JPS6054328A - Manufacture of methane-rich gas - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention [Industrial Field of Application 1] The present invention is directed to a mixture of hydrocarbons and steam, a mixture of hydrocarbons, steam, and methanol, and a mixture of methanol and steam. The present invention also relates to a process for converting methanol to a methane-rich gas using a nickel catalyst on a thermally stable oxide carrier, a regenerated nickel catalyst useful in the process, and a process for making the same.

[Prior Art] The method for producing methane-rich gas in this scale is the British Gas C
6ri) and its predecessors, the Gas Council and the North-Western Gas Board.
Gas Board), then Heinrich Kottbers Gesellschaft Mituto Beschlenchtel Hatsurank (lleinrich oppers Gn+
b Old, LURGI Hetallaesell Shaft Akchen Gesell Shaft (LURGI Hetallaesell)
schaft AG) and Japan Gasoline Kan. The catalysts used in these methods are manufactured by ICIL Ltd.
SF) and Nikki Chemical Company (Nikk
Various products have been developed by i Chemical Company.

Many of these methods are described in DE-8-1545463, 1
1 S-A-4182926, Its-A-414
No. 0493, No. 0B-A-1437957, 11S-A
-342064-2, RoE-B-1227603,
GB-A-1265481, GB-A-144327
It is described in each specification of No. 7, and all of them have two points in common.

(1) A mixture of hydrocarbons is heated to a temperature of 350 to 550°C and under a pressure of approximately 0.5 to 2.5 HPa using water vapor to form a gas mixture containing mostly methane, hydrogen and carbon dioxide, and a small amount of carbon monoxide. converts into

(2) Most of the catalysts used have nickel as an active component in MW.

In order to make this type of process economical, it has been noted that the water vapor supply, in addition to the hydrocarbon supply, is maintained at the minimum required level to cause Ni1 closure outside the carbon deposition area. ing. Furthermore, the hydrocarbon feedstock (f
It is also desirable to have greater flexibility in composition (eedstock).

However, as is well known, variations in feed composition and the [thermodynamically approximated] water vapor to hydrocarbon ratio can occur as a result of catalyst deactivation, carbon [, and its binding]. Increased pressure drop with incomplete conversion of hydrocarbons across the reactor creates various problems.

When pushing the conversion reaction toward the thermodynamic limits of carbon deposition, the reaction is greatly influenced by the nature of the catalyst.

Therefore, much effort is being put into finding better catalysts. Overall performance can also be improved by improving catalyst properties or by improving handling. In this regard, many documents describe reactions consisting of several steps. The most important of these steps is to decompose hydrocarbons on the nickel catalyst surface, release hydrogen into the gas phase, and leave no carbon-rich intermediates on the catalyst surface in the first step (this step is an endothermic reaction). a second step in which the carbon-rich intermediate is reacted with water vapor to produce methane (this step is an exothermic reaction). The first step reaction produces carbonaceous material on the catalyst in the inlet section of the catalyst bed.

This results in a temperature drop in that portion of the catalyst bed, furthering the deactivation of the catalyst. By increasing the amount of water vapor added and raising the inlet temperature, the reaction between the water vapor and the carbonaceous deposits can be promoted and the deactivation of the carbon catalyst can be delayed. However, clearly the operation reduces production efficiency. In order to vent a large amount of gas, the reactor volume is adjusted to a certain space velocity.
Must be increased to maintain □. Therefore, efforts in catalyst research are directed toward enhancing the reaction between water vapor and carbonaceous deposits.

Many nickel catalysts are used, examples +! Niji T Hatatoeha O[-B-11H427@Oclll[-
B-1227603 Listed in each town am.

Belgian Patent No. 634920 describes a catalyst suitable for the modification of hydrocarbons by means of steam, which comprises a metal of the platinum group fixed on a heat-resistant support such as alumina, together with nickel or It contains Kobal 1- in the form of a metal or in the form of a compound that becomes a metal when reduced.

These catalysts contain small amounts of alkali metals or alkaline earth metals to prevent carbon from depositing on the catalyst. Furthermore, the Belgian patent specifies that the steam reforming of hydrocarbons with a boiling point of up to 350° C. at temperatures from 600 to −12 to 1000° C. results in synthesis gas or gas with a low methane content; It is disclosed that when the reforming is carried out at 450 to 700°C, methane-rich gas can be converted.

According to specification FR-8-1394202, RoE-8
-1180481 specification [
The lifetime of the catalyst can be significantly extended by recycling the hot reaction product gas containing water vapor into the catalyst bed and mixing it with the hydrocarbon vapor and water vapor fed to the catalyst bed.

11s-A-4140993 describes a nickel catalyst with a calcium phosphate support and containing barium and uranium as promoters. Canadian Patent No. 848,888 describes that by adding an alkali metal to a nickel catalyst, the catalyst can be used for heavier hydrocarbon feedstocks.

Recent developments in this field include US-A-421612
It is described in the specification of No. 3. Here, we address the above problem by considering an endothermic reaction as a function of displacement along the catalyst bed in the reactor.
The first solution is to influence the occurrence of photothermal reactions and photothermal reactions. The disclosed catalyst uses alumina and consists of a metal of Group I of the Periodic Table and optionally an alkali metal or alkaline earth metal with a specific 70° distribution of fractions. This particular pore size distribution separates successive reactions, giving a good balance between endothermic and exothermic reactions. Although this method is an excellent method, it also has some drawbacks. The most serious problem is that due to the conversion reaction mechanism of I, the overall conversion reaction is limited because the hydrocarbons diffuse into the pores and make the activity of the catalyst relatively low. In order to solve the problem (8!1), the only way is to increase the number of WM, which of course creates a need to increase the size of the reactor, and the economical efficiency decreases due to bundling.

The main points of the present invention are the following four points.

(1) To find a catalyst that can convert a hydrocarbon-steam mixture into a methane-rich gas near the critical zone f where carbon is deposited without being substantially deactivated.

(2) To find a catalyst that can convert hydrocarbon feedstocks of various compositions.

(3) To find a catalyst that is already active at relatively low temperatures to promote the reaction.

(4) To find a catalyst that can be reactivated and used in the reactivated form after losing its initial activity.

Additionally, it would be advantageous to find a catalyst that tolerates large 214 differences across the catalyst bed.

In conventional methods, the temperature difference in the catalyst bed is limited to 80° C. or less in most cases due to the usage conditions of the catalyst.

Conventionally, excessive water vapor was added to maintain this temperature difference, but this caused the same problems as mentioned above.

The conversion of methanol to methane-rich gas proceeds according to the Habotsuki reaction equation.

4CH3 → 3CIIa + 21120 + CO2 Therefore, theoretically, there is no need to add water vapor to the catalytic conversion reaction of methanol. Its-A-282926 describes two methods of carrying out methanol conversion at 200 DEG -455 DEG C. using cobalt molybdate catalysts. Methanol conversion using nickel-containing catalysts is described in DE-A-2341288. To reduce carbon adhesion,
It has been proposed to recirculate the methane and to add water vapor to the feed gas. These methods can reduce catalyst deactivation by keeping the composition of the gas mixture supplied to the reaction outside the range that would result in carbon deposition.

However, it is clear that these methods degrade the overall production efficiency, especially the thermal efficiency.

Means for Solving Problem E" The present invention provides thermally stable oxidation of mixtures of hydrocarbons and steam, mixtures of hydrocarbons, steam, and methanol, mixtures of methanol and steam, or methanol. A method for producing methane-rich gas by conversion using a Nirakur catalyst on a metal carrier, characterized in that metal + one Nickle particles are chemically bonded to a nuclear thermally stable oxide carrier. The present invention relates to a method for producing a gas enriched in methane.

[Function and Examples] As the thermally stable oxide carrier used in the present invention, compounds used as catalyst carriers in various fields can be used.

Such carriers are those with a large specific surface area, such as alumina, silica, magnesia, silica-alumina, silica-magnesia, zirconia, silica-zirconia, titania, silica-zirconia-titania, crystalline or amorphous. aluminosilicate molecular sieves, metal phosphates, etc., especially zirconia, HQO, A120a and 5in2, especially A12
03 and 5102 are preferred.

In this specification, [basic elements (tease element)]
nt) J is an element whose oxide is used as a carrier, such as aluminum, silicon, and magnesium.

When using silica as a carrier, commercially available products such as Aerosil may be used, and commercially available products such as Aerosil may also be used for other oxides.

In a preferred embodiment of the present invention, the chemical bond between the metallic nickel particles and the oxide chelary is formed in an interface layer different from the oxide chelary.
yer). Such an interfacial layer is composed of nickel, at least one of one or more of the following basic elements, and an oxygen-containing compound.

In general, the interfacial layer is composed of (1) a compound containing nickel ions, or (1) a stable non-stoichiometric oxide of the basic element of the carrier;
or (to) a compound containing the basic element of nickel carrier A7.

If the carrier is an oxide of a basic element that forms only stoichiometric oxides, the interfacial layer contains nickel ions. On the other hand, if Kirelya is an oxide of a basic element that can form a stable non-stoichiometric oxide, the interfacial layer contains a non-stoichiometric oxide of the basic element and also contains nickel ions. May contain.

Basic elements that form only stoichiometric oxides include:
At least one element selected from the group consisting of silicon, aluminum and magnesium is preferred. The interfacial layer is very thin, typically 0.2-10 nm, preferably 0.5 nm.
~5nllI thick. In fact, the thickness of this interfacial layer is several atoms thick. What is essential is that essentially all the metallic nickel particles are chemically bonded to the carrier. The active catalyst metallic nickel particles do not form a continuous layer, but exist as individual, independent particles chemically bonded to the carrier.

It has been observed that when the active catalyst contains certain amounts of metallic nickel particles that are not chemically bonded to the carrier, those particles enhance carbon formation. Therefore, in the present invention, metallic nickel particles that are not chemically bonded to the carrier, for example, via an interfacial layer,
-19- 0.059 or less per cm3 of catalyst bed, preferably 0
．． 03 (J or less, preferably o, oi g or less is included in the doku).

The particle size distribution of the nickel particles used in the catalyst used in the method of the present invention is preferably such that less than 10% by volume of the particles are smaller than 2 nm, and less than 10% by volume of the particles are larger than 30 nm. Nickel is an oxide
7.1- Precipitates in the form of hydroxides or oxides, such as:

However, since hydroxides or oxides do not have catalytic activity for the reactions involved in the present invention, they must be reduced to metals. A common method for forming chemical bonds is to partially reduce the nickel hydroxide or oxide that has been preliminarily fixed on the nickel. As a result, the generated nickel particles are chemically bonded to the remaining nickel oxide, and the nickel oxide is bonded to the carrier. However, once the reduction of nickel oxide particles starts, it progresses rapidly, and all particles tend to be reduced to metallic nickel.
0- Yes. Therefore, some of the nickel ions must be supplied in a form whose reduction rate is slower than that of the pure oxide. This can be achieved by reacting with nickel ions to give a less reducible compound, or by using a partially reducible carrier. In the latter case, the carrier material is reduced to form an alloy with metal atoms, often nickel. They strengthen the interaction between nickel and carrier.

A method of reacting at least a portion of the nickel ions with a carrier material to produce a compound that is less reducible than the hydroxide or oxide of nickel can be accomplished using 5102 as a carrier. For example, when using a suspension of 5 in2 in a nickel salt solution, optionally with an excess of alkaline compound added over the solution, the 5 in2 carrier is reacts to form some nickel hydrosilicate. 5i becomes hydrosilicate
The portion n2 varies depending on the reactivity of the SiO2 used and the excess amount of alkaline bamboo compound used.

The reaction of 5 iOz to hydrosilicate-1 was described by Van [1jck], Van VooNhuiJsen and Franzen [In Rec, Trav,
This is more completely accomplished by co-precipitation of nickel with 5102, as described in Chill, J., page 70.793 (1951). According to this method, by thoroughly mixing the water glass solution with the nickel salt solution,
Sooner or later the reaction producing nickel hydrosilicate will be completed. Generally, nickel hydrosilicate takes the form of relatively large, plate-like crystals.

For the reduction of the coprecipitate, J: contains nickel ions.5
This produces nickel particles that adhere extremely well to 102. The catalyst obtained by this method is preferably used in the present invention.

Specific examples of common methods for producing nickel catalysts will be shown, but the invention is not limited to these.

(a) mixing an aqueous solution of a nickel salt and an aqueous solution of a salt of a basic element for forming KiV, raising the pH of the mixture to a level at which dissolved nickel ions and ions of the basic element precipitate; If necessary, the precipitate in the solution is aged, and if necessary, the obtained solid is treated with hot water,
Method of drying, firing and reducing.

(b) a nickel salt solution and a solution of a salt of the basic element, the oxide of which is the thermally stable oxide carrier;

mixing the liquid with an aqueous solution of an oxalate or formate in an aqueous medium, separating the precipitate, drying and calcining;
How to give back.

A fine powder of a +C1 thermally stable oxide carrier is suspended in a dilute solution of a nickel salt, and the nickel compound is added under the surface of the stirred suspension with vigorous stirring at an elevated temperature if necessary. By implanting hydroxide ions or by forming them by a chemical reaction known per se of a compound contained in the solution in an amount of 1 to 10% of the stoichiometrically required amount. A method of precipitation, followed by separation, drying, calcination, and reduction of the supported carrier.

(Put a nickel salt solution under the liquid surface of a suspension of a small heat-stable oxide 4V A7 > 9 people 1), and set the pl+ of the suspension to 4 to 7.
method of maintaining, separating, drying, calcining, and reducing compatible carriers.

In order to obtain a sufficiently large activity per unit volume, it is desirable that nickel be supported at least 5% by weight of the total catalyst weight.

The method (C) is D! b, which is similar to the method described in E-C-1767202. According to this method, a particularly suitable catalyst can be obtained. DE-C-17
No. 67202 further describes that the nickel catalyst obtained can be used for methane production from small amounts of carbon dioxide and carbon monoxide present in the gas for ammonia synthesis. This is in line with the methanogenesis of the very small amounts (approximately 0.1% by volume) of carbon dioxide and carbon monoxide present in the hydrogen-nitrogen gas mixture. α
-^1203 Kirelya forms a chemical bond with nickel on the carrier surface only at relatively high temperatures -24- Therefore, the following two methods are suitable for creating a chemical bond between α-At203 and old. There is.

(+) The heterogenization reaction of cyanate is carried out at a temperature below 60° to homogeneously precipitate 10011 on alumina.
, dried, fired at 850-950°C, and then heated to about 450°C.
How to reduce at ℃.

(Ii) A method in which the pl+ of the Ni2+ solution in which α-AI203 is dispersed is set to 3 or less, a homogeneous precipitate is obtained using urea, and this is used to perform the same treatment as in (1) below.

In the method for producing methane-rich gas of the present invention, the number of hydrocarbons in the supplied gas is 2 to 16 carbon atoms per molecule.

The temperature of the feed gas at the beginning of the catalyst bed is between 300 and 38
The temperature is maintained at 0°C, preferably between 320 and 350°C.

If a mixture of methanol and steam is fed to the catalyst bed, the mixture contains less than 0.8 mole, preferably less than 0.2 mole, of water vapor per mole of methanol. The temperature of introduction into the catalyst bed is kept between 150 and 500°C, preferably between 200 and 250°C.

Temperature adjustment on the catalyst bed is 150-300°C, preferably 2
A hydrogen-containing gas in an amount of 00 to 250° C. may be added to the feed gas.

Methanol has a wide range of hydrocarbons present in the feed gas. In practical operation, in many cases more than 0.05 mole per mole of carbon hydrogen in the feed gas.
Preferably more than 0.2 mol of methanol is present. Alternatively, the feed gas may be essentially free of hydrocarbons and may be composed of methanol and steam. In that case, the amount of water vapor per liter of methanol is less than 0.8, preferably less than 0.2. In the absence of methanol, the ratio of water vapor to hydrocarbons is 1.35 or more, expressed as moles per mole of carbon atoms in the hydrocarbons.
It is preferably 1.3 or less, more preferably 1.21 or less. This ratio is 0.8 or more, preferably 0.9L! J
It is particularly preferably a power of 1 or more and a power of 11.

Since the nickel particles need to be chemically bonded independently to the carrier V, a material with a large specific surface area and high reactivity must not be used as the carrier A7. The maximum loading of chemically bound nickel depends on the reactivity and specific area of the carrier.

In the present invention, the old/5in2 catalyst can be particularly preferably used.

The presence of an interfacial layer containing nickel ions attached to the active catalyst can be confirmed by several methods. The normal oxidation state of nickel in this type of catalyst is that of nickel ( ).According to the first method, the total nickel content in the catalyst is first determined, for example by atomic absorption spectrometry, and then the The amount of metallic nickel per unit weight is found by measuring the saturation magnetization of the catalyst sample.Saturation magnetization directly indicates the amount of metallic nickel present.The difference between the total amount of nickel and the amount of metallic nickel indicates the amount of nickel present in the interfacial layer in the form of old (II) ions.

Ni exists as nickel ions in the interface layer 27
- Another way to check the hydrogen content is to touch it in an atmosphere containing hydrogen. 1IIt Chen Zuo tl! 11 while reducing the catalyst precursor in degrees! There are ways to measure the amount of hydrogen consumed. Next, the amount of hydrogen required for complete reduction of all the nickel ions present is compared with the amount of hydrogen consumed.

From the difference between these values, the amount of N1 (1) ions is calculated by 1J.

The third method for confirming the presence of N1 (Ill ions) in the active catalyst is to measure the weight increase when a catalyst sample that has been reduced in advance in the reduction process (f) is oxidized again in an atmosphere containing oxygen. If some of the nickel is present in the form of old fl[) ions in the interfacial layer after reduction, the weight increase due to the incorporation of 02 during the re-oxidation is due to the total nickel content after reduction. is smaller than when it is reduced. In order to compare the actual increase in weight with the theoretical increase in the amount of nickel derived from the total amount of nickel in the sample.
f) Information on the amount of nickel present as ions can be obtained.

-28 The catalyst used in the present invention contains nickel ions in the interfacial layer at least 5% by weight, preferably at least 10% by weight, particularly preferably at least 20% by weight of the total amount of nickel in the catalyst. The upper limit is 60% by weight, preferably 50% by weight, particularly preferably 40% by weight.

Two methods have been shown above to create a strong interaction between the nickel particles and the carrier material. One method is to use a carrier that is to be partially reduced. The compounds or metal atoms produced in the reduction of the carrier exhibit strong interactions with both the nickel particles and the carrier. Such carriers include, for example, TiO2. When heated in a reducing gas, TiO2 is reduced to TiOx oxide (x is less than 2). If the nickel particles adhere uniformly and intimately to the surface of the carrier, the reduced oxide at the interface of the nickel particles ensures a strong bond of the nickel particles to the carrier. Catalyst is Fn-A-234
Impregnation, drying, as described in US Pat.
If subsequently produced by pretreatment, the active ingredient is distributed only non-uniformly on the support L. Moreover, especially when an attempt is made to increase the amount of support, the result is grape-like clusters, and only a portion of them is chemically bonded to the support. Part J: The interaction between the "dangly" particles and the support is small even after reduction. Therefore FR-
Catalysts prepared by the method described in No. A-2347326 are unsuitable for the process of the present invention.

The presence of partially reduced carrier under reducing reaction conditions can be confirmed in two ways in active catalysts.

The first method determines the metallic nickel content of the catalyst by measuring the saturation magnetization of a previously reduced sample of known weight. The sample is then re-oxidized in an oxygen-containing atmosphere and at the same time the weight gain due to oxidation of the metallic nickel and, if partially reduced, the carrier is measured. The degree of reduction of the support can be calculated by comparing the actual weight increase with the weight increase estimated from the oxidation of metallic nickel alone. In the catalysts used in the present invention, the weight gain during oxidation should be at least 10%, preferably at least 20%, greater than the increase caused exclusively by oxidation of metallic nickel.

An alternative method for measuring the degree of reduction of the carrier is to measure the amount of H2 consumed during the reduction of a completely re-oxidized catalyst at the temperatures used in the process of the invention in a hydrogen-containing atmosphere. be.

The measured 2 consumption is compared to the amount of 2 required to produce the amount of nickel that is ultimately present as metallic nickel particles in the reduced catalyst. The amount of metallic nickel in the catalyst is calculated from the measured value of saturation magnetization as described above. The degree of reduction of the support can be determined from the difference between the actually measured H21 and the amount of 2 required only to reduce nickel in the oxide form.

In the catalyst used in the present invention, the amount of 112 consumed during the reduction of the catalyst is required only for the reduction of the nickel oxide. Should.

The particle size distribution of nickel particles can be examined using an electron microscope.
A faster and more accurate method is to use magnetism.

Magnetization is measured as a function of magnetic field strength and particle size distribution is calculated by reproducing the experimental curve of magnetization. This curve shows a clear particle size distribution, which is consistent with that determined by electron microscopy.

The method of the present invention is carried out as follows.

The equipment used consists of the following three sections.

1st section: Hydrocarbons are reacted with hydrogen at 300-400° C. in a cobalt-molybdate catalyst fixed bed reactor to convert the organic sulfur compounds present to hydrogen sulfide.

Second section: Sulfur produced in the zinc oxide bed in a fixed bed reactor -32
- Absorption of hydrogen chloride at 300-350°C. Hydrogen sulfide is converted to water vapor in this section.

Third section: This section is the actual low temperature reforming section, where steam and optionally hydrogen-containing gas are added to the treated hydrocarbon feed gas and a fixed bed reaction packed with the catalyst of the present invention. Guided by the vessel, add another 300 to 450 as appropriate.
℃ preheated to produce methane-rich gas. This product gas is subjected to further processing.

Typical product gas compositions are shown in the literature. It is also possible to realize a low-temperature reforming process using divided catalyst beds as described in DE-A-2314804. Similarly, the method described in EP-8-0028835 may also be embodied in the present invention. A further advantage of the method of the invention is that ML-^-82
As can be concluded from the disclosure of specification No. 00544,
Comparatively low in the first step of the method described in EP-A-0028835.

It also works with gases with a H2/CO ratio.

Regarding the method, Fe2O3/8 instead of the oxide bent bed
The use of 102 is described in No. 0 [-8-3131257 and DE-A-3228481 in each of the Mei I11 areas.

The major advantage of this method is that it can be regenerated, unlike ZnO, which must be discarded after use, and it also satisfies the final concentration of sulfuric acid on the order of parts per million (PPM) required for the next stage of reforming. The primary advantage is that heavy oil J: achieves great economic benefits when using feedstocks with relatively high sulfur content. In addition, when using methanol that does not contain hydrocarbons as a raw material in the present invention, since no sulfide exists in methanol, the step of converting it to hydrogen sulfide and the step of absorbing it with zinc oxide can be omitted. . Other conditions are the same as those in the prior art, so further explanation will be omitted.

As a result of research by the present inventors, it has been found that when a nickel catalyst is used for the conversion of methanol or hydrocarbons, deactivation of the catalyst is caused by carbon formed between the nickel particles and the carrier. This carbon grows in the form of fibers (so-called whiskers) and pushes the nickel particles out of the carrier. This phenomenon does not occur if the nickel particles are chemically bonded to the carrier.

According to the invention, the catalyst may contain small amounts of chemically unbound nickel particles, but the amount should not exceed 50 mg, preferably 30 mg, particularly preferably 10 n+g per cm3 of reactor volume. If the amount of unbound nickel particles exceeds the above,
The catalyst bed gradually becomes clogged due to the growth of carbon whiskers.

It has been found that large nickel particles with a particle size of about 1100 nm are slowly deactivated under the reaction conditions described above. Such large-sized nickel particles contain grain boundaries. Carbon adheres to such grain boundaries and destroys the particles [Carbon J, 601~
611 (1972). The growth of carbon whiskers continues even after the nickel particles are broken up, ultimately resulting in clogging of the warper. On the other hand, 30r+n+
Nickel particles with a particle size smaller than 100% generally do not contain grain boundaries. Grain boundary induced carbon whisker growth therefore does not occur with such small grain sizes.

- Therefore, the catalyst should be essentially free of particles with a size greater than 30 nm.

There is no significant change in the particle size distribution of nickel particles even if carbon is intentionally deposited on the catalyst used in the present invention by passing pure CO at 275°C and then heated at 450°C in a hydrogen stream to remove carbon. This proves that no carbon is attached between the nickel particles and the carrier.

In contrast, in conventional regenerated catalysts with carbon deposited between the nickel particles and the carrier, larger nickel particles were formed than those present in the original catalyst.

In the present invention, first, all metallic nickel particles must be chemically bonded to carrier particles. If the appropriate amount of metallic nickel-36 particles is not chemically bonded to the carrier,
These "battery nickel particles form carbon whiskers, deactivate the catalyst, and clog the reactor."

The relative amount of particles bound to the carrier through the interfacial layer can be determined in three ways.

(1) Using an electron microscope, count the number of metallic nickel particles per gram of catalyst in a sample of the reduced active catalyst and examine the particle size. A similar sample is treated with pure CO gas at 60-100° C. under ambient atmosphere until all metallic nickel is removed from the catalyst by forming Ni(CO) 4 gas. As a result, only ionic nickel contained in the interface layer in the catalyst is present. Then, using an electron microscope, catalyst 1
Count the number of interfacial layers with approximately the same surface dimensions as the original metallic nickel particles per g.

In the present invention, the number of interfacial layers should essentially match the number of initial metallic nickel particles. From the difference between the number of metallic nickel particles and the number of interfacial layers, the "free" or dangling nickel particles and the heavy explosion of dangling metallic nickel particles are calculated.

(2) A sample of the reduced activated catalyst was heated to 400'C at normal pressure.
k-T 10-60vgml mixed waste (N290%, C
o 10%). The sample is cooled and passivated. Next, the presence or absence of carbon whisker formation is observed using an electron microscope to determine whether the catalyst is suitable as a catalyst in the present invention. Since carbon blinkers are formed only on "dangling" metallic nickel particles that are not bonded to a carrier, the amount of unbonded particles per gram of catalyst can be determined.

(3) If the carrier material is a partially reducible oxide of the basic element, unbound nickel particles can be determined quantitatively by means of electron microscopy.

The catalyst produced according to the specification of February 0E-C-176720 may be used for reforming hydrocarbons using steam and, if appropriate, methanol, or for reforming methanol directly or using steam, as appropriate. Its use as a catalyst for conversion is not taught. However, surprisingly, when these catalysts are used,
Catalyst deactivation and carbon deposition are greatly reduced compared to conventional catalysts. The noticeable formation of unreduced nickel atoms is generally considered undesirable since nickel is the active ingredient.

What is even more surprising is that even though the ratio of water vapor to hydrocarbons is within the range that thermodynamically produces carbon deposits,
The catalyst should not be deactivated.

Even under conditions where carbon deposition is unavoidable, the catalysts of the present invention have another notable property: they can be "regenerated" or "reactivated" by oxygen and then by hydrogen.

This is particularly noteworthy in view of the inability of conventional reforming catalysts to be regenerated, and clearly provides a significant technical advantage.

Since the catalyst of the present invention is difficult to form carbon, the number of moles of water vapor per carbon atom in the hydrocarbons in low-temperature reforming of hydrocarbons is less than 0.9, generally less than 0.8. , and even less than 0.7. In conventional methods, the ratio of water vapor to carbon atoms is often greater than 1.2 (mol/atom), since catalyst deactivation progresses rapidly when the ratio of water vapor to carbon atoms is low.

By being able to reduce the ratio of steam to hydrocarbons, the catalyst volume can be reduced, and as a result, the reactor can be made smaller for the same space velocity.

It is also surprising that the catalyst of the present invention does not cause measurable deactivation of the catalyst over a period of 500 to 1000 hours when converting methanol directly without using steam. This provides great flexibility in the feedstock that can be used for methane production processes from liquid feedstocks.

-40- Another interesting phenomenon is the high catalytic activity at low temperatures. While conventional commercially available catalysts for steam reforming of hydrocarbons are active at temperatures above 350°C, often above 400°C, the catalyst of the present invention is already fairly active at 300°C.

This is illustrated in the examples.

A further advantageous property of the catalyst according to the invention is that the activation operation, ie the reduction of the previously reduced and passivated catalyst with hydrogen, is not very dangerous. Activation takes place with a gas having a relatively high temperature and high hydrogen partial pressure. This clearly shows that the step −
Up time can be reduced. This activation procedure is illustrated in Example 2.

EP-A-0028835 describes a two-step process for producing methane. In the first step, a gas mixture containing 25-90% by volume hydrogen along with carbon monoxide and carbon dioxide is passed through a nickel catalyst at 250-550°C to produce a methane-rich gas. A nickel catalyst with alumina as oxide carrier as described in DE-C-1767202 can be used in this process.

However, that method is not an embodiment of the method of the present invention. This is because the method does not yield a catalyst with chemically bound nickel. This requires the specific manufacturing operations mentioned above. Also EP-A
Adding a hydrogen-rich gas to the gas fed to the reactor, as described in US Pat. No. 0,028,835, will reduce catalyst deactivation. Although the catalyst of the present invention has significantly reduced deactivation due to carbon adhesion compared to conventional catalysts, the use of hydrogen-rich gas or hydrogen-containing gas in general has attracted attention from a technical perspective. It is something that The advantages of the catalyst of the present invention also exist in such cases. That is, in the catalyst bed, due to the exothermic heat generated by the hydrogenation reaction due to the hydrogen present, a digastomia occurs at temperatures of up to 200° C. or even 300° C. For example, if the catalyst bed inlet temperature is 350°C, the reactor outlet temperature will be 550°C, and if the catalyst bed inlet temperature is 300°C, the reactor outlet temperature will reach 600°C.

The present invention further provides a method for producing a methane-rich gas by converting a mixture of hydrocarbons and water vapor, a mixture of hydrocarbons and water vapor, a mixture of methanol and water vapor, or methanol. This is a regeneration method in which the nickel catalyst is a catalyst in which metallic nickel particles are chemically bonded to a thermally stable oxide carrier. a step of stopping the supply of the gas mixture while leaving behind the spent catalyst which has lost its content; (C) burning off carbon deposits by supplying oxygen-containing gas to the reactor and limiting the maximum temperature in the reactor to 600°C; Until no oxygen remains -43
- A step of purifying the reactor with an inert gas, preferably nitrogen gas, and a step of reducing the catalyst with hydrogen gas at a temperature of 200 to 450°C to bring it into an active state. The present invention relates to a method for regenerating a nickel catalyst characterized by regenerating it.

The maximum temperature in step (C) is preferably 550°C, particularly 500°C.

Furthermore, the present invention relates to a regenerated nickel catalyst obtained by regenerating a nickel catalyst in the method described above, and also to the use of the regenerated nickel catalyst in the method for producing a methane-rich gas.
Ru.

Preferred parameters of operation in the regeneration method are shown below.

Preferably, purification is carried out using nitrogen gas at ambient temperature. During the purification process the temperature inside the reactor decreases. A nitrogen stream containing 0.01 to 1% oxygen, preferably about 1%, is then fed to the reactor at about ambient temperature to (partially) passivate the catalyst. To avoid hotspots due to oxidation reactions, the oxygen concentration is gradually increased up to a maximum of 20% (equivalent to air). The temperature inside the reactor should always be kept below 600°C, preferably below 500°C.

It is then purified again with nitrogen gas to remove any oxygen present, followed by a reactivation operation that is essentially the same as the initial activation of the catalyst using hydrogen-containing gas. The operation is preferably carried out at 200-450°C, particularly at 400-450°C.

Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Production example 1 Ni (NOs) 2 6H2043,6(1(
Metallic nickel a, ag) with a specific surface of 380 x/g 5
i02 (Aerosil manufactured by Degussa) 9. OQ was dissolved in water 1j in which it was dispersed. After stirring the suspension vigorously, the temperature was raised to 90° C. and nitric acid was added dropwise to acidify the suspension to a pH of 2.

Then, when 27.0Q of urea is added and the pH is gradually raised, nickel is deposited on the silica in the form of oxide and/or hydroxide. did. The supported carrier is separated from the liquid, dried at 120°C, compressed into pellets, and
．． Cut into pieces ranging from 5 to 2.5 +++ m. The catalyst pieces were dehydrated at 450°C in a stream of nitrogen and then in a stream of argon gas containing 10% hydrogen for at least 8 hours.
Restored for 0 hours.

The obtained catalyst was heated at 450°C before being used in the next example.
The mixture was treated in a nitrogen stream for 2 hours to remove absorbed hydrogen. The particle size distribution of the nickel particles of the obtained catalyst is not shown in Table 1.

[Margin below]

Table 1-47- Preparation Example 2 This preparation concerns the activation of a so-called passivated catalyst. Catalysts containing metals as active components are generally obtained from manufacturers in so-called passivated form. This involves first reducing the catalyst completely to form the active metal and then, for example, diluted air or CO
2 to form a very thin oxide layer that coats the metal particles and prevents further oxidation. Therefore, although the reduced catalyst is generally susceptible to ignition in air due to the presence of tight and small metal particles, it is easy to handle and transport. Catalysts in their reduced state are difficult to handle and expensive.

The simple catalyst obtained in Example 1 was held at 400°C for 5 hours to completely remove the hydrogen absorbed from the nickel surface. The nickel surface area was then measured by hydrogen absorption at 30°C.

At hydrogen pressure of 40kPa, intake of 112 is 25#+1!1
lzSTP10 was old. The catalyst was then heated to 400°C to remove hydrogen, and then heated to 0.5% 0.5% at room temperature. airflow passed through. During that time, the temperature was raised from 75°C to 300°C over 3 hours. The catalyst was then heated at 300°C under a reducing atmosphere for an additional 3
Saved time. After carrying out the above-mentioned discharge treatment for the absorbed hydrogen, the amount of hydrogen taken in was measured at 30° C. and a hydrogen pressure of 40 kPa and found to be 25me 1123TP/g old. This indicates that the original nickel surface area is still usable after 6 hours of reactivation treatment.

Example 1 A cylindrical reaction tube made of stainless steel was filled with the pretreated catalyst sample prepared in Preparation Example 1 to prepare a catalyst bed. The catalyst bed had a diameter of 1.8α and a height of 6.3 g of reduced nickel. Before introducing the reaction mixture gas consisting of 14.3% and 8285.7% C4■1o into the reactor, water in an amount of 6°7% mol/min was added to the mixed gas in a preheater kept at 450°C. Added (1120/C=
0.8). The inlet temperature of the reactor was maintained at 400°C.

The space velocity inside the reactor was 700/hour at atmospheric pressure.

A pressure drop of 1-+ across the catalyst bed was constantly recorded to monitor catalyst clogging due to carbon deposition. The experiment was conducted continuously for about 10 hours.

The composition of the gas obtained was Cl1431. '1%, C027
,4%,COo,2%,112 2.5%,++211
(Mainly condensed and could not be quantified) Oagebi N2
Met. This composition remained constant throughout the experiment and did not contain butane. No pressure drop was observed during the experiment. This indicates that fibrous carbon adhesion was not formed and the catalyst was damaged.

At the end of the experiment, the reactor temperature was lowered to 350° C. for 4 hours. Complete conversion of butane was achieved at this temperature. The composition of the generated gas is C11432, 4%, CO27
,3%, CO0,06%, 1121.3%, 1120(
They were mainly condensed and could not be quantified) and N2. After 4 hours of contact, the humidity is further increased from 350℃ to 300℃.
lowered to Butane conversion was only reduced by 6%. 3
After holding at 00°C for 2 hours, the temperature was raised to 350°C.

Although the butane was completely converted before the temperature was lowered to 300°C, the conversion rate was only 50%, which gradually decreased to about 40% after 18 hours. Then up to 400℃? When increasing 1 lJt, the conversion rate increased to 96%. After 72 hours at 400° C., the experiment was stopped and the used catalyst was subjected to the regeneration process described in Example 2.

Example 2 The experimental sample performed in Example 1 was regenerated according to the following procedure.

The catalyst sample was cooled to 25° C. in a nitrogen stream.

The catalyst was then passivated in a gas mixture consisting of approximately 0.02% and 8299.5%. This thing 0220%
and 25°C at a heating rate of 50°C/hour in an air flow of 80% N2.
It was heated from .degree. C. to 450.degree. C. to burn off carbon from the nickel surface. The temperature was kept constant at 450°C for 5 hours and N2
The catalyst was cooled to 100°C in a stream of air. Then 8210%
Then, the temperature was raised to 450°C again in a 90% N2 stream at a rate of 50°C/
I gave -51- in hours.

IC kept at 450°C for 16 hours in the above +12-82 gas
Thereafter, absorbed hydrogen was removed by treatment at 450° C. for 2 hours in a N2 stream. Immediately thereafter, the experiment described in Example 3 was performed.

Example 3 A catalyst sample regenerated in Example 2 was treated with the same reaction mixture as in Example 1 (14.3% C4I+ 10 and 85.7%
% N2 plus 6.7% mole 1120). The reactor inlet thirst mark is 35
It was kept at 0°C. The space velocity in the 43.2ciu reactor was between 700/M at atmospheric pressure. The composition of the generated gas is 5
The quantity of the experiment over 0 hours did not change and butane contained /υ
(t120/C ratio was 0.8).

In Example 1, the butane conversion at 350°C was only 40% before regeneration. The absence of butane in the regenerated catalyst product gas indicates that the treatment performed in Example 2 is effective. The composition of the produced gas is
CI+432.4%, -52-CO27.3%, Co 0.06%, 82 1.3
%, N2 0 (mainly condensed and could not be quantified) and N2.

During the approximately 260 hours of processing in Examples 1 to 3,
The pressure drop was almost negligible. This shows that there was no noticeable carbon adhesion.

Example 4 A 50% by weight Ni-8in2 catalyst was produced in the same manner as in Example 1. This catalyst was immediately heated in air at 120°C for 2 hours.
Dry for 4 hours and compress into tablet form (1500ko/c
m2) L, , granulation was performed and pellets with a size of 0.15 to 0.30 mm were sieved. This thing 02 10%
Calcined at 450°C for 16 hours in a hydrogen stream containing 10% N2, and then fired at 450°C for 7 hours in an argon gas stream containing 10% N2.
It lasted for over 2 hours. The average diameter of the nickel particles in the obtained catalyst was 6% m.

2.0 d of this catalyst was packed into a cylindrical quartz reactor with a diameter of 1.0 cm. The catalyst bed contained 0.52 liters of nickel, which was about 4511+2 liters of nickel exposed to the gas phase.

Nitrogen gas containing 7% methanol by volume at a space velocity of 175
0/hour feed 1 tube to the reactor:. After steady state was reached (typically within 15 minutes), the composition of the product gas was monitored by gas chromatography for at least 3 hours. The steady-state fluctuations in the produced gas composition were within 1%. Other components except water were measured directly. Water was sieved for mass balance.

J shown in FIG. 1: Before 367°C, the produced gas composition is equal to equilibrium within experimental error (approximately 2%). The small discrepancy in the IJ in the low temperature region is due to the incomplete hydrogenation reaction of carbon monoxide at the above space velocity. Other compounds not shown in Figure 1, such as methanol, ethanol, etc., were not detected at concentrations above 10 ppH1.

In another experiment, a steady state composition of 329° C. could be maintained for more than 40 hours. Further operation at various temperatures up to 447°C for about 100 hours and then back to 309°C did not change the performance of the initial catalyst given the exit gas composition shown in FIG.

Example 5 The same reactor and catalyst used in Example 4 were used.

Nitrogen gas containing 5.5% methanol by volume and 10% hydrogen by volume was fed into the reactor containing the 2 m catalyst at a space velocity of 1750/hour.

Even when hydrogen was added, the composition of the gas produced from the reactor reached an equilibrium state at temperatures above 368°C, as shown in Figure 2. Small differences in the low temperature range are
This is considered to be because hydrogenation of carbon monoxide was incomplete at the space velocity used in the same manner as in Example 4.

Example 6 The catalyst prepared by the method of Preparation Example 1 and pretreated was prepared in Example 1.
It was filled into the reactor used in .

The catalyst contained 5.6 g of metallic nickel.

-55- This catalyst was used at a reactor inlet temperature of 400°C to produce Ca 1110
(2,1m1Ilole/m1n), +120 (water vapor, 11,2mmol e/m1n) and 82 (
12,41+mole/m1n). The ratio of water vapor to carbon atoms was 1.35. The space velocity was approximately 150/hour at atmospheric pressure. The absolute pressure inside the reactor was 120 kPa. During the experiment, the temperature in the height direction in the catalyst bed was measured at each of nine equal positions along the axis of the reactor. Furthermore, in order to confirm whether or not the reactor was clogged due to adhesion of Ill-shaped carbon, the pressure drop as it passed through the catalyst bed was continuously recorded.

After much of the unreacted water is condensed, the structure of the gas produced after one cycle is CI1, 131.3%, CO2, 7.6%, N2.
3.7%, Co 0.07%, +120 (predominantly condensed and not quantifiable) and N2, butane was completely converted. During the 450 hour experiment, there were no notable changes in the temperature regime across the height of the catalyst bed. Furthermore, the pressure drop in the reactor at the end of the experiment was negligible. This shows that the reactor was not clogged due to carbon adhering to the catalyst. This conclusion was confirmed by the fact that when the used catalyst was observed under an electron microscope, no string-like carbon was present at all.

Example 7 The catalyst prepared by the method of Preparation Example 1 and pretreated was prepared in Example 1.
It was filled into the reactor used in .

This catalyst contained 5.1 g of metallic nickel. This catalyst was heated at 400℃ to C4 old O(18,61nlllOI
/m1n), 820 (12,2mmole/m1n)
and N2 (12,4 mmole/m1n).

The space velocity was approximately 1100/hour at atmospheric pressure. The butane addition rate was initially 50%, but it rapidly decreased to 7.
After 0 hours, it was less than 10%. Apparently, this phenomenon is due to the fact that the activity of the catalyst decreases when the ratio of water vapor to carbon atoms is 0.1.
6, which shows that it is not possible to fully counter the extremely small case. During this experiment, the experiment was stopped after 75 hours and the IC5
No increase in pressure drop was observed. This phenomenon is not observed with other catalysts. This is because in the absence of water vapor or in the presence of very little water vapor, sulfur is rapidly deposited on the nickel catalyst in an atmosphere of hydrocarbons.
This is because it is known that bongs adhere to the reactor and clog the reactor within a few hours. Note that when the catalyst used in the above experiment was observed using an electron microscope, it was found that a very small amount of fibrous carbon of about 10 nm was formed.

As described in Example 8 below, the deactivated catalyst of the present invention is treated in air at elevated temperatures to re-establish its initial activity. You can go back 1.

In this type of process, product gas is continuously removed and the equipment is operated to collect thousands of hours' worth of product gas.

Incidentally, an emergency situation may occur due to a sudden stop of the supply of steam, and an emergency treatment system is incorporated into the equipment in preparation for such an event. In this operation, catalyst performance is of great importance. Therefore, if the catalyst is highly susceptible to carbon deposits, it will be severely damaged in such an emergency situation. Therefore, the emergency handling system is very precisely designed. However, in cases such as the catalyst of the present invention, where carbon deposition does not occur rapidly on the catalyst in an emergency situation such as the one described above, and therefore the emergency situation does not require a very rapid response, the emergency treatment system may not be as strict. There is no need to make it a thing,
Therefore, equipment costs can be reduced.

Example 8 The catalyst prepared by the method of Preparation Example 1 and pretreated was prepared in Example 1.
It was filled into the reactor used in .

The catalyst contained 5.0 g of metallic nickel. The inlet ml of the reactor was set to 400°C, and Ca 1110 (1
8,6 mmol/1n), thO (12,2 mmol
e/m1n) and 82 (12,4R1111Ole
/m1n). The ratio of water vapor to carbon atoms was 0.85. The space velocity was -59 - about 730/hour at atmospheric pressure. During the experiment, the temperature in the height direction in the catalyst bed was measured at each of nine equal positions along the axis of the reactor. Furthermore, in order to determine whether or not the reactor was clogged due to deposition of Ill-shaped carbon, the pressure drop when passing through the catalyst bed was continuously recorded.

After condensing most of the unreacted water, the structure of the generated gas is CI + 459.4%, CO2 13.6%, 112
6.6%, Co 0.07%, 1120 (mainly condensed and could not be determined) and N2. Note that butane was completely converted. The reaction zone gradually passed through the catalyst bed due to the change in moisture content in the catalyst bed. Obviously the activity of the catalyst was steadily decreasing. Due to this catalyst deactivation, a very small amount of butane was mixed in the generated gas after about 200 hours. Upon intercalation of 5501Fj, butane conversion decreased to 42%. On the other hand, no increase in pressure drop in the catalyst bed was observed, indicating that no fibrous carbon was deposited. Therefore, the gradual decrease in catalytic activity is believed to be due to the deposition of carbonaceous material that poisons the Ni 60-nickel surface but is not fibrous.

Reactivation of this partially deactivated catalyst was carried out by treatment in air at elevated temperatures and reactivation by a reduction step. The reactivation was carried out using the passivation, oxidation and re-reduction treatments in Example 2 as they were.

Then, when a reaction mixture gas having the same composition as above was passed through the regenerated catalyst under the same conditions, it was confirmed that the butane was completely converted. Even after an additional 200 hours of reaction, the butane was completely converted. The catalyst was then deactivated by incompletely increasing the partial pressure of butane for several hours. This deactivated catalyst was reactivated again by the same treatment as above. Then, when a reaction mixture gas having the above composition was passed through the catalyst bed, there was almost no change in the temperature state of the catalyst bed even after 200 hours had passed. After that, it was found that the catalyst gradually became deactivated due to changes in temperature within the catalyst bed.

The experiment was stopped after about 400 hours, but even at that point the conversion rate of butane was still over 99.9%. The pressure in the catalyst bed remained unchanged at the beginning of the experiment, indicating that there was no deposition of fibrous carbon.

[Brief explanation of drawings]

FIGS. 1 and 2 are graphs showing changes in composition with respect to temperature of the produced gases obtained in Examples 4 and 5, respectively. Patent Applicant Behehehe Hujins Temperature ('C) - FIG, 1 Continued from Page 1 0 Inventor Vinicil Klaas Ora: De Boxt, / Kingdom of N.L.-3523 Sewage Utrechijaderan 76

Claims (1)

[Scope of Claims] 1. A mixture of hydrocarbons and steam, a mixture of hydrocarbons, steam, and methanol, a mixture of methanol and steam, or methanol as a nickel catalyst on a thermally stable oxide carrier. A method for producing a methane-rich gas by converting it into a methane-rich gas, characterized in that metallic nickel particles are chemically bonded to the heat-stable oxide main oxide A7. A method of producing rich gas. 2. The method according to claim 1, wherein the carrier is an oxide of at least one element selected from the group consisting of silicon, aluminum and magnesium. 3. The method according to claim 1, wherein the carrier is 8102. 4. The method according to claim 1, wherein the carrier is ^12o3 or H (70). 5.
5. A process according to claim 1, 2, 3 or 4, wherein more than 0.5 moles of methanol are present, preferably more than 0.2 moles of methanol. 6 the supplied mixture is essentially free of hydrocarbons;
Consists of methanol and water vapor, water vapor is methanol 1
5. A method according to claim 1, 2, 3 or 4, wherein the amount is less than 0.8 mol per mole, preferably less than 0.2 mol. 7 The number of moles of water vapor in the supplied mixture is 1.35 or less, preferably 1.35 or less per mole of carbon atoms of hydrocarbons.
．． 7. The method as claimed in claim 1, 2, 3, 4, 5 or 6, wherein the temperature is less than or equal to 3, particularly preferably less than or equal to 1.2. 8 The number of moles of water vapor in the supplied mixture is 0.8 or more per mole of carbon atoms of hydrocarbons -1 preferably 0
．． 9 or more, particularly preferably 1 or more.
The method described in section. 9 The nickel catalyst is prepared by mixing (a) an aqueous solution of a nickel salt and an aqueous solution of a salt of a basic element for carrier formation, and the nickel ions and ions of the basic element that have dissolved pl+ in the mixed solution are precipitated. level and, if necessary, remove the precipitate in the solution by 2 L-
If necessary, the solid obtained is treated with hot water, dried and calcined.The nickel salt solution and its oxide are the heat-stable oxide carriers. A solution of the salt of MW Motosaku is mixed with an aqueous solution of sikolic acid sprue or formic acid ester in an aqueous WG, the precipitate is separated, dried 1 time, calcined and reduced, or
(C) A fine powder of a thermally stable oxide carrier (v) is suspended in a dilute solution of a nickel salt, and if a nickel compound is required, the stirred suspension is stirred vigorously at an elevated temperature. Hydroxide ions are formed either by subsurface implantation of hydroxide ions or by chemical reactions known per se of compounds contained in the solution in an amount of 1 to 10 times the stoichiometrically required amount. The supported carrier may be reduced by precipitation, followed by separation, drying, calcination, or (by introducing a nickel salt solution below the surface of a suspension of a small heat-stable oxide carrier; Claims 1 and 2 are produced by maintaining the p++ of the suspension at 4 to 7, separating, drying, calcining, and reducing the supported carrier.
8. The method according to paragraph 3, paragraph 4, paragraph 5, paragraph 6, paragraph 7, or paragraph 8. 10 Nickel catalyst used in a method for producing methane-rich gas by conversion of a mixture of hydrocarbons and steam, a mixture of hydrocarbons, steam, and methanol, a mixture of methanol and steam, or methanol conversion A regeneration method in which the nickel catalyst is a catalyst in which metal 11 nickel particles are chemically bonded to a thermally stable oxide carrier 17, and the catalyst is (a) The feed of the gas mixture is continued until there is essentially no feed gas mixture or reaction product gas remaining in the reactor (culm, mountain), leaving the catalyst in the used stream that has lost its initial activity. a step of purifying the reactor with a gas, preferably nitrogen gas; (C) supplying a Myk-containing gas to the reactor and burning carbon 44 to limit the maximum temperature in the reactor to 600°C; J culm, (two culms, purify the reactor with an inert gas, preferably nitrogen gas until no oxygen remains woody in the small reactor, and catalyzed by hydrogen gas at a temperature of te 1200-450 ° C. -4- A method for regenerating a nickel catalyst, characterized in that the carrier is regenerated by carrying out a step of reducing and bringing it into an active state.11 The carrier is at least one selected from the group consisting of silicon, aluminum and magnesium. 12. The method of claim 10, wherein the carrier is an oxide of an element. 12. The method of claim 10, wherein the carrier is 5in2.
The method described in section. 13. A method according to claim 10, wherein the carrier is Al103 or H (10). Raise the pH of the solution to a level at which dissolved nickel ions and basic element ions precipitate, age the precipitates in the solution if necessary, and treat the resulting solids with hot water if necessary. Immediately,
drying, calcining and reducing; Mix, remove the precipitate, dry, calcinate, reduce or
A fine powder of the thermally stable oxide Te3 and A7 was suspended in a dilute solution of nickel salt. If necessary, the nickel compound is stirred at an elevated temperature with vigorous stirring. Inject 1J of hydroxide ions below the liquid surface or [,1
．． 1 to 10 times the stoichiometrically required concentration is precipitated by a chemical reaction known per se of the compounds contained in the solution, avoiding the formation of hydroxide ions, followed by separation and drying. Then, calcination (), 1-holding: 1-reducing yarya, or mako (low heat-stable oxide carrier lli!) Introducing a nickel salt solution below the surface of the suspension, The pl+ of the suspension is 4-7
Claim No. 10, which is produced by supporting, separating, drying, baking, and adding jq parts of the carrier leaf.
The method according to paragraph 11, paragraph 12 or paragraph 13. 15 Mixtures of hydrocarbons and steam, mixtures of hydrocarbons, steam and methanol, mixtures of methanol and steam, or methods for producing methane-rich gases by catalytic conversion of methanol. A regenerated nickel catalyst is a catalyst in which metallic nickel particles are chemically bonded to a thermally stable oxide carrier, and the catalyst deactivated in the conversion is placed in a carbon reactor. (b) stopping the supply of the gas mixture while leaving behind the spent catalyst which has lost its original activity due to the deposition of a step of purifying the reactor with a gas, preferably nitrogen gas, (a step of burning out carbon deposits by supplying an oxygen-containing gas to the C1 reactor and limiting the maximum temperature in the reactor to 600 ° C., a small reaction React with an inert gas, preferably nitrogen gas, until essentially no oxygen remains in the reactor. A regenerated nickel catalyst characterized in that it is regenerated and reactivated by carrying out a step of reducing the catalyst and bringing it into an active state.