in anhydrous product

Me than 0.7 1.1 C 2 -C 4 hydrocarbons 1.0 5.7 C 2 + hydrocarbons 1.0 1.8 2.7 8.6

As shown, the contact times (the reciprocal values of space velocities.). relative to the methanol catalyst component very similarly - in the two experiments, the value being slightly lower with the composite catalyst. -

The composite catalyst exhibits a much greater production of hydrocarbons, especially hydrocarbons whose carbon numbers are greater than methane, than the carbon monoxide reducing agent itself.

EXAMPLE 4

The carbon monoxide reducing component was a commercial iron oxide type ammonium synthesis catalyst containing small amounts of K, Ca and Al promoters. The zeolite component contained 65% HZSM-5 and 35% alumina binder defect. The heterogeneous composite catalyst contained 75% of the iron component and 25% of the zeolite component, and it was prepared by treatment in a ball mill of the components and then tableting the resultant. · Corrosive powder.

p

Three tests were performed at 371 ° C, 18.6 kg / cm absolute and with a mixture of hydrogen and carbon monoxide having a ratio Hg / CO of 1.0.

The results are summarized in Table 4.

18 145460

Catalyst (H) (j) (K) - Fe Fe / HZSM-5 Fe + HZSM-5

Components not compound mixed. Compact catalytic converter in separate reactive reaction zone down in series

Contact time - seconds 15 30 15 (under reaction conditions) _

Conversion, wt% CO 95.5 96.9 98.4 H2 67.8 76.9 72.5 wt% total hydrocarbons from the reaction materials 22.6 25.6 25.5

Hydrocarbon distribution (wt% J

Methane 44.6 50.1 52.6 CO-C, hydrocarbons 50.1 41.1 41.4 C5 + 5.5 8.8 6.0

Aromatics in C +. weight% 1.9 2.3 15.0

Experiment H illustrates the selectivity of the iron component in the absence of HZSM-5; The C + hydrocarbons contain only 1.9% aromatics. In experiment (J), a reaction zone containing HZSM-5 was introduced after the reaction zone containing the iron catalyst. It is clear from the foregoing that the selectivity for aromatics had not changed significantly. In experiment (K), however, the thorough mixing of HZSM-5 with the iron component produced about a sevenfold increase in the selectivity for aromatics.

EXAMPLE 5

The catalyst in this example was prepared by impregnating NH 4 ZSM-5, containing 35% alumina binder, with a solution of Fe (NO 2) 2, by drying the catalyst and by calcining at 538 ° C for 10 hours. The finished catalyst contained 3% iron. Synthesis gas (Ho / CO = 1) was reacted over this catalyst at 371 ° C

36.2 kg / cm absolute and a contact time of 30 seconds, resulting in the following conversions and products.

19 TABLE 5

Catalyst FeHZSM-5

Contact time. - seconds (under reaction conditions) 30

Conversion, wt% co 19.7 H2 12.0 ^ wt% total hydrocarbons emitted from the reaction 8.1

Hydrocarbon distribution (weight%)

Me than 33.4 ----- C2-C4 hydrocarbons 47.5 C5 + 19.1

Aromatics in C₂ +, wt% 24.6 Λ Example 6

The catalyst in this example was a thorough mixture of 57> 4% ilmenite sand (FeO * TiO2), 21.3% HZSM-5 and 21.3% alumina binder **. Synthesis gas (H2 / CO = 1) was reacted over this catalyst at 371 ° C and 18.6 kg / cm 2 absolute and a contact time of 10 seconds to give the following conversions and products. y / '"Γ ..." i TABLE 6 20 146460

Catalyst Ilmenite + HZSM-5

Contact time - seconds (under reaction conditions) 10

Conversion, wt% CO 62.3 H2 48.3 wt% total hydrocarbons from the reaction materials 21.5

Hydrocarbon distribution (wt%)

Methane 29.2 C2-C4 hydrocarbons 59.1 C5 + 11.7

Aromatics in C₂ +, wt% 29.9 EXAMPLE 7

The catalyst in this example was a thorough mixture of 41.2% magnetite (Fe₂O₂), 29.4% HZSM-5 and 29.4% alumina binder part. Synthesis gas (ΗΗ / CO = 1) was reacted over this catalyst at 371 ° C. 18.6 kg / cm absolute and a contact time of 10 seconds, resulting in the following conversions and products: TABLE 7

Catalyst Magnetite + HZSM-5

Contact time - seconds (under reaction conditions) 10

Conversion, wt% CO 41.8 H2 37.6 wt% total hydrocarbons from the reaction materials 16.6

Hydrocarbon distribution (wt%)

Methane 31.0 C2 + C4 carbides 55.0 c5 + 14.0

Aromatics in C, - +, wt% 1919 2i U5460 EXAMPLE 8

The catalyst in this example was a thorough mixture of 41.2% edible carbide, 29.4 # HZSM-5 and 29.4% alumina binder. Synthesis gas (H 2 / CO = 1) was reacted over the catalyst at 371 ° C, 18.6 2 ^ kg / cm absolute and a contact time of 10 seconds to give the following conversions and products.

TABLE 8

Catalyst iron carbide + HZSM-5

Contact time - seconds (under reaction conditions) 10

Conversion, wt% CO 11.7 h2 11.1 wt% total hydrocarbons emitted from the reaction 4.5

Hydrocarbon distribution (wt%)

Methane 40.8 C9-Ca hydrocarbons 50.1 V 9.1

Ar omates in C₂ +, wt% 6.2; . EXAMPLE 9

The catalyst in this example was prepared by impregnating -> an extrudate comprising ZSM-5 crystalline zeolite containing about * 35% alumina as a binder with a solution of iron nitrate [Fe (NO temperature of approx. 510 ° C. Three different levels of iron impregnation were produced, as indicated in Table 10. Synthesis gas (H2 / C0 = r 2) was contacted with the catalyst at a temperature of <316 ° C .ν ': p and a pressure of 14.1 kg / cm gauge pressure. The results obtained are as follows: TABLE 9

Effect of Fe Concentration "Impregnated" ZSM-5 extrudate

5l6 ° C. Sedimentation of the pulp. 14.1 kg / cm 2, 2 H_ / CO, 3300 CHSV

Iron, weight% 8.6 14.8 21, ^ CO conversion, weight 6 43 65 83 Weight% C converted to: CO 30 30 36

Hydrocarbon 70 65 64

Hydrocarbon composition, weight% G1 38 42 38 C2 16 16 14 C3 9 8 7 C4 10 8 8 C5 4 5 6

Cfi + 23 21 27 100 100 100 Cg + aromatics, weight-I 46 42 34 EXAMPLE 10

The catalysts used in this example included a mixture of ZSM-5 alumina extrudate (ratio 65/35) with a copper-based methanol synthesis catalyst. In experiments 912-1 and -2, the volume ratio of ZSM-5 / Cu synthesis catalyst was 2.9 / 2, and in experiments 913-3 to -5, the volume ratio was ZSM-5 / Cu synthesis catalyst. 1.4. The ZSM-5 alumina extrudate was also mixed with an iron-based ammonia synthesis catalyst in a 4/1 ratio and used as the catalyst in experiments 903-1, -2 and -6. The operating conditions used and the results obtained in the tests concerned are given in the following Table 10.

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A thorium oxide ZSM-5 catalyst (no alumina) prepared as set forth in Example 1 was used for comparison purposes in two separate experiments with a similar catalyst containing the alumina binder as shown below. In these examples, synthesis gas (Ho / CO = 1) was contacted with the catalyst at a temperature of 427 ° C and a pressure of 84.4 kg / cm pressure gauge.

The results obtained are given in the following Table 11.

TABLE 11

Syngas conversion over ThCu / HZSM-5 427 ° C 84.4 kg / cm 2, Hg / CO = 1

ThO 2 / HZSM-5 ThO 2 / HZSM-5 (no AloO-r) + Al 2 O 2 binder GHSV (STP), h

Operating time, h 26 267 94

Conversion, weight # CO 36.9 58.1 10.1 H2 21.3 45.6 12.9 ....

Total product, weight #

Hydrocarbons 9.09 14.98 3.66

Oxygenates - - - H2 O 0.57 0.38 1.18 CO2 25.69 29.99 4.10 CO 60.36 39.93 84.90 H2 4.29 ^ 48 6.16

Hydrocarbons, by weight

Methane 13.6 11.3 9.7

Ethane 36.7 28.0 19.5

Ethylene 0.2 0.1 -

Propane 33.0 24.8 14.1 ………….

Propylene 0.2 0.2 i-Butane 5.4 4.3 1.7.

n-butane 3.8 2.7 0.9

Butenes - i-pentane 1.8 0.9 0.6 n-pentane 0.2 trace trace

Pentener - - -

Cg + 0.4 - trace

Aromatics 4.7 27.7 53.3

Total C5 + 7.1 28.6 53.9

Aromatics in C ^ + + 66.2. 96.9 98.9 EXAMPLE 12

Ruthenium dioxide has been used as a Fischer-Tropsch catalyst to convert synthesis gas to paraffin wax under high pressure and low temperature (120-220 ° C). However, at higher temperatures (300 ° C), only methane is formed. Ruthenium-on-aluminum has also been used for synthesis conversion to produce gaseous, liquid and solid hydrocarbons; however, in this case too, methane is the main product at temperatures higher than 250 ° C. No aromatics are produced using these catalysts. It has now been found that ruthenium in combination with HZSM-5 gives rise to the production of gasoline containing aromatics in high yield from synthesis gas over a wide range of temperatures.

EXAMPLE A

A 5% ruthenium-on-ZSM-5 catalyst was prepared by vacuum impregnating 10 g of NH After drying in vacuo, the catalyst was air calcined in an oven at 538 ° C for two hours. This resulted in a conversion of the ammonium form of ZSM-5 to the hydrogen form.

EXAMPLE B

A 1% Ru / ZSM-5 catalyst was prepared using the procedure of Example A, except that 20 g of NH 2 -ZSM-5 was used with a 36 ml aqueous solution containing 0.5 g of RuCl ^ * 3H20.

EXAMPLE C

The conversion of synthesis gas (H2 / CO) was carried out in a continuous flow reactor with fixed mass. To the stainless steel reactor was added 5.5 g of the 5% Ru / ZSM-5 catalyst, the preparation of which is given in Example A; the catalyst was pre-reduced with flowing hydrogen at 399 ° C and a pressure of 52.7

ISLAND

kg / cm pressure gauge for three hours.

p

The conversion of synthesis gas (H2 / CO) was carried out at 52.7 kg / cm 2 pressure for three hours.

p

The conversion of synthesis gas (H 2 / CO) "was carried out at 52.7 kg / cm pressure gauge. 304 ° C. V / HSV = 0.52 and H2 / C0 = 2/1. The results and detailed hydrocarbon distribution are given in the following Table 13. A high conversion with good selectivity to liquid products (C + +) appears, the liquid product containing 25% aromatics and having octane numbers R + 0 = 77 and R + 3 = 92.

EXAMPLE D

Synthesis gas conversion was carried out under substantially the same conditions as in Example C except that 5> 5 g of 1% Ru / ZSM-5 as prepared in Example B. The results are set forth in the following Table 13. yielded high conversion to hydrocarbons rich in C2 + containing 13.8 $ aromatics.

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28 145460 TABLE 12

Synthesis gas conversion over ruthenium / HZSM-5 catalyst at _52.7 kg / cm2 304 ° C WHSV = 0.32 and H2 / C0 = 2 / l

EXAMPLE C EXAMPLE D

Catalyst 5 # Ru / HZSM-5 1 # Ru / HZSM-5

Method of catalyst preparation Impregnation Impregnation

Conversion, weight # CO 82.91 79.31 H2 88.32 84.84

Total material emitted from the reactor, weight #

Hydrocarbons 37.54 31.83 H2 1.46 1.92 CO 14.95 18.07 CO2 2.31 2.66 H2 O 43.74 45.53

Hydrocarbon composition, weight% 31.11 20.42 C2 6.61 4.02 C3 6.82 7.79 C4 9.22 16.78 C5 + 46.24 50.99

Aromatics in C ^ + + 24.84 27.04

Aromatics in Cg + 29.57 34.78

Aromatics in total hydrocarbons 11.51 13.79

Hydrocarbon selectivity * 98.50 97.60

Octane number of C5 + 77 (R + 0) 92 (R + 3) K (Total carbon converted - Total carbon in CO 2) / Total carbon converted