DE1097601B - Process for the production of activated nickel catalysts for the conversion of hydrocarbons - Google Patents

Description

GERMAN

The present invention relates to a process for the preparation of activated nickel catalysts for Transformation of hydrocarbons, in which the hydrocarbons with oxygen-containing compounds, such as B. water vapor, are treated in this way to hydrogen and carbon oxide mixtures to represent.

Process for the preparation of hydrogen and carbon dioxide by converting hydrocarbon mixtures and oxygen-containing gases are already known under the general name hydrocarbon vapor conversion process. A large number of different catalysts, commonly referred to as reforming catalysts, are made which are specifically designed for these processes. These commonly used catalysts consist of nickel compounds, such as. B. nickel oxides, nickel hydroxides and nickel carbonates, to which metal oxides are added as activating agents. Usually these activating agents are clays or magnesium compounds or pure magnesia. In addition to the catalytically active nickel compounds and activating agents, these catalysts naturally also contain inert carrier substances or binders. Experience has shown that certain metal oxides, e.g. B. Alumina and magnesium oxides, greatly increase the effectiveness of the nickel catalysts. For example, mixtures of nickel and aluminum oxide or nickel-aluminum and magnesium oxide have been used as active ingredients in the conversion catalysts. During the reshaping process, which is carried out in general at temperatures of about 65O ⁰ C, these oxides, for. B. nickel oxides, reduced to nickel metals. But on the other hand, the clays and bitter stone magnesium oxides are not reduced. The proportion of the activating agent in the catalyst can vary within the broadest limits, so that from 0.1 to 10 mol of activating agent can be used for each mol of nickel. Since the activating agents, namely magnesia and alumina, are much cheaper than nickel and nickel compounds, it is common practice to use alumina and magnesia not only as activating agents but also as a carrier material. For this reason, in the known catalyst preparation processes, the alumina and also the limestone are used in much larger quantities than the catalytic metals. Generally the catalytic metal constitutes from 10 up to 35 weight percent of the total catalyst.

Usually the commercially available hydraulic cements, e.g. B. Portland cement or calcium aluminate cement, used as a carrier and binder for these reforming catalysts. However, a method of production is preferred
of activated nickel catalysts

for forming
of hydrocarbons

Applicant:

Chemetron Corporation,
Chicago, 111. (V. St. A.)

¹ S Representative: Dr.-Ing. J. Schmidt, patent attorney,

Munich 13, Hohenzollernplatz 8

Claimed priority:
V. St. v. America January 26, 1959

Arne Eriksen, Burlingame Calif. (V. St. A.),
has been named as the inventor

Portland cement because on the one hand it is very cheap and on the other hand its use is the representation of a Catalyst body allowed, which is particularly characterized by excellent body strength and long service life excels.

The reforming catalysts according to the invention have a much higher initial reforming effect compared to known catalysts of this type and can be produced in the simplest way by using as a carrier and binding agent burned mixtures of lime and clay-like substances, in particular a mixture of limestone, clay and slate is preferred. The aforementioned limestone, clay and slate mixture is burned at firing temperatures within the limits of 1400 to 1500 ^° C., which are within the initial stage of the fusion. The finished binder is obtained in the form of a sintered agglomerate, which is usually not usable for the production of catalysts

.V would be. According to the invention, this sintered agglomerate is trimmed for the production of catalysts by is milled as it arises. The particles ready for the production of catalysts have after the grinding process the texture of wheat flour particles.

009 699/459

3 4

The binder obtained in this way represents a mixture of many properties and resistance of the finished catalyst

Metal oxides and generally has the following sators not of too great importance, one can

Composition: choose a simpler way of presentation. In this

",. , ^ _n,. , _nn ■,. , Trap all components of the mixture, the nickel-calcium oxide ... 60 up to 67 percent by weight ^ _{1 Ά} . ,,. . ...,,,. °,,
<,.,. ^{,, J} wori- · or c / - · xi j. 5 salts, the activator and the unfired

Silicates 18.5 up to 25.5 percent by weight -DJ-Xx ₁ IJ-Ji-I χ · · ■ τ_χ j

Clay 3 up to 7.5 percent by weight Bmdemrttel constituents, first thoroughly mixed, and

Limestone. 1.5 to 6 percent by weight then the entire mixture is a single combustion

τ ,. j _n - ,. he ^ · i_x χ subject. However, in the latter case it is

Iron oxide 0.5 up to 5.5 percent by weight _{,, j o} j- ri tir-j χ J ₁ r, j ■, ■

j απ "τ χ ii J j απ TJ χ I ₁ j that the high resistance and the

and alkali metal oxides or alkali earth metal oxides,. -, ' _yr .. ,, ",.,,. . ,

diV the Rpst of TVrirTniTT? ai ^ marhpTi ^{10 specific} physical activity, which one in the former

which make up the rest of the mix. _FaUe ^^ ^ _{second PaU mcM received}

With the method of the invention, the following examples make some preferred

Forming catalysts in the simplest possible way - process methods for the production of the aforementioned, provided by a nickel salt, limestone or alumina explains the reforming catalysts according to the invention, and a clay or loam binding preparation with each other 15 Using these examples it is also possible to use the be mixed. It is best to use the nickel-catalytic effect of the catalynitrates according to the invention, Nickel carbonates, nickel acetates and similar catalysts in the hydrocarbon forming process Nickel salts, which at temperatures from 370 up to 650 ° C of the catalytic effect of the already known Katalyin the corresponding oxides are converted. comparators. Therefore, in the second example

The mixture of nickel salt, limestone or clay 20 is a well-known, commercially available one for comparison purposes and the clay or loam binding preparation is shown at Tempe hydrocarbon conversion catalyst, such as Temperatures of 370 up to 650 ° C are fired until all of them become nickel salts in the usual steam forming process finds a turn completely formed into nickel oxides. A comparison between example 1 and 2 have been. The mass body obtained then gives information about the representation as well as the pulverized and with clay and limestone-containing binding properties of the catalysts according to the invention in medium and water mixed. The amount of water, compared to the properties and effectiveness which is used is dimensioned so that one of the commercially available, already known catalysts, Include a deformable slurry when mixing to provide a good basis for comparison forms, which either by ejection molding process the catalyst according to the invention in Example 1 and the can be shaped or the dried and tabletted 30 commercially available known catalyst in Example 2 can be. the same amount of active nickel.

When comparing the examples, it is immediately from example 2

Catalysts shown driving can be seen from their that the commercially available, known catalyst has a particularly high effect when carried out with steam and has a low initial effectiveness, which is characterized in hydrocarbon transformations. In these 35 forming processes it has major disadvantages. After transformation reactions, a methane loss of 4.5% is observed from the hydrocarbons, using commercially available catalysts for 5 hours, and the steam into hydrogen and carbon monoxide.
shown. After 5 hours of using the invention

The catalysts according to the invention are particularly catalysts if a loss of methane is observed in transformation processes within the temperature range of only 0.24%. Accordingly, the loss at limits of 590 up to 1090 ° C is applicable, the methane when using the commercially available catalyst body preferably "in the form of catalysts about 20 times the loss that occurs with beads, pills, tablets or in the form of through use of the catalysts of the invention can be used with ejection of pressed bodies. The same conditions occurs. In Examples 3 and 4, the catalyst bodies shown in this way are characterized by their high degree of efficiency within the broader range, with limits being shown. Thus, it is the purpose of Example 3 to determine this efficiency immediately and in the initial stage and 4 to determine the limits within which the reaction occurs, and these bodies are also catalysts according to the invention which are characterized by their long-lasting effectiveness. Has forming process.
Furthermore, these catalyst bodies have a high 50

Abrasion resistance and compressive strength, the Example 1

the abrasion resistance and pressure resistance

common and commercial catalysts of the same A mixture of 211 parts of nickel carbonate and

Kind far exceeds. The use of the calcined 820 parts of alumina was in a mill for 5 minutes Limestone-alumina substances enables the representation 55 grind until the mixture has a uniform distribution a particularly strong binder that had the invention. The finished mixture then became a solution according to catalyst bodies this excellent of 1000 parts of nitric acid nickel hexahydrate and Body properties conveyed. 200 parts of water were added and mixing ceased

The inventive method, as described above, then continued for a further 20 minutes until one requires that the nickel salts in the presence 60 first received a uniform slurry. The finished one Activating agent was fired and the slurry was then dried in a heating oven Nickel oxides are converted. These nickel oxides and after drying in a kiln at 650 ° C the ground, already fired binder is then fired for 8 hours. Added over the course of the 8-hour period. The mixing of the nickel oxides and the voltage became the nickel carbonate and the nitric acid The binder is preferably converted by a single nickel to the corresponding nickel oxides, multiple mixing process, in which all ingredients together - the finished product was then treated as a soft, be mixed. This simple mixing process enables easily pulverizable cakes to be obtained. The cake The appearance of tablets of immeasurably high levels was then cooled and put in a mill to close again Body strength, which also grinds and pulverizes the desired cataly- powder. The powdered one have a high level of effectiveness. In the event that the body material was then 774 parts of finely powdered,

added to burned binding material, which is made of limestone and clay-like materials. The resulting mixture was then made into a dough-like mass to prepare, add another 74 parts of Kentucky clay and sufficient amounts of water.

An anarytic examination of the finished binding material gave the following approximate composition values:

SiO ₂ .
Al ₂ O ₃
Fe ₂ O ₃
CaO.
MgO

23%

5.5o / _o

2.5%

66%

1%

Alkali and alkaline earth metal oxides 2%

The mixture thus obtained had a consistency sufficient for ejection molding, but too moist for that Tableting was done, and therefore it was further dried. The drying was done in the air and at carried out at normal temperature. The finished, dried mass was then tabletted, taking her before 3% graphite was added to the tabletting. When tableting, spheres with a diameter were obtained of about 3.5 cm. shown. The finished beads or tablets were then left in the air for 16 hours long dried. The dried beads were then steamed below 80 atmospheres and at temperatures treated at 816 ° C for 8 hours. Analysis of the finished catalyst showed a nickel content of 13.4%. LTm to precisely determine and establish the efficiency of the catalyst according to the invention, the extent to which the catalyst according to the invention promotes the hydrocarbon transformations with steam made the following attempts.

The catalyst tablets according to the invention prepared by the above-mentioned process were ground and then sieved so that catalyst bodies in the form of assemblies are obtained. 50 ecm of these catalyst clusters were then stored in a stainless steel reagent tube, which had a diameter of 19 mm. A desulphurised town gas, which mainly consisted of methane, was then passed through a water enrichment system, the throughput speed being 62.5 1 per Hour. The water enrichment system was set so that a steam-gas mixture was represented, in which the ratio of steam to dry gas was 3: 1. This gas-steam mixture was then passed through the reaction vessel under atmospheric pressure, so that the mixture with the catalyst body layer came in contact. During the reaction process, the reaction vessel was heated from the outside, so that the catalyst body layer was kept at a temperature of 815 ° C. After 5 hours of uninterrupted execution of this process under the above-mentioned conditions, the gas that flowed out from the catalyst layer became one Subject to analysis to measure the percentage of methane loss. The analysis showed a very low one Methane loss. The amount of methane found in the outflowing gas was only 0.24%. After the analysis the process was continued until the total process time was 56 hours. After The methane loss was again measured for a process time of 56 hours. This analysis showed that the methane loss had decreased and was only 0.19%. This analytical finding thus resulted in none further that the effectiveness of the catalyst according to the invention during the duration of its use had not been weakened.

Example 2

A catalyst was prepared by following the procedural methods as in Example 1, but on Place the calcined shale and alumina binders in place of the calcined oxides when mixed with alumina and Water instead of baked shale and calcareous binders Portland cement in equal parts added. In this way a known, commercially available catalyst was prepared. This catalyst was then checked for its effectiveness using the same procedure as in Example 1 became. After a process duration of 5 hours, the methane loss was measured and it was found that that the methane loss was 4.5%. Accordingly, the methane loss was when using commercially available Catalysts about 20 times the methane loss that occurs when using the inventive Catalysts occurred. The catalyst used in the second example was also subjected to an analysis, to determine its nickel content. It was found to contain 13.3% nickel, which is the nickel content of the catalysts according to the invention in Example 1 was the same.

Example 3

A catalyst matrix was prepared by mixing the following ingredients in one for 5 minutes Mixing mill shown:

Kentucky Ball Clay 230 g

Graphite 180 g

Fired mixture of 846 parts of nickel nitrate hexahydrate; 430 parts of nickel carbonate; 330 parts of Kentucky ball clay and 240 parts of limestone after firing

46% NiO and 22% MgO contained 4.5 kg

A calcined mixture, consisting of shale and clay, which had the following composition:
CaO 65%

SiO, 22%

Al ₂ O ₃ 6%

Fe ₂ O ₃ 3%

MgO 3%

Alkali 1%

1.5 kg

Mixing was continued for 10 minutes and about 3 liters of water was added to the mixture to make mixing easier. The finished mass was then air dried and granulated and made into rings of Molded 19mm diameter. The finished formed rings were then air dried for 3 hours, subjected to water immersion and then treated with steam under pressure of 80 atmospheres for 8 hours. To After completion of the steam treatment, the rings were fired at a temperature of 870 ° C. for 8 hours. The finished catalyst bodies obtained in this way contained 24.9% nickel and had compressive strength of 27 kg with static load. The finished catalyst bodies were then on the tested as follows: The bodies were first grated and sieved to obtain catalyst heaps with an approximate diameter of Forms 9.6 mm. 50 ecm of this catalyst body were then stored in a reaction tube, the one 19 mm in diameter.

Desulfurized town gas, which mainly consisted of methane, was then passed through a water retention system passed through and passed over the catalyst layer. In the reagent vessel were the following Maintain conditions: normal atmospheric

Pressure, the ratio of steam to gas in a 3: 1 preparation, and temperatures from 650 to 870 ° C. The hourly flow rate was kept variable within the limits of 5,000 to 10,000.

To start the reaction, nitrogen was passed into the reaction vessel. Then we switched to gas after the temperature in the reaction vessel had reached 870 ° C. The results of the course of the procedure can be seen in the following table:

Day ° c Pass
swiftly
speed 5,000
10,000 7.7
7.4 7.9
8.5
12.5 »/“ CO 15.6
14.9 % CH ₄ 0.5
4.0
6.9 5,000
10,000
5,000
5,000 7.3
7.9
12.2
13.8 17.0
15.8
10.8
6.4 0.17
2.4
5.0
10.5 5,000
10,000
5,000
5,000 6.9
7.8
11.9
13.8 18.3
16.8
11.7
6.6 0.13
2.4
4.6
10.5 at 501 / hour and 954 ° C N ₂ WithH ₂ at 501 / h and 980 ° C for 10 hours WithH ₂ at 501 / h and 954 ° C for 10 hours M. 870
870 Start with 5,000
10,000
5,000 0.6
3.7 870
870
705
650 870
870
705
650 WithH ₂ 1 , lo for hours ■ \ 870
870
704 16.3
15.8
9.7 Ι

burned limestone and 440 parts of nickel carbonate in a mixing mill until the mixture was uniform Mixture was obtained. 1285 parts of a nickel nitrate solution were then added to this mixture, which contained a Contained equivalent of 206 parts of nickel. Mixing was continued for an additional 20 minutes, and then the wet mass was dried at a temperature of 120 ° C. and for 8 hours at one temperature Fired at 540 ° C.

ίο 1000 parts of the fired material on the previously The manner described was then prepared with 50 parts of Kentucky clay and 330 parts of a binder offset, which had been made by burning slate and clay and the following composition exhibited:

CaO

SiO ₂

Al ₂ O ₃

Fe ₂ O ₃

MgO

Other meta-oxides of groups I and II
in the periodic system 0.2%

61%
21%

7%

6%

4.8%

Example 4

A nickel-limestone catalyst was prepared by adding 1090 parts of Kentucky clay, 364 parts Mixture was then milled for an additional 20 minutes while adding enough water to to obtain a semi-dry slurry. After milling, the slurry was air dried and granulated and sieved. The finished sieved mixture was added 3% graphite, and they was then tabletted to produce tablets approximately 1.27 cm in diameter. The finished tablets were then dried in air for 16 hours, then treated with steam at a pressure of 80 atmospheres. After steaming, the tablets were baked at 870 ° C for an additional 8 hours.

The catalyst bodies obtained in this way were then tested in a hydrocarbon vapor conversion process, the conditions being the same as those in Example 3. The following results were obtained:

Day [ O \ 3. · Time ⁰ C Pass-through
speed 7o CO ₂ 5,000 6.4 7 “co 7o CH ₄ footnote Δ. 9.45 Start with N ₂ 10,000 6.8 1 [ 13.30 870 5,000 7.0 16.7 0.17 15.30 870 10,000 8.0 15.7 3.2 2 10.30, 870 5,000 11.6 16.6 0.19 12.00 870 5,000 12.0 14.5 2.4 14.00 704 5,000 6.8 7.85 8.9 15.30 650 5,000 6.2 13.8 3 10.00 870 10,000 8.6 15.4 0.48 12.00 870 5,000 12.8 16.0 0.23 14.00 870 5,000 12.9 11.65 3.9 15.30 704 6.12 8.3 16.30 650 4.24 19.0 4th

Footnote 1.

The reaction vessel was heated to 870 ° C using nitrogen; after 870 ° C had been reached, became converted to methane.

Footnote 2.

At a temperature of 954 ° C and a steam-gas ratio of 3.2: 1, during the night from methane to hydrogen changed.

Footnote 3.

At a temperature of 954 ° C and a steam-gas ratio of 3.1: 1 was overnight from methane to hydrogen changed.

Footnote 4.

The reaction vessel was shut down and a change to hydrogen was made with the temperature unaffected.

Time 9 ⁰ C Pass
speed % CO ₂ 5,000 7.4 10 % CO % CH ₄ footnote 9.30 Start with N ₂ 5,000 6.6 5 Day 11.15 870 10,000 8.4 17.4 0.20 12.00 870 5,000 13.0 15.6 0.27 15.15 870 5,000 7.0 13.0 4.6 9. ■ 16.30 704 5,000 7.0 4.69 8.6 6th 9.30 870 10,000 8.3 15.1 0.43 11.30 870 5,000 12.8 16.2 • 0.29 870 5,000 12.1 13.2 4.2 14.30 704 0.3 8.2 10. · 16.30 650 5.7 14.0

Footnote 5.

The reaction vessel was heated to 870 ° C using nitrogen and increased to 870 ° C when it was reached Methane converted.

Footnote 6.

At temperatures of 954 ° C., methane was switched to hydrogen overnight.

Claims (5)

Patent claims: 1. A process for the production of activated nickel catalysts for the catalytic conversion of hydrocarbons in the presence of oxygen-containing compounds, e.g. B. steam, characterized in that nickel oxides or when heated in air in nickel oxides passing nickel compounds with an activating agent of alumina or limestone compounds and a binder of 60 to 67 weight percent calcium oxide, 18.8 to 25.5 weight percent silicate, 3 to 7.5 percent by weight of clay, 0.5 to 5.5 percent by weight of limestone and the remainder of alkali or alkaline earth metal oxides are ground in the presence of water to form a dough-like mass and this mass is shaped and fired. 2. The method according to claim 1, characterized in that as much nickel compounds are used be that the finished catalyst body contains 10 to 35 percent by weight nickel. 3. The method according to claim 1 and 2, characterized in that the catalyst bodies are fired at about 860 to 87O ⁰ C. 4. The method according to claim 1 to 3, characterized in that the nickel compounds with spherical tone and then mixed with clay and limestone, then heated so high that the nickel compounds converted into oxides, the calcined mass with a binding agent from 60 to 67 percent by weight Calcium oxide, 18.8 to 25.5 percent by weight silicate, 3 to 7.5 percent by weight alumina, 0.5 to 5.5 percent by weight limestone and the remainder of metal oxides of the I. and II. Group des Periodic table is wet milling, deformed and fired. 5. The method of claim 1 to 4, characterized in that the first firing at temperatures in the range of about 370 to 538 ° C and the second firing is carried out at temperatures well above 537 ⁰ C. © 009 699/459 1.61