DE2359116A1 - 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

St. NKHL KERN FEILER HÄNZEL MÜLLER

DR 1 * 1111. IHPI. ING. I) It. RUR. ΝΛΤ. IMI'L.-INCi. MPL.-INC ».

'''' ^y '■ ii ^ Ki i> IU) UAIU) -SCH MI D-STRASSE 2 ιιλυ ι ri.se in; ιιυρογηι = .κ.ι-.ν- and

im him »» !!, «III,.» »·» »! ·«: ■, ■ vvu iishdank. mcnchi ν mi. uk-kmii

IIIIi, ItAMMI I I 1 ll'SCIIIl MONCIlIN Ii-IlUlHI MUNl 11 U CN v (l P OS I S C 111 (.'K MITtIN 162147 K09

Japan Gasoline Co., Ltd., ^ ₁ , ^

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

Process for the production of a methane-containing gas in the context of a low-temperature steam reforming or low-temperature steam "reforming process for Koh lenwasserstoffe to produce a methane-rich gas

The invention "relates to a method for catalytic Steam reforming of hydrocarbons with at least 2 carbon atoms per molecule at temperatures of 300 ° to 600 ° C, in particular a method for producing a methane-containing gas, preferably one methane-rich gas, for example by adiabatic steam reforming of a hydrocarbon starting material in the presence of a low temperature steam reforming process a superior, improved nickel-containing catalyst.

For the production of a methane-containing gas by low-temperature steam reforming of a hydrocarbon feedstock in the presence of a nickel-containing catalyst, various methods have been used suggested. In the method described in Japanese Patent Application 11047/1965

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a nickel, aluminum trioxide and an element from the Series of the lanthanide-containing catalyst used. The process described in Japanese patent application 11048/1965 works with a nickel / aluminum trioxide / iron catalyst. In Japanese patent application 19174/1970 a method is described in which a wound / aluminum trioxide / alkaline earth metal catalyst is used.

With prolonged use of these common catalysts as part of a low temperature steam reforming process, particularly a high pressure, low temperature steam reforming process must with some unstable factors, e.g. a decrease in the catalytic activity of the catalyst per se or a deposit of carbonaceous material on the catalyst, can be expected * In addition these common nickel-containing catalysts are poisoned by sulfur-containing impurities, which is why hydrocarbon feedstocks with a relatively large proportion of sulfur compounds under quite drastic Conditions must be subjected to a desulphurizing pretreatment.

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 it out the unstable factors to be taken into account when using the known nickel-containing catalysts without let control.

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The invention thus provides a process for producing a methane-containing gas, wherein said reacting a hydrocarbon having at least 2 carbon atoms per molecule containing hydrocarbon feedstock and preheated to a temperature of 250 ° to 600 ⁰ C steam in the ratio of steam to hydrocarbon (H ₂ 0 / C - mol / atom) from 0.9 to 5.0 in at least one steam reforming reactor. introduces that is packed with i

(a) a catalyst containing nickel and magnesium with a Ni: Mg atomic ratio of 0.5 to 5.0, preferably 1.0 to 3.0; or

(B) a by applying a catalyst described under (a) to an inorganic, refractory Carrier material that is both against nickel and against a magnesium, especially magnesium oxide component is inert and, based on the total catalyst, less than 70 wt constitutes, obtained catalyst; or

(c) a catalyst containing nickel and magnesium with an atomic ratio of nickel to magnesium of 0.5 to 5.0, based on the nickel content in metallic form, additionally less than 25, preferably 10 to 20% by weight copper / chromium oxide or Contains pluckers / chromium / manganese oxide; © the

(d) a by applying a catalyst described under (c) to an inorganic ₉ refractory carrier material, which is inert to both nickel and a magnesium, insb@sond.ere magnesium oxide component and, based on the total catalyst, less than 70 wt _e »% makes up the catalyst obtained

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and that the hydrocarbon feedstock is through

Applying a reaction pressure of 10 to 100 kg / cm · G at a catalyst bed temperature in the ert or the reactor (s) of 300 ° to 600 ⁰ C, preferably 400 ° to 570 ⁰ C, dampfreformi.

As a hydrocarbon starting material, refinery waste gases, light natural gas, (LPG), light naphtha, heavy naphtha, Use kerosene and the like. These hydrocarbon feedstocks are combined with steam in the Mixing ratio steam to hydrocarbons (J ^ O / C, i.e. the number of moles of steam relative to one carbon atom in the hydrocarbon feedstock) is expedient 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 become: a) Wi-MgO or Ni-NiO-MgO; b) Ni-MgO- (carrier) or Ni-NiO-MgO- (carrier); c) Ni-MgO- (Cu * Cr oxide or Cu »Cr« Mn oxide) or Ni-JMiO-MgO- (Cu-Cr oxide or Cu-Cr-Mn oxide) and d) Ni-MgO (Cu «Cr oxide or Cu'Cr'Mn oxide) - (carrier) or Ni-NiO-MgO- (Cu »Cr oxide or Cu · Cr «Mn oxide) - (carrier) each at a point in time on which the catalyst in question has been activated by reduction and where it is MgO is an active magnesium oxide that accelerates the low-temperature steam reforming in question able. Examples of support materials which can be used for catalysts b) and d) are inorganic, Refractory supports, which with the remaining catalyst components, namely the nickel component or components (en) and the magnesium oxide component, during the

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Reformation reaction do not enter into a chemical reaction, eg 06-Al ₂ O ,, SiC, oc- quartz., ZrO ₂ and the like. In this connection it should be pointed out that known materials such as

^ -Al ₂ O ₅ , silica gel, kaolin and the like, are unsuitable as supports for the catalysts of 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 of the formula Cu ₂ Gr ₂ Oc exist. The manganese represents a component which increases the efficiency of a catalyst according to the invention even further in the presence of the copper / chromium component.

Without considering a quantitative ratio and only with regard to the individual components of the catalyst As such, US Pat. No. 2,083,795 discloses a steam reforming process for hydrocarbons using a binary catalyst corresponding to the catalyst according to the invention a) known. In the process known from the US Pat Hydrocarbon feedstocks are produced. There is no reference to any reference to this in the US patent mentioned the possibility of using the binary catalysts concerned in the context of low-temperature steam reforming s method for the production of methane-containing, in particular methane-rich gases, such as this according to the invention is intended.

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In addition, the catalysts used in the known process differ from those according to the invention Catalysts used in the ratio of the components 1Mi / Mg, i.e. in the atomic ratio of the winding component (e) to an atom of magnesium, quite considerably, as will be shown later in more detail.

Regardless of the materials used as supports, nickel / magnesium oxide / supported catalysts have also been used corresponding to the inventive catalyst b) within the scope of the Japanese patent application 11047/1965 described steam reforming process used. When such catalysts are used in high pressure, low temperature steam reforming reactions are used, there is a chemical reaction between during the reforming reaction the aluminum trioxide of the support, the catalytically active IM ickelbe was part and the cocatalyst alkaline earth metal (e.g. magnesium oxide) that acts or promotes the catalytic activity of the nickel component, whereby the catalytic activity of the catalyst as such is considerably impaired. at Using such catalysts in the context of a steam reforming process it is therefore impossible to use a to produce high pressure methane-containing gas by adding the hydrocarbon feedstock to prior pressure increase is steam reformed under high pressure.

Nickel-containing catalysts for low temperature steam reforming with copper / chromium oxide or copper / chromium /

Manganese oxide corresponding to catalysts c) and d) according to the invention are already in GB-PS 1,061,797

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described. Between those described in the aforementioned GB-PS However, a sharp dividing line can be used for catalysts and the catalysts used according to the invention draw.

As far as the catalytic efficiency is concerned (cf. the following examples), the catalysts used according to the invention are the catalysts described in the GBPS even in the case of low-pressure low-temperature steam reforming processes, but even more so in the case of low-temperature steam reforming processes operating under high pressure far superior. With regard to the composition, the catalysts used according to the invention differ from the catalysts described in the GBPS in particular in that the former contain as essential components nickel and magnesium oxide in a certain atomic ratio of nickel to magnesium, and also in that the amount of copper / chromium oxide or copper / chromium / manganese oxide based on the amount of nickel in mecallischer form below 25, preferably between 10 and 20 wt -% is _t.. In the above-mentioned GB-PS it is mentioned that magnesium oxide can serve as a carrier, but there is no indication of the critical atomic ratio of nickel to magnesium. In addition, according to the teachings of the GBPS mentioned, the amount of copper / chromium oxide or copper / chromium / manganese oxide in the catalysts described above, based on the nickel content in metallic form, must be less than 10% by weight.

According to the invention it has surprisingly been found that nickel and optionally nickel oxide and magnesium oxide containing catalysts at low temperature,

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Steam reforming processes are particularly effective when the atomic ratio Wi: Mg is in the range of 0.5 to 5.0, preferably 1.0 to 3.0 (see the following comparative examples)

If the atomic ratio Mi is ϊ Mg is below 0.5, a atisreichende catalytic activity at low temperature can not be expected "when the Atosr / erhältnis Wi: Hg exceeds 5 _s ö, ss comes with progressive reforming reaction to deposition of carbonaceous material on the Catalyst surface, tr / o by which catalytic activity "is impaired.

The nickslhaltigeii catalysts used in the invention könneii in most ^ irkaassr Wsise at Wisdrigtem = pera ⁼ bur Steam Reforffii3rusgsveFfaii2 / sn ₉ unt-K? relatively Lohen printing of 10 ms 100 kg / cm ¹ * " ■ => G, in particular 30" to 100 kg / caT "· G ₃ aröslten ₃ " Fvi ^ sienäet be ^ where-

csi your special abilities _s namely sine high activity IAID high stability "show"

3a iat generally DeisaHirb that to promote a reform through steam! He uiig received methaahaltigen gas instead of or as Sra-s / cz for natural gas to the proper inspection "c-3llen pipelines used i? rsrden ₅ in. which the gas in question under iioiiera Brande is transported. To a standing below the required lieiisn bridge Gas To obtain it, it is customary to increase the pressure of the gas after it has been produced. It is also known to first increase the pressure of a liquid carbon starting material and then to increase the pressure of a gas under high pressure .

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Substance starting material is steam reformed under high pressure «The latter process for increasing the pressure of a liquid starting material is comparatively cheap, since the costs required for increasing the pressure are considerably lower than the costs for increasing the pressure for a gaseous substance _{or the like}

In consideration of this, the invention further ensure serves dazUj to provide a method for producing a high pressure methane-containing gas ^ blank in which to keep the costs low for the pressure increase in the gas _o D © r reason why the catalysts used in the invention also develop the excellent properties described under high pressure "has not yet been fully clarified" The fact _? that the catalysts according to the invention, did not use a third component ₀ ■ as t -Älum-iniumtrioxid and the like ^ as commonly werdenj used contain as carrier (and thereby an impairing supply of the catalytic activity due to solid-phase · = reactive with the MgO during the steam reforming at high pressure experienced), may be one of the reasons for the successful usability of the catalysts according to the invention,

In the following, the production of according to the invention usable catalysts are described ^ whereby it is expressly pointed out that the manufacturer position of the catalysts which can be used according to the invention does not depend on the processes described in detail is limited «. In principle, any customary process is suitable for this, provided the catalysts obtained meet the specified requirements «Furthermore, in the

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the following also explains in more detail how a steam reforming process using such catalysts is carried out.

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

1. Process for the production of a catalyst by precipitation:

By mixing an aqueous solution of a nickel salt such as Ni (JNO,) _2f iiiSO ^, IMiCl ₂ , Ui (CH ₃ COO) ₂ , Iu (HCOO) ₂ and the like, an aqueous solution of a magnesium salt such as Mg (NO ₃ J ₂ , MgSO ₄ , MgCl ₂ , Mg (CH ₃ COO) ₂ , Mg (HCOO) ₂ and the like, and an aqueous solution of an alkali metal salt such as WaOH, KOH, IUa ₂ CO, K ₂ CO, and the like observing an atomic ratio Ni: Mg in the final catalyst of 0.5 to 5.0, preferably 1.0 to 3.0, at a temperature from room temperature to 90 ⁰ C, preferably from 30 ° to 70 ⁰ C, a precipitate of The suspension obtained in this way was stirred at the desired temperature for a certain time, for example 0.5 to 3 hours, during which the precipitate was allowed to age; the aged precipitate was then filtered off and with a large amount of hot water, if necessary Repeatedly until practically no more alkalis originally added in the form of an aqueous-alkaline solution were detectable in the wash water, ie until the pH was between 7 and 9. In the case that a copper / chromium oxide or copper / chromium / manganese oxide-containing catalyst is produced

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• should be _s was added to the precipitate a given amount of a copper / chrome = ammonium double salt or = oxide or a copper / chromium / manganese ammonium double salt or oxide added The precipitate finally obtained was then dried at a temperature of 40 ° to 130 ⁰ C, mixed with less than 10 weight "=% a FormhilfsmittelSj such as graphite., stearic acid and the like, and mesh shaped in a tableting machine into tablets of a size of 1 to 10 The tablets obtained were then calcined at a temperature of 300 ° to 800 ⁰ C ₉ before = preferably 400 ° to 700 ° C _p calcinedj, whereby a nickel = containing catalyst of the specified atomic ratio was obtained _o

Of course, it was also possible to ^ ₉ undried wet precipitation = go to a Strangpreßver to extrude or to granulate by rolling _o

If a coated supported catalyst be prepared ^ so this was possible ^ by the components used to form the re-strike solution mixture of one of said carriers of a particle size of mesh of less than 200 in an amount of less than 70 Gewo ~% based ₉ on the total amount of catalyst _{5 was} added and the whole thing was then worked up in the schilferten manner _o

Of course, the carrier could also be mixed with the rebound after filtering off and washing, _{or the like}

2 _a process for the production of a catalyst by precipitation work %

A commercially available active MgO = powder for industrial use Use and corresponding nickel and alkali metal

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Salt solutions as in the procedure described under 1 were, taking into account an atomic ratio Ni: Mg in the finished catalyst of 0.5 to 5.0, preferably 1.0 to 3fO, at a temperature of room temperature to 90 ° C, preferably 30 ° to 70 ° C, mixed, with a precipitate of nickel hydroxide or basic nickel carbonate precipitated and deposited on the MgO surface. The entire precipitate was then filtered off and washed in the manner described under 1. Became if a copper / chromium oxide or copper / chromium / manganese oxide-containing catalyst was desired, this could be achieved Adding and mixing a certain amount of copper / chromium-ammonium double salt or oxide or copper / chromium / manganese ammonium double salt or oxide with the obtained Precipitation can be produced. Finally, the precipitate ultimately obtained was in the under 1.Dried, shaped and calcined as described, whereby a nickel-containing catalyst having an atomic ratio in the specified range was obtained.

Should a supported catalyst be prepared, this could be done in that a given amount of the carrier was combined with the precipitate after filtering and washing.

3. Production of a catalyst using a mixing process:

The same nickel and alkali metal salt solutions as in the method described in 1., were mixed together at a temperature from room temperature to 90 ⁰ C, preferably 30 to 70 ° C, whereby a nickel hydroxide or basic nickel carbonate precipitated · The obtained

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Precipitation was then, as described under 1., at Stirred at the specified temperature for a while, then filtered off and finally washed.

• The precipitate obtained was then thoroughly industrialized with commercially available active MgO powder Use mixed in such an amount that the atomic ratio üi: Mg in the finished catalyst was between 0.5 and 5.0. In the event that a copper / chromium oxide or Catalyst containing copper / chromium / manganese oxide produced should be, the resulting mixture with a given amount of copper / chromium-ammonium double salt or oxide or copper / chromium / manganese ammonium double salt or oxide mixed and dried in the manner described under 1., shaped and calcined, wherein a nickel-containing catalyst of the specified atomic and quantitative ratios was obtained.

Should be a supported catalyst be prepared, this could be accomplished by adding a given amount of carrier to the mixture from precipitate and MgO powder combined and the whole was then worked up in the manner described.

The low-temperature steam reforming process according to the invention is started when a nickel / magnesium oxide catalyst produced by one of the processes described under 1. to 3. is filled into (at least) one steam reforming reactor and hydrogen is passed through as a reducing gas stream 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 is supplied

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turned off, whereupon a mixture of the respective hydrocarbon starting material and steam in a mixing ratio (H ₂ 0 / C - mol / atom) of 0.9 to 5.0 after preheating to a temperature of 250 ° to 600 ° C passed through the catalyst bed and there at one

Temperature from 300 ° to 600 ° C, preferably 400 ° to 570 ° C, steam reformed to a methane-containing gas will.

The methane-containing gas formed in this process generally contains more than 40% methane, based on dry weight together with gaseous accompanying substances such as hydrogen and carbon monoxide and carbon dioxide.

If necessary, a gas containing even more methane can be produced by feeding the gas stream emerging from the reactor (s) to at least one methanation reactor for methanation of the carbon oxides contained in the gas stream.

The methane-containing gas obtained is suitable as heating gas in any case.

The attached drawings are intended to explain the invention in more detail. Show in detail:

Fig. 1-.5 are graphs showing the relationship between that contained in the respective catalyst Amount of support and activity of the catalyst in question, and

6-12 graphical representations of the degree of wrapping in the context of one with one according to the invention Catalyst working low temperature steam · reforming reaction.

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The following examples are intended to illustrate the process according to the invention in more detail. In Examples 1 to 3, a nickel-containing catalyst according to a) is a nickel-containing catalyst in accordance with b) _s in Examples 6 to 8, a nickel-containing catalyst c respectively in Examples 4 and 5) and d in Example 9, a nickel-containing catalyst used accordingly) .

example 1

In compliance with the conditions and proportions given in Table I below, four were various nickel / magnesium oxide catalysts (according to the invention) M-1, M-2 and M-3 as well as a den © rfin = according to the invention catalysts largely in terms of the composition of the catalytically active components corresponding conventional winding / magnesium oxide / ^ - aluminum trioxide catalyst S-1 produced, the catalyst M-1 was made according to the procedure described under 1., the catalyst M-2 according to the process described under 2 and the catalyst M-3 according to the process described under 3. the process described

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Table I.

Catalyst, atomic, nickel-plated ratio of salt Ni: Mg (g)

Magnesium salt

(G)

Alkali metal salt (g)

3. Stock
part
(G)

Amount of water required to completely dissolve all components (1)

Drying temperature ( ⁸ C)

lot CaI- part lot at ci- chen to him Per never- size hold 100 g guessing of nem As tempe- Kata Kata the rature lysa lysa blow ( ⁰ C) tors gate Trains (mesh) (G) set tem Gra phit (G)

M-1

M-2

M-3

S-1

1.7

1.24

1.24

1.7

Mg (NO ₅ I _2. Na ₂ CO-

6H ₂ O 6H ₂ O 250 290 150 Wa ₂ CO ₃ NiSO ₄ * Mgo 6H ₂ O 200 290 30th Na ₂ CO ₃ WiSO ₄ ' MgO 6H ₂ O 200 290 30th Wa ₂ CO ₃ Ni (WO ₃ J ₂ , Mg (WO, J ₂ . 6H ₂ O 6H ₂ O

290

150 400 145

350 3x3

350 3x3

4 350 3x3

ro

4 350 3x3

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co

The catalysts M-1, M-2, M-3 and S-1 were each introduced in an amount of 40 g into (at least) one steam reforming reactor and subjected to a reduction treatment at a temperature of 450 ° C. for 12 hours. A mixture of naphtha with an average of 6.04 carbon atoms per molecule, an IBP of 33 ° C., an FBP of 122 ° C., a specific gravity of d ^ of 0.675 and a sulfur content of 1 ppm was then passed through the catalyst bed at a rate of 200 g / h passed together with steam in the ratio H ₂ O: C of 2.0 'i and reformed steam at a reaction temperature of 500 ° C and a reaction pressure of 50 kg / cm · G. The low temperature steam reforming reaction was carried out continuously for 2500 hours under the specified conditions. The results obtained are shown in Tables II and III below.

Table II shows the tendency to impair the activity of the catalysts in question in the course of the reaction time (in the case of the low-temperature steam reforming reaction), the upper numerical value in each column being the amount of gas produced over time in l / h and that in each column Lower numbers written in brackets indicate the amount of unreacted oil-like hydrocarbons in g / h over time. To determine these proportions, the gas stream emerging from the reactor (s) was initially ^{cooled to a temperature of 10 °} C. in order to separate it into a gaseous part and a liquid part. Finally, the liquid fraction was separated into unreacted oil-like hydrocarbons on the one hand and moisture or water on the other, so that the individual constituents could be quantified.

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10 M-1 1Ö - M-2 catalyst 338 2359116 S-1 368 1 / hour Table II 369 M-3 6) (15.0) 367 1 / hour time in 100 (0) g / h ] (0) 1 / hour 367 1 / hour 310 (0) g / h hours 369 368 g / h (0) g / h O) (27.1) 368 300 (0) (0) 369 (0) 368 368 (0) 300 500 (O) (O) 368 (36.2) 368 367 (O) 23 700 (0) (0) 368 (190.3) 368 368 (0) 1000 (0) (0) 367 367 368 (0) 1500 (0) (0) 368 368 366 (0) 2000 (0) 363 363 (0.4) (0.6) 2500 (2.0) 342 352 (13, (7.9) 328 (24,

From Table II it can be seen that when using the invention Nickel / magnesia catalysts M-1, M-2 and M-3 even with continuous low temperature steam reforming No unreacted hydrocarbons were detectable for over 1000 hours. at Use of the usual nickel / magnesium oxide / aluminum trioxide catalyst were unreacted oil-like after continuous reforming for at most 300 hours Detectable hydrocarbons. A more than 500-hour

No continuous reforming was possible.

flat 100-hour continuous reform; τ tion possessed the one or more with the catalysts M-1, M-2,

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M-3 and S-1 charged reactor (s) exiting gas on dry weight, approximately the following composition!

CH ₄ 63 Volume-% H ₂ 14th Volume-% co ₂ 22nd Volume-% CO 0, 5 volume%

The following Table III shows the properties of the various Catalysts and the amount of carbon deposited on the catalysts, respectively before and after their use in the low-temperature steam reforming described.

after usage catalyst
M-1 M-2 M-3
Time in hours
1000 1000 1000 60 61 S-1
500 Table III before use 41 28 28 180 Catalyst properties after usage 25th 200 ' 200 31 specific surface in front of
(m ² / g) need before use 250 1000 1000 50 after usage 980 4.7 4.7 250 Ni crystallite (£) 5.2 4.8 4.8 4.8 5.2 9.4 Carbon content (Wt%)

As can be seen from Table III, the carbon deposition is in the case of the Mckel / magnesia catalysts according to the invention M-1, M-2 and M-3 in spite of the lowering of the specific surface area and the growth of the Nickel crystallites not increased after use and consequently very stable. Already in half of the

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with the usual catalyst S-1 the Carbon content greatly increased. This increase in carbon content is probably due to a deposit of carbon on the catalyst,

This confirms that a catalyst with a third constituent, for example f-aluminum _{trioxide f} , which is customary as a carrier, cannot be used in practice in the described low-temperature steam reforming process in continuous operation. On the other hand, the catalysts according to the invention retain their stability and extremely high activity in the context of the low-temperature steam reforming process described, even after a long period of operation.

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■ Example 2

First, six different catalysts of the composition given in Table IV below were used for performing a low temperature steam reforming process.

In Table IV are those used in the preparation of the
Catalysts with different atomic ratios of the main constituents in the context of the procedure described under 1. specified conditions complied with «If catalysts with corresponding atomic ratios
are obtained, show catalysts produced by the processes described under 2. and 3. almost the same efficiency ₆

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Table IV

catalyst

Atomic

ratio

Wi: Mg

Winding salt magnesium) n * salt

₃₂ 6H ₂ O Cg)

6H ₂ O (g)

Amount of water required to dissolve the nickel and magnesium salts (D.

Alkali metal salt Na ₂ CO ₃

amount of water required to dissolve the alkali metal salt (D.

ZuI ro ρ Γ ze? it.

(hours)

m-1
m-2 m-3 m-4 m-5 m-6

0.3 150 0.6 300 1.7 290 3.0 555 4.6 560 6.0 555

440 440 150 157 110 80

3 4 2 4 4 4

330 300 250 350 300 300

2.5

Catal research sodium Dry lot Calcinie «. _t 500 Particle Amount of received I. gate derli concentrate potential at tion tem- 500 size of the tenem cataly ISO che tration tempe- per 100 temperature 500 Catal sator (g) I. lot in the down rature g Never ( ⁰ C) 500 tors at blow ( ⁸ C) the 500 (mmxmm) ' Washing (based blow 500 water on dry Trains (D kenge satem weight) graphite m ~ 1 30th 0.007 110 4th 3x3 90 O m-2 30th 0.007 110 4th 3x3 120 t "
OO m-3 30th 0.006 110 4th 3x3 70 PO
ro m-4 30th 0.007 110 , 4 3x3 150 m-5 30th 0.005 110 4th 3x3 140 090 m-6 30th 0.006 110 4th 3x3 130

ro -ι-ι

co

15 g each of the catalysts m-1, m-2, m-3, m-4, m-5 and m-6 prepared under the conditions given in Table IV were introduced into (at least) one reforming reactor and about 12 there subjected to a reduction treatment at a temperature of 500 ^{° C. for hours.} An i \! Aphtha starting material with an average of 6.04 carbon atoms per molecule, an IBP of 33 ° C., an FBP of 122 ° C., a specific gravity of d ^ of 0.675 and a sulfur content of 1 was then added to the reactor (s) ppm at a rate of 100 g / hr together with steam in a ratio of H ₂ O to C of 1.5 where it is separated at a reaction temperature of 500 ⁰ C and a reaction pressure of 70 kg / cm · g steam reformed. The low-temperature steam reforming reaction was carried out continuously for 1000 hours under the specified conditions. The results obtained here are compiled in Tables V and VI below.

Table V shows the tendency of the individual catalysts to lose their catalytic activity during the low-temperature steam reforming reaction. The meaning of the individual values and the measuring methods correspond to the meaning of the values and the measuring methods of Example 1 (in connection with Table II). Table VI shows the change in the carbon content of the catalyst (in% by weight) before and after use in the iLow temperature steam reforming reaction shows _a

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-as-.

m-1 Table V 174
l / h m-4 m-5 m-6 time in
hours 123
1 H catalyst
m-2 m = 3 ^ (O) L / "t-. 174
l / h 174
l / h 174
l / h 10 · (29), / ^ 174
l / h 174 (O λ, / - a t ,; (O) / ^ t ;. »(0) g / h 109 i (O) j / üt (O) 174 175 158 100 (37) 174 174 (O) (O) (9) 96 (O) (O) 174 174 84 300 (44) 174 174 (O) (O) (51) 83 (O) (O) 174 173 23 500 (52) 168 175 (O) (O) (86) 71 (3) (O) 174 168 700 (59) '160 169 (O) (3) 59 (7) (2) 164 162 1000 (46) 153 (5) (6) (12)

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From Table V it can be seen that when using the catalyst m-1 something already after 10 hours of use unreacted oily hydrocarbon detectable was. When using the catalyst m-β, after 100 hours of use it was unreacted, oily Detectable hydrocarbons. In both cases, the amount of unreacted oily hydrocarbon increased increases rapidly in the course of the further reforming reaction. When using the catalysts m-2 and m-5 could no unreacted oily hydrocarbon can be detected even after prolonged use. In particular using the catalysts m-3 and m-4 could even after 700 hours of continuous use no unreacted oily hydrocarbon is found. Wake up 10 hour continuous Reforming possessed the reactor (s) packed with the catalysts m-2, m-3, m-4, m-5 and m-6 Escaping gas has the following composition (based on dry weight):

CH ₄ H ₂ CO CCU

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Table VI

Catalyst m-1 m-2 m-3 m-4 m-5 m-6

Time in hours 1000 1000 1000 1000 1000 500

Coal before use 0.10 0.05 0.05 0.08 0.05 0.08 halides ^{after use} 0 * ¹ ^ ° ^'08 °' ¹⁰ ° ^'10 ° » ^{15 9} ' ⁵³ catalyst (wt .-%)

409822/1 090

As can be seen from Table VI, the carbon content is of the catalyst m-6 (in% by weight) greatly increased after its use. This increase in carbon content is believed to be due to a deposition of carbon on the catalyst surface, which is why it becomes the rapid increase in the amount of unreacted oily hydrocarbon comes.

Example 5

15 g of the nickel / magnesium oxide catalysts prepared under the conditions given in Table IV m-1, m-2, m-3, ra-4, m-5 and m-6 were in (at least) Filled into a reforming reactor and subjected there to a reduction treatment for about 12 hours. On that a naphtha feedstock having an average carbon content was introduced into the reactor (s) of 6.04 carbon atoms per molecule, an IBP

of 33 ⁰ C, an FBP of 122 ⁰ C, a specific ge

15th
weight d ^ of 0.675 and a sulfur content of 0.5

ppm rai't a rate of 100 g / hr together introduced of 2.0 and steam reformed at a reaction temperature of 500 ⁰ C and a reaction pressure of 10 kg / cm · G with steam in relation to KUO C. The low-temperature steaming reaction was carried out continuously for 1000 hours. The results obtained are summarized in Tables VII and VIII below.

The meaning of the information in Tables VII and VIII corresponds to the information in Tables V and VI.

+) at a temperature of around 500 ° c

-2Q-

409822/1090

m-1 Table VII 213
1 H m-4 m-5 m-6 time in
hours 155
i / std catalyst
m-2 m-3 (0)
g / h 213
1 H 212
1 H 213
1 H 10 (26)
g / h 212
1 H 212 (O)
g / h (O)
g / h (O)
g / h 143 (0)
g / h (0) 212 212 190 100 (32) 212 212 (O) (O) (10) 131 (0) " (O) 211 212 179 ·. 300 (37) 210 212 (O) (O) (15) 120 (0) (0) 212 212 166 500 (43) 202 211 (O) (O) (21) 110 (4) (O) 212 204 155 700 (47) 185 206 (O) (3) (26) 101 (12) (2) 206 196 144 1000 (52) 178 (2) (7) (3D (16)

-30-409822 / 1090

As can be seen from Table VII, when the catalyst was used, m-1 was already after 10 hours of use a larger amount of unreacted oily hydrocarbon verifiable. When using the catalyst m-6, there were unreacted after 100 hours of use oily hydrocarbons detectable. In contrast, when using the catalysts m-2 to m-5 even after prolonged continuous steam reforming reaction no unreacted oily hydrocarbons are detected.

Awake for 10 hours of continuous steam reforming reaction possessed the reforming reactor (s) packed with the catalysts m-2, m-3 »m-4, m-5 and m-6 (en) Escaping gas has the following composition (based on dry weight):

^ 51 volume- ^

H ₂ 26 "

CO 1 "

CCU 22 ⁿ

-31-

409822/1090

Table VIII

Catalyst m-1 m-2 m-3 m-4 m-5 m-6

Time in hours 1000 1000 1000 1000 1000

Carbon before

content in use 0.10 0.05 0.05 0.08 0.05 0.08

des ütalysa- "". ~

+ rtT.c rpow ο / λ according to

-cors (, uew.-zb; custom ₀ , 11 0.06 0.07 0.08 0.10 3.85

- " ⁷ P-

409822/1090

As can be seen from Table VIII, the carbon content of the catalyst m-6 after its use was µm increased a relatively large amount. However, the increase in carbon content is compared to the increase the carbon content of the catalyst m-6 in Table VI is considerably lower, which is presumably due to the different pressure and the different ratio of HpO to C as well as the different reaction conditions is due.

The previous (comparative) tests have clearly shown that the desired success is achieved with the winding / magnesium oxide catalysts corresponding to a) only with atomic ratios Ni: Mg of 0.5 to 5.0, preferably 1.0 to 3.0.

Even when performing the low-temperature steam

Reforming process under a pressure of 70 kg / cm · G show the catalysts according to a) a high catalytic activity and a high stability.

Example 4

According to the procedure described under 1., various Catalysts manufactured.

First, six different catalyst materials A to F with different atomic ratios Wi: Mg manufactured as follows:

Production of the catalyst material A:

A solution of 2120 g Wa ₂ CO, in 20 1 hot water was made

409822/1090

within about 1 hour at a temperature of 60 ° C in a solution of 870 g of Ni (NO,) ₂ »6H ₂ O and 2560 g of Mg (IMO,) 2 * 6H ₂ O in 15 liters of water (and mixed with the latter solution). The resulting precipitate was filtered off and washed with a large amount of water until the sodium content of the filter cake (based on dry weight) was below about 0.01% by weight. The filter cake obtained in this way - hereinafter referred to as catalyst material A - was divided into ten equal parts and used for the production of the catalyst in the manner described below. An analysis of the catalyst material A showed an atomic ratio Ni: Mg of 0.33

In a corresponding manner, but with different amounts of Ni (iMO,) ₂ ^# 6H ₂ O, Mg (NO ^) ₂ -6H ₂ O and Na ₂ CO, different catalyst materials ß, C, D, E and F with atomic ratios Ni : Mg of 0.59, 0.97 »2.88, 4.5 and 5.95 made.

Thereafter, the individual Katalysatorraaterialien A to F were combined with those indicated in Table IX carrier materials was calcined and then the respective mixture at a temperature of 450 ⁰ C. The 48 different catalysts given in Table X below were obtained. The support materials labeled 1 to 4 in Table IX are suitable for preparing the catalysts of the invention. The support materials labeled 5 and 6 in Table IX are common carriers for making common catalysts.

4098 2 2/1090

carrier Table IX specific m ² / g grain Accompanying 8th% Weary purity sch size components _; : 1.2 ger- Surface MgO, f
Fe ₂ O ₃ loading che m ² / g drawing tion • Λ -Al ₂ O, 2.8 under a 99% (commercial ρ 200 pure) m ² / g mesh : 0, SiC 1.0 Il SiO ₂ : b 90% (through Al ₀ Ο-, 0, Electrofusion m ² / g CaO,
K ₂ O, : 0, Λ. -Quartz zen here
represents) 2.0 I! 0, C. ZrO ₀ over 99% 3.6 It 1% d C- at 1500 ^° C m ² / g ^ a ₂ O 20 hours long , T-Al ₂ O ₃ calcined 190 Il Fe ₂ O ₃ e 99% (commercial SiO ₂ : pure) Wa ₂ O: SiO ₉ gel 600 It Fe ₂ O ₃ .02% f 99.5% commercial .02% pure ¹ ) .02% 02% 09%

Table X

catalyst

Aa ₂ Ab <|

A-e> | ΰ-a-z

ß-a _e

Atomic ratio Ni: Hg

Carrier content (% by weight) Mixing process

0.33 0.33 0.33 0.33 0.33 0.59 0.59 0.59 9.8 50.5 9.5 31.0 48.5 5.1 69.0 80.8

A + a A + a

A + b A + d A + e

ß + a B + a ß + a

409822/1090

-3b-

Port ₃ Port ₄ Be ₂ ^B " ^f l Vol ₂ Vol ₃ C-a 0.97 ^C " ^a 8 - Cb ₅ Cb _c Ce ₃ ^C ~ ^d 3 ^C ~ ^d 4 cd ₅ Since ₉ ^D " ^a 10 DC ₁ DC _2nd • DC ₃ DC _4th De ₄ D + f ₂ Df ₃ ^E " ^a ll ^E " ^a 12 ^E " ^a 13 Ea ₁₄ Ee ₅ 20.3 Ed, -
D. Ed ₇ Ed ₈ ^E " ^d 9 ^F " ^a 15 ^F " ^a 16 Fb _? ^F " ^C 6 Ff ₅ 0 _; 59 0.59 0.59
f 0.59 0.59 0.59 0.97 49.5 0j97 0.97 0.97 0 _r 97 0.97 0 _; 97 Oj 95 2 _f 88 2.88 2.88 2.88 2 _T 88 2.88 2.88 2 _f S8 2 _; 88 ⁴ I ^{5 4} ! ^{5 4} f ^{5 4} f ^{5 4} I ⁵ E + f 4.5 4.5 ⁴ f ^{5 4} ; ⁵ 5 _r 95 5 ₇ 95 5.95 5.95 5.95 64.3 80.5 59.5 40.3 52 78 _r 8 10.0 ¹ C + a 82 28 _f 8 81 46 _f l 10.8 59 _f 5 80.3 50.5 80.2 ⁹ T ⁷ 28.7 68.5 79.8 38 _; 8th 19 _; 8th 60 _; 3 10.8 .29 _; 5 65.9 84 ^ 1 24 ^ 8 40.4 65.3 80.7 30 _r 5 ■ 49.9 31.0 21.3 21.1 B + b B + b B + e B + f B + d B + d C + a C + a C + b C + b C + b C + d C + d C + d D + a D + a D + C D + C D + C D + C D + e D + f D + f E + a E + a. E + a E + a E + e E + d E + d E + d E + d Q + a Q + a F + b F + e F + f Port ₂ 0.59 9 _T 9 B + b

409822/1090

Z3b9116

In each case 15 g of the 48 different DJickel / magnesium oxide / supported catalysts of the atomic and quantitative ratios of the individual components given in Table X were introduced into (at least) one adiabatic reactor (s), whereupon a reactor (s) operating at a rate of 200 g / hr together with steam in a ratio of 2.0 C to HPO supplied Naphthaausgangsmaterial having an average atomic ratio C of 6.0 and H of 13.4 at a temperature of 500 ⁰ C and a reaction pressure of 70 kg / cm · G was steam reformed.

After 3 hours of continuous reforming, the amount of gas emerging from the reforming reactor (s) was determined. As a result of these measurements, it was found that from the or those with other than the catalysts Aa. , Aa _? , AD ₁ , Ad,., Ae ^, Ba, -, Bb ₄ , Bd ₃ , Ca ₈ , Cbg, Cd ₅ , Da _1Q , DC ₄ , Ea _iZf and Ed _g packed reactor (s) (based on dry weight) practically 36O l / h of gaseous reaction product emerged. The respective gaseous reaction product had the following composition (based on dry weight):

₄ 64.8% by volume

H ₂ 12.5 "CO 0.44"

CO ₂ 22.26 »

In the one or those with the catalysts Aa ^, Aa ₂ , Ab ^, A-Ol ₁ , A ^ ₁ , Ba ₅ , Bb ₄ , B-dj, Ca ₈ , Cb ₆ , Cd ₅ , Da ₁₀ , DC ₄ , Ea _i4 and E-dg packed reactor (s), the escape of unreacted naphtha was detectable. Furthermore, the amount of gaseous reaction product was very small, so that the respective experiment after one

409822 / 109Ü

gen was canceled for 10 hours. The results of the measurements of the respective gas amount after certain time intervals using the various catalysts are 'summarized in the following Table XI To measure was the cooled from or to the reactor (s) exiting gas stream to a temperature of 10 ⁰ C to him
to be separated into a gaseous portion (ie the gaseous reaction product) and a liquid portion (consisting of unreacted IM aphtha and water), whereupon the amount of the gaseous portion was determined.

409822/1090

2 3 b 9 1 Ί 6

Time
hours Table XI Time in'
hours Amount of
Gas pro-
duct
(1 H) catalyst 3 in amount of
Gas pro-
duct
(1 H) 52 93 A-a ^ 3 118 40 61 A-ap 3 73 55 113 From ₁ 3 134 35 73 A- (I ₁ 3 90 40 80 A "" θ Λ 3 91 40 101 Ba ₅ · * 120 40 105 Port ₄ 3 123 40 93 B-d, 3 115 45 115 Ca _Q 3 133 45 120 cb ₈ 3 141 45 105 cd ₅ 3 139 40 132 IUa ₁₀ 3 154 40 131 DC _4th 3 158 40 128 Ea _i4 3 163 40 130 Ed ₉ 161

409822/1090

Example 5

With the 48 different catalysts given in Table X, the steam reforming reaction described in Example 4 was repeated, but at a reaction ^{temperature of 500 °} C. and a reaction pressure of

10 kg / cm · G and a ratio of H ₂ O to C (mol / atom) of 1.5 was worked.

When the amount of the gaseous reaction product formed was measured 3 hours after the start of the reforming reaction in the manner described in Example 4, it was found that from the catalyst or those with catalysts other than Aa ,,, A-ap, Ab ₁ , Ad ₁ , A- e * \ _T Ba, -, ß-b., Bd *, Ca _Q , C-bg, C-dc * Da ₁₀ , DC ₄ , ^E -a>] ₄ and Ed _g charged reactor (en ) (based on dry weight) practically 400 l / h of gaseous reaction product flowed out. The gaseous reaction product had (based on dry weight) about the following composition %

CH ₄ 55.9% by volume

H ₂ 20.9 "

CO 1.3 "

CO ₂ . 21.9 "

In the one or those with the catalysts Aa ^, Aa ₂ , Ab ₁ , Ad ₁ , Ae _1f Ba ₅ ; BD ₄ , Bd ₃ , Ca ₈ , Cbg, Cd ₅ , Da _1Q , DC ₄ , Ea ,, ₄ and E-dq charged reactor (s), the escape of unreacted naphtha was detectable. Furthermore, similar to Example 4, the amount of gaseous reaction product formed was so small that every attempt in this regard was terminated after a few tens of hours.

-40-

409822/1090

From the measurement results obtained it can be seen that catalysts with atomic ratios JMi: Mg of less than about 0.33 or catalysts in which the carrier content is more than about 78.8% at a low reaction temperature develop only a very low catalytic activity. When using such catalysts in the frame of reforming reactions is an escape of unreacted naphtha immediately after the start of the reaction detectable, at the same time the amount of formed gaseous reaction product is very low. In contrast, have catalysts other than those mentioned Sufficient catalytic activity immediately after the onset of the reaction, which is why the life of these catalysts or their loss of activity were determined. The results of these measurements for each individual catalyst are from FIGS to see 5. In Figs. 1 to 5, the ordinate is that for lowering the activity of each catalyst to half the time required, on the abscissa the proportion of support (in% by weight) of each catalyst applied. In these graphs, for example, the term "ß-a ^ (70)" means that the Catalyst B-a, in the context of the process according to Example 4 (in which the reaction pressure is 70 kg / cm · G was used. The term "ß-a ·, (10)" means that the catalyst B-a, in the context of the process according to Example 5 (in which the reaction pressure 10 kg / cm · G) was used.

An analysis of FIGS. 1 to 5 shows that in the case of catalysts with conventional supports, for example in the case of the catalysts β-Gnt β-f * and the like, the time required to lower the catalytic activity is inherent

+) to half

409822/1 090

—A ι -

-Hi -

short, at high pressures, e.g. 70 kg / cm · G extremely short is. Figure 5 shows the result of a determination of the catalytic life of catalysts by Adjusting the atomic ratio Ni: Mg to 5.95. It was found that the such catalysts, even if they contain a carrier which can be used in accordance with the invention, the amount necessary to reduce the catalytic activity to half Time is very short. In contrast, that is the case with other catalysts that use a according to the invention usable carrier and while maintaining an atomic ratio Ni; Mg below 5.0 produced was very long to lower the catalytic activity to half the time required.

On the basis of the analytical results described, it can be seen that catalysts according to b) are particularly effective when their atomic ratio Wi: Mg is between O ₅ 5 and 5.0, preferably between 1 * 0 and 3 ₉ O, and the carrier content is below 70% by weight . -% is.

The information contained in the following Table XII confirm the different catalytic life of catalysts with supports according to the invention and catalysts with conventional supports and between catalysts with atomic ratios M: Mg of more than 5 _p 0 and catalysts with atomic ratios below 5.0, but not less than 0.5.

The measurement results contained in Table XII represent the numerical values from a comparison of the various with hydrogen at a temperature of 500 ⁰ C

-42-

409822/1090

sufficiently activated catalysts (catalyst before use) after 1000 hours of steam reforming reaction according to Example 4 (at a reaction pressure of 70 kg / cm * G) or 1000-hour steam reforming reaction according to Example 5 (at a reaction pressure of 10 kg / cm · G) (each "catalyst after use"). The "percentage Ratio of escaped MgO "puts that through

Divide the amount of MgO that has escaped from the used one Catalyst per unit amount of catalyst by the amount of escaped MgO of the catalyst Use per unit amount of catalyst and multiplying by 100 the numerical value obtained. The "content of Carbon "(in wt%) represents that by dividing the amount of carbon per unit weight of catalyst represents the amount of catalyst and multiplication by 100 numerical value obtained. The amount of escaped MgO was determined in such a way that the catalyst pulverizes to a particle size of 50 to 10Ou, 10 g of the powdered catalyst obtained in 500 ml of water, which continuously with gaseous carbonic acid was saturated (60 mm water column), the suspension obtained was suspended with the aid of a stirrer for 2 hours stirred (in order to make the MgO in it escape) and finally the weight of the escaped MgO was determined (n).

A09822 / 1090

Table XII

Catal
gate

BI ₁

D-f

Ba ^
ß-b,
B-Td,
B-dj
Ca _£

MgO outflow ratio (%) under a pressure of 10 kg / cm ² · G 70 kg / cm ² .G

63.3 60.5 72.4 68.9 71.3 60.7 59.8

100

99.8 100 100 100 100

99.7

82.5 81.8

89.1 82.2 85.5 90.0 83.5

100 100 100 100 100

99.9 100 reaction conditions

Carrier portion (wt .- ^) before use after use under a pressure of pressure of 70 kg / cm ² · G 10 kg / cm ² · G

category

0.10 0.20 0.10 0.05 0.20 0.20 0.13

8.5 7.7 10.3 14.1 14.0 15.3 17.1

0.05 0.07 0.20 0.08 0.10 0.10 0.05

0.07 0.07 0.20

0.09 0.12 0.11 0.05

4.3 3.1 4.4

5.1 7.2 6.3 6.2

0.05 0.07 0.21 0.08 0.10 0.10 0.05

ro co

CO

I. (H VD (H - - σι ιη 9 I. ϋ U * co (H CM ο CO CM - O γΗ I. ο I. - ο ■ CO CM • co • I. m (H co CO ■ I. (H J O in - - I. in U (H .Η (H ο ο I. I. ο υ , —Ι f— \ O Γτ "Ί
• (H CM CM (H CO (H σι r— - CM - O fa ο # - CM - ί- Q Q (H I. O <ο ο Π3 9 * I. C. r Ό (Ö in σ » co , —Ι ° (H O O O «~ Ο Q O I. r- I. O O O O I. I. - co ο CM ιη CO O ιη. Ch rl N O ■ Η W. O W. CO O CO W. co Pn in CM CO Oil in in H (H ιΗ CM ο (Ö CO 9— O (H (H r (H - - σ » rH ο 4 » 9- CM I. (H O O ι- O - O (H (ti O he" O Q ο O Q Ο O iH rH I. in ο O O O co O ιη • in in CM i-l σ » O ιη (H m rH ο O I. O (H O O O in H (H (H O ο O O ο (H O O O σι ο O ο O CM ^ν ο * ~ Ή O O co ο O ι I. I. .σΓ I. CM O ο O ι I. O vo σι ο O ο O I. O O O co ο (H rH γΗ O σι rH - I. γΗ f (H σι ti in H ιη I. I. ^ I. O σι O cn O O cn O O Ό ON O (H O (H I. ΐΗ ΐΗ W. CO • Vi ιη Ό «Α I. ι ϋ ϋ

A 0 9 8 22/70 9 0

Table XII shows that in the case of catalysts with conventional carriers (category X) not only the ratio of escaped MgO is very low, but also the The carbon content of the catalyst is greatly increased after use. The fact "that the relationship at escaped MgO is small in this case, presumably due to a chemical reaction between the in the Catalysts as constituents promoting the catalytic activity of H / contained MgO and the accompanying constituents, especially to the carrier, to recycle the catalyst during the reforming reaction. With this chemical Reaction, the MgO is apparently insoluble in the aqueous carbonic acid solution. The catalytic one MgO promoting the activity of the catalysts of the invention plays a role in accelerating the reforming reaction plays an essential role in that it activates the reactant-forming water and facilitates reaction with the hydrocarbon feedstock. In the case of catalysts with conventional carriers, however, the MgO has its own due to a chemical reaction with the carrier component properties in this regard are lost. For this reason, the catalytic life is common Catalysts using supports (category X) are relatively short.

In the case of catalysts of category Z, in which the atomic ratio Wi: Mg exceeds 5.0, the carbon content has increased of the catalytic converter after use. This increase in carbon content is believed to be due on a deposit of carbonaceous material on the catalyst. For this reason also own the catalytic converters belonging to category Z only have one relatively short catalytic life.

-46-409822 / 1G90

- k6 -

In contrast, in the case of the catalysts according to the invention (Category Y), the percentage ratio is applied escaped MgO in the order of 100 or 100, with the carbon content of the Catalyst has only experienced a slight increase, if at all, after use. The catalytic The life of the catalysts according to the invention belonging to category Y is very long. According to the invention Winding / magnesium oxide / supported catalysts according to b) can be used for about half the cost of i '^ ikkel / magnesium oxide catalysts according to a).

Example 6

Under the conditions given in Table XIIE below various catalysts were produced

As can be seen from Table XIII, 20 different catalysts were used according to the process described under 1. of groups W-1, iM-2, W-3 and W-4, according to FIG Method described under 2. five different catalysts of group i-J-5 and after that described under 3. Process five different catalysts of the group ίί-6 produced. For comparison purposes, five different Group T-1 catalysts are made by using silica gel as a carrier component in an aqueous solution a winding salt and a magnesium salt was suspended (see. Table XIII). In this context it should be noted that the content of copper / chromium / manganese oxide and the atomic ratio Wi: Mg den Oxide content and the atomic ratio Wi: Mg of the desired catalyst mean.

409822/1090

I.
-pr Kata salary Atom- Nickel salt - Ni (NO ₃ ) ₂ Table XIII Alkali Carrier to the complete Calcining he lyser to Kup ver (ε) 6H ₂ O magnesium tall salt (g) digen dissolution r-ung s tem fer / holds- 555 salt (g) (G) sen all temperature Chrome/ nis 'Components ( ⁶ C) manganese Ni: Mg required oxide Amount of water (Cu: Cr: Mn = (D 1: 1: 0.1) (Wt%) a 0 Ni (NOj) ₂ - Na ₂ CO ₃ CD
CD b 6th 0.6 6H ₂ O Mg (NO ₃ ) ₂ . 6.5 350 CO N-1 c 11 300 6H ₂ O 300 d 17th 440 e 25th O
CD a 0 Ni (NO ₃ ) ₂ NapCO, CD b 6th 1.7 6H ₂ O Mg (NO ₃ ) ₂ 7th 350 N-2 c 11 485 6H ₂ O 350 d 17th 250 e 25th a 0 Na ₂ CO ₃ b 6th 3.0 Mg (NO ₃ ) ₂ 7th 350 ^ j N-3 -c 11 6H ₂ O 350 CO d 17th 157 cn
CO e 25th

ο co

in ro

o in co

in co

ro

ro

• A

• H Q)

co tn

CM

co O U

CM

CO

O O ro

CM

co O U

O O CM

co O U

CNJ

CM

CO O

O CM

tn

co

CD CO

CM

ro

in

CM

VD

<M

CO

53 * _- CM ■ A K ! S VD

in

1 O O O CM cn co W. CM •H

O O

cn cm

■ a te

S VD

CM

tM

ro

-H

CM

VD

σ *

CM

VO

¹ ti

in

CM

(D

co

in

CM

VD I

pH

ORfGfNAL INSPECTED

409 822/1 over 90

" ^kd " ■ 2.3 b 911

25 g of the 30 different catalysts of groups Γ »-1, JU-2, JN-3, JM-4, JM-5 and i \ l-6 (see. Table XIII) were introduced into separate reforming reactors and lasted for about 12 hours with gaseous hydrogen at a temperature of 500 ⁰ C reduced. After the reduction of the various catalysts, a naphtha starting material with an average of 6.09 carbon atoms per molecule, an IbP of 33 ° C, an FBP of

ο 15

122 C, a specific gravity d ^ of 0.675 and

a sulfur content of 15 ppm at a rate of 80 g / h together with steam in a ratio of HpO to C of 2.0 and introduced there continuously for 200 h at a reaction ^{temperature of 500 0} C and a reaction pressure of 10 kg / cm '«G steam reformed.

In Fig. 6 is the relationship between the content of copper / chromium / manganese oxide and the degree of reaction.

of the catalysts belonging to the groups mentioned When the _{carbon deposited on the individual catalysts of groups JM >> 1 s} N-2 _y iM-3 and fi-4 was determined after the reforming reaction, the results listed in Table XIV below were obtained.

409822/1090

Table XIV

O catalyst N-1 N-2

abcdeabcde

ξ content of copper / chromium /

«~. Manganese oxide (the values in _n r _ΛΛ ^ r _{7 oc} - _n α ii -w οκ

Brackets correspond to ° ^{6 11 17 25} ° 6 11 17 25

actually determined (0.0) (6.1) (10.8) (16.4) (24.2) (0.0) (6.3) (11.3) (17.0) (24, 1)

Values) (wt .-%)

Carbon content (g) 0.05 0.00 0.00 0.00 0.00 0.05 0.00 0.00 0.00 0.00 ο

. ^ ₁ K "t-ilyi3 '"' tur a be d eabede

ο content of copper / chromium /

to manganese oxide ^(w Response in _n r _{ΛΛ ΛΓ? n oe.} / _{■ ΛΛ} ΛΎ _ot

«Brackets correspond to ° ^{6 11 17 25} ° 6 11 17 25

actually determined (0.0) (5.9) (11.5) (16.2) (24.4) (0.0) (5.2) (1O, 3) (17.1) (24, 0)

Values) (wt. %)

Carbon content (g) 0.08 0.00 0.00 0.00 0.00 0.10 0.00 0.00 0.00 0.00

- Sf -

It can be seen from FIG. 6 that when the catalysts according to the invention are used in a steam reforming reaction, favorable results are achieved, regardless of the particular catalyst preparation process and the atomic ratio Wi: Hg, provided the latter is in the range from 0.5 to 5.0 . Particularly good results are achieved with catalysts in which the content of copper / chromium / manganese oxide (in metallic form), based on the nickel content, is between 5 to 20, preferably 10 to 20 Gevr .- '/ s, lies..

In order to clearly illustrate the advantages achievable according to the invention, the reforming reaction in the present case was carried out with careful control of the degree of reaction p -, by using a sulfur-rich u'aphthas and by increasing the amount of starting material fed per unit amount of catalyst (even in this case was the initial reaction rate 100 ^) '' were conditions, adjusted so that 'In FaIIe ₅ that the degree of reaction diejBe- 100 ^ι; ό was possessed of the same, the resultant gaseous reaction product JMaphthaausgangsmaterial following composition:

_4th 51.9 volume-sat

Ii ₂ 27.3 "

CO 1.1 "

CO ₂ 19.7 "

Example 7

25 g of the catalysts belonging to groups iI-2 and T-1 (cf.Table XIII) were placed in separate reforming

A 0 9 B 2 2 I 1 0 9 0

reactors filled and in the described in Example 6 Way subjected to a reduction treatment. This was followed by a 200-hour continuous steam reforming reaction performed by using a maphtha raw material corresponding to the naphtha raw material of Example 6 into the respective reactor at a rate of 80 g / h together with steam in the ratio HpO initiated at C of 1.5 and there at a Reaction temperature of 500 ° C and a reaction pressure of 20 kg / cm · G was implemented. The relationship between the content of copper / chromium / manganese oxide and the degree of reaction that can be achieved with each catalyst for the present steam reforming experiments shown in FIG.

Corresponding results from steam reforming tests,

at which the reaction pressure from 20 kg / cm · G to 70

kg / cm · G was increased are shown in FIG.

As can be seen from FIG. 7, the degree of reaction in the case of catalysts belonging to group T-1 with a copper / chromium / manganese oxide content of less than 6 wt relatively low reaction pressure, for example at 20 kg / cm · G, is carried out. If the copper / chromium / manganese oxide content is increased to over 6% by weight, the degree of reaction decreases. In particular, when the oxide content is increased to over 10 % by weight , only a slight influence of the presence of the oxide can be determined. If, on the other hand, the reforming reaction is carried out at relatively high pressure, for example at 70 kg / cm · G (see FIG. 8), the

409822/1 090

inventive catalysts have a degree of reaction that corresponds almost to the degree of reaction that can be achieved at low pressure. The catalysts belonging to group T-1 showed no evidence of the presence of the copper / Chromium / manganese oxide-related effect. These results thus confirm that the invention Catalysts the degree of reaction or the reaction rate in low-temperature steam reforming reactions able to improve both under relatively low pressure and under relatively high pressure.

Were the catalysts belonging to group N-2 in Within the framework of the steam reforming experiment described under Adjustment of the reaction conditions to a 100% degree of reaction used, possessed that here formed gaseous reaction product following composition ί

-54-

409 822/1090

Table XV

when applying a reaction pressure of 20 kg / cm ^ 'G kg / cm ² * G

67.7 % by volume 9.6 »0.5"

22.2 »

CH ₄ 61.7 VoI, - H ₂ 16.5 Il CO 0.9 Il CO ₀ 20.9 ti

-55-

409822/1090

Example 8

Under the same conditions as in the preparation of the catalysts of groups N-2 and N ~ 3 _S, but replacing the copper / chromium / manganese oxide with a copper / chromium oxide, different; Catalysts N'-2 and IM'-3 prepared. These catalysts were then used in the steam reforming reaction described in Example 6. The relationship between the copper / chromium oxide content and the degree of reaction of each catalyst is shown in FIG.

As can be seen from Figure 9, the degree of reaction decreases when using the catalysts JM'-2 and JM'-3 in comparison to use the catalysts W-2 and N »3 somewhat, however, these catalysts also exhibit a low temperature steam reforming reaction another excellent effect ο

Example 9

Under the conditions given in Table XVI below 33 different supported nickel-containing catalysts were prepared. As carrier materials were the in table ξ [νοη example 4 listed carrier used

Those belonging to groups P ~ 1, P = 2 and P = 3 Sators were like catalyst a of group W-1 "catalyst c of group N - = »5 and catalyst a of group JM-6 of Table XIII 'in Example 6, however with the exception that they contained the carriers listed in Table XVI.

+) with a mongan component

409 8 22/1090

Table XVI

Catalyst atomic content of carrier carrier ratio copper / part

Ni: Mg Chromium / (wt. %)

Manganese oxide

(Cu: Cr: Mn =

1: 1: 0.1

a 10

b 30

c dC quartz 50

d 70

e 80

g h i

P-1 3 0.6 k

1 10

m 30

η oC -Al ₂ O, 50

ο 70

P; 80_

q ^ -Al ₂ O ₃ 50

50 SiC 70 80 50 ZrO ₂ 70 80

r silica gel 30

s _s 50

b P-2 c 1.7

b c d

P-3 e 1.7

i SilTkagel

409822/10 90 -57-

oC quartz 70
80 SiC 30th <Γ ~ ^Α1 2 ° 3 30th ^ -Quartz 50
80 SiC 50
80 ZrO ₂ 70
80 ^ -Ai ₂ O ₃ 70
80

Example 10

25 g of the catalysts belonging to groups P-1, P-2 and P-3 in Table X ¥ I were introduced into separate reforming reactors and subjected there to a reduction treatment in the manner described in Example 6. A series of steam reforming tests were then carried out by introducing the same naphtha starting material as in Example 6 into the individual reactors for 200 hours at a rate of 80 g / h together with steam at a ratio of HpO to C of 1.5 and there at a temperature of 500 ⁰ C and one pressure

of 70 kg / cm · G was reacted. The Results are shown in Figures 5-7.

Each time after the end of the steam reforming experiment, the individual catalysts became a powder a particle size of 50 to 100 u pulverized, whereupon 10 g of the powder obtained with stirring in 500 ml of water were suspended. In the suspension obtained gaseous COp (60 mm water column) was introduced for 2 hours in order to allow the MgO in the suspension to escape. Eventually that was Weight of the escaped MgO is determined. In the event that the respective catalyst has a customary support, such as ί-ΑΙρΟ, or silica gel, was contained as a carrier portion the amount of MgO escaped is very low. In the case of catalytic converters, the carriers useful in the present invention contained as the carrier portion were more than about 80% of that therein contained MgO escaped. The reason for this large difference in the ratio of escaped MgO is presumably due to the fact that in the case of the catalysts with conventional supports during the reforming reaction a chemical reaction has taken place between the MgO and the carrier.

-58 -4098 2 2/1090

The results described show that some according to the invention Ifefcalysatoren containing usable carrier have excellent catalytic properties. Furthermore, the results also show (see Figures 10 to 13) that catalysts in which the carrier content, based on the total amount of catalyst, is 70% by weight exceeds, in low temperature steam reforming reactions according to the invention cannot be used successfully.

In order to facilitate the understanding of the advantages that can be achieved according to the invention, in the present example reforming reaction described with careful control of the degree of reaction by use a high sulfur naphtha and increasing the amount of feedstock per unit amount Catalyst carried out. In this case, too, the initial degree of reaction was 10090. In the event that the reaction conditions were adjusted so that the degree of reaction was 100%, that possessed from the same iMapirtha starting material obtained gaseous reaction product of the following composition:

CH ₄ 67.7% by volume

H ₂ 9.6

CO 0.5 "

CO ₉ 22.2 "

409822/1090

Claims (1)

A process for producing a methane-containing gas (as part of a (low-temperature steam) reforming), wherein reacting a hydrocarbon having at least 2 carbon atoms per molecule containing Kohlenwasserstoffausgangsniv- Aerial and to a temperature of 250 ° to 600 ⁰ C preheated steam into (at least ) a steam reforming reactor packed with a nickel-containing catalyst and reforming the hydrocarbon material under a reaction pressure of 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 the presence of a nickel and magnesium containing catalyst with an atomic ratio NisMg of 0.5 to 5.0. 2. The method according to claim 1, characterized in that the reforming is carried out in the presence of a catalyst containing nickel and magnesium applied to a carrier, the carrier being made of an inorganic, refractory and with the other catalyst components during the reforming chemical reaction incoming material, and, based on the total weight of the catalyst, weiliger than 70 wt% makes _e ~ '. 3 «The method according to claim 2 ^ characterized _{ the reforming is carried out in the presence of a nickel and magnesium containing catalyst applied to an aC-AlpO, -, SiC-j, oC> -quartz-» and / or ZrOp support " -60 = 409822/1090 4. The method according to one or more of the preceding claims, characterized in that iaan the iaan ileforination in the presence of a nickel and magnesium containing Carries out a catalytic converter, which, based on the nickel component in metallic form, less than 25 wt .- ^ o copper / chromium oxide or copper / Contains chromium / manganese oxide. 5. The method according to claim 4, characterized in that the Reformierunp; in the presence of a nickel and Performs a magnesium-containing catalyst, which, based on the nickel component in metallic form, 10 to 20 wt .-> j copper / chromium oxide or copper / chromium / Contains hangan 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 are used. 7. The method according to claim 1, characterized in that the hydrocarbon starting material and the Introduces steam into (at least) one steam reforming reactor in the ratio I ^ O / C (Kol / Atom) of 0.9 to 5.0. G. Method according to claim. 1, characterized in that e.
is working. at a reaction pressure of 10 to 100 kg / cm · G 409822/1090 BATHROOM 0RK3INAL 9 "The method according to claim O ¹ , characterized in that raan at a reaction pressure of 30 to 100 kg / cm · G is working. 10. The method according to claim 1, characterized in that one at a catalyst bed temperature of 400 ° to 570 ° C works. 11. The method according to claim 1, characterized in that one with a nickel and magnesium containing catalyst an atomic ratio of Ni; Mg from 1.0 to 3.0 works. 12. Niedrigtenperatur vapor-R-eformierungsverfahren for Kohlenwasserstoffe'zur producing 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 (HpO / C - mol / atom) from 0 _s 9 to 5.0 in (at least) a steam reforming reactor packed with a nickel / magnesium oxide catalyst having an atomic ratio Ni: Mg of 1.0 to 3.0 and introduces the hydrocarbon starting material under a Reaction pressure of 30 to 100 kg / cm · G at a catalyst bed temperature in the or «, the reactor (s) of 400 ° to 57O ⁰ C steam reformed. 13. Low temperature steam reforming process for Hydrocarbons to produce a methane-rich. Gas, characterized in that one is a hydrocarbon with at least 2 carbon atoms • -62- 40982 2/1090 Hydrocarbon starting material containing per molecule and steam preheated to a temperature of 250 ° to 60 ° C in the ratio of steam to hydrocarbons (H ₂ OfC - mol / atom) of 0.9 to 5.0 in (at least) one with a metallic oxide / magnesium oxide / Supported catalyst with an atomic ratio liickel to magnesium of 1.0 to 3.0, the support of which consists of o6-AlpO ^, SiC, o6 -quara and / or ZrO ^ and, based on the total amount of the catalyst, less than 70 wt. - / ό, introduces packed steam reforming reactor, and steam reformed the hydrocarbon starting material under a reaction pressure of 30 to 100 kg / cm · G- and at a catalyst bed temperature in the reactor (s) of 400 ° to 57O ° C. 14. 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 preheated to a temperature of 250 ° to 600 ° C steam in the ratio of steam to hydrocarbons. serstoffen (H ₂ 0 / C - IIol / Aton) γοη 0.9 to 5.0 in (at least) one with a nickel and magnesium-containing catalyst with a molar ratio Ni: Mg of 1.0 to 3.0, which is additionally based on the nickel content in metallic form, containing 10 to 20 wt .- ^ copper / chromium oxide or copper / chromium / manganese oxide, packed steam reforming reactor and introduces the hydrocarbon starting material under a reaction pressure of 30 to 100 kg / cm · G and at a catalyst bed temperature in the steam reformed and the reactor (s) of 400 ° to 570 ⁰ C. 409822/1090 15. Low-temperature steam reforming process for hydrocarbons for the production of a methane-rich gas, characterized in that a hydrocarbon starting material containing hydrocarbons with at least 2 carbon atoms per molecule and on. a temperature of 250 ° to SOO ⁰ C preheated steam in the ratio of steam to hydrocarbons (H ₂ 0 / C - Hol / atom) of 0.9 Ms 5.0 in (at least) one, with a nickel and magnesium-containing catalyst of one atomic ratio Ni: Hg from 1.0 to 3.0, which, based on the nickel part in metallic form, additionally contains 10 to 20 wt .- / ό copper / chromium oxide or copper / chromium / manganese oxide and on one, based on the total catalyst, less than 70% by weight of inorganic, refractory support in the form of ^ -AlpO- ,, SiC, - X-quartz, and / or ZrOp is applied, packed steam reforming reactor and the hydrocarbon starting material under a reaction pressure from 30 to 100 kg / cm · G for a catalyst bed temperature in the reactor (s) from 400 to 570 ⁰ C is steam reformed. 409822/109 0