DE1272898B - Process for the production of nickel oxide carrier catalysts for the hydrogenation of carbon monoxide and / or unsaturated hydrocarbons in industrial gases - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY GERMAN 4i07 ¥ W PATENT OFFICE

EDITORIAL

Int. Cl .:

German class:

Number:
File number:
Registration date:
Display day:

BOIj

C07c

12 g -11/46

12 ο -1/02

12 ο -1/03

P 12 72 898.2-41 (O 10101)

April 23, 1964

July 18, 1968

The catalysts, which are generally used for hydrogenation reactions in the gaseous phase, consist of nickel, which is on an inert carrier, optionally in the presence of promoters, is upset. However, the use of this type of active mass is limited to starting products that are free from sulfur compounds, as nickel is resistant to poisoning by the latter Connections is very sensitive.

Much work has been carried out to seek means of eliminating this disadvantage without to carry out a previous desulfurization of the starting products, but are the proposed Solutions are not economical, as these are often based on replacing nickel with palladium proved to be less sensitive.

The present invention relates to a type of nickel-based catalyst which is particularly active and resistant and enables the hydrogenation of unsaturated hydrocarbons to be carried out in industrial gases with excellent yields having a bound sulfur content of up to 50 mg / m ³ can be. The reaction is carried out at relatively low temperatures of the order of 180 to 350 ^° C., which makes it possible to avoid the thermal decomposition of the heaviest, gaseous hydrocarbons which may be contained in the initial mixture. This catalyst also makes it possible to carry out the methanation reaction from carbon oxide at temperatures from 320 to 360 ^° C. and the selective hydrogenation of acetylenic derivatives to olefins at temperatures from 20 to 120 ^° C. with good yields.

The support of the catalysts according to the invention consists of a mixture of varying proportions of zinc oxide and calcium carbonate, which is a special kind of production at the same time a large one gives mechanical strength and increased porosity.

The process for the production of supported nickel oxide catalysts for the hydrogenation of carbon monoxide and / or unsaturated hydrocarbons in industrial gases with incorporation or impregnation with a heat-decomposable nickel compound is characterized in that one for Production of the carrier zinc oxide and calcium oxide in a weight ratio of 2: 1 with a maximum of one the amount of ammonium bicarbonate theoretically required to convert the oxides into the corresponding carbonates and the amount of water required in processes of manufacture to achieve the desired consistency

of supported nickel oxide catalysts

for the hydrogenation of carbon monoxide

and / or unsaturated hydrocarbons

in industrial gases

Applicant:

Office National Industriel de l'Azote,

Toulouse (France)

Representative:

Dr.-Ing. W. Abitz and Dr. D. Morf,

Patent attorneys,

8000 Munich 27, Pienzenauer Str. 28

Named as inventor:

M. Robert Garlet,

M. Louis Grander, Toulouse (France)

Claimed priority:

France 23 April 1963 (4874)

pulpy phase mixed, the mass dries and in an oxidizing atmosphere at a temperature of Calcined about 250 to 350 ° C. The water used as the reaction medium is added to the mixture Beginning of the operation in such an amount that the pasty mass has the desired consistency having. Preferably the raw, blended mass is in the form of prior to drying Granules, thin flexible rods, rolls, spherical bodies, tablets or rings. and preferably the water required to achieve the desired consistency of the pulp is brought in in whole or in part in the form of an aqueous solution of the nickel salt.

The nickel is thus incorporated into the mass in the course of blending in the form of an aqueous solution of a incorporated decomposable nickel salt of known concentration. This can then be the entire

809 570/574

Water or part of the water required to achieve a pulpy phase of adequate consistency is to feed.

However, it is also possible that this salt in the mixture of components in the form of a solid nickel compound, such as the carbonate, is introduced.

You can also put the nickel in the porous support structure after the final thermal treatment of the molded and dried mixed product by immersing the latter in an aqueous solution a decomposable nickel salt of known concentration. This salt is beneficial Nickel carbonate, nitrate, formate or oxalate.

800 g of ammonium bicarbonate in a pulpy phase in the presence of the required amount of water so that the Mass had the desired consistency, produced. This operation takes 1 to 2 hours, and the The mass is shaped and then dried in the air or in a drying cabinet.

example 1

undergoing treatment to convert the nickel salt into the oxide by decomposition. The development of derived from zinc carbonate-

A commercially available propane with a content of 1.3% ethane, 75.7% propane, 23.0% propylene and 5 mg bound sulfur per cubic meter a slight excess of hydrogen, based on the propylene that one in propane In this case, it is necessary to convert the product to 15, to.

Drying of an additional thermal oxydie- The preheated to 150 ⁰ C mixture is with the

Hydrogenation catalyst brought into contact, the hourly space flow rate (space velocity) about 600 [parts of gas / h / part of catalyst

the carbon dioxide in the course of the thermal aerator]. The volume composition of the action gives the catalyst a large porosity of the gas obtained, which has a temperature of 180 ⁰ C, and the zinc oxide, which is highly distributed in the mass in the first catalyst layer and a temperature, is particularly suitable, the sulfur of 23O ⁰ C am The exit of the contact mass corresponds to compounds, such as hydrogen sulfide, is specified in the table below under "A" in the carbon oxysulfide, carbon disulfide, mercaptans 25 column for the analysis of the end system,
and the like, to destroy and / or absorb. The for comparison purposes will be the same as the initial one

Calcium carbonate, in turn, treated under the tempe gas mixture in the presence of the same catalyst temperature conditions of thermal treatment and stable to several successive Reder reactions, contributes to a large extent to which has been subjected to generations and 5 weightis exceptional mechanical strength of the 30 percent bound sulfur in the form of calcium catalyst. Which is made up of the dis- sulphate. At a room throughput of about 600, an initial temperature of 21O ⁰ C and a sulfur is bound by the very reactive zinc oxide of the end temperature of 250 ° C, a gaseous carrier in the form of zinc sulfide, a product of which Volume composition under "B" bond, which is much more stable in reducing medium 35 in the last column of the table below given the temperatures used as nickel sulfide. According to the content of non-hydrogenated is. If the content of zinc oxide bound
Sulfur becomes too large and the top of the catalytic layer has a significant nickel sulfide content
it is necessary to turn the catalyst through 40
moderate heating at temperatures from 420 to
45O ⁰ C in an oxidizing atmosphere that consists of
Air or oxygen, preferably diluted in one
inert gas such as nitrogen, heating gases
and the like, is to regenerate. 45

The oxidation of zinc sulfide and possibly nickel sulfide leads to the formation of the corresponding Oxides. Successive regenerations carried out at moderate temperatures so that the suitable catalyst activity is not harmed, but does not allow the entire bound Remove sulfur. A more or less considerable proportion of this element combines with Calcium in the form of sulfate. The formation of this under

Propylene is found that the activity of the regenerated catalyst by about 16%, based on the Activity of new catalyst, is decreased.

C ₂ H ₆
C ₃ H ₈ .

Volume composition, ° / o
End system

Initial system A. B. 1.0 1.2 1.2 58.1 90.5 81.6 17.7 0.8 3.7 22.4 6.5 12.6 0.8 1.0 0.9

In contrast, if you use a conventional catalyst for hydrogenation or hydrogenation Cracking used, which is 25% nickel oxide

The normal conditions of use of the catalyst _{contains an Al a} O _{3 support} , then this sator-stable compound provides every catalyst initially with the same results as the poisoning of active nickel, at least avoiding the "catalyst A" of the example 1, however, its falls until a considerable proportion of the calcium carbonate is converted into activity because of the irreversible poisoning by the sulfate. S-connections from quickly; such a catalyst

The following examples, some of the numerous 60, are also not regenerable.
Show areas of application of the catalysts of the invention, explain the invention. Example 2

For the purpose of simplifying the description, these examples correspond to the results obtained with a catalyst containing 24.5% NiO, 6g 40.0% ZnO and 35.5% CaCO ₃ . This catalyst was made by mixing 500 g of nickel

y
carbonate, 500 g zinc oxide, 250 g calcium oxide and

A gas containing hydrogen and olefins is subjected to cracking of a gasoline originates and is contaminated with about 5 mg of bound sulfur per cubic meter, an autohydrogenation these olefins in the presence of the catalyst. Of the

Operation is carried out at temperatures at the inlet and outlet of the reaction vessel of 210 and 25O ⁰ C, at a hourly space throughput of about 700th

The volume percentages of the initial system and the final system are in the compiled in the following table.

CO ₂

H ₂

N ₂

CO

CH ₄

C ₂ H ₆

C ₂ H ₄

C ₃ H ₈

C ₃ H ₆

Higher hydrocarbons ..

Volume composer, ° / o initial system [final system

1.8 29.7

1.6

5.3 23.8

3.0 21.5

0.6

9.0

3.7

2.4

7.3

2.2

7.0

31.3

29.1

3.3

6.0

6.6

4.8

Example 3

One hydrogenates ethylene and propylene, which at the same time with hydrogen in one from the cracking a gas obtained from a light gasoline with a content of 10 mg bound sulfur per cubic meter are included. The operation is carried out in the presence of a catalyst, several successive Has undergone regenerations and in its structure 5% bound sulfur in the form of Contains calcium sulfate, with an hourly space flow of about 700 and with an initial and Final temperature of 260 or 300 ° C carried out.

The analyzes of the initial system and the final system are given in the table below.

CO ₂

H ₂

N ₂

CO

CH ₄

C ₂ H ₆

C ₂ H ₄

C ₃ H ₈

C ₃ H ₆

Higher hydrocarbons.

Volume composition,% initial system final system

8.2

41.6

0.2

3.5

23.3

1.9

19.3

0.7

0.7

0.6

9.7

31.5

0.2

4.1

27.3

19.2

5.6

1.2

0.5

0.7

Example 4

CO ₂

ίο C ₂ H ₆

C ₂ H ₄

C ₃ H ₈

C ₃ H ₆

Higher hydrocarbons.

Volume composition,% initial system I final system

3.0

48.8

0.8

14.5

10.6

2.3

9.0

1.8

6.1

3.1

7.5

23.4

1.2

6.7

27.8

14.2

2.7

8.8

3.1

4.6

The upper calorific value is from 7615 to 10930 kcal per cubic meter.

Example 5

An industrial gas containing 45 parts per million of sulfur components is subjected to selective hydrogenation of the acetylene it contains in the presence of ethylene. The operation is carried out at temperatures of 15 to 60 ^° C. with an hourly room throughput in the order of 1000. The catalyst used had not yet been subjected to regeneration.

The analyzes of the initial system and the final system are summarized in the following table.

35 H ₂ ..

N ₂ ..

40 CH ₄ .

C ₂ H ₆ C ₂ H ₄ volume composition, ° / o start system ' end system

44.5

17.2

30.2

0.0

1.5

6.6

40.5

18.4

32.4

0.1

8.2

0.4

45

Claims (3)

Claims: 55 60 One hydrogenates at the same time olefins and carbon oxide, which are contained in a cracking gas, which is contaminated with 7 mg sulfur impurities per cubic meter, in the presence of an unused catalyst with an hourly room throughput of 500 and an average temperature of 340C. The analyzes of the initial system and the final system are given in the table below. 1. Process for the production of supported nickel oxide catalysts for the hydrogenation of carbon monoxide and / or unsaturated hydrocarbons in industrial gases with incorporation or impregnation with a heat-decomposable nickel compound, characterized in that that for the preparation of the carrier zinc oxide and calcium oxide in a weight ratio of 2: 1 with a maximum of the theoretical amount of ammonium bicarbonate required to convert the oxides into the corresponding carbonates and the amount of water required to achieve the desired consistency mixed in a pulpy phase, the mass dries and in an oxidizing atmosphere at one temperature calcined from about 250 to 3 50 ° C. 2. The method according to claim 1, characterized in that the raw, mixed mass is before drying in the form of granules, thin flexible rods, rolls, spherical ones Brings bodies, tablets or rings. 7 8 3. The method according to claim 1 and 2, characterized _{in Betiadbt genes} publications:. characterized that one has to achieve the desired consistency of the pulp, required German Auslegeschriften No. 1121 757,1 097 601; Water in whole or in part in the form of a patent specification No. 16,735 of the Office for Aqueous Invention Brings solution of the nickel salt. 5 and patents in East Berlin. 809 570/574 7.68 © Bundesdruckerei Berlin