DE2401617A1 - PROCESS FOR PRODUCING A METHANE CONTAINING GAS IN THE CONTEXT OF LOW-TEMPERATURE STEAM REFORMING OR LOW-TEMPERATURE STEAM REFORMING PROCESS FOR HYDROCARBONS FOR THE PRODUCTION OF A METHANE-RICH GAS - Google Patents

Description

PATENTANWÄLTE HENKHL KFRN FEILER - KANZEL - MÜLLER

I) R. PHIi .. DIP! -ΙΜί. DR. RLR. NAT. DIPL.-ING. UII'l.-INU.

■ ii. ■■■ · HNKi. ι Hi) UARD-SCHMID-STRASSE 2 βλυι lasers: hyiothiken- and

Ui I · ■ - ■ - i "1 '7. (, .. -M), -. ₍ WICHMI.BANK MUNICH NO. 3I8-8S P I.I ι ...: ■ ;; . Ii ll'vill) Ml N (U. .N IJ MUH) MUNLHtIlN VU POST CHECK: MCHN 1621 47-K09

Japan Gasoline Co., Ltd., \ 4. Jau. 1374

Tokyo, Japan and Nikki Chemical Co., Ltd., Tokyo, Japan

Process for the production of a methane-containing gas as part of a low-temperature steam reforming or Low temperature steam reforming process for hydrocarbons to produce a methane-rich gas

The invention relates to a method for the catalytic steam reforming of hydrocarbons with at least two carbon atoms per molecule at temperatures of 300 ° to 600 ⁰ C, in particular a method for the production of a methane-containing gas, preferably a methane-rich gas, by for example adiabatic steam reforming of a hydrocarbon starting material in the presence of a Improved nickel-containing catalyst exhibiting a superior effect at any low temperature steam reforming process.

For the production of a methane-containing gas by low-temperature steam reforming in the presence of a nickel-containing catalyst, the most diverse Method proposed "at" the one in Japanese patent application 11047/1965 described procedure a catalyst containing nickel, aluminum trioxide and an element from the series of lanthanides is used.

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The one described in Japanese Patent Application 11048/1965 Process works with a nickel / aluminum trioxide / iron catalyst. In Japanese patent application 19174/1970 a method is described with -which a nickel / aluminum triOXide / alkaline earth metal catalyst is used.

The usual nickel-containing catalysts, including the catalysts mentioned, have when used in the context of low temperature steam reforming processes not always the required service life. Especially with the more and more widespread, under high These catalysts are capable of their catalytic properties, using low-temperature steam reforming processes under pressure Properties cannot be retained over a long period of time, as carbonaceous materials are found on them, among other things deposit. In addition, the usual nickel-containing catalysts are affected by sulfur-containing impurities poisoned, which is why hydrocarbon feedstocks with a relatively large proportion of sulfur compounds must be subjected to a sulphurizing pretreatment under rather drastic conditions.

The invention was based on the object of a method for producing a methane-containing gas, in particular a methane-rich gas, for example by adiabatic steam reforming of hydrocarbon feedstocks to create in the presence of a novel nickel catalyst, when carrying out the catalytic Properties of the nickel catalyst used are retained over a long period of time.

The invention thus provides a method for producing a methane-containing gas, in which one

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Hydrocarbon feedstock containing hydrocarbons having at least 2 carbon atoms per molecule and steam preheated to a temperature of 250 ° to 600 ° C in the ratio of steam to hydrocarbons (HpO / C mol / atom) from 0.9 to 5.0 in at least one steam reforming reactor that is packed with:

(a) a catalyst containing nickel and magnesium and having an IMi: Mg atomic ratio of 0.05 to 7.0, preferably 0.5 to 5.0, and a solid solution content of nickel oxide and magnesium oxide; or

. (b) a by applying a catalyst described in (a) on an inorganic refractory support material which is inert to the other catalyst ingredients during the reforming reaction, and, based on the total catalyst, less than 70 wt - constitutes%, the catalyst obtained;

(c) a catalyst containing nickel and magnesium and having a nickel: magnesium atomic ratio of 0.05 up to 7.0, preferably 0.5 to 5.0, and a content of a solid solution of nickel oxide and magnesium oxide, which, based on the nickel content in metallic form, additionally less than 25, preferably 10 to 20% by weight copper / chromium oxide or copper / chromium / Contains manganese oxide; or

(d) a by applying a catalyst described under (c) to an inorganic, refractory carrier material, which is inert to the other catalyst components during the reforming reaction and, based on the total catalyst, makes up less than 70% by weight of the catalyst obtained,

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and in that the hydrocarbon feedstock by applying a Re.aktionsdrucks from 10 "to 100 kg / cm · G at a catalyst bed temperature in the or the reactor (s) of 300 ° to 600 ° C, preferably 400 ° to 570 ⁰ C, steam reformed .

Low-temperature steam has already been used to effectively control the occurrence of the unstable factors described Reforming method proposed (DT-OS 2 359 116), in which

(a) a new binary nickel-containing catalyst consisting of nickel and magnesium oxide, or

(b) one obtained by mixing special support materials with a catalyst described under (a) Catalyst or

(c) a nickel and magnesium oxide and also containing a copper / chromium oxide or a copper / chromium / manganese oxide nickel-containing catalyst or

(d) a obtained by mixing certain support materials with a catalyst described under (c) catalyst

is used.

These nickel-containing catalysts undoubtedly have better properties than the usual catalysts for Low temperature steam reforming process. Nonetheless the former catalysts could be further improved according to the invention. This further improvement

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serung is based on the knowledge that the catalytic effectiveness is particularly high when the catalyst contains a solid solution of nickel oxide and magnesium oxide at a certain molar ratio Ni: Mg.

As a hydrocarbon starting material with at least 2 carbon atoms per molecule can be used in the context of Process according to the invention refinery waste gases, light natural gas (LPG), light naphtha, heavy naphtha, kerosene and the like. These hydrocarbon feedstocks are mixed together with steam in the mixing ratio Steam to hydrocarbons (HpO / C, i.e. number of moles of steam based on one carbon atom in the hydrocarbon feedstock) expediently from 0.9 to 5.0 introduced into one or more reactor (s).

The catalysts (a) to (d) which can be used in the context of the process according to the invention can be reproduced as follows are: (a) Ni-solid solution of nickel oxide and magnesium oxide (reproduced below as NiO-MgO); (b) Ni (NiO-MgO) - (carrier); (c) Ni (NiO-MgO) - (Cu-Cr oxide or Cu-Cr-Mh oxide) and (d) Ni (NiO-MgO) - (Cu-Cr oxide or Cu-Cr-Mn-oxide) - (carrier) in each case at a point in time at which the catalyst in question is activated by reduction has been (here, NiO and / or MgO can also be present in a form other than a solid solution be) and where the MgO is an active> magnesium oxide that is responsible for the low-temperature steam reforming in question able to accelerate.

Examples of support materials which can be used for catalysts (b) and (d) are inorganic, refractory supports

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ger, which do not enter into any chemical reaction with the other catalyst components, namely the nickel component and the magnesium oxide component, during the reforming reaction, for example _o 06-Al ₂ O, SiC, oC-quartz, ZrO ₂ and the like. In this connection it should be pointed out that known materials as supports for conventional catalysts for low-temperature steam reforming reactions, such as ^ -Al ₂ Q ,, silica gel, kaolin and the like, are unsuitable as supports for the catalysts according to the invention.

The chemical composition and the oxidation state of the copper / chromium oxide or copper / chromium / manganese oxide contained in the catalysts (c) and (d) are not particularly critical, but the copper / chromium oxide should expediently be in the form of a copper chromite Formula Cu ₂ Cr ₂ Oc ₁ exist.

The term "solid solution" means the same here and below as is customary in inorganic chemistry. Such a solid solution can be analyzed by X-ray diffraction and the like. For example the peak of the solid solution NiO-MgO in the case of X-ray diffraction analysis with CuKoC - though fluctuating according to the ratio Ni: Mg - always between the peak of MgO and the peak of NiO.

Now it is generally known that in catalyst compositions having a nickel component and a Magnesiumoxidbestandteil for use in high temperature steam Refonnierungsreaktionen, upon calcining at temperatures ranging from 700 ° to 1200 ⁰ C, in particular in the range of 1000 ° to 1200 ⁰ C, due to partial oxidation

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readily forms a solid solution of nickel oxide and magnesium oxide. However, there is one in this way in the form The catalyst obtained from a solid solution has poor activity and, with the lapse of time, strong If its activity is impaired, it has hitherto been the case with a view to the further use of such catalysts considered necessary in the most varied of reactions, this in the form of a solid solution to convert the nickel oxide contained into metallic nickel beforehand by adding a sufficient amount of the catalyst in question Hydrogen gas reduction treatment and the like. In contrast to It is imperative in the case of the nickel-containing catalysts used according to the invention that the relevant solid solution also ndch at a time after activation (of the catalyst) by reduction treatment is available. Such solid solution containing nickel-containing catalysts can be most effective Manner in the context of a low temperature steam reforming process according to the invention. In particular at high pressures in the range of 50 to 100 kg / cm »G they can retain their valuable properties, i.e. their high activity and high stability, fully develop. The atomic ratio of nickel to magnesium is in the Catalysts which can be used according to the invention 0.05 to 7.0. In contrast to the aforementioned proposal ^ nickel and magnesium containing catalysts with an atomic ratio Ni: Mg of 0.5 to 5.0 can be used in the catalysts used according to the invention a broader range for the atomic ratio Ni: Mg are maintained, since all or most of the magnesium oxide contained therein is converted into a solid solution became.

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If the atomic ratio Wi: Mg is less than 0.05, leaves sufficient catalytic activity at low Do not expect temperature. If the atomic ratio Ni: Mg exceeds 7.0, it occurs with progression Reforming reaction to a deposition of carbonaceous material on the catalyst surface, thereby whose catalytic activity is impaired.

The highest possible content of the inert support in the catalyst is 70% by weight. In the event that the carrier portion of the catalyst exceeds this upper limit, sufficient catalytic activity can be obtained at lower Do not expect temperature. Furthermore, as already mentioned, the content of copper / chromium oxide or copper / chromium / manganese oxide, based on the nickel content in metallic form, are less than 25% by weight.

The reasons why the presence of a solid solution in the low temperature steam reforming process Catalysts which can be used according to the invention are advantageous in contrast to the previous ideas are not yet fully clarified. However, the two factors described below certainly contribute in addition to:

1. Since the magnesium oxide, which _{is supposed to activate the H 2} O molecule forming a reactant and is present together with the metallic nickel forming the active constituent, is already in the form of a solid solution, takes place during the steam reforming reaction, especially that carried out under high pressure Steam reforming reaction, no noticeable crystallite growth takes place. This is due to the stability of the solid solution.

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2. A catalyst containing a solid solution exhibits _{a stronger activity towards H 2} O than a catalyst containing no solid solution. When using a catalyst without a solid solution, the reaction rate does not increase significantly even if the partial pressure of EUO is increased. When a solid solution catalyst is used, increasing the partial pressure of HpO dramatically increases the reaction rate, so that a solid solution catalyst is very useful in a high pressure steam reforming reaction.

The copper / chromium oxide or copper / chromium / manganese oxide-containing catalysts (c) and (d) have a particular one excellent activity at low temperatures and a particularly good shelf life. When using them It is possible to carry out steam reforming of hydrocarbon feedstocks with relatively a lot of sulfur compounds, i.e. from hydrocarbon feedstocks with 10 to 20 ppm sulfur compounds, make it relatively easy.

In the following, the preparation of catalysts which can be used according to the invention is first described, expressly it should be noted that the preparation of the catalysts which can be used according to the invention does not occur the method described in detail is limited. In principle, any common method is suitable for this, provided that the catalysts obtained meet the specified requirements. Furthermore, in the following also explains in more detail how a steam reforming process using such catalysts is carried out.

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Process for the preparation of catalysts which can be used according to the invention:

1. Process for the preparation of a catalyst by Coprecipitation:

By mixing an aqueous solution of a nickel salt such as Ni (NO _{3 I 2} , NiSO ^, NiCl ₂ , Ni (CH ₃ COO) ₂ , Ni (HCOO) ₂ and the like, an aqueous solution of a magnesium salt such as Mg (NO ₃ ) ₂ , MgSO ₄ , MgCl ₂ , Mg (CH ₃ COp) ₂ , Mg (HCOO) ₂ and the like, and an aqueous solution of an alkali metal _{compound, e.g. of NaOH, KOH, Na 2} CO ₃ , K ₂ CO ₃ and the like, in compliance with an atomic ratio Ni: Mg 0.05 to 7.0 and a carrier content of below 70 wt .-%, at a temperature from room temperature to 90 ⁰ C, preferably from 30 ° to 70 ⁰ C, a precipitate of nickel - and magnesium hydroxide 'or basic nickel and magnesium carbonates. The suspension obtained in this way is stirred at the desired temperature for a certain time, for example 0.5 to 3 hours, during which the precipitate can age a large amount of hot water, if necessary fer / chromium oxide or copper / chromium / manganese oxide-containing catalyst is to be prepared, a given amount of a copper / chromium (atomic ratio: 1: 1) ammonium double salt or oxide or a copper / chromium / manganese (atomic ratio : 1: 1: 0.1) ammonium double salt or oxide was added. The precipitate finally obtained is then dried at a temperature of 40 ° to 130 ⁰ C, with less than 10 parts by weight 96 of a molding aid, such as graphite, stearic acid and the like, and mixed in a tabletting

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machine formed into tablets with a size of 0.5 x 20 ram. The tablets obtained are then at a Calcined suitable temperature, a nickel-containing catalyst with a solid solution of nickel oxide and magnesium oxide is obtained. Of course, the moist precipitate can be extruded before drying or be granulated in a roller drum.

If a catalyst which is applied to a support is to be produced, this is possible by using the for formation the mixture of solutions used for the precipitate is one of the said carriers with a particle size of less than 200 mesh in an amount less than 70% by weight to the total amount of catalyst, added and the whole is then worked up in the manner described.

2. Process for making a catalyst by precipitation work:

A commercially available active MgO powder for industrial use and corresponding solutions of nickel and alkali metal compounds as in the process described under 1. are, taking into account an atomic ratio Ni: Mg in the finished catalyst from 0.05 to 7.0 at a temperature from room temperature to 90 ⁰ C, preferably ⁰ to 70 C, mixed for 30 °, whereby a precipitate of nickel hydroxide or basic nickel carbonate precipitates and is deposited on the MgO surface. The entire precipitate is then filtered off and worked up in the manner described under 1. If a copper / chromium oxide or copper / chromium / manganese oxide containing catalyst is desired, this can be achieved by adding and mixing a certain amount of copper / chromium ammo -

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double salt or oxide or copper / chromium / manganese ammonium double salt or oxide can be produced with the resulting repetition. After all, that will ultimately obtained precipitate dried in the manner described under 1., shaped and calcined, wherein a nickel-containing catalyst is obtained with a solid solution of nickel oxide and magnesium oxide.

If a catalyst applied to a carrier is to be produced, this can be done in that a given amount of carrier is combined with the precipitate after filtering and washing.

3. Production of a catalyst by a wet mixing process:

The same solutions of nickel and alkali metal compounds as described under 1 · methods are ⁰ to 70 C, mixed together at a temperature from room temperature to 9O ⁰ C, preferably 30 °, whereby a nickel hydroxide or basic nickel carbonate precipitates. The resulting precipitate is then stirred for a while at the specified temperature and finally worked up in the manner described under 1..

The precipitate obtained is then thoroughly mixed with commercially available MgO active powder for industrial use mixed in such an amount that the atomic ratio Ni: Mg in the finished catalyst is between 0.05 and 7.0. In the case that a copper / chromium oxide or copper / chromium / manganese oxide-containing catalyst is produced is to be, the mixture obtained with a given amount of copper / chromium-ammonium double salt or oxide or copper / chromium / manganese ammonium double salt or

-13-409840 / Ü27A

-oxid mixed and in the manner described under 1. dried, shaped and calcined, with a nickel-containing Catalyst is obtained with a solid solution of nickel oxide and magnesium oxide.

If a catalyst which is applied to a carrier is to be produced, this can be achieved by that a given amount of carrier combined with the mixture of precipitate and MgO powder and then in is worked up in the manner described.

4. Manufacture of a catalyst by contract work:

When producing a catalyst mass according to one of the items 1., 2. and 3. (the catalyst mass obtained in this way can be used as it is as a reforming catalyst are) described method, it is either immersed in an aqueous solution of a nickel salt or with the precipitate of hydroxides or basic precipitates obtained in the context of the process described under 1 Carbonates of nickel and magnesium mixed. The mixture obtained is then dried, shaped, and dried again calcined, wherein a nickel and magnesium oxide containing catalyst with a nickel component, which can easily be converted into metallic nickel by reduction, and obtained a content of a solid solution will. In this process, the calcination conditions, for example the calcination temperature, not so narrowly limited in the production of the catalyst mass, i.e. there is hardly any need to do so reducible solid solution can be formed.

Calcination Conditions:

In the preparation of the catalysts of the invention

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Calcination conditions are essential. In other words, the calcination conditions must be considered from such considerations as e.g. the mixture form of the nickel component and magnesium oxide component in the catalyst mass before calcination, and the like.

Generally speaking, high calcination temperatures and long calcination times are readily obtained a solid solution. In the event of excessive calcination, however, the finished catalyst can hardly be reduced, which is undesirable for reasons of catalytic activity.

In the production of a catalyst in accordance with the process described under 4. there are no related problems. In the preparation of a catalyst by one of the processes described under 1., 2. and 3., the state of the mixture between a nickel salt and a magnesium salt deteriorates while the process in question is being carried out, so that higher temperatures or longer calcination times are required for correct calcination. Further, the need to prepared under 1. method described catalysts depending on the starting salts and the precipitation conditions, calcination temperatures of about 700 ⁰ C, while sufficient in other catalysts calcination temperatures of about 35O ⁰ C. Furthermore, there are cases where a solid solution is formed only after long-term treatment at low temperatures.

In the event that all factors, with the exception of the falling temperature , are kept constant, a calci-

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tion temperature after previous precipitation at a low temperature, for example at 20 ⁰ C, from 300 ° to 400 ° C. On the other hand, if the precipitation temperature is increased, the calcination temperature must also be increased beyond the specified range.

Taking into account the previous statements, the choice of calcination conditions should always be taken into account numerous other factors at the time of precipitation, namely the salts used and their production, the salt concentration, the temperature and duration of aging in the production of the precipitate and the like, or combinations of these factors.

That should conveniently in the range of 350 ° to 1200 ⁰ C in the preparation of catalysts according to be observed under 1. to 4. The method described calcination temperatures, preferably of 600 °, are up to 800 ⁰ C. In the case of the catalyst preparation by the method described in section 4 method, the first calcination at higher temperatures can be carried out, however, the calcination after immersion in an aqueous solution of a nickel salt and the like should be suitably carried out at a temperature of 300 ° to 600 ⁰ C.

The low temperature steam reforming process according to the invention is started when one of the processes described under 1. to 4. is produced Nickel / Martian oxide catalyst in (at least) a steam reforming reactor is filled and hydrogen is passed through as a reducing gas stream

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at a temperature of 300 ° to 60O ⁰ C, preferably 400 ° to 500 ⁰ C, has been activated. When the catalyst is fully activated, the hydrogen supply is switched off, whereupon a mixture of the respective hydrocarbon starting material and steam in a mixing ratio (H ₂ O / C - mol / atom) of 0.9 to 5.0 after preheating to a temperature of 250 ° to 600 ⁰ C is passed through the catalyst bed, and is preferably steam reformed from 400 ° to 570 ⁰ C to form a methane-containing gas there at a temperature of 300 ° to 600 ⁰ C.

The methane-containing gas formed in this process generally contains, based on dry weight, more than hO% methane together with gaseous accompanying substances such as hydrogen, carbon monoxide and carbon dioxide.

If necessary, a gas containing even more methane can be produced by removing the gas from the reactor (s) exiting gas stream for methanation of the carbon oxides contained in the gas stream at least one Methanation reactor feeds. The methane-containing gas obtained is primarily suitable as heating gas.

The attached drawing is intended to explain the invention in more detail. In detail, Figures 1 to 5 show graphical Representations of the relationship between the amount of copper / chromium oxide contained in the respective catalyst or copper / chromium / manganese oxide and the degree of conversion.

The following examples are intended to illustrate the process according to the invention in more detail.

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For better comparison, the tests of the following Examples 1 to 13 were carried out under the same (in more detail below explained) conditions. Of course, you can also work under other conditions, provided that the desired success is achieved.

First, all of the catalysts to the provisions of the following examples were prepared in accordance with 10-hour reduction in a 50O ⁰ C hot hydrogen gas stream activated. Was JMachdem each 1 g of the activated catalysts in a reactor filled, was formed through the catalyst bed a mixture of naphtha with an IBP of 33 ⁰ C, a FBP of 122 ⁰ C,

a specific gravity dr of 0.675, a sulfur content of 0.2 ppm and an average of 6.04 carbon atoms and 13.4 hydrogen atoms per molecule at a rate of 35 g / h together with steam in the ratio HpO: C (mol / atom) of 2 , 0 passed and at a reaction temperature of 50O ⁰ C and a reaction

p ρ

pressure of 70 kg / cm · G or 10 kg / cm · G steam reformed. The original activity of each catalyst was determined.

There was also 25 cm of all activated catalysts filled into a pressure reaction tube, whereupon the same naphtha starting material (as used in the determination the original activity of the catalysts was used) at a rate of 30 g / h became. The 500-hour steam reforming was carried out under the same conditions as in the determination the original activity of the catalysts were maintained. iMun became part of the catalysts from the relevant reaction tubes removed and used for determination

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of the properties used. The remainder of all the catalysts were poured into the reaction tubes again and another 500 hour steam reforming used under the specified conditions. All the catalysts were then removed from the reaction tubes. A part of all the catalysts served as a sample for determining the properties. 1 g of all catalysts was again filled into reactors to reduce the catalytic activity after 1000 hours of use to be determined under the same conditions as were observed when determining the original activity.

The determination of the "properties" was used to determine the crystallite growth by X-ray diffraction. The measurement of the initial activity and the determination of the activity after 1000 hours of use are used to determine the degree of conversion of the naphtha starting material into a gas containing methane, hydrogen and carbon oxides.

The quality of the individual catalysts can be assessed on the basis of the results of these tests.

The experiments to determine the catalytic activity were carried out using a control to facilitate comparison the transformation during steam reforming. In the event that the steam reforming under such conditions occurred that reached 100% conversion was, i.e. in the case that the amount of catalyst relative to the fed starting material is above a given Amount was also increased, the gas formed at the Redtor outlet had approximately the following composition:

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In the case of steam reforming under a reaction pressure of 70 kg / cm «G:

about 65 vol .-? f H ₂ about 12.5 vol. 56 CO about 0.5 vol. 36 CO ₂ about 22 vol. 96

For steam reforming under a reaction pressure of 10 kg / cm ² G:

about 56% by volume H ₂ about 21 volume-96 CO about 1 volume-96 CO ₂ about 22 volume-96

example 1

If the procedure described under 1 the various catalysts prepared under "A" in Table I below used in the experiments described, those in the following Table I under "B" were summarized Get results.

"H" indicates the results of steam reforming

under a reaction pressure of 70 kg / cm »G. "N" indicates the results of steam reforming under a reaction pressure of 10 kg / cm * G «This marking applies for all of the following tables.

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Table I.

catalyst

a - 2

a - 3

a - 4

a - 5

Properties of the liquid at the beginning of the precipitation

used salt
Precipitation temperature Duration of aging Atomic ratio Ni: Mg Calcination ^{temperature (0} C) Tableting

Presence or absence of a solid solution

absent

NiSO

₄ ,

5.0
500

alkaline 2 ^C0 3 2.0 SOi, well 450 40 ³ C 1 H 5.0 550

3 mm χ 3 mm pellets

absent

present

present

2.0 500

present

HN HN HN HN HN

strong strong strong medium little little little little little w €

Printing conditions

Crystal start up to 500 hours after the start of B turn _{500 hours after the beginning}

up to 1000 hrs

Start medium little little little no no no no no no

Active start (original
^ tat (um-before activity) 52 50 49 48 48 46 53 50 52 50

^Swan ^ ^Ung 1000 hrs after loading

<g ^ln * J start 34 38 34 32 47 46 52 50 52 49

Q)

CQ

co

• Η ■ d (D .Ω CQ

H H (U ■ Ρ

U 0

Catalyst a -

Properties of the liquid at the beginning of the precipitation

used salt

Precipitation temperature

Duration of aging

Atomic ratio Wi: Mg 2.0

Calcination ^{temperature (0} C)

Tableting

Presence or absence

a solid solution present

a - 7

a -

a -

alkaline MgSO ₄ , hours 0.5 Na ₂ CO ₃ 0.5 NiSO 4 ' 40 ⁰ C 500 550 1 mm large 0.5 450 χ 3 Pellets 3 mm

absent

present

Printing conditions

IN THE

(D

•H

(D do

(D (D

Crystallite growth

Activity (conversion in %)

Start up to 500 hours after the start

500 hours after the start to .1000 hours after the start

Start (original activity)

1000 hours after the start

present

little no strong strong little little little none

no no
49
47

medium little no no no no 49 46 49 47 47

32

49

46

47

45

-SSO-

As can be seen from paragraph "B" of Table I, when using catalysts which do not contain a solid Solution, namely when using the catalysts a-1, a-2 and a-7, not only a clear crystallite growth, but also notice an extreme deterioration in catalytic activity after 1000 hours of use. In contrast, catalysts containing a solid solution at very stable catalytic Activity (only) a small amount of crystallite growth. In this context - as from paragraph "A" of the table I can be seen - also pointed out that with atomic ratios Ni «Mg in the region of 2.0 very easily forms a solid solution. At atomic ratios Ni: Mg in the region of 0.5 or 5.0, there was a tendency that the formation of the solid solution depends somewhat on the choice of the manufacturing conditions, e.g. the calcination temperature and the like, depends.

Example 2

Were the according to the procedure described under 1 those summarized in the following table IE under "A" Various catalysts prepared under conditions were used in the experiments described the results summarized under "B" in Table II below were obtained. The different catalysts were in the present case only in a steam reforming under a reaction pressure of 70 kg / cm * G tested.

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catalyst Table II a-10 a-11 0 H a-12 a-13 a-14 a-15 '3 2 dev. appl. a-16 a-17 a-16 ^ Properties of the liquid
£ j at the beginning of the felling 600 strong
middle alkaline 700 H H ^ Salt used Ni (N 47
27 o ₃ ) ₂ , Mg (NO,) ρ ,, K ₂ CO 3 mm pellets strong
middle little
no • g temperature during precipitation absent absent 70 ⁰ C dev. 45
24 43
43 ¹ S Ni: Mg atomic ratio H 3.0 H QU
A jgDuration of aging (hours) 0 strong
middle 0 2 2 strong
middle 5 5 5 *> ηcalcination temperature ( ⁰ C) 500 48,
27 700 500 600 45
24 500 600 700 O
co ■ £ Tableting 3 mm χ OO
■ ^^ (»Presence or absence
^w a solid solution dev. dev. appl. appl. -Ρ »
CD
"V.
t-l Printing conditions H H H H ^ ₉ <| Crystal start up to 500 hrs
glit wax after the beginning
B ω turn
* £ <500 hours after the start
■ g up to 1000 hrs
ω start middle
little strong
little middle
no we
nig
no P- <§ Start of activity (original
ω (conversion before activity)
in %) _{1000 hours after loading} _
start 45
28 46
26th 45
43 41
41

-24-

As can be seen from paragraph "A" of Table II, the higher the temperature, the more difficult it becomes for the precipitation to obtain a to form solid solution. In order to be able to form a solid solution, either the duration of the To prolong aging or to increase the calcination temperature. In this case, too, was a corresponding example 1 the activity of catalysts containing a solid solution is very stable.

Example 3

Were the according to the procedure described under 1 the various catalysts prepared under "A" in Table III below used in the experiments described, those in the following Table III under "B" were summarized Get results.

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Table III

Catalyst a - 19

a - 20

a- 21

j? » ο co

(D Properties of the liquid at the beginning of j * Precipitation Sp used salt £ j Precipitation temperature (D • g Duration of aging A ρ? Atomic ratio Ni: Mg ^ Calcination ^{temperature (0} C). P Tableting

CQ ^ Presence or absence of a fixed w solution acidic

, Mg (N. O ₃ ) ₂ , K ₂ CO ₃ 70 ⁰ C 6 hours 5.0 1.0 600 500

3 mm χ 3 mm pellets

absent

present

present

ο, printing conditions co Kristalö lit wax-B-gtum

0 activity

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

Start (original activity) 1000 hours after start

H N H N H N strong middle middle little little little middle little little no no no 49 47 49 46 52 50 33 31 45 45 51 50

-26-

CD ■ CD

catalyst

a

ω properties of the liquid at the beginning of the S precipitation

ö used salt
'S precipitation temperature
ω duration of aging

a - 22

a - 23

angry

a -

A § atomic ratio Ni

Mg

ηcalcination temperature (C) "ra tableting

ω presence or absence of a solid ^w solution

present

70 ⁰ C * 6 hrs

0.3
500

K ₂ CO ₃

0.3 600

mm χ 3 mm pellets

absent

present

Printing conditions

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

wCrystal- • £ j lit wax

BP turn
o>

hO

^ Activity start (original activity) ° 3 (conversion

1000 hours after the start

H N H N H N little no strong middle little no no no middle ivfenig no no 50 49 42 38 40 37 50 49 23 22nd 40 36

-27-

ο cn

As can be seen from paragraph "A" of Table III, even if the liquid was at the start of the precipitation was pissed off, a solid. Solution can be obtained. When the Ni: Mg atomic ratio is 1.0 or around was set to 1.0, a solid solution could be obtained very easily. This was also the case in this case Example 1 the activity of catalysts containing a solid solution is very stable.

Example 4

Were those summarized under "A" in the following Table IV according to the method described under 2. Various catalysts prepared under conditions were used in the experiments described the results summarized under "B" in Table IV below were obtained.

409840/0274

catalyst a-25 Tabel IV I. 3.0 3 appl. a-28 a-29 appl. a-30 a-31 a-32 CD
^ ^ Properties of the liquid a-26 a-27 700 τ τ
1 H CD speed at the beginning of the precipitation angry .... \
a-33 ^ used salt little MiSO ^, well ₂ co little ό precipitation temperature 40 ° C ¹ S duration of aging 1 H A g atomic ratio Ni: Mg, 3.0 no 1.0 1.0 no 1.0 0.5 0.5 ^ J calcination ^{temperature (0} C) 500 3.0 500 600 700 500 600 -Ρ » ■ p tabletting 600 49 mm χ 3 mm in size 51 Pellets 0.5 O
(O ο presence or absence 7Ö0 00 K of a solid solution dev. 47 appl. 50 appl. dev. appl. O Printing conditions H dev. 11 H H 1! O £ Crystal start up to 500 hrs π appl. ISJ co litwachs- after the start strong middle no strong little J! ρ » BTl turn ■ _crs ~. ,. ".
J3 500 hours after the start middle ω up to 1000 hours after no Sh beginning middle little no middle no (D
^ Activity start (original little S (conversion before activity) 53 53 48 46 45 no in %) _{1000 hours after loading} _ 51 start 29 50 47 28 44 43 28 43

-29-

As can be seen from paragraph "A" of Table IV, even when the catalyst was subjected to the precipitation work described under 2. a solid solution would be formed. If the atomic ratio ivii: Mg in was around 1.0, it was found that a solid solution was easily formed. In this case, too, was how in the previous examples, the activity of the catalysts containing a solid solution is very high stable.

Example 5

Were the methods described under 2. in the following: Table V summarized under "A" Various catalysts prepared under conditions were used in the experiments described the results summarized under "13" in Table V below were obtained.

-30-

409840/0274

Table V

catalyst

a - 34

a - 35

a -

4N O CO OO ■!> * O * v. O AI

^ Properties of the liquid at the beginning of «Precipitation ^ Salt used ■ aPrecipitation temperature ■ ^ Duration of aging A S Ratio Ni: Mg ^ JCalcination temperature ( ⁰ C) • pTabletting ^ Presence or absence of a solid solution, alkaline

JNiSO

3.0
600

absent

7O ⁰ C
2 hours

3.0 1.0

700 600

mm χ 3 mm pellets

present

absent

© Printing conditions wKristal-'filitwachs-

B -gtum

ωactivity

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

Start (original activity) 1000 hrs after

H N medium little

little little 51 50 30 29

HN
little little

no

49

48

no

medium little

little little 49 28

O CO

Catalyst a - 37

a - 38

a - 39

■ ο · ο co

Ö • Η

(U

• Ρ

Properties of the liquid Salt used at the beginning of precipitation Precipitation temperature Duration of aging Atomic ratio Wi: Mg Calcination ^{temperature (0} C) Tableting Presence or absence of a solid solution

present

alkaline

7O ⁰ C

2 hours

0.5 x 0.5 600 700

3 mm χ 3 mm pellets

absent

present

ο printing conditions

% Crystals lit wax-B φ turn

activity

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

Start (original activity) 1000 hours after start

H N H N H N little little middle little little little <j> no no little little no no 48 45 47 45 45 42 48 45 27 25th 45 42

-52-

K3

CD CD

2AO1617

As can be seen from paragraph "A" of Table V, even with slight modification of the manufacturing conditions a solid solution can be obtained, provided the manufacturing conditions, e.g. the calcination temperature and like, have been appropriately selected. The activity of the catalysts containing a solid As in the previous examples, the solution was very stable.

Example 6

Were those summarized under "A" in the following Table VI according to the method described under 3 Various catalysts prepared under conditions were used in the experiments described the results summarized under "B" in Table VI below were obtained.

-33-

409840/0274

- 33 Table VI

catalyst

a-4i

a-42

a-43

a-44

a-45

a-46

a-47 a-48

^ Properties of the liquid oil speed at the beginning of the precipitation

^ Salt used precipitation temperature angry

■ ^ Duration of aging

Mg

Aß atomic ratio IMi ^ calcination temperature ( ⁰ C) ■ p tableting

£ j presence or absence W of a solid solution

2.0 2.0 NiSO ^ , Na ₂ CO. 0.3 0.3 0.3 600 700 40 ⁰ C 500 600 700 3 mm χ 1 H 2.0 1.0 1.0 1.0 T 500 appl. appl. 500 600 700 abv /. dev. appl. 3 mm large pellets dev. appl. appl. appl.

Printing conditions

Crystallite wax turn

Activity (conversion in %)

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

Start (original activity)

1000 ginn

medium little little little little little medium medium little

little no no little no no 53 50 47 50 49 45

little little no

49

48

50

44

44

25th

42

24

-34-

As can be seen from paragraph "A" of Table VI, even if the catalyst was mixed according to the mixing procedure described under 3 a solid solution can be formed. When the Ni: Mg atomic ratio is in the region of 1.0, it was found that a solid solution was easily formed. In this case too there was activity of the catalysts containing a solid solution are very stable.

Example 7

If the various catalysts prepared according to the process described under 4. under the conditions summarized under "A" in Table VII below were used in the experiments described, the results summarized under "B" in Table VII below were obtained. In this case, the catalysts were first prepared according to one among 1st, 2nd or 3rd-described method, after which at a temperature of 800 ⁰ C a solid solution obtained by calcining the catalyst compositions obtained and finally the calcined catalysts in an aqueous Nikkeisulf atlösung have been dived.

409840/0274

• d yes catalyst

Table VII

a-49 a-50 a-51 a-52 a-53 a-54 a-55 a-56

O CO OO

co atomic ratio Ni ^ ff solid solution

Mg in the

Aη ratio of Ni to solid solution

<d at the time of immersion calcination ^{temperature (0} C) tableting

1.0

500

0.5

0.5

0.2

0.2

5 wt. 96

350 500 350 500 3 mm χ 3 mm pellets

0.1

350

0.1

500

Printing conditions φ crystal start up to 500 hrs

$ litwax-Β η turn

after the start

500 hours after the start to 1000 hours after the start

eq activity start (original (conversion activity) development in %) _{1 (? 00 hrs after}

start

little little little little little little medium little

little little little little little little little little 38 37 37 36 37 36 33

35

34

35

32

-36-

• tr »CD

As shown in paragraph ¹¹ B "is apparent from Table VII, was the catalytic activity of the catalysts since the calcination tinter temperature conditions was conducted (ie, at a relatively high temperature in the order of 800 ⁰ C), in which forms a solid solution, from the beginning was not so good, but the stability of the catalytic activity was excellent.

With regard to the ratio of Ni to solid solution at the time of immersion, it should be noted that the applied The amount of nickel salt (expressed as metallic nickel) was only 5% by weight of the solid solution. This is presumably responsible for the described lowering of the catalytic activity from the beginning. The catalytic However, activity can be improved somewhat by increasing the amount of nickel salt.

Example 8

If the various catalysts prepared according to the method described under 4. under the ^{conditions summarized in Table VIII below under 11} A "were used in the experiments described, the ^{results summarized in Table VIII below under 11} B" were obtained. In the present case, the catalysts were prepared in such a way that a catalyst mass was first obtained in the manner described under 1., 2. or 3., then a solid solution was formed by calcining the catalyst mass at a temperature of 800 ° C. and finally the whole with a precipitate obtained using aqueous solutions of NiSO ^ r, MgSO ^ and Na ₂ CO.

The precipitate was obtained under the following reaction conditions:

-37- 409840/0274

Property of the liquid at the start of precipitation: acid precipitation temperature: 7O ⁰ C
Duration of aging: 5 hrs
Atomic ratio Ni: Mg: 3.0.

S Table VIII

^ Catalyst a-57 a-58 a-59 a-60

a> atomic ratio Ni / Mg

-in the solid solution 1.0 0.5 0.2 0.1 & o
A «ratio of Ni to more solid

^ Solution at the time

3 immersion 20 wt%

"ω calcination ^{temperature 500 0} C, ^ tableting 3 mm χ 3 mm large pellets

Printing conditions HHH H ICri start up to 500 hrs

stallit-little little little after beginning. little

500 hours after the start to 1000 hours
g after beginning no no no no

vi- start (original

(Surrounding activity) 49 48 49 47

_i 1000 hours after loading
^ ⁿ ginn 47 45 45 44

From Table VIII it can be seen that the catalysts prepared in the manner described are excellent and very good have stable activity.

Example 9

Were the according to the procedure described under 1 those summarized under "A" in Table IX below Conditions produced different catalyst

-38-

409840/0274

Ren used in the experiments described were
the results summarized in the following Table IX under ¹¹ B "were obtained. SiC was used as the carrier.

-39-

409840/0274

Table IX

Catalyst b - 1

b - 2

b -

O
CO
OO

Ö • H

-P (O

Properties of the liquid Salt used at the beginning of precipitation Precipitation temperature Duration of aging Atomic ratio Ni: Mg Calcination temperature Content of carrier (% by weight) Tableting Presence or absence of a solid solution alkaline

40 ⁰ C
1 hour 3

35O ° C 60. mm χ 3 mm size pellets

absent

absent

absent

03

■ Η

Q)

bO

Printing conditions

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

Start (original activity) 1000 hours after start

Crystallite wax tum

activity

H N H N -44 H middle middle middle middle middle strong less little little little little little 36 55 52 54 52 39 21 30th 32 28 31 21 IND
-P-
O

CT)

Catalyst Td - 4

b - 5

b -

H H Φ ■ Ρ

Properties of the liquid at the beginning of the precipitation

Salt used Precipitation temperature Duration of aging Atomic ratio Ni: Mg Calcination temperature Carrier content (% by weight ) Tableting

Presence or absence of a solid solution alkaline

Ni (NO,) ,,, Mg (NO,) «, NapCO,

40 ⁰ C
1 H
3

600 ⁰ C
60

80 mm χ 3 mm pellets

present N
little present N
little present N
middle H
little little
52
52 H
little little
50
49 H
strong little
35
26th little
56
55 little
53
51 little
38
25th 240 -Vl-

_φ printing conditions μ crystal oil wax-B-gtum ω ω activity

Start up to 500 hours after the start

500 hours after the start to 1000 hours after the start

Start (original activity) 1000 hours after start

It can be seen from paragraph "B" of Table IX that a solid solution could be obtained even in the case of a supported catalyst. The one such solid Solution containing catalysts were very stable. In the event that the proportion of the carrier in the catalyst is 80 Wt%, not only was the initial activity insufficient, but also the stability very bad.

Example 10

If the various catalysts prepared according to the process described under 2. under the ^{conditions summarized in the following table X under 11} A "were used in the experiments described, the results summarized in the following table X under" B "were obtained ^ used.

409840/0274

Table X

catalyst

b - 7

b-8

b-9 b-10

b-11

b-12

b-13

"b-14 b-15

Properties of the liquid g at the beginning of the precipitation

bO

ö used salt

pP precipitation s temperature
ό Duration of aging
AS atomic ratio Ni: Mg '5.0 5.0 Calcination ^{temperature (0} C) 500 600

Content of carrier
■ g tabletting

φ presence or absence

& a solid solution dev. appl.

angry

(D

MSO ₄ , ^ _d

70 ° C
hours

5.0 2.0 2.0 2.0 500 600 700% by weight '
mm χ 3 mm pellets

0.5 500

appl. appl.

appl.

appl.

dev.

0.5 600

dev.

Printing conditions H HHH

g crystal- onset up to 500 hours wax- strong after the start

B ^ tum _{500 hours after the start}

g> up to 1000 hrs

u start little

§ Activity start (original p (Conversion before activity) 54

in %) ₁₀₀₀ ... _B.

start 32 51 50

medium little little little little medium medium little

little little little little little little little little 50 51 49 45 44 42

49

45

24

23

From paragraph "A" of Table X it can be seen that even with slight modification of the manufacturing conditions a solid solution could be made, provided the Production conditions, for example the calcination temperature and the like, are appropriately selected. The catalysts obtained in this way with solid solution content had very stable activity.

Example 11

In Examples 9 and 10, SiC and oC -Al ₂ O were used as the carrier component. In the present example, tests were carried out with other carrier components. The catalysts with these carrier ingredients were prepared under the conditions set forth in Section "A" of Table XI. The property "MgO outflow ratio" given in paragraph "B" of Table XI stands for the numerical value obtained by determining the weight ratio of the catalyst after being suspended in water from an unused and 1000 h used catalyst into the continuously gaseous carbon dioxide at a Pressure of 60 mm water column was introduced, into which water escaped MgO and multiplying the weight ratio by 100 was obtained.

-44-

409840/0274

Table XI

catalyst

b - 16

b - 17

b - 18

Properties of the liquid at the beginning of the precipitation

used salt
j ^ precipitation temperature
Mduration of aging
A 'a Ni: Mg atomic ratio
■ ^ calcination temperature

c ^ carrier component
^ Content of carrier

$ Tabletting
ω

^ Presence or absence of a solid K solution

cL -

alkaline
NiSO ₄ , MgSO ₄ , IMa ₂ CO ₃

40 ⁰ C

1 H

450 ⁰ C
, O ₃ SiC

30 wt -.%
mm χ 3 mm pellets

oi quartz

present

present

present

Printing conditions

wKristal-.nlitwachs-B | j turn

Start up to 500 hours after the start

500 hours after the start to 1000 hours _ω after the start

^ ⁰ MgO outflow ratio (%)

Start (original activity) 1000 hours after start

<g activity

H
little

little 99.8 53 53

N
little

little
100.0
50
49

HN
medium little

H N little little

little little little little

99.5 99.9 100.0 100.0

52 49 55 52

50 49 52 51

-45-

catalyst

b -

b - 20

b - 21

Properties of the liquid at the beginning of the ZrO ₂ WIi N alkaline 3 SiO ₂ gel N K) precipitation little 3O ₄ , MgSO ₄ , Na ₂ CO little ^ used salt 40 ⁰ C O G precipitation temperature little 1 H little % Duration of aging 99.7 2 84.3 Ao atomic ratio Ni: Mg 48 450 ⁰ C 47 ^ Calcination temperature
Wi 48 f -Al ₂ O ₃ 37 £ j carrier component 3 mm χ 3 30 wt -.% present ** \ η content of carrier mm large pellets H ■ £ Tableting present middle ω presence or absence of a fixed H present * Solution middle H N little Printing conditions strong little 68.0 <g crystal start up to 500 hours after the start little 56 B "" turn ^a ^ ^{00 s} ^ ^{d nac: n} start up to 1000 hrs 99.3 little little 30th j = j after the beginning 51 63.0 81.5 fcoMgO outflow ratio {%)
Cj 51 54 49 -46- ^ Activity start (original activity) 29 38 ^S lunff ^ n '^) ^ ^^^ ^s ^ ^{d nacil} ßeS ^ ¹¹¹¹

The carrier materials used were those in the following compilation listed carrier used.

carrier

06 -Al ₂ O ₃ SiC

oo quartz 2

Pure Ness Specific
surface m ² / g Grain size ' 99% (commercial) 2.8 Il less than
200 mesh 90% (by electro
melt here
represents) 1.0 Il Il above 99% 2.0 Il It at
long 1500 ⁰ C 20 hrs
calcined 3.6 Il Il 99% fcandelsrein) 190 Il It 99.5% (commercial grade) 600 Il

^ -Al ₂ O ₃

SiO ₂ gel

As can be seen from paragraph "B" of Table XI, those containing an inert carrier which can be used according to the invention show Catalysts b-16, b-17, b-18 and b-19 in the frame of the method according to the invention a subordinate crystallite growth, a high MgO outflow ratio and a very stable catalytic activity. On the other hand, the catalysts possessed b-20 and b-21 in spite of Solid solution content is not as favorable Properties.

Example 12

Energy studies have been conducted to determine the preferred range of the atomic ratio of the nickel component to the magnesium oxide component (M / Mg) in the nickel and magnesium oxide which can be used according to the invention to determine containing catalysts. The results given in Table XII below were obtained obtain.

409840/0274

The catalysts a-6i, a-62, b-22 and b-23 were prepared in such a way that first a solid solution with an atomic ratio Ni: Mg of 0.15 was prepared by the method described under 1., then the obtained solid solution was suspended in an aqueous magnesium nitrate solution in such a way that the weight ratio of solid solution to MgO (derived from magnesium nitrate) of 3: 7 was reached, then by adding Na ₂ CO to the resulting suspension, a precipitate was precipitated and then the After drying, the precipitate was immersed in an aqueous nickel sulfate solution to impregnate it with 1 or 3% by weight of nickel oxide. In this way, catalysts with the appropriate ratio of the components were obtained.

The described catalysts can also be prepared directly by the process described under 1. In the catalysts produced in this way, however, the atomic ratio Ni: Mg is so low that the peak of the content of solid solution in the catalytic converters with the X-ray diffraction devices currently in use is easy to determine. In the present case, however, the catalysts were used in the manner described above manufactured. The catalysts a-63, a-64, b-24 and b-25 of Table XII were according to the under 1. described Process made. The other preparation conditions are given in paragraph "A" of Table XII.

409840/0274

Table XII

catalyst

a a - 62

Properties of the liquid at the beginning of the precipitation

0) «salt used g> precipitation temperature £ duration of aging atomic ratio Ni j

Mg

Calcination temperature

3 Carrier content (% by weight) -ρ tableting w

yyy Presence or absence of a solid W solution a -

alkaline ) ₂ , Well Ni (NO ₃ ) ₂ , Mg (NO ₃ 40 ⁰ C 6 hours 6.9 0.044 0.059 600 ⁰ C 0 0 0

mm χ 3 mm pellets

a -

present present

present

8.2 0

present

_φ printing conditions

w Crystal start up to 500 hours after the start

olite growth

H N little little

φ activity

500 hours after the start to 1000 hours

little little after the beginning

Start (original activity) 21

1000 hours after beginning 13

H N

little little

little little

34 31

34 31

HNHN little little medium medium

little little little little 55 50 49 54 51 19

-49-

K)

CD CO

Catalyst b - 22

b - 23

b - 24

b - 25

Properties of the liquid at the beginning of the precipitation ^ Salt used

^ Precipitation temperature dduration of aging A § atomic ratio Ni / Mg a calcination temperature 3 Carrier content (wt .- ^) • p tableting

^ Presence or absence of a solid solution alkaline

40 ^u C 7.0 8.2 : 6 hrs 0.043 0.059 30th 30th '60O ⁰ C Pellets 30th 30th 3mm χ 3mm in size

present

present

present

present

φ printing conditions

«Crystal start-up to 500 _{hours after the start of φ-cum- 5 () 0 gtd after the start up to 1000 hours} φ-cum _{after the start}

ω Start of activity (original activity) i ^ / o) 1000 hours after the start of ENT a little little little little little little medium medium

little little little little little little little little 18 17 32 28 52 48 47 45 10 11 31 28 52 47 20 22

-50-

K) O CD

From Table XII it can be seen that the catalysts a-61 and b-22, the Ni: Mg atomic ratio of which was less than 0.05, had both poor initial activity and exhibited poor stability and despite the presumed presence of a solid solution as steam reforming catalysts were unsuitable. The catalysts a-64 and b-25, whose atomic ratio is Ni * Mg above 7.0 were about satisfactory in their initial activity but showed a tendency to very poor stability. The catalysts a-62 and b-23, their atomic ratio Ni: Mg on about 0.05 did not show particularly good initial activity, but they were outstanding Stability. Your performance in practice was satisfactory. The catalysts a-63 and b-24, whose Ni: Mg atomic ratio was set below about 7.0 showed excellent initial activity and satisfactory stability.

Example 13

Various copper / chromium oxide were obtained under the conditions given in Tables XIII to XVI below or catalysts containing copper / chromium / manganese oxide.

-51-

409840/0274

Table XIII

Production of catalysts according to the process described under 1

catalyst

c-1

c-2 c-3 c-4 c-5 c-6

Properties of the liquid at the beginning of the precipitation

Salt used Precipitation temperature Duration of aging Atomic ratio Ni: Mg 5 Calcination ^{temperature (0} C) 500

Shaping

Presence or absence, a solid solution dev.

Amount of added

Cu-Cr oxide (wt .-? 0 15 Amount of added Cu-Cr-Mn oxide (wt .-? 0-alkaline
, MgSO ₄ , Na ₂ CO ₃ 40 ⁰ C
1 H
2 2 0.5

500 '500 450 mm χ 3 mm pellets

0.5 500

anw «anw. appl. dev. appl.

15th

-52-

409840/0274

Table XIV

Production of catalysts according to that described under 2 procedure

catalyst

c-7 c-8

c-9

c-10

c-11

Properties of the liquid Salt used at the beginning of the precipitation * Precipitation temperature Duration of aging Atomic ratio Ni: Mg 3 Calcination ^{temperature (0} C) 600 Forming

Presence or absence of a solid solution dev.

Amount of Cu-Cr-Mn oxide added (wt .- ^) 5

angry Yes ₂ CO ₃ 0.5 0.5 NiSO ₄ , ί 500 600 40 ⁰ C 1 H 1 3 500 700

mm χ 3 mm pellets, etc.

appl.

dev.

15th

appl.

15th

* Commercially available MgO was used as a magnesium component used.

Table XV

Production of catalysts according to the process described under 4

catalyst

c-12 c-13

c-14

Atomic ratio Ni / Mg in the

solid solution * 0.5

used salt

Ratio of Ni to solid solution at the time of immersion

Calcination ^{temperature (0} C) molding

Amount of Cu-Cr-Mn oxide added (% by weight)

0.2

0.1

5 wt% 450

350

mm χ 3 mm pellets

15 wt .- ^

* Ni / Mg atomic ratio in the solid solution; The solid solution was one previously calcined at a temperature of 800 C according to the method described under 1. prepared solid solution. "

409840/0274 " ^{5 :?} "

Table XVI Preparation of catalysts according to the process described under 1.

Catalyst d - 1 d-2 d-3 d-4 d - 5 d - 6 d-7

Properties of the liquid Salt used at the beginning of the precipitation

Precipitation temperature 4 ^. ' Duration of aging ° Atomic ratio Ni: Mg °° Calcination ^{temperature (0} C) ο Forming

_o Presence or absence of one

ho fixed solution absent present present present present present anw.

Jj carrier component SiC

Carrier content * 30 30 60 80 30 60 80

Amount of added Cu-Cr-Mn-

Oxide (wt-96). 10

1 5 3 alkaline 3 2 2 550 tfi ( _{NO,) 2} , Mg (NO ₃ ) ₂ , Na ₂ CO 500 500 40 ° C 1 H 2 5 5 5 500 500 550 550 mm χ 3 mm pellets

ro

CD

alkaline Ni (NO ₃ ) ₂ , Mg (NOj) ₂ , Na ₂ CO ₃
40 ⁰ C 60 ⁰ C

Catalyst. d-8 d - 9 d - 10

Properties of the liquid Salt used at the beginning of precipitation Precipitation temperature Duration of aging Atomic ratio Ni: Mg Calcination temperature ( ⁰ C) Forming Presence or absence of a solid solution

Carrier component. SiC

Carrier content * 30

Amount of added Cu-Cr-Mn-

Oxide (wt%) d - 11

d - 12

angry

d -

1 hours 0.5 2 2 2 hours 2 2 0.5 500 500 500 500 500 450

mm χ 3 mm pellets

absent present present present present

oC quartz ZrO,

35

35

Silica gel ^ T 35 35

15th

-55-

* The properties of the carrier materials on a Supported catalysts of Table XVI are shown in Event II. Were these in the depicted Catalysts prepared in this way were subjected to the tests outlined in the table below XVII obtained results compiled.

409840/0274

Table XVII

Catalyst symbol

Amount of to-react crystallite growth

set start up to 500 hours after loading

Cu-Cr-Oxide pressure ₂ 500 hours start to 1000

or Cu-Cr- (kg / cm · G) after beginning std after beginning Mn-Oxid
(% By weight )

Activity (conversion to Jb) start (original 1000 hrs borrowed activity) after beginning

c-1 15th 10 mxttel little 70 strong middle c-2 15th 10 little little co
00 70 middle little c-3 15th 10 middle little O
• ν, 70 strong little O c-4 15th 10 middle little 70 strong little c-5 VJl 10 middle little 70 strong middle c-6 5 10 little little 70 middle little c-7 5 10 middle little 70 strong middle c-8 5 10 little little 70 little little c-9 VJl 10 little little 70 little little

63 65 62 63 59 61 58 59 57 59 58 60 59 61 62 63 60 61

38 in 35 r » 59 59 56 57 56 57 37 ro 35 Jr- 58 CD
\ 57 CD 39 38 59 59 58 58

Catalyst symbol

Amount of added
Cu-Cr oxide
or Cu-Cr-Mh oxide
(Wt .- #)

Reaction pressure ρ (kg / cm -G)

Crystallite growth activity (conversion in %)

Start up to 500 hrs after the start (original 1000 hrs

500 hours start to 1000 hours of activity; after Benach Start hour after start

c-10

c-11

0-12

c-13

c-14

d-1

d-2

d-3

d-4

15th
15th
15th
15th
15th
10
10
10
10

10 70 10 70 10 70 10 70 10 70 10 70 10 70 10 70 10 70 medium

middle

middle

middle

medium medium

little

middle

little

little

no

no

no

no

no

no

little

middle

little

little

little

little

little

little

65 40 co ro
O 66 39 cn 64 62 64 61 49 - 47 51 47 VJT -P-
O VD 46
47 49 46 49 46 61 36 63 36 63 62 64 62 54
56
39 52
53
27 42 27

-58-

Catalytic amount of add symbol set
Cu-Cr oxide
or Cu-Cr-Mh oxide
(Wt .- #)

Reaction crystallite growth starts up to 500 hours after printing 2 500 hrs start to 1000 (kg / cm * G) after the start hrs after the start

Activity (conversion in %) start (original 1000 hrs activity) after start

d-5

d-6

409841 d-7 ο d-8 0274 d-9 d-10 d-11. d-12 d-13

10
10
10
10
10
15th
15th
15th
15th

10
70
10
70
10
70
10
70
10
70
10
70
10
70
10
70
10
70

middle

middle

little

little

middle

strong

middle·

strong

little

middle

middle

middle

little

little

middle

strong

middle

strong

middle

58 54 , d ro 59 55 -P- 53 51 σ 55 53 cn 38 27 42 28 58 40 59 34 58 57 ' 58 56 58 ' 57 58 56 66 65 68 66 69 39 70 38 67 38 68 38

-59-

From Table XVII it can be seen that when using catalysts without a solid solution content, namely when using the catalysts c-1, c-5, c-7, c-10, d-1 and d-8, in the context of a Steam reforming reaction not only an extreme crystallite growth took place, but also a strong impairment of the catalytic activity had occurred 1000 hours after the start of the reaction. When using the catalysts d-4 and d-7 with, based on the total weight of the catalyst, more than 70 wt. The catalysts with silica gel or Jf-Al ₂ O ,, ie with customary support components for customary catalysts, namely the catalysts d-12 and d-13, showed the same tendency as the described catalysts without a solid solution content. In this connection it should be pointed out that the catalysts d-12 and d-13 contained a solid solution at the beginning of the reaction, that the presence of the solid solution was no longer detectable after prolonged use as part of a reforming reaction (for example after 1000 hours). The reason for this disappearance of the solid solution is not fully understood, but there is no doubt that this disappearance in some way adversely affects the activity of the catalyst.

Example 14

In the table in Tables XIII to XVI for catalysts c-2, c-3, c-4, c-6, c-8, c-9, c-11, c-12, c-13, c-14 , d-2, d-3, d-5, d-6, d-9, d-10 and d-11 Manner, but modifying the amount of copper / chromium oxide or copper / chromium / manganese oxide in the range of

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O to 25 g, were catalysts c ^f -2, c'-3, c * -4, c'-6, c «-8, c« -9, c «-1.1, c'-12, c« - 13, C »-14, di2, d'-3, d ^f -5, d'-6, d ^! -9, d «-10 and d« -11. In each case 25 g of the catalysts obtained were introduced into a reforming reactor and activated ^{by reduction in a hydrogen gas stream at a temperature of 500 ° C. for 10 hours.} Then a naphtha starting material with an IBP of 33 C, an FBP of 122 ⁰ C, a specific gravity d ^ ⁵ of 0.675, a sulfur content of 13.5 ppm and 6.04 carbon atoms per molecule and 13.4 hydrogen atoms per was in the reforming reactor Molecule introduced at a rate of 80 g / h together with steam in the ratio H ₂ 0 / C (mol / atom) of 2.0 and there continuously for 200 h under a reaction pressure of 70 g / cm ^· G and at a reaction temperature of 500 ° C steam reformed.

The relationship between the content of copper / chromium oxide or copper / chromium / manganese oxide in each catalyst and the degree of conversion 200 hours after the start of the reaction (in the context of this experiment) is evident from FIGS. 1 to 5. In this context, it should be noted that that the present example was used to evaluate the sulfur resistance of the catalysts in question by a relatively high sulfur compound containing naphtha feedstock was used. In this example, the degree of conversion was deliberately controlled in order to as with the previous examples, to make the comparison easier.

From Figures 1 to 5 it can be seen that those catalysts their content of copper / chromium oxide or copper / Chromium / manganese oxide, based on the nickel content in metal

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Lischer form, 5 to 20, especially 10 to 20 wt. % , have not only excellent sulfur resistance, but also long-lasting and stable activity in low-temperature steam reforming processes.

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Claims (18)

Claims 1. Process for the production of a methane-containing gas
(in the context of a (low-temperature steam) reforming), in which one contains a hydrocarbon with at least 2 carbon atoms per molecule
Hydrocarbon feedstock and (at least) introducing to a temperature of 250 ° to 600 ⁰ C preheated steam in a packed with a nickel-containing catalyst Dampfreformierreaktor and .the hydrocarbon material under a reaction pressure of
reformed at least 1 atmosphere and at a catalyst bed temperature (in the reactor) of 300 ° to 600 ° C, characterized in that the reforming is carried out in
In the presence of a catalyst containing nickel and magnesium with an atomic ratio Ni.:Mg of 0.05 to 7.0 and a content of a solid solution of nickel oxide and magnesium oxide. 2. The method according to claim 1, characterized in that the reforming in the presence of one on one
Carried out nickel-containing catalyst applied, the carrier made of an inorganic,: refractory and with the other catalyst components
there is no chemical reaction during the reforming process and, based on the total weight of the catalyst, is less than 70% by weight, 3. The method according to claim 2, characterized in that the reforming in the presence of one on one
O6-Al ₂ 0, -, SiC-, oC -quartz and / or ZrO ₂ carrier applied, nickel and magnesium-containing catalyst carries out. A09840 / 0274 - 63 - 4. The method according to one or more of the preceding claims, characterized in that the Reformierimg in the presence of a nickel-containing catalyst "carried out, the additional, based on the nickel component in metallic form, contains less than 25 wt .- ^ copper / chromium oxide or copper / chromium / manganese oxide. 5. The method according to claim 4, characterized in that the reforming in the presence of a nickel-containing Carries out catalyst, based on the nickel component in metallic form, 10 to 20 wt .- #> Contains copper / chromium oxide or copper / chromium / manganese oxide. 6. The method according to one or more of the preceding claims, characterized in that the hydrocarbons Hydrocarbon feedstock containing at least 2 carbon atoms per molecule Refinery off-gases, light natural gas (LPG), light naphtha, Heavy naphtha and / or kerosene. Used. 7. The method according to claim 1, characterized in that the hydrocarbon starting material and the steam are introduced into (at least) one steam reforming reactor in the ratio H ₂ O / C (mol / atom) of 0.9 to 5.0. 8. The method according to claim 1, characterized in that one works at a reaction pressure of 10 to 100 kg / cm · G. 9. The method according to claim 8, characterized in that at e:
is working. at a reaction pressure of 50 to 100 kg / cm "G A09840 / 0274 10. The method according to claim 1, characterized in that one works at a catalyst bed temperature ^{of 400 ° to 570 0 C.} 11. The method according to claim 1, characterized in that one with a winding and magnesium containing catalyst an atomic ratio i-; i: £ Ig of 0.5 to 5.0 is working. 12. The method according to claim 1, characterized in that, the solid solution uses a nickel-containing catalyst in which nickel oxide and magnesium oxide by calcination at a '.Temperature of 350 ° C was generated ⁰ to 1200. 13. The method according to claim 12, characterized in that, the solid solution uses a nickel-containing catalyst in which magnesium oxide and from iviickeloxid by calcining at a temperature of 600 ° C was generated up to 800 ^0. 14. The method according to claim 1, characterized in that one works with a nickel-containing catalyst which either by immersing one according to the precipitation, deposition or mixing process (see description IMr. 1, No. 2 and Mr. 3) produced catalyst mass with a solid solution of winding oxide contained therein and magnesium oxide into an aqueous solution of a nickel salt or by mixing them together Catalyst mass with a hydroxide or basic carbonate of winding and magnesium and then renewed Calcining the resulting mixture at a temperature of 300 ° to 600 ° C was obtained. 409840/0274 - 05 - 15 »^ iedrigtemperatur-steam reforming process for hydrocarbons for the production of a methane-rich gas, characterized in that a hydrocarbon having at least 2 carbon atoms per molecule containing 'hydrocarbon starting material and to a temperature of 250 ° to 600 ⁰ C preheated steam in the ratio of steam to hydrocarbons (H ₂ O / C - mol / atom) of 0.9 Ms 5.0 in (at least) one with a wound / magnesium oxide catalyst with an atomic ratio JMiiMg of 0.5 Ms 5.0 and a solid solution content introducing packed from lMickeloxid Dampfreformierreaktor and magnesium and the hydrocarbon feedstock under a reaction pressure of 50 to 100 kg / cm "G at a catalyst bed temperature in the steam reformed and the reactor (s) of 400 ° to 570 ⁰ C. 16. ii low-temperature steam reforming process for hydrocarbons for the production of a methane-rich gas, characterized in that a hydrocarbon starting material containing at least 2 carbon atoms per molecule and at a temperature of 250 ° to 600 ° C is vorerhita th steam in the ratio of steam to hydrocarbons ( hpO / C - mol / atom) from 0.9 to 5.0 in (at least) one with a backel / magnesium oxide carrier catalyst with an atomic ratio of nickel to magnesium from 0.5 to 5.0, a content of a solid Solution of nickel oxide and magnesium oxide and a carrier consisting of ^ C / -Alp ⁰ - * »SiC, oC quartz and / or ZrOp, which, based on the total amount of catalyst, makes up less than 70% by weight, packed steam reforming reactor introduces and the hydrocarbon feedstock 409840/0274 - 66 - under a reaction pressure of 50 to 100 kg / cm »G and steam reformed at a catalyst bed temperature in the reactor (s) of 400 ° to 57O ° C. 17. wiedrigtemperatur-steam reforming process for hydrocarbons for the production of a methane-rich gas, characterized in that a hydrocarbon having at least 2 carbon atoms per molecule containing hydrocarbon feedstock to a temperature of 250 ° to 600 ⁰ C preheated steam in the ratio of steam to hydrocarbons (H ^ O / C - mol / atom) from 0.9 to 5.0 in (at least) one with a winding and magnesium-containing catalyst with a molar ratio 1Mi: Mg of 0.5 to 5.0 and a content of a solid solution of rock oxide and magnesium oxide, which additionally contains 10 to% by weight copper / chromium oxide or copper / chromium / manganese oxide based on the winding portion in metallic form, introduces the packed steam reforming reactor and the hydrocarbon starting material under a reaction pressure of 50 to 100 kg / cm * G and steam reformed at a catalyst bed temperature in the or the reactor (s) of 400 ° to 570 ⁰ C. 18. ^ low temperature steam reforming process for Hydrocarbons for producing a methane-rich gas, characterized in that a hydrocarbon is used Hydrocarbon feedstock containing at least 2 carbon atoms per molecule and steam preheated to a temperature of 250 ° to 600 ° C in relation to steam to hydrocarbons (H ^ O / C - mol / atom) from 0.9 to 5.0 in (min- 409840/0274 at least) a catalyst containing nickel and magnesium with an atomic ratio iJi: Mg of 0.5 to 5.0 and a content of a solid solution of nickel oxide and magnesium oxide, which, based on the nickel content in metallic form, is 10 to 20 Contains% by weight copper / chromium oxide or copper / chromium / mangah oxide and on an inorganic, refractory carrier in the form of <? C -AlpO, which makes up less than 70% by weight, based on the total catalyst ^ SiC, oO quartz and / or ZrO _{2 is} applied, packed steam reforming reactor and introduces the hydrocarbon starting material under a reaction pressure of 50 to 100 kg / cm * G at a catalyst ^{bed temperature in the reactor (s) of 400 ° to 570 0} C steam reformed. 409840/0274 4 * Blank page