DE2621314A1 - CATALYST PRECURSOR AND ITS REDUCTION PRODUCT, AND PROCESS FOR MANUFACTURING THE SAME AND METHANE FORMATION PROCESS - Google Patents

Description

TDI / # ^ Patent Attorneys:

IEDTKE - BUHLING - IVlNNE - UrUPE Dipl.-Ing. Tiedtke

Dipl.-Chem. Biihling 21314 Dipl.-Ing. Chins

Dipl.-Ing. Group

8000 Munich 2, PO Box 202403 Bavariaring 4

Tel .: (0 89) 53 96 53-56

Telex: 5 24845 tipat

cable. Germaniapatent Munich

May 13, 1976

B 7361 / case B 27850 /

IMPERIAL CHEMICAL INDUSTRIES LIMITED
London, UK

Catalyst precursor and its reduction product as well as process for the production of the same and methane formation process

The invention relates to a catalyst precursor composition, a catalyst produced from it and its production as well as on processes, in particular methane formation processes, where the catalyst is used.

The catalyst precursor composition according to the invention consists of shaped bodies, each of which is a mixture of

(a) limited particles (as defined below) of coprecipitated thermally decomposable compounds of nickel and / or cobalt and / or iron, of at least one trivalent metal, whose oxide is difficult to metal

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is reducible and possibly also of at least one divalent metal, the oxide of which is difficult to redr.zlerbe metal. ^ is and / or of thermal decomposition products of such compounds and

(b) comprise confined particles (as defined below) of catalyst support material.

Information on the periodic table of the elements in the context of the present description refers to the Abridgments of Specifications published by the English Patent Office. The definition of catalyst compositions is percentages by weight of the non-volatile constituents, ie of constituents which are not removed by heating in air to 550 ° C. or above. The contents of nickel and / or cobalt and / or iron are given as a percentage of monoxide based on the oxidic composition to which the partially or completely undecomposed precursor compositions or the active catalysts that can be generated by reducing such oxidic compositions correspond.

As is customary in catalyst technology, the shaped units or shaped bodies are, for example, pressed Cylinders or rings, extrusions like cylinders or rings, approximately spheres. Or irregular pieces

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for use in fixed beds, small to medium-sized particles for use in fluidized beds or suspendable Masses or beds and coatings that are applied to surfaces such as reactor walls, fibers and honeycomb structures are applied.

Within each shaped unit are the nickel and / or cobalt and / or iron or theirs Limited particles containing compounds or oxides are separated from one another by the catalyst support material. This causes sintering of the catalytic crystals of metallic nickel and / or cobalt and / or iron in the catalyst apparently held within each finite particle (separately); alternatively or additionally seem any trace constituents with a tendency to accelerate sintering at a penetration or migration the overall fineness of the form and thus an influence from being hindered from any substantial part of the active material. So the catalyst support material has the effect of increasing the mechanical stability of the molded units during use in gas reactions such as "methanation" or methane formation processes.

The limited particles of the coprecipitated compounds and / or their thermal decomposition products have a size that is preferably in the range of 10 to 10 'Å

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in particular 10 to 2 χ 10 Å. For example, particles are suitable which pass through a sieve with a mesh size of 105 / U (10 ×), in particular particles with an average size of about 5 × 10 ⁵ Å. The particle size of the catalyst support material can be within the same range as defined for the jointly precipitated compounds and / or their thermal decomposition products. For example, particles that pass through a sieve with a mesh size of 45 μ (4.4 χ HK X) are particularly suitable Particles with an average size of 10X. These particles can be aggregates of smaller final particles

■ χ ho

be the maximum dimensions in the range of 10 to 4 χ 10 A to have.

The proportion of the catalyst support material depends on the nature of the material used and its physical properties, in particular the specific surface area and its particle size relative to that of the jointly precipitated compounds and / or their thermal decomposition products, but a typical proportion of catalyst support material is in the range from 2 to 40%, especially 8 to 25 wt.% of the present non-volatile ingredients.

The term "co-precipitated" includes compounds which (a) by double reacting soluble compounds of all metal components with a precipitant and (b)

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due to the interaction of poorly soluble compounds of the metals in aqueous suspension, especially under conditions which lead to the formation of phases, the compounds of more than one contain such metals. For method (b), the sparingly soluble compounds can be freshly but separately precipitated be.

In a preferred precursor or intermediate product, the thermally decomposable compounds comprise one or several complex compounds with a composition corresponding to the general formula (I):

«Γ ^ ⁺ (OH) _{2x + 3y} . _2z (A ") _z . A H ₂ O (I)

where M ^{++ denotes} nickel and / or cobalt and / or iron, optionally in combination with a further divalent metal which is normally solid and whose oxide is difficult to reduce to the metal;

M ⁺⁺⁺ stands for one or more trivalent metals, the oxide of which is difficult to reduce to the metal; A is a divalent inorganic anion and x, y, ζ and a are positive integers or fractions that satisfy the following relationships:

I is between 0.25 and 8.0 x + y is between 0.167 and 0.05

a
χ + y is between 0.25 and 1.0

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and / or thermal decomposition products of one or more such compounds are present.

In such compounds are preferably χ = * 2 to 16; y = 2; ζ »0.5 to 2.5; a = 1.5 to 6.0 with the proviso that 2x + 3y - 2z is not less than 7.5 or greater than 34; are in particular χ - 2 to 8; y = 2; ζ ■ 0.5 to 1.4 and a »1.5 to 5.0 with the proviso that 2x + 3y - 2z is not less than 7.5 or greater than 20. Values of χ «6 are very suitable; y = 2; ζ = 1 and a = 4.

A definition for "difficult to reducible ¹ · can be found in the" Handbook of Chemistry and Physics ", 32nd edition, 1950-51, pages 1521-1523 Atmospheric pressure and 100 ⁰ C is not reduced.

The further metal M ⁺⁺ is preferably from group HA of the periodic table. The metal M ⁺⁺⁺ is expediently formed by one or more metals from the group of chromium and metals from group IHA of the periodic table, including the rare earth metals.

Preferably, at least part of the further divalent metal and the trivalent metal are common

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Formation of a mixed oxide with a spinel structure enabled. So a suitable compound has a composition that the formulas

M ₅ Mg Al ₂ (OH) ₁₆ CO ₃ . 4H ₂ O (II) and / or M ₆ Al ₂ (OH) ₁₆ CO ₃ . AH ₂ O (III), where M is nickel or K _{0 is} DaIt.

The divalent anion α "is expediently by Carbonate is formed, but other anions are also possible, provided that they do not contain interfering elements such as sulfur or contain halogen, which could act as catalyst poisons.

Among the catalyst support materials that may be present are oxides of silicon, metals of Group IIIA and Group IVA such as alumina, titania, zirconia, thorium oxide and uranium oxide as well as mixtures or compounds of two or more of the same, particularly advantageously aluminum silicates such as kaolin and Montmorillonite clays, magnesium silicates, magnesium aluminum silicates such as attapulgite and sepiolite and spinels such as magnesium aluminum spinel. Such oxides and compounds can be natural or synthetic products. It seems to be advantageous if the carrier material has a layered structure as it can be found in clay minerals and in which the above-mentioned maximum dimensions of

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preferred end particles are to be assigned to a dimension which is considerably smaller (than the others) and, for example, between 5 × 10 and 2 10 K (kaolin) or even less for other materials. A suitable specific surface area for the carrier material is in the range from 1 to 30 m / g.

The catalyst support material should preferably be in water-insoluble form have been introduced. This allows control of its particle size and distribution within the molded units. So it is preferably not a component of a hydraulic cement, since during the Hardening or setting of hydraulic cements soluble materials are formed.

The ratio of the components made from such compounds and other nickel, cobalt or iron containing components The catalyst is preferably such that the proportion of these metals in the catalyst is more than 35% by weight (calculated as chemical nickel metal equivalent based on the non-volatile components of the catalyst in the reduced - i.e. active - state. This corresponds to a lower limit of 40.6% by weight (calculated as a chemical NiO equivalent and based on the non-volatile constituents of the catalyst in oxide form before the reduction). One is preferred Nickel and / or cobalt and / or iron content of at least

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AO % (as metal in the active catalyst) ie at least 46% by weight as oxide, based on the oxide form. Preferably, no substantial amount (such as over 5 %) of active metal above the stoichiometric ratio should be present in the compound from the decomposition product of which the catalyst is made.

It is believed that the catalyst support material in addition to its function of separating the nickel and / or Limited particles containing cobalt and / or iron also occur during catalyst manufacture and / or use Ingestion of alkali metal compounds, which are usually present in compositions, caused by precipitation and which can promote sintering of the crystals of nickel and / or cobalt and / or iron. That Catalyst support material therefore preferably has an alkali binding capacity, which is preferably due to its ability to form stable crystalline alkali metal compounds decreases. For example, aluminum silicates are apparently because of the Formation of nepheline (empirical formula: NaAlSiO ^) or kalsilite (empirical formula: KAlSiO ^) is suitable. Indifferent Whichever catalyst support material is used, should be the alkali content when mixed with the other components the composition should preferably be low; so the material can be acid washed to remove alkali be. The catalyst support material can be structural

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Have acidity and, for example, a silica-alumina cracking catalyst or be a zeolite.

The alkali metal aluminum silicate compounds such as nepheline and / or kalsilite have a useful effect as Cements for the cohesion of the limited particles making up the precursor and the content of such compounds can therefore be controlled for the greatest possible mechanical resistance of the catalyst produced therefrom when used while at the same time the content of alkali-free aluminum silicate or other catalyst support material for achieving any required alkali binding capacity and secretion is chosen.

For a typical proportion of aluminum silicate catalyst support material in the range from 2 to 40 % _t, in particular 8 to 25 % , the presence of 0.15 to 7.5, in particular 0.3 to 3.0 % alkali metal oxide (calculated as K ^ O- Equivalent) in the form of aluminum silicate compounds are preferred. If the composition contains too little residual alkali to achieve such an alkali metal oxide content to combine with the aluminosilicate catalyst support material, the compound can be added as such mixed with the aluminosilicate or through incomplete neutralization of the aluminosilicate. In the latter case, the aluminum silicate should be very homogeneous or uniform

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ⁿ alkalized "or treated with alkali in order to avoid local accumulations of free or available alkali and the ⁿ alkalized" aluminum silicate should preferably be added to the other constituents of the composition, for example at 500 to 1000 ^° C. to form the compound have been burned. The deliberate introduction of alkali metal aluminum silicate compounds is of particular value when the content of alkali metal compounds would otherwise be very low and, for example, below 0.75 % _t in particular below 0.15% (calculated as KpO equivalent).

The total free alkali metal content of the catalyst is preferably below 1.0 %, in particular below 0.5 % (calculated as percent by weight ^ O equivalent).

According to the invention there is also a method of manufacture of the catalyst precursor or pre-product proposed, after the jointly precipitated (as defined above) Compounds are generated which thermally give rise to oxides of nickel and / or cobalt and / or iron or of a trivalent Metal, the oxide of which is difficult to reduce to the metal and possibly also of a divalent metal, its oxide Difficult to reducible to metal, and the compounds are decomposable and / or their thermal decomposition products, preferably after being reduced to a particle size as here

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described, have been brought with the water-insoluble finely powdered catalyst support material, preferably in the form of particles, as described here, are mixed and the mixture is molded into molded units.

The jointly precipitated compounds are preferably used under such conditions of quantitative proportions Alkalinity, temperature and aging time (if necessary) produced that the above complex compounds formed will. Generally, the process involves reacting the metal ions with hydroxyl ions and the required divalent ones Ions in an aqueous medium. This can be done in a single step or in several steps; for example For example, a compound can be created with a set of divalent anions and then subjected to anion exchange. The reaction mixture is expediently alkaline to about 4 pH units on the alkaline side from the neutral point counted on. The water-insoluble product is then washed to remove undesirable substances. Especially when the coprecipitated compounds are made in the presence of carbonate and then in the presence of hydroxyl ions have been aged so that a very complete removal of, for example, alkali metal ions is slow, the addition of catalyst support material makes it possible to achieve a higher alkali metal ion content in the washed lower

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to tolerate blow. The washed precipitate is then ^{dried at 70 to 150 °} C., so that (if at all) only a slight decomposition to oxides occurs. Finally, the product is fired to the oxide form, for example at 250 to 60O ⁰ C, in particular 350 to 50O ^{0 C.}

Mixing with catalyst support material can be done wet or dry and before or after forming, Washing, drying or burning the joints. Mixing is preferably carried out after washing so that the Alkali metal compound amount with which the catalyst support material comes into contact, is kept as low as possible. When shaping or forming the shaped units can Auxiliary materials be present if the mixing has to be done in the presence of water and the mixing is carried out Wet pressing or extrusion is to be shaped. A corresponding Lubricants such as graphite or stearic acid may be present.

Firing can take place before or after mixing with the carrier material and before or after shaping into shaped units or partly before and partly after such operations. It is preferably done before mixing and this is followed by grinding to the required particle size.

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Once molded into molding units, the precursor composition is ready for storage and delivery to the user. In order to produce an active catalyst, the precursor to a reducing gas, suitably hydrogen (optionally diluted with a non-reactive gas such as water vapor or argon), for example at 300 to 600 ⁰ C exposed. Since the reduced product is easily oxidized by air, the reduction is usually carried out in the reactor in which the catalyst is to be used.

The invention also encompasses a method of methane formation or a "methanation process", the one Comprises reacting carbon monoxide and / or carbon dioxide with hydrogen over the catalyst. In such a procedure Methane formation can be the only reaction, as when the starting mixture is carbon monoxide and stoichiometric Contains quantities or excess of hydrogen but no other reactive gas. However, methane formation can the carbon monoxide / water vapor ("shift") reaction with the formation of carbon dioxide and hydrogen, if the starting gas is water vapor and carbon monoxide and either no hydrogen or too little hydrogen to produce methane from everything present Has carbon monoxide. If the starting mixture contains carbon dioxide, methane can be formed from carbon monoxide be accompanied by the reverse shift reaction.

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If the starting mixture is water vapor and a hydrocarbon of higher molecular weight than methane or " contains a compound that reacts with water vapor such as methanol, methane formation can be caused by a reaction from be accompanied by the following type:

CH ₂ + H ₂ O > CO + 2H ₂

CH ₂ + 2H ₂ O> CO ₂ + 3H ₂

(where ¹¹ CH ₂ "is the approximate empirical formula for normally liquid hydrocarbons) or

CH ₃ OH > CO + 2H ₂

CH ₃ OH + H ₂ O -> CO ₂ + 3H ₂

The process of the invention thus includes processes for producing methane from a variety of starting materials and it forms the basis for processes for the production of natural gas substitutes from raw materials such as coal, liquid hydrocarbons and methanol.

The temperature at the exit of the methane formation process can be as low as 250 ⁰ C be and are, for example, at 250 to 400 ° C as in processes in which the occurring by exothermic heat of reaction by external cooling or by a-substantial content of diluent gas or both agents is recorded. Such processes can, for example, the later stages of a sequence of "methane! Erations" with the creation of a natural gas substitute

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(with at least 90% by volume methane after removal of water vapor and carbon dioxide) or they can be carried out in the presence of recycled product gas.

However, the method is particularly useful for "Methanierungen" or methane formation at outlet temperatures over 400 ⁰ C, in particular above 500 ⁰ C and up to for example 600 to 900 ⁰ C. Such "Methanierungen" _r generation than the earlier stages in the E a Natural gas substitute from carbon monoxide is important, which comes from a partial oxidation of coal or hydrocarbons, in particular non-vaporizable hydrocarbons or from methanol. A particularly useful process has a first stage at 600 to 900 ^° C., the second at 500 to 850 ^° C., but the temperature of the second stage being below that of the first; these temperatures are outlet temperatures. Such high-temperature methanation steps can be used to provide heat for steam generation and thus generation of electrical energy; In a proposed procedure, the methanatable gas is generated in an endothermic catalytic methane / steam reforming stage at a first point at which heat is available and passed from this first point to a second, where water vapor is to be generated and over at this second point methanated a catalyst according to the invention, cooled in one or more boilers to produce the required

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steam and returned to the first digit for a conversion back to methanable gas in the endothermic catalytic steam reforming stage. With such a System it is undoubtedly of great importance that a methanation catalyst of long-lasting activity, as provided according to the invention, is available. (In the second place are the boilers with common Combined heat recovery units such as boiler feed water heaters).

Such a high-temperature methanation using the catalyst can take place in the presence of "dampening" gases such as water vapor or methanation product gas with or without carbon dioxide. The methanable hydrogen content of the gas entering the catalyst is expediently in the range from 10 to 50 %, in particular 15 to 30% by volume of the total mixture (including the steam).

The pressure at which the methanation takes place is typically in the range from 1 to 100 ata, in particular 5 to 70 ata. When gas to be methanated by the reaction of normally liquid hydrocarbons with water vapor was generated, the methanation using the crude product gas from such a reaction or under Application of such a gas can be carried out after removal of water vapor or carbon dioxide or both. Usually

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there is a small amount of steam present, sufficient to inhibit the formation of carbon. If desired, the gas can be in front of the Entrance to the methanation stage are compressed.

Considering the high exothermic heat of the methanation reaction the process should be carried out under conditions that allow temperature control and / or recovery of the Allow warmth. This means that the process can be carried out with heat exchange with boiling water under pressure or with direct current heat exchange be carried out with cold feed gas. If the initial feed is formed by methanol, the Temperature can be controlled by heat exchange with liquid water or methanol or both, as in the one with of the present coherent GB application 13 109/73 the applicant is described. The high stability of the catalyst is particularly useful in processes where the temperature is allowed to rise to the ranges mentioned above and the gas is then passed through the boiler.

example 1 Catalyst precursor manufacture

An aqueous solution of nickel nitrate (20 kg of Ni), magnesium nitrate (0.8 kg MgO) and aluminum nitrate (13 »2 kg AIPO,) was treated for coprecipitation (metals) at 85 ⁰ C with a slight excess of aqueous sodium carbonate. A slurry of alumina trihydrate

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(6.6 kg Al ₂ O,) in 100 1 water was stirred with the precipitate. The entire slurry was heated to boiling for 15 minutes, filtered, washed thoroughly, dried for 18 hours at 120 ° C, and fired 4 hours at 380 ⁰ C. The product, a lumpy powder, was ground for passage through a sieve with a mesh size of 0.105 mm; the mean particle size was about 5 x10 ^ Ä. Five samples of the milled product were prepared, namely: A: Without further treatment;
B: Diluted with 20 % of their weight on dry

o (-aluminum oxide trihydrate powder; C: diluted with 25 % of its weight of dry o (. -aluminum oxide trihydrate powder;

D: diluted with 20 % of your weight of kaolin (with passage through a sieve with 45 μ clear mesh size; mean particle size 4.4 χ 10 ¹ ^ X); E: Diluted with 25 % of their weight of kaolin (of the same particle size).

Each of the samples was mixed with 2.5 wt% graphite and to cylindrical tablets 3 »6 mm high and 5.4 mm Dry-pressed diameter.

A sample of the precipitate was subjected to X-ray diffraction analysis after drying but before firing; the main phase was a mixture of the compounds

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Ni ₆ Al ₂ (OH) ₁₆ CO ₃ . 4H ₂ O and Ni ₅ Mg Al ₂ (OH) ₁₆ CO ₃ . 4H ₂ O found.

The burned precipitate had the following composition (in percent by weight):

NOK 61.4 %. MgO 2.7 Na ₂ O 0.20 κ ₂ ο 0.04 Al ₂ O ₃ rest Loss at 550 ° C: 8.5

Methanation process at an outlet temperature of 730 ° C

A mixture of carbon monoxide, carbon dioxide, hydrogen and water vapor at 30 ata pressure (simulation of a gas generated by partial oxidation of coal with subsequent addition of steam and partial displacement reaction) was heated to 400 ° C. and dried at a dry gas space velocity of 10,000 hours over catalysts A. , B and C sent, which had been generated by reducing the above compositions with hydrogen at 500 ⁰ C and 30 ata pressure.

The composition (in% by volume) of the dry inlet gas and the product gases as well as the water vapor ratios (in moles per 100 moles of dry gas) are given below:

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CO CO ₂ H ₂ N ₂ + Ar CH ₄ vapor ratio inlet 31.1 24.7 42.9 1.2 0.1 67.3 product 14.5 40.2 35.5 1.3 8.5 72.3

The experiments were continued and the life of the catalyst was monitored by measuring the temperature at various points along the direction of gas flow in the catalyst bed. The distance at which the temperature reached 65O ⁰ C was taken as a measure of the activity of the catalyst and recorded over a period of a few hundred hours. For Catalyst A, a speed of advance of 65O ⁰ C was observed point of about 12.7 cm per 1000 hours. The experiment was interrupted after 580 hours; the catalyst tablets proved to be mechanically very weak (mean vertical crush strength less than 4.54 kg per tablet). Catalyst B worked well for 260 hours (650 ° C. lead below 12.7 cm per 1000 hours), after which the experiment was interrupted because of a system defect. The catalyst worked 980 hours D long good (65O ⁰ C Flow: about 5.1 cm per 1000 hours), after which the test was interrupted due to a system failure, (In a repeat of the experiment with catalyst D over 680 hours, a 65O ⁰ C Advance speed of approximately 3 inches per 1000 hours was observed until the experiment was interrupted). At the end of these tests, both catalysts were in excellent mechanical condition (middle

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vertical crush strength from 68 to 91 kg per tablet).

Methanation process with an outlet temperature of 590 C

This test was similar to the 730 ° C process, however, the effluent of the 730 ° C process at an inlet temperature of 325 ⁰ C was used as feed gas. The stability of the catalyst was determined by observing the distance along the catalyst bed at which the temperature reached a value of 525 ° C.

The compositions of the dry inlet gas and the product gases (in% by volume) and the water vapor ratios (in moles per 100 moles of dry gas) are given below:

CO CO ₂ H ₂ N ₂ + Ar CH 4 vapor ratio inlet 14.5 40.2 35.5 1.3 8.5 72.3 product 4.3 53.9 20.3 1.7 19.8 94.4

Catalyst C showed a 525 ° C advance rate of 38.1 cm per 1000 hours; however, he was still usable after 410 hours when the experiment was interrupted. Catalyst E exhibited a forward rate of less than 5.1 cm per 1000 hours and was after the voluntary termination of the test after 1600 Hours still satisfactorily active. All._e catalysts were in excellent mechanical at the end of their test Condition (mean vertical crush strength of about 91 kg per tablet).

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Example 2 Catalyst precursor manufacture

An aqueous solution of nickel nitrate (18.5 kg Ni), magnesium nitrate (2.5 kg MgO) and aluminum nitrate (7.46 kg AIpCU) a common precipitation with slight excess of aqueous sodium carbonate at 85 ⁰ C was subjected. Aqueous sodium hydroxide (15 kg NaOH) was added to the precipitate. The entire slurry was heated to boiling for 30 minutes, filtered, washed thoroughly, dried for 18 hours at 120 ⁰ C for 6 hours fired at 425 ° C. The product, a lumpy powder, was ground for one pass through a sieve with a mesh size of 0.105 mm; its mean particle size was about 5 x Kr Ä. The ground product was mixed with 17.6% of its weight of kaolin (particle size as in Example 1) and 2.3% of its weight of graphite. The mixture was dry pressed to give cylindrical tablets 3.6 mm in height and 5.4 mm in diameter (Catalyst F) or 3.2 mm in height and 3.2 mm in diameter (Catalyst G).

A sample of the precipitate examined after drying but before burning showed a content of Nie Mg Alp (OH), ^ CO,. 4H ₂ O as the main phase.

The mixture of burned precipitate and kaolin had the following composition (in percent by weight):

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NiO 53.3

MgO 3.7

Al ₂ O ₃ 19.7

SiO ₂ 9.6

Na ₂ O 0.8

K ₂ O 0.33 loss at 900 ⁰ C 12.5

Methanierungsprozeß with an outlet temperature of 73O ⁰ C

When applying the same procedure as in Example 1, but with improved sulfur separation of the catalyst F worked well for 2200 hours (flow rate lower than 1.27 cm per 1000 hours) after which the test because of a defect position A _n interrupted.

Methanierungsprozeß at an outlet temperature of 590 ⁰ C.

When using the same procedure as in Example 1, but with improved sulfur separation Catalyst F showed an advance rate of less than 5.1 cm per 1000 hours and it was at voluntary Completion of the experiment after 1500 hours, still of satisfactory activity.

Methanierungsprozeß with an outlet temperature of 430 ⁰ C. This test was similar to the procedure 590 ⁰ C outlet temperature, however, the effluent was as feed gas to the

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590 ⁰ C method was applied and the inlet temperature was 30O ⁰ C. The stability of the catalyst was determined by observing the distance along the catalyst ^{bed at which the temperature reached 400 0} C.

The compositions of the dry inlet gas and the product gases (in volume%) and the water vapor ratios (in moles per 100 moles of dry gas) are given below:

CO CO ₂ H ₂ N ₂ + Ar CH ^ vapor ratio

Inlet 4.3 53.9 20.3 1.7 19.8 94.4

Product 0.34 62.7 5.8 2.0 29.1 118.2

The catalyst F showed a 40O ⁰ C flow rate of less than 1.27 cm per 1000 hours and was still satisfactorily active after 1500 hours when the experiment was terminated arbitrarily.

Example 3

Further reactions via catalysts according to the invention: methanol gasification to gas with 30 to 40 vol.% Methane (dry basis )

In this process, a methanol / water mixture (molar ratio of 2: 1) was evaporated and fed into a reactor having an inlet temperature of 45O ⁰ C at a liquid space velocity of 33 hr. An adiabatic equilibrium was adjusted with an outlet temperature of about 725 ⁰ C. The stability of the catalyst was

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determined by observing the distance along the catalyst bed at which the temperature reached 600 ° C. Catalysts A and D were tested under these conditions. Catalyst A worked for 350 hours at a 600 ° C. advance rate of 10.2 cm per 100 hours, but the catalyst tablets exhibited poor cohesion when removed. The catalyst worked 750 hours D long with a 600 ⁰ C Flow rate of 5 _t 6 cm per 100 hours before the experiment was interrupted. The catalyst tablets then showed a good physical condition.

Low temperature steam / naphtha reaction to gas with about 60 % Methane (dry basis)

In this process, naphtha and water (weight ratio 1: 2) were evaporated, mixed and ^{fed into a reactor with an inlet temperature of 450 0} C, with a naphtha liquid space velocity of 9 hours "* An adiabatic equilibrium was established with an outlet temperature of 510 ⁰ C. The stability of the catalyst was determined by observing the distance along the catalyst bed at which the temperature reached 500 ^° C. In this experiment, the catalyst G worked well for 750 hours with a feed rate of 4.6 cm per ^{500 ° C.} IOC hours, after which the experiment was stopped. When the catalyst tablets were removed, it was good

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Condition was determined and an average vertical crush strength of about 18 _f 2 kg was found.

Example 4

The catalyst preparation of Example 2 was carried out by adding kaolin to the slurry immediately prior to the Filtering (instead of adding kaolin to the oxides after firing) modified. The composition of the tablets (in percent by weight) was the following:

NiO 54.8

MgO 4.0

Al ₂ O ₃ 19.2

SiO ₂ 5.0

Na ₂ O 0.4

K ₂ O 0.4

Loss at 900 ⁰ C 15.0

In the methanation with einerAuslaßtemperatur of 73O ⁰ C This catalyst worked 516 hours long with a 650 ° mLtbleren feed speed of 5.1 cm per 1000 hours. At the end of this test, the catalyst showed a good mechanical condition.

Example 5

A catalyst was prepared similarly to Example 2, but with the difference that no magnesium

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nitrate was applied, no sodium hydroxide treatment was carried out and the precipitated phase was not very crystalline. The tablets had the following composition (in percent by weight):

NiO 49.6

Al ₂ O ₃ 21.7

SiO ₂ 6.7

Na ₂ O 0.04

K ₂ O 0.8

Loss at 900 C 20.1

In the methanation with an outlet temperature of 730 ⁰ C, this catalyst worked 1,300 hours at an average feed rate of 650 ° 7.6 cm per 1000 hours. At the end of the test, the catalyst showed a good mechanical condition.

The precursor preparation given in Examples 1, 2 and 4 is of particular interest.

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Claims (19)

26213U claims 1. Catalyst precursor in the form of shaped units, characterized in that each unit a mix of (a) limited particles of co-precipitated thermally decomposable compounds of nickel and / or Cobalt and / or iron, of at least one trivalent metal, the oxide of which is difficult to reduce to metal and possibly also a divalent metal, the oxide of which is difficult to reduce to metal and / or thermal Decomposition products of such compounds and (b) comprises limited particles of catalyst support material. 2. Catalyst precursor according to claim 1, characterized in that the limited particles of the common precipitated compounds and / or thermal decomposition 4 settlement products of the same size in the range of 10 up to 2 χ 10 ⁶ p . 3. Catalyst precursor according to claim 1 or 2, characterized in that the limited particles of the catalyst support material have a size in the range from 10 to 2 χ 10 K. 6093A7 / 095 1 " ³⁰ " 26213H 4. Catalyst precursor according to one of the preceding claims, characterized in that the proportion of the Catalyst support material in the range of 8 to 25 wt.96 of the non-volatile constituents present. 5 · Catalyst precursor according to one of the preceding claims, characterized in that the thermally decomposable Compounds one or more complex compounds having one expressed by the following general formula Composition include: M ⁺ > ⁺⁺⁺ _y (OH) _{2x + 3y} . _2z (A ") _z . A H ₂ O (I) in which M is nickel and / or cobalt and / or iron, possibly in combination with a further divalent metal which is normally solid and the oxide of which is difficult to reduce to metal; M ⁺⁺⁺ for one or more three-valued Stands for metals whose oxide is difficult to reduce to metal; A is a divalent inorganic anion and
x, y, z and a are positive integers or fractions which satisfy the following relationships: - is between 0.25 and 8.0 χ + y is between 0.167 and 0.05 a
χ + y is between 0.25 and 1.0 609847/0951 26213U and / or thermal decomposition products of an or several such connections are present. 6. Catalyst precursor according to claim 5, characterized in that χ «6, y« 2, ζ = 1 and a * 4. 7. Catalyst precursor according to claim 6, characterized in that the compound has a composition the the formulas M ₅ corresponds to Mg Al ₂ (OH) ₁₆ CO, 4H ₂ O and / or M ₆ Al ₂ (OHJ ₁₆ CO ₅ , where M denotes nickel or cobalt. 8. Catalyst precursor according to one of the preceding claims, characterized in that the catalyst carrier material has been added in water-insoluble form. 9. Catalyst precursor according to one of the preceding claims, characterized in that the catalyst support material is an aluminum silicate. 10. Catalyst precursor according to one of the preceding claims, characterized in that the proportion of nickel, Cobalt or iron over 40.6% by weight (calculated as the chemical equivalent of NiO based on the non-volatile substances present Components). 609847/0951 26213U 11. Catalyst precursor according to one of the preceding claims, characterized by a content of free alkali less than 0.5% by weight (calculated as KpO equivalent). 12. catalyst precursor according to any one of the preceding claims, characterized by 8 to 25 wt.% Aluminosilicate catalyst support material and 0.3 to 3 _f 0 wt.% Alkali metal oxide (expressed as kpo equivalent) in the form of aluminum silicate. 13. A method for producing a catalyst precursor according to any one of the preceding claims, characterized in that characterized that co-precipitated thermally to oxides of nickel and / or cobalt and / or iron, of a trivalent Metal, the oxide of which is difficult to reduce to metal and possibly also of a divalent metal, its oxide difficult to reduce to metal, decomposable compounds are produced, the compounds in particulate form with a p la Brought in size in the range of 10 to 10 Å and with water-insoluble finely powdered catalyst support material in p rj Particle shape ranging in size from 10 to 10 Å are mixed and the mixture is molded into molding units. 14. The method according to claim 13, characterized in that the jointly precipitated compounds thermally 6 0 9 8 A 7/0 9 B 1 26213U Oxides are decomposed before they are brought to the specific particle size. 15. Catalyst with metallic nickel and / or cobalt and / or iron, characterized in that it is reduced by reduction of a catalyst precursor according to any one of claims 1 to 12 has been obtained. 16. Methanation process, characterized in that carbon monoxide and / or carbon dioxide with hydrogen be reacted over a catalyst according to claim 15. 17. The method according to claim 16, characterized in that the methane formation reaction from the conversion of carbon monoxide with water vapor with the formation of carbon dioxide and hydrogen and / or the conversion of a hydrocarbon of higher molecular weight than methane with water vapor to form carbon monoxide and / or carbon dioxide and Hydrogen and / or accompanied by the decomposition of methanol to carbon monoxide and / or carbon dioxide and hydrogen will. 18. The method according to claim 16, characterized in that the methanatable mixture of hydrogen and carbon monoxide and / or carbon dioxide in an endothermic catalytic 609847/0951 26213U lytic methane / steam reforming stage has been generated at a first point where heat is available and from the first point is routed to a second point where water vapor is to be generated and at the second point is methanated over a catalyst according to claim 15 and cooled in one or more kettles to produce of the required water vapor and then sent back to the first place for conversion back into methanatable Gas in the endothermic catalytic methane / steam reforming stage. 19. A method for generating steam and / or electrical energy in a procedure analogous to claim 18. 609847/0951