DE2311756A1 - PROCESS FOR THE PRODUCTION OF GASES RICH IN METHANE, CARBON OXIDES AND HYDROGEN - Google Patents

Description

Badische Anilin- 3b Soda-ifebrix a'J 2311756

Our reference: O.Z. 29 709 Vo / AR 6700 Ludwigshafen, 5. 3 = 1973

Process for the production of methane-rich, carbon oxides and Gases containing hydrogen

The present invention "relates to a method of manufacture methane-rich, carbon oxides and hydrogen-containing gases by conversion of methanol over catalysts that Elements of the 8th subgroup of the periodic system,

contain. Mixtures containing methanol can also be used in this reaction, for example methanol-water mixtures or mixtures of methanol / water and hydrocarbons.

When it comes to the energy supply of the industrialized countries, the need has Natural gas has increased more and more in recent years. In some countries, such as the USA, the demand for natural gas has already exceeded the "naturally available" quantities. In order to cover the shortfall in natural gas demand for the future years, it is planned to use natural gas once through the low-temperature splitting of light petroleum distillates, such as naphtha, or through the gasification of cheap open-cast coal and subsequent methanation to cover the gases containing carbon oxides. Another possibility is to use natural gas where it is available in excess, to liquefy and to be transported by deep freeze ships to the place of potential need, to be stored there and for covering of the peak demand. Other models are currently being investigated to respond to increasing energy demand meet. For example, it is considered to produce methanol in countries with cheap natural gas and this, in the highly industrialized countries, such as the USA, for underfiring in power plants or, if necessary, to cover peak demand to be used in large cities after prior conversion into methane.

It can therefore be assumed that in the production of methane-rich Gases or gases that can be exchanged for natural gas are increasingly used in addition to the lighter hydrocarbons, such as

604/72 4Ö9837 / 0189

- S- - O.Z. 29 709

Ethane, propane, butane, or light naphtha or heavy naphtha fractions, increasingly heavier hydrocarbon fractions, for example middle distillates or even residual oils after appropriate pretreatment (generally Cleavage) and other raw materials that can be easily and relatively cheaply made available, such as methanol, as a starting material for the production of synthetic natural gas, must be considered.

The basic process for the production of methane-rich gases by the low-temperature cracking of hydrocarbons (Naphtha on nickel catalysts with steam) has been known since the end of the 1950s (see DAS .1 180 481). The further development of this process essentially relates to the use of improved catalysts (cf. DAS 1 199 427 and 1 227 603) and the implementation of this process in several reaction zones (cf. DOS 1 922 182).

On the other hand, processes are known for the production of gases which, in addition to hydrogen, also contain carbon oxides and small amounts of methane, which proceed from hydrocarbons, such as methane, LPG, and light or heavy naphtha traces. By converting these hydrocarbons in the presence of water vapor over nickel catalysts at temperatures in the range between 700 and 900 ^° C., these raw materials produce essentially hydrogen-rich fission gases. (For information on carrying out the high-temperature cleavage of naphtha and the catalysts to be used for the cleavage, see British patents 1,029,235, 1,022,978, 1,032,756, 1,752, 916 216, 953 877, 1 003 702 and 1 032 755 or 1 040 066, as well as the German patent specification J 26 540 IVa / 12g).

A steam reforming process is described in the laid-open German application 1 645 844. This method deals with the generation of fuel gases, e.g. town gas. In the case of existing town gas systems that are after a High-temperature steam reforming processes are operated, The quantities of fuel gas emitted are generally sufficient not enough to meet peak demand. This is supposed to be in the

409837/0189 ~ ³ ~

-> - O.Z. 29 709

procedure described above. To increase the emission of combustion gases the gaseous or liquid hydrocarbons in the conversion zone methanol (75O ⁰ C) is added. In general, lean gases are obtained from which gases with a higher calorific value are obtained by adding an enriching gas, for example methane or LPG. Another way to increase the output of gas generation systems is to add methanol to the raw gas generated in the high-temperature Spa It stage after it has cooled, but before entering the conversion stage. In the conversion stage, preference is given to using catalysts which promote the splitting of the methanol into the constituents CO + Hg. Here too, after leaving the conversion stage, the gas becomes enriching gases, e.g. CH. or LPG, added to increase the calorific value.

In summary, it can therefore be stated that it was already known in the high-temperature cracking of gaseous or to add liquid hydrocarbons to the Increase emissions from gas generation plants. Equally was it is known to add methanol in the conversion stage of a gas generation plant, also with the aim of reducing the output to increase the gas generation plant. When increasing the The addition of methane oil causes emissions from the gas generation system essentially no change in the composition of the gas, only the amount of gas generated increases. In both In some cases, the desired calorific value of the gas is set by post-treatment (adding methane or LPG).

It is the object of the present invention to provide a process available to convert from methanol by catalytic cleavage to produce gases with a high calorific value (methane-rich gases), in particular gases that can be exchanged for natural gas.

It is another object of the invention in a known method to add methanol to the raw material for the catalytic low-temperature cleavage of hydrocarbons to form methane-rich gases. -4-

409837/0189

- 4 - O.Z. 29 709

By adding methanol, the water vapor required for the cleavage of the naphtha can be reduced Others can lower the preheating temperature when using naphtha-methanol mixtures, since the conversion of Methanol to methane-rich gases on low-temperature split catalysts starts at considerably lower temperatures than when using pure hydrocarbons (naphtha).

The present invention therefore relates to a method of manufacture gases rich in methane, carbon oxides and hydrogen. This method is characterized in that one Methanol, optionally together with water, is evaporated and the vapors thus obtained are converted to a catalyst which Contains at least one element of the 8th subgroup of the periodic system, including precious metals.

The invention also relates to a method for producing methane-rich gases containing carbon oxides and hydrogen. This process is characterized in that mixtures of hydrocarbons, methanol and water are produced in vapor form converts a catalyst containing nickel and / or cobalt.

It was surprising that methanol or water-methanol mixtures already a little above the respective dew point on the ones usually used for the low-temperature cleavage of naphtha used nickel or cobalt catalysts in methane-rich Gases is or are converted. (The conversion of methanol on low-temperature cleavage catalysts presumably takes place in two steps. The primary step can be seen in the splitting of the methanol to CO + Hp. Following this primary step The cleavage products then set themselves into thermodynamic equilibrium on the catalyst).

The conversion of methanol over catalysts to methane-rich gases is, in contrast to the splitting of methanol to CO + H _2, exothermic. It can therefore be carried out in the economically advantageous shaft furnace. When using appropriately active catalysts, the reaction can already take place at temperatures around

b ( -5-

or even below 100 ⁰ C can be carried out. However, since

409837/0189

- 5 · - O.Z. 29 709

the catalytic conversion of methanol on these catalysts In addition to methane and hydrogen, carbon monoxide is also formed, because of the fact that some elements belong to the 8th subgroup of the periodic System expected carbonyl formation (especially e.g. with nickel and cobalt) work at such temperatures where no carbonyl formation occurs, because otherwise the active component is likely to be discharged from the catalyst bed.

For the conversion of methanol or methanol-water mixtures to methane-rich gases, temperatures of 200 to 300 ^° C., in particular those of 250 to 280 ^° C., are therefore suitable. It is expedient to proceed in such a way that methanol or methanol / steam mixtures are preheated to temperatures in the range mentioned above and the vapors are introduced into the catalyst bed at this temperature. A temperature profile forms in the catalyst layer, the maximum temperature corresponding to the reaction temperature. This means: with ideal insulation of the reactor, the maximum temperature reached is at the same time the exit temperature of the gas from the contact layer and thus the equilibrium temperature.

When using pure methanol as a raw material and at a preheating temperature of 200 ⁰ C to obtain a reaction temperature of 708 ⁰ C. At this temperature, one obtains a gas of the following composition (all figures in percent by volume):

Before drying After drying

CH ₄ 33.60 42.5 CO 9.4 11.9 H ₂ 23.4 29.1 co ₂ 12.7 16.5 H ₂ O 20.9 -

Gases of this composition can be methanated at temperatures below 400 ⁰ C and 300 ⁰ C by passing it over nickel catalysts to further increase the methane content after partial or complete removal of water in known manner. After removing CO ₂ , gases are obtained that contain less than 1 percent by volume of CO + H _2.

409837/0189 -6-

- if - OZ 29 709

switch and consist of almost pure methane (natural gas substitute gas). These gases can be modified by adding liquefied petroleum gas or, if necessary, nitrogen to a natural gas of the desired quality will.

In addition to pure methanol, mixtures of methanol with water are also suitable as raw materials for the generation of methane-rich gases. Preferably 30 to 80 follow aqueous solutions are used by methanol. Of course, when using methanol-water mixtures, depending on the methanol content of these mixtures, lower temperature rises occur in the reactor when the reaction is carried out adiabatically. The composition of the gas obtained changes accordingly. If the temperature in the reactor increases less, the methane content of the cracked gas increases. (The catalyst used also plays a role).

Mixtures of methanol, hydrocarbons and water can also be used as raw materials for the cleavage. As already mentioned at the beginning, it has proven to be very advantageous to add methanol in the cleavage zone during the low-temperature splitting of hydrocarbons. Suitable hydrocarbons are those with 2 to 30 carbon atoms, in particular mixtures thereof. These have a boiling range of 30 to 300 ⁰ C.

The proportion of methanol in the methanol / hydrocarbon mixture should be 10 to 90% based on the total amount, but mixtures should preferably be used which contain 20 to 60% methanol. In the case of low-temperature natural splitting of hydrocarbons with steam, values of not less than 1.6 for the ratio of steam to hydrocarbon are generally adhered to in order to prevent soot formation when the splitting is carried out in one stage (cf. DAS 1 180 481 British Gas Council). Somewhat lower values of 1.4 to 1.6 for this ratio can only be used when the process is carried out in a special way (hydrogasification cf. DOS 1 922 182). It has now been found, surprisingly, that soot formation does not occur during the low-temperature naphtha cleaning in the presence of methanol, even with significantly lower values of this ratio. -7-

409837/0189

- ψ - OZ 29 709

When using a mixture of 50 i »methanol and 50 $> hydrocarbons it takes only a ratio of greater than 0.6 to 0.8 kg of steam / kg of hydrocarbon in the one-step cleavage observed, occurs without soot formation. The addition of methanol in the low-temperature cracking of hydrocarbons is therefore characterized by high economic efficiency, since lower values have to be used for the ratio of water vapor to hydrocarbon, and a methane-rich gas is obtained from the methanol to be evaporated for the cracking.

For the hydrocarbons to be used, the chlorine- and sulfur content do not exceed the value of 0.5 ppm each, since chlorine and sulfur compounds are catalyst poisons. Methanol can be used directly without purification, since chlorine resp. Sulfur compounds are removed because of the copper catalysts used. Generally one will do so in synthesis Use any raw methanol that contains approx. 20% water.

The catalysts for the process according to the invention are Metals of the 8th subgroup of the periodic system are suitable. In particular, nickel and cobalt or mixtures of the two are used mentioned metals are used. However, the noble metals or mixtures of the aforementioned metals with noble metals can also be used in the same way be applied. In general, however, nickel catalysts are particularly preferred for the inventive method Procedure applied.

The catalysts are preferably used on a carrier. In particular, inert ceramic materials that are stable under the reaction conditions are suitable for all catalyst supports. Suitable carriers for the active component are: aluminum oxides, in particular boehmite, bayerite, hydrargillite or the surface- rich J or ^ aluminum oxides obtained from the oxide hydrates of aluminum, also spinels, TiOp »ZrO ₂ » synthetic or natural magnesium silicate, aluminum silicates or mixtures of the aforementioned carriers.

-8th-

409837/0189

-er - ο.ζ. 29 709

The active component is expediently 20 to 80 #, based on the finished catalyst, selected, preferably contents of the active metal, in particular of nickel, between 30 and 64 # ♦ calculated as reduced nickel, applied. As already mentioned, nickel catalysts are particularly preferred and, in turn, the catalysts known for low-temperature naphtha cleavage, as described in US Pat German Auelegeschriften 1 180 481, 1 199 427, 1 227 603 (Brit. Gas Council) and the published German applications 1,417,798 (Pullmans) and 1,545,428 (BASF / Lurgi) are used. However, preference is given to using catalysts which are prepared as indicated in Example 1 under 0 have been.

The generation of methane-rich gases can be pressureless or under pressure can be carried out up to 150 at; preferably pressures of 20 to 100 at, in particular those of 20 to 80 at, are used.

When using methanol or methanol-water mixtures, preheating temperatures of 200 to 300 ^° C. are recommended. As already mentioned, the catalysts known for the low-temperature naphtha cleavage are already so active that the cleavage of the methanol already takes place at significantly lower temperatures, however, especially when using nickel or cobalt catalysts, there is a risk of the catalyst component being carried off carbonyl formation given at substantially below 200 ⁰ C temperatures, so that the aforementioned Bereioh to be maintained for the preheating of the raw material useful for this reason. With the use of hydrocarbon-methanol Waeser mixtures, ie, in the low-temperature cracking of hydrocarbons with the addition of methanol, the starting materials are preheated to temperatures from 250 to 400 ⁰ C. It is possible to warm up all three components or optionally two of the three components and mix in the third component in vapor form. The preheating temperature depends on the activity of the catalyst. In the case of a low methanol content in the mixture, higher temperatures in the aforementioned range are used; in the case of a high methanol content in the mixture, correspondingly lower temperatures can be used. Preheating temperatures of 250 to 35O ⁰ C are preferred.

ο 23? * 796

turns.

When using pure methanol or a methanol-water mixture A catalyst space velocity of from 1.5 to 3.5 kg of mixture / l of catalyst can be considered. When using hydrocarbon -Methanol-water mixtures can depending on the activity of the catalyst used and the composition of the mixtures, loads of 1 to 3 kg of methanol + naphtha / kg of catalysis tor (hour can be selected. E.g. if a hydrocarbon-methanol mixture of 1: 1 is used, a load of 2, based on the sum of methanol and hydrocarbon, selected.

In the two subsequent experiments, naphtha was used once with and once without the addition of methanol (standard method) Nickel catalyst converted into a methane-rich gas in one step. The tests were carried out so that max. Reaction temperatures and loading of the catalyst chosen to be the same became. Ea the following results were obtained:

KW HC + methanol 1: 1 a) b) H ₂ 0 / KW ratio: 1.4 kg / kg 1.0 kg / kg Space velocity over the catalyst 2 kg / 1 cat 2 kg / lKat.h Preheating temperature 39O ⁰ C 300 ⁰ C max reaction temperature 514 ⁰ C 517 ⁰ C Gas composition CH ₄ 67.4 72.7 H ₂ 9.2 2.7 CO 1.2 0.4 co ₂ 22.2 24.2 (Example 6) (Example 4)

The results show that when methanol is added, the preheating temperature of the raw material used can be reduced considerably. In addition, the methane concentration achieved in the cracking by the process according to the invention is considerably higher; Soot formation could not be observed

409837/0189

ORIGINAL INSPECTED

- 10 -

- ie - ο.ζ. 29 709

The two aforementioned experiments were repeated under a higher load (space velocity over the catalyst 5 kg / lh). After a term of 186 hours in case a) there was a breakthrough of uncleaved Petrol hydrocarbons detected. In case b) the first unconverted hydrocarbons appeared at the exit of the reactor only after 252 hours. From these results it follows that when carrying out the low-temperature cleavage with the addition of methanol in addition to reducing the. Preheating temperature for the starting mixtures and the catalyst are spared.

However, the invention is not intended to be limited by the foregoing be limited. For example, methanol or methanol-water mixtures can be split in one reaction zone perform as follows:

Part of the methanol or methanol-water-steam mixture is Introduced at one point into the reactor, another part is used for cooling, for example, this part is in a Quench zone introduced or introduced at other points in the reactor. This measure can reduce the temperature rise are limited in the reactor. This makes it possible to change the gas composition (see Example 8).

It is equally possible to carry out the cleavage in more than one stage and one between the individual stages Make quenching with methanol or water.

When using hydrocarbon, methanol and water mixtures Various modifications of the invention are also possible. In addition to the one-step implementation already described the cleavage can limit the temperature rise in a reactor by cooling or quenching with a the input materials, i.e. methanol, hydrocarbons or water vapor, are provided. The cleavage can also take place in two reaction zones be carried out, with methanol being metered into the first reaction zone and naphtha into the second reaction zone will. This arrangement is beneficial for the following reasons:

409837/0189

- 11 -

- Η - O.Z. 29 709

In the splitting of τοη methanol, a very high heat release occurs on; the split gases releasing the first reaction zone can then be cooled with liquid or vaporized haphtha, the latter being used to carry out the cleavage in the second reaction zone required temperature is heated.

The following advantages result for carrying out the naphtha cleavage in the second reaction zone: Saving Costs for preheating the hydrocarbons, using a lower water vapor / hydrocarbon ratio and protecting the catalyst through its presence of methane or hydrogen and carbon monoxide in the second reaction zone. For further details on this process variant, refer to the relevant statements in the case of the low-temperature cleavage τοη Haphjtha (cf. DOS 1 922 182 - British Gas Council).

The invention is illustrated by the following examples. Example 1 describes the production of three catalysts, two of which are already known to be suitable for the low-temperature cracking of gasoline-hydrocarbons. In the following examples 2 to 4- these catalysts are used for the conversion of τοη methanol or hydrocarbon mixtures containing methanol into methane-rich gases.

example 1

A) There are introduced into a vessel about 7.5 1 Tollentsalztes water, this is allowed with stirring at 20 to 40 ⁰ C within τοη about one hour and at a pH of 7 τοη accrue to 7.5 following solutions:

1) 0.218 kg SiO ₂ in approx. 1.45 1 dilute waterglass _{solution with an SiO 2} content τοη 15 wt .- ^;

2) 0.146 kg MgO in approx. 2.5 1 dilute magnesium nitrate solution with a MgSO, content τοη approx. 20 wt .- ^;

3) 0.718 kg of HaOH as 25 percent strength by weight hatron hydroxide solution.

409837/0189 _ ₁₂ -

O.Z.

Thereafter, it is heated to 5O ⁰ C and at a pH of 7 to 7.5 within approximately one hour under stirring, the solutions specified below further to the failed amorphous magnesium silicate suspended (carrier) added:

a) 0.637 kg NiO in approx. 4.0 1 approx. 15 weight percent nitrate solution,

b) 1.25 kg Na ₂ CO ₃ dissolved in about 1,250 1 _H2O.

The deposited precipitate is carefully washed free of alkali on the filter press. The filter cake is ^{dried at 20O 0} C, ground, mixed with 2 $> graphite and pressed to form 5 × 5 mm tablets.

The pelletized catalyst was calcined for 6 hours at 450 ° C. and has a Ni content of 40% by weight, based on NiO; The remainder is amorphous Mg-silicate.

B) 2.4 kg of a nickel oxide paste (25 # NiO) are slurried together with 1.48 kg of boehmite (this aluminum oxide hydrate contains 27 # Al ₂ O ₃ ) in 6 1 H ₂ O and ^{stirred at 60 °} C. for 1 hour, then filtered off , dried overnight at 95 ⁰ C, calcined for 6 hours at 450 ⁰ C and pressed with the addition of $ 2> graphite to 5 x 5 mm tablets. 1.02 kg of catalyst (oxidic) were obtained which contained # Ni, calculated as NiO, and had a bulk density of 0.96 kg / l.

C) For the preparation of the catalyst precursor Ni ₅ MgAl ₂ (OH) ₁ ^.

CO ₃ 4H ₂ O the following two molar solutions were prepared:

1) 0.463 kg of Mg (NO ₃ I ₂ · 6 H ₂ O were dissolved in such an amount of H ₂ O that a total solution of 0.9 1 was formed.

2) 2.845 kg Ni (NO ₃ J ₂ · 6 H ₂ O and 1.450 kg Al (NO ₃ J ₃ '9 H ₂ O) were dissolved in H ₃ O to make a solution of 7.0 1.

3) 1.85 kg of Na ₂ CO ₃ were dissolved in 9 1 H ₃ O.

_{2.5 1 of H 2} O were placed in a stirred kettle which was provided with a glass electrode for continuous pH measurement, heated to 50 ^° C. and a suitable amount of solution 3 was added

409837/0189

-13-

- ΐ3 - O.Z. 29 709

adjusted the pH value of 10.

At a constant pH value and constant temperature, magnesium was continuously converted into the hydroxide or basic carbonate Combining solution 1 and 3 precipitated. After solution 1 had run in completely, the other Addition of solution 3 stopped.

With a small amount of solution 2, the pH value in the receiver was now adjusted to 8 and at this pH value and a temperature of 50 ^° C., solutions 2 and 3 were continuously combined over the course of 40 minutes. The partially crystalline precipitate which separated out was filtered off. The filter cake was again suspended in 12 l of water at 50 ^° C. and stirred for a longer period of time. After about 4 to 5 hours, the precipitate was sucked off, for 5 hours at 95 ⁰ C, 5 hours at 11O ⁰ C dried and then calcined 4 hours at 500 ⁰ C while heated by the drying to calcination temperature within 2 hours. The analysis showed 50.3 wt .- # Ni, based on the oxidic contact · The ready-to-use catalyst is obtained by reduction (see Example 4).

D) First, the following 2 molar solutions were prepared: Solution 1:

873.0 g Co (NO ₃ ) ₂ '6 H ₂ O
512.8 g of Mg (NO ₃ ) ₂ · _{6H 2} O
9 H ₂ O - 825.4 Al (NOj) ₃ g
and dissolved in 5 1 H ₂ O.

Solution 2: 1.6 kg of K ₂ CO ₃ are dissolved in 5 1 of H ₂ O.

In a precipitation vessel provided with a stirrer and pH electrode was added 3 1 H ₂ O and heated to 4O ⁰ C. Solutions 1 and 2 were continuously combined within 30 minutes at constant temperature and a pH of 9 * 0. It was then filtered off with suction on a suction filter and washed free of alkali. The filter cake was ^{dried at 110 °} C. for 12 hours and ^{calcined at 400 °} C. for 4 hours. Subsequently, with 2 $> graphite became 5 χ 5 mm

409837/0189 -H-

-K- O.Z. 29 709

Compressed tablets. The catalyst had a cobalt content of $ 35 in the oxidic state.

Example 2

200 ml of catalyst A (Example 1) were introduced into a reaction tube with a diameter of 24 mm. The reaction tube was heated externally by an aluminum block. After the catalyst had ^{been reduced with hydrogen at 450 °} C. and about 30 atmospheres of H ₂ , the catalyst bed was cooled down ^{to 200 ° C. again.} Then, pure methanol was evaporated and passed at a temperature of 240 ⁰ C through the bed of catalyst A. The adiabatic reaction temperature was 715 ⁰ C, the loads 2 kg of methanol / liter and hour. The reaction gave 415 standard l / hour of a drying gas which had the following analytical composition (all data in percent by volume): CH. = 41.54; CO - 13.43; H ₂ = 30.06; CO ₂ = 15.07.

Example 3

In a reaction tube of 32 mm inside diameter 200 ml of catalyst B (Example 2) was charged, and ₂ pressure of 30 ata for 20 hours at 450 ⁰ C at a reduced H. A mixture of methanol / water 1: 1 with a loading of 2 kg / liter of catalyst and hour and a temperature of 280 ^° C. was then passed over the contact. The final adiabatic temperature rose up to 588 ⁰ C. After drying, the gas emerging from the reaction zone had the following analytical composition (all data in percent by volume): CH ₄ = 39.03; CO = 2.24; H ₂ = 35.13; CO ₂ = 23.60.

Example 4

In a reaction tube of 32 mm inside diameter 200 ml contact C (Example 1) are charged and reduced long with 30 ata of H ₂ for 12 hours at 45O ⁰ C. A mixture of equal parts by weight of methanol, naphtha and water is then evaporated and passed into the contact ^{bed at a preheating temperature of 300 ° C.} The naphtha used had a boiling range from 80 to 155 ⁰ C and

409837/0189 - ¹ 5-

O.Z. 29 709

a density of 0.727 kg / l. The space velocity over the catalyst was 1 kg Methanol + 1 kg naphtha / liter of catalyst and hour.

The maximum temperature in the contact bed was 517 ⁰ C. At the end of the contact bed were measured 428 ° C because of the insufficient insulation of the reactor. The cracked gas emerging from the reactor was dried and then had the following analytical composition (all data in percent by volume): CH, = 72.7; CO = 0.4; H ₂ = 2.7; CO ₂ = 24.2.

Example 5

200 ml of catalyst C (Example 1) were installed in a reaction tube with a clearance of 24 mm and reduced as described in Example 2, 3 \ bmA. At 30 ata and with a preheating temperature of 250 ^° C., a mixture of methanol and water in a ratio of 1: 2 was passed through the bed of the catalyst. The space velocity was 2 kg of methanol / liter of catalyst and hour. The adiabatic reaction temperature was 500 ° C. A sample of the cracked gas taken had the following analytical composition (all data in percent by volume): CO = 0.10; CO ₂ = 6.7; CH ₄ = 12.00; H ₂ = 8.5; H ₂ O = 72.7.

This reformed gas is mixed with 4 kg of gasoline vapor (specification as in Example 4) retracted and with a preheating temperature of 300 ⁰ C in a second reactor, also containing 200 ml of catalyst C in a reduced state. The adiabatic reaction temperature door of this stage is 472.0 ⁰ C, pressure 30 ata. The gas leaving the catalyst layer has the following composition after drying (all data in percent by volume): CH ₄ = 70.3; CO ₂ = 23.56; CO = 0.7; H ₂ = 5.4.

Example 6

200 ml of contact C (Example 1) and as described in Examples 2, 3 and 4 were reduced into a reaction tube with an internal diameter of 24 mm. Then a mixture of water and naphtha in the ratio 1.4: 1 kg / kg was evaporated and with a preheating temperature of 390 ⁰ C and a pressure of 30 ata through the Ka ta

409837/0189 _ ₁₆ _

- f6 - OZ 29 709

led lysatorbett. The adiabatic reaction ^{temperature was 515 °} C. (the specification of the naphtha is the same as in experiment 4).

The dry cracked gas emerging from the reactor had the following analytical composition (all data in percent by volume): CO = 1.15; CO ₂ = 22.25; CH ₄ = 67.36; H ₂ = 9.24.

Example 7

200 ml of catalyst no. D (Example 1) were installed in a reaction tube with a clearance of 24 mm and ^{reduced at 400 °} C. for 10 hours.

A mixture of 2 kg of methanol and 4 kg of H ₂ O was then evaporated and passed over the contact over a period of 1 hour. In adiabatic reaction the maximum temperature rose to 524 ⁰ C. The dry gas leaving the catalyst layer had the following composition (all data in percent by volume): CH. = 40.0; CO = 0.7; H ₂ = 35.1 and CO ₂ = 24.2.

Example 8

In a reaction tube having an internal diameter of 24 mm 200 ml of catalyst C is charged and at 45O ⁰ C in hydrogen stream under the specified reduced in Example 4 conditions. The subsequent reaction is carried out in both reaction zones at a pressure of 50 ata. For this purpose , a mixture of methanol and water is evaporated and passed onto the catalyst with a loading of 2 kg of methanol per liter of catalyst and hour and 4 kg per liter of catalyst and hour at a preheating temperature of 250 ° C. In this reaction zone (first stage) the temperature rises to a value of 508 ^° C. when the reaction is carried out adiabatically. After the first reaction zone, a cracked gas of the following composition (all data and volume ^) is obtained. Water: 72.73; CH ^ 12.08j CO 0.17; CO ₂ 6.69.

-17-409837 / 0189

This cracked gas is abgekihlt in heat exchange with 2 kg of methanol per liter of catalyst and hour and passed at a temperature of 250 ⁰ C, without further addition of water vapor in a second reaction zone (second stage). This reaction zone also contains 200 ml of catalyst C, which had been reduced as indicated above. The reaction temperature in the 2nd reaction zone in this case was a maximum of k9JC. A cracked gas was obtained from the outlet of the 2nd reaction zone which, after drying, had the following composition (all data in volume-Jl: CH ^ 55.20; CO Ο, όΟ; CO ₂ 25.00; Η _£ 19.20.

409837/0189

ORIGINAL INSPECTED

Claims (3)

Claims 1. A process for the preparation of methane-rich gases containing carbon oxides and hydrogen, characterized in that methanol is evaporated, optionally together with water, and the vapors obtained are converted over a catalyst which contains at least one element of the 8th subgroup of the periodic table, including the noble metals , contains. 2. The method according to claim 1, characterized in that mixtures of methanol, water and hydrocarbons are used « 3. The method according to claim 2, characterized in that mixtures of methanol, water and hydrocarbons are reacted in vapor form at preheating temperatures of 250 to 400 ⁰ C over a catalyst which contains nickel and / or cobalt. Badische Anilin- A Soda-Pabrik, AjGr L INSPECTED 409837/0189