DE1026472B - Circular process for producing a combustible gas rich in oil - Google Patents

Description

Circular process for producing a combustible gas rich in oil gas The invention relates to a novel method for producing a high quality Oil gas rich flammable gas that is produced by a cycle process using a Nickel catalyst is produced, with efficiencies in gas production result, which are significantly higher than those in the gas processes previously carried out scored.

The production of oil by gas Ölpyrolyse, ie, by the thermal cracking of 01 without a catalyst, is known. In normal practice, however, real oil gas values that are below 8920 kcal / m3 cannot be produced by the thermal process without excessive carbon formation. As this carbon is converted to water gas by steam from the process, the calorific value of the resulting mixed gas is further reduced.

It i, -, t also known that coblene hydrogen in the presence of nickel can be fully reacted with water vapor to form a gas that essentially of hydrogen and oxides of carbon, mainly carbon monoxide, consists. The ones involved in this "reshaping" or "reforming" process in general applied hydrocarbons are the gaseous hydrocarbons, in particular -NIethaai, although under certain circumstances liquid hydrocarbons are also used can be. The resulting gas product, consisting essentially of hydrogen and carbon monoxide as the combustible components has a relative low calorific value, usually in the vicinity of 2225 to 3115 kcal / m3, and therefore requires enrichment with a gas with a higher calorific value, such as natural gas or oil gas to deliver the desired calorific value before it enters the city's main gas pipelines comes to distribution.

It has been proposed to subject the hydrocarbons to partial catalytic conversion into a combustible gas which contains some gaseous hydrocarbons and has a higher heating value than the fully converted gas described in the previous section. A method recently developed is that 01 sprayed onto a hot nickel-containing body, and is thereby converted to a combustible gas with a calorific values lying in the oil-gas region. The efficiencies achieved by this process in oil gas production are very low, however, and over 50 to 851 / e of the bound carbon content of the oil is obtained as the product of the water gas reaction with a low calorific value and as carbon, tar and the like. That is, the higher calorific value gas produced, although mostly composed of oil gas and a small amount of water gas, is produced at the expense of producing a large amount of carbon, tar and the like; whereas the lower calorific value gas is predominantly water gas and its formation is still accompanied by the formation of large amounts of carbon, tar and the like. In addition, the gas generating capacity of this process is relatively small.

The invention now relates to a novel catalytic cycle process for the production of a combustible gas consisting essentially of oil gas a liquid petroleum hydrocarbon, the process being much more efficient of transformation, as hitherto achievable, delivers.

One might assume that it was produced by an oil gas Treatment of the hydrocarbon with a catalyst is only necessary Hydrocarbon with the catalyst is shorter than that for complete conversion to bring the required time into contact. When trying to get such an oil gas out of a Light oil by reducing the thickness of the catalyst zone through which the oil passed, the catalyst was used because of excessive carbon deposition and penetration, of carbon ineffective in the catalyst. To the extent that in the carbon is deposited on the catalyst, the effectiveness of the Catalyst is reduced, and the process approaches the ordinary thermal Columns. Try to remove the excessive carbon build-up during each heating stage removing them completely resulted in excessively high surface temperatures and resulted for rapid mechanical destruction of the catalytic converter.

However, it has been found that it is possible to use liquid hydrocarbons, including heavy oils, in oil gas and even in high calorific value catalytically split, obtaining unusually high conversion efficiencies which are significantly higher than those obtained in conventional oil gas processes. Although a small amount of water gas is also generated in this process but according to the invention mainly liquid petroleum hydrocarbons effectively in Olgas converted. Furthermore, the formation of a combustible one rich in oil gas can occur Gases at high degrees of conversion with maximum production capacity while maintaining the optimal catalyst activity can be achieved. This becomes more certain through regulation Conditions within fixed limits and by observing certain relationships achieved between certain of these regulated conditions. These conditions are: Hydrocarbon feed rate, concentration of what is present Nickel on the catalyst, mass of the catalyst body in relation to its Surface and temperature. The success of the procedure depends on the catalvtic Effectiveness of the nickel. This in turn does not only depend on the correct distribution the feed to be split with respect to the catalyst surface and available nickel concentration, so that the carbon and sulfur deposits not overly concentrated in any limited part of the catalyst zone but also of the way in which the heating-regeneration stage of the Cyclic process is passed, so that a regeneration of the catalyst by practically complete removal of carbon and sulfur during this part of each Cyclic process is possible, while the temperatures within the catalyst zone be kept within narrow limits.

The process of the invention is a circular process; H. it exists from alternating heating, regeneration and gas production stages, wherein a vaporized, normally liquid petroleum hydrocarbon in the gas generation stage and passing water vapor in contact with a heated nickel-containing catalyst and the stream from the hydrocarbon and water vapor during the heating and the regeneration part of the cycle process is interrupted. The procedure is now characterized in that during the gas generating part of the cycle process the vaporized hydrocarbon and water vapor through a catalyst zone which has a temperature gradient not exceeding 55 ° C and nickel-containing refractory bodies whose: mass between about 4.7 and 50 kg / m2 surface area and a nickel concentration in the outer 0.8 mm of the surface of about 0.07 to 0.15 kg / m2 of the surface, namely with a speed that has a value between 2 and 6 for the ratio of the amount of hydrocarbon feed (kg C / h) to catalyst surface (m2) X Ni concentration (kg / m2 surface), with the consisting of the hydrocarbon and water vapor Gas flow is interrupted before the temperature in the catalyst zone by noticeably, drops by more than 55 ° C. The above ratio is preferably between 3 and 5 and is the concentration of nickel in the outer 0.8 mm of the catalyst surface 0.1 to 0.15 kg / m2 of the catalyst surface.

If the conditions are observed and coordinated in the manner indicated above, liquid petroleum hydrocarbons can easily be converted into combustible gas, which consists largely of oil gas and has a calorific value between 6250 and 10 700 kcal / ms (calculated on a N2-free basis). Furthermore, the gasification can be achieved with an unusually high conversion efficiency, ie a high proportion of carbon in the feed appears in the gas. In fact, conversion efficiencies between 70 and 85% are easily achieved in the present process, which are in great contrast to the efficiencies of the usual oil gas processes of 40 to 50,010 with the same calorific value range. These efficiencies are also achieved with large throughputs. The process can: be carried out with a device for which a minimum of investment per unit volume of gas produced. is required because the device is simple and can easily be built from the usual gas generating apparatus by appropriate modification, as can be seen from the drawing.

A valuable feature of the procedure is that it can treat each common liquid petroleum hydrocarbons from light distillates to heavy oils with high carbon and sulfur contents can be used. examples for Liquid petroleum hydrocarbons that can be treated are gasoline, light gasoline, Luminous oil, diesel oil, bunker C oil, or heavy residue oil.

The catalyst used in the process consists of individual bodies made of refractory material which has nickel on at least its surface. That Nickel only needs suitable refractory bodies on the surface, such as aluminum oxide, Aluminum silicate, or magnesium oxide, to be dispersed, but it can also be inside of the entire refractory body as long as it is also on the surface the same is present. In making a preferred type of catalyst pre-formed refractory bodies, such as aluminum oxide, are impregnated with nickel salt; then the impregnated bodies are strongly heated to remove the oxide. to create, which is then reduced. The catalyst is in the form of individual bodies, z. B. in the form of cubes, cylinders, beads or cookies. The catalyst body also have a relatively high density; H. They have. one not over about 351% and preferably between about 10 and 201% porosity.

It has been found that the reactions taking place in the process are limited to the very thin surface layer of the catalyst body. It it was found that at the relatively high throughput rates used the effective nickel is within the outer .0.8 mm of the catalyst body. The concentration of nickel in this outer layer is crucial Factor. When there is too little nickel in the surface layer of the catalyst is approaching its mode of action is that of a non-catalytic one refractory body, causing predominantly thermal cracking, as with the conventional oil gas process, results; it is difficult to control gas production. It was found that the amount of nickel in the outer 0.8 mm of the catalyst body should be at least 0.07 kg / m2 of the catalyst surface. Preferably is the amount of nickel on this basis is about 0.1 to 0.15 kg / m 2 of the catalyst surface area. On the other hand, however, it was found that when the concentration of nickel on the surface is too large, the conversions on a relatively thin part of the Surface layer of the catalyst become concentrated and excessively large amounts Carbon can be deposited per unit quantity of catalyst. These carbon deposits not only reduce the effectiveness of the nickel during the gas generation stage of the cycle, so that thermal cracking is promoted, but they are also difficult to remove because of long burning times or excessively high temperatures which in turn would require high local surface temperatures and mechanical Destruction of the catalytic converter. Amounts of nickel that are significantly above 0.16 kg / m2 of catalyst surface can cause the difficulties just mentioned cause in terms of carbon deposition. Within the above mentioned Combinations of catalyst bodies can be applied that have different limits Have concentrations of available nickel.

Another important factor is the mass of the catalyst body in Relationship to their surface. Temperature changes of the catalyst surface during the gas generation stage of the cycle must be kept to a minimum. During the gas generation stage of the cycle, heat is removed from the catalyst surface deducted. The greater the mass of the catalyst body in relation to its surface area is, d. i.e., the greater the weight of the catalyst per unit surface area, um the temperature on the catalyst insulating surface falls less quickly during the Gas generation in the cycle. Therefore, each catalyst body must act as a reservoir for stored.-, heat that is used during the gas-generating conversions for Catalyst surface can be passed. Therefore, the individual catalyst body not be less than what is needed to ensure that sufficient Heat is stored in order to prevent the temperature on the surface of the catalyst from falling too quickly to prevent. On the other hand, however, too large a catalyst body has a excessive mass and volume per unit catalyst surface area and therefore causes ineffective utilization of the catalyst space. It was established. that the mass of each catalyst body is about 4.7 to 50 kg / m2 of catalyst surface should be. In the case of spherical catalytic converter bodies made of aluminum oxide with less than 35 0/0 porosity exist as a carrier substance, this means z. B, one Diameter between 1.25 and 7.5 cm.

The exact size of the catalyst body can vary to a certain extent depend on the type of liquid petroleum hydrocarbon being treated. It was determined, that when using heavier petroleum hydrocarbons, larger catalyst bodies are more recommendable. While the larger catalyst bodies both in the treatment the lighter liquid petroleum hydrocarbons, as well as heavier hydrocarbons can be used, the reverse is not generally true, since the smaller catalyst bodies are not as effective as the larger catalyst bodies on the heavier hydrocarbons. For heavier hydrocarbons, such as diesel oil or Bunker C oil, a catalyst mass is used preferred, which is about 39 to 50 kg / m2 catalyst surface.

Combinations of catalyst bodies with different masses can be used or sizes are applied. However, there are supposed to be extreme differences in size the catalyst body, such as those that have close packing and excessive flow resistance cause to be avoided. The empty spaces between the catalyst bodies preferably make up about 30 to 40% of the volume of the catalyst zone. In order to one also avoids excessive local carbon deposits.

According to the invention, the flow rate of the hydrocarbon into the catalyst zone is regulated in relation to the type of nickel catalyst used. The absolute flow rates of the hydrocarbon can of course vary within wide limits depending on the size of the apparatus. The decisive factor with regard to the present process, however, is the relationship between the flow rate of the hydrocarbon to be converted and the catalyst mass, the surface area and the available nickel. Since the mass of the catalyst body and the concentration of nickel have been related to the surface area, this ratio is most easily expressed as a function of the rate of hydrocarbon feed and the total available nickel. Since the nature of the petroleum hydrocarbon changes with respect to molecular weight, ratio of carbon to hydrogen and the like, it is most expedient to express the flow rate of the same in kilograms of carbon content of the hydrocarbon used per hour. It has been found that in order to produce a gas with a calorific value within the oil gas range with the above conversion efficiencies, one must control the rate of charge of the hydrocarbon with respect to the nickel present so that a value between about 2 and 6, preferably 3 and 5, is obtained for the following ratio, the weight of the nickel being based on the nickel present in the outer 0.8 mm of the catalyst body: Hydrocarbon feed rate (kg C / h) Catalyst surface (m2) X Ni concentration (kg / m2 surface) During the gas generation stage of the cycle, steam is used with the hydrocarbon reacted, which serves as a diluent, promotes the conduction of heat to the evaporated hydrocarbon and is optionally available for water gas conversions. The amount of steam used is generally not less than 800 g per kg of carbon in the hydrocarbon used. Although the vapor content can be 2 to 3 kg, it is usually not necessary to use more than 1 kg per kg of carbon in the hydrocarbon. Air can also be added during the gas generation stage of the cycle if a gas with a higher density is desired. If air is added, the temperature does not drop quite as quickly during gas generation.

The above statements apply provided that the catalyst bodies are practically completely effective; d. that is, the catalyst body practical during the initiation of the carbon and sulfur gas generation stage are free; d. That is, the catalyst is regenerated during each cycle. Therefore, in the stage of the cycle that is usually used to store Heat in, the gas generating zone is used, in the present process also the Catalyst can be regenerated. This stage of the cycle is described below referred to as the "heating-regeneration" stage of the cycle, in contrast from the other main stage of the cycle, the "gas generation" stage.

In order to partially reheat the catalyst zone, hot heating gases are used required, which can be produced by burning a fuel. the hot combustion products are passed through the catalyst zone. Partly The reheating of the catalyst zone is also done by burning off the carbon during regeneration, as will be explained below. Part will the heat required for reheating also in accordance with the present method a catalyst-oxidation-reduction and combustion sequence obtained that also will be discussed below.

Oxidation conditions are required to regenerate the catalyst, thus the one on the catalytic converter during the gas generation stage of the cycle deposited carbon and all sulfur burned and both as gaseous oxides removed. Therefore, it must be sometime during the heating-regeneration stage free oxygen are passed through the catalyst zone in such an amount that almost all of the carbon and sulfur contaminating the catalyst is oxidized. This can be B. by burning the fuel in the presence of a Excess air can be achieved, so that the hot products of combustion that through flow through the catalyst zone, contain free oxygen. On the other hand, you can however, and this is preferably done, only air through the catalyst zone conduct, especially if the hydrocarbon involved in the reaction contains more than 0.021 / o sulfur. In the latter case it is particularly advantageous Free air through at the beginning of the heating-regeneration stage of the cycle to direct the catalyst zone. For the quick and complete removal of the bug are not only correspondingly high temperatures, but also, like in air, a relative one high oxygen concentration required. When air is passed through the catalyst zone the carbon is burned off quickly with the development of high temperatures. on this way if you have air at the beginning of the heating-regeneration stage of the cycle by. the catalyst zone passes, the removal of the last traces are used Sulfur required high temperatures and high oxygen concentrations achieved. By analyzing the gases exiting the catalyst zone at this point or later during the heating-regeneration stage of the cycle one can determine when the removal of the carbon and sulfur is complete is. Increasing sulfur contents in the gas produced over a longer period of time Working period is also an indication that the sulfur is lost during the heating-regeneration step every cycle is not sufficiently removed.

As stated earlier, one of the determining factors is when Method according to the invention the maintenance of controlled temperature changes during the gas generation stage of the cycle, d. H. the temperature fluctuation and the temperature gradient during the gas generation stage must be at a minimum value being held. The term "temperature fluctuation" means the change in temperature at any given point in the catalyst zone during the gas generation stage, whereas under "temperature gradient" the difference between the mean temperature the entry half and the exit half of the catalyst zone to a given one Time is to be understood during the gas generation stage. As the observed temperature fluctuation depending on the particular means and procedures used to: measure it, can change, it should be noted that the temperature fluctuation given here by Measurements with a thermocouple is determined, which is enclosed in a stainless steel sheath Steel is embedded and extends about 30 cm laterally into the catalyst zone and is located within the central 800/9 of the catalyst zone.

According to the invention, the temperature gradient and temperature fluctuation exceed not the value of about 55 ° C. In other words: it exists for everyone according to the invention treated hydrocarbon a relatively narrow temperature range within the same promoted the conversions leading to the desired gas with a high calorific value and Side reactions, such as water gas conversion, deposition of carbon and the like, be kept to a minimum. The exact limits of this area depend of the petroleum hydrocarbon to be treated and are between approx 760 and 925 ° C.

The temperature fluctuation is regulated, ind ° in one catalyst body with the appropriate ': mass produces the gap reactions above the surface the same appropriately distributed and limited the duration of the gas generation stage. With regard to on the latter, the temperature drop is gasified by the amount of per cycle Reactant depend, as the reactions during the gas generation from the Catalyst zone consume heat. In general, the aim is to achieve higher Capacities necessary flow velocities of the complete cycle of the present method be limited to about 1.5 to 3 minutes, the Gas generation stage takes about 35 to 55% of this time.

The temperature gradient is mainly determined by a heating process regulated, in which the passage of hot combustion products through the stationary Catalyst zone causes a temperature gradient, so that the temperatures in the part the zone where the hot gases enter are significantly higher than the temperatures in the exit part. However, it has been found that when the catalyst is a easily oxidizable metal, e.g. B. \ Tickel, contains and if, during the catalyst is hot, air or some other oxygen-containing gas to remove the nickel to oxidize, and then passed a reducing gas through the catalyst zone in order to reduce the oxidized nickel to the metal, the temperature gradient within the catalyst zone is reversed, d. that is, in this latter heating method the exit part of the catalyst zone has a higher temperature than the entry part. Naturally, when the nickel is oxidized, heat is released. Although the reduction of the oxidized nickel back to metallic form theoretically the same amount of heat consumed, this reduction is, however, at the same time from the oxidation of the reduction of the catalyst oxide used is accompanied by the reducing gas. This oxidation (or combustion) creates another amount of heat. Hence, a total of while this catalyst oxidation - catalyst reduction - combustion sequence the heat generated, which is stored in the catalyst zone and thus to the above-mentioned increasing temperature gradient. To within the entire catalyst zone relative The heating-regeneration stage can be used to achieve uniform temperature conditions of the cycle consist of a combination of these two types of heating, by passing hot combustion products through the catalyst zone and the aforesaid Oxidation - reduction - combustion sequence carries out. By voting this Types of heating with that released by burning off the deposited carbon Heat can cause the temperature gradient in the catalyst zone to be slightly below a value kept at 55 ° C.

The oxidation of the catalyst during the catalyst oxidation-catalyst reduction-combustion sequence described above can take place at the same time as the hot products of combustion through the Catalyst zone are passed to store heat therein. Included in this case the hot products of combustion free oxygen, the z. B. by burning the Fuel gets into the products in the presence of excess air. The oxidation the catalyst can also be used at another point during the heating-regeneration step of the cycle can be achieved than at the time in which through the catalyst zone the hot products of combustion (as when air is passed through the Catalyst zone) are passed. In any case, it will take some time during the Heating-regeneration stage of the cycle process enough free oxygen the catalyst zone passed to during the gas generation part of the cycle, as already stated above, the oxygen and any sulfur that has been deposited burn off almost completely in the catalyst zone and around the contained therein _ To oxidize nickel for the catalyst oxidation phase of the specified sequence.

In connection with the foregoing, the temperature gradient in the catalyst zone can also be further controlled by gases such as. B. the hot combustion products or reaction participants, in the opposite direction passes through the catalyst zone.

The drawing illustrates an apparatus in which the method is carried out can be.

In the drawing, 1 represents a chamber lined with refractory material 2 which serves to delimit the catalyst zone. Chamber 1 can, for. B. be the superheater of a conventional water gas apparatus, which has been modified as appropriate, as can be seen from the drawing. Figure 3 shows a chamber lined with refractory material, the bottom of which communicates with the bottom of the chamber 1 for the passage of gases. Chamber 3, which can be the gasifier of a conventional apparatus for generating carbonized water gas, contains the combustion zone 4 in which liquid fuel is burned to supply hot gases for internal heating of the apparatus including the refractory material and the catalyst zone obtain. The individual catalyst bodies supported by the arch of refractory bricks 6 are represented by 5. One or more of the aisle-forming refractory bricks 16, which are arranged in the known framework pattern, or other heat-storing, refractory bodies can be arranged between the support floor 6 and the catalyst zone 5 in order to serve as further heat storage material. Such additional heat storage material is referred to below as heat storage zone 16. To prevent the catalyst bodies from falling through the arches or - if used - the heat storage zone, the catalyst mass can rest directly on a heavy metal sieve (not shown) or on a layer of perforated refractory bricks or building blocks (not shown).

The numbers 7 and 8 denote the supply lines for the air or the liquid fuel used to generate hot gases for heating the apparatus, and 9 represents the vent valve through which exhaust gases are released into the atmosphere or to an exhaust-gas boiler (not shown) before entering the atmosphere will be deflated. Part or all of the regeneration air and the one used in the described catalyst-oxidation-reduction-combustion sequence Air can also be supplied through line 7. As described above, it can be convenient be air along with the hydrocarbon and steam during the gas generation stage of the cycle through the reaction zone, with a part or the total amount this so-called process air can be fed through line 7. The supply line for the liquid petroleum hydrocarbon to be implemented is represented by 10 and the supply line for the steam through 11. Appropriate devices (not shown) for preheating for the reaction - coming hydrocarbon can be provided to ensure that this is vaporized in the reaction zone, though some or all of the heat required for evaporation by the in delivered stored heat to the refractory material or to the catalyst itself can, but it can also be provided a feed 12 to a part or the total amount of process air or that during the regeneration of the catalyst and during the catalyst oxidation phase of the described oxidation-reduction sequence to supply used air. 13 denotes the pipe through which the generated gas leaves the reaction chamber, passing through the washing tank 14 via the valve line 15 is passed into a storage container. As with the usual gas generation, you can the gases exiting from the reaction chamber to the storage container through a Exhaust gas powered boilers (not shown) are directed before they go into the washing tank reach. The flow of the respective substances into the Apparatus into it and out of it through the pipelines described, as shown, through suitable valves regulated.

A first heat storage zone 17 for preheating a part or the total amount for regeneration, for oxidation of the catalyst or for gas generation required air or steam can and will, preferably as in the drawing shown, created. The heat storage zone 17 consists of heat-storing refractories Bodies, e.g. B. refractory bricks in the well-known half-timbered pattern or arbitrarily or in a combination of both types. The heat-retaining material can be supported by arches made of refractory bricks 18.

Where a first heat storage zone such as 17 is employed, a Part or all of the steam required for gas generation beforehand by conduction 19 will be introduced. It usually proves beneficial to have at least one Part of the steam and / or air for gas generation through into the combustion zone introduce the lines 19 and 7, respectively, to prevent excessive storage of full heat to avoid this point. The creation of a heat storage zone between the Combustion zone and the entry of the hydrocarbon coming to the reaction (see drawing) represents the preferred embodiment of the present invention This feature ensures the maintenance of high temperatures in addition to the Combustion zone that are needed for rapid and even ignition Burning of the liquid fuel during the heating stage of the cycle to achieve.

This procedure is carried out, as indicated, in a cycle, it comprises an acquisition regeneration time during at least a portion of the time this time air and liquid fuel, allowed through lines 7 and 8, respectively and the `combustion takes place in the combustion zone 4. The hot combustion gases are lined with refractory material, enclosed chamber 1, with heat being stored in the liner 2 and through the catalyst zone and the arches supporting them, whereby heat is also stored in these, and then drained through the trigger valve 9. If a heat storage zone (like 16) is placed between the catalyst bed and the supporting arches, the hot gases also pass through there and store heat in them. The hot combustion gases also store heat in the lining of the combustion zone and on your way between the combustion zone and chamber 1, and if a main heat storage zone, As 17, is applied, the gases also go through this and store heat in it.

As indicated, preferably air itself is passed through the catalyst directed to burn the carbon and sulfur deposited on the catalyst. This is best done in the first part of the heating-regeneration period, immediately before the fuel is fed into the combustion zone. To this end the air is supplied through line 7 and / or 12.

For the initial stage of the catalyst-oxy date-reduction-combustion sequence described oxidizing conditions are also required, and air can be used for this purpose through the line 7 and / or 12 are supplied. The reduction combustion part this consequence requires reducing conditions, i. 1i., It must be an oxidizable gas be passed through the catalyst zone to deliver the catalyst oxide to the metal reduce, burning the gas itself. To this end, a through Combustion of fuel in 4 in the presence of not to complete combustion sufficient air produced gas are passed through the catalyst zone 5. However, this part of the given sequence can - and preferably is - during of the first portions of the gas generation period are performed when the first quantities of the hydrocarbon to be reacted are introduced into the catalyst zone will. A sufficient amount of this substance is found in reducing gases, especially Hydrogen, which causes the reduction of the metal oxide to metal. During this stage, the gases formed can optionally pass through the vent valve 9 can be vented to the atmosphere.

As soon as the reaction chamber is at working temperature and the catalyst is almost completely freed from carbon and sulfur the gas-generating part of the cycle started. The connector 10 is opened to allow the liquid petroleum hydrocarbon to be implemented allow. At the same time, steam can pass through the connectors 11 and / or 19 and all the air required for generating the gag through the connecting pieces 12 and / or 7 are fed. The liquid hydrocarbon will, if not already, be at the introduction into the chamber is vaporized due to the high temperature in the same evaporates. By contact with and by radiation from the hot refractory materials the liner and the arches supporting the catalyst zone become the hydrocarbon and the steam and the air which may be used are practically at reaction temperature brought. When some or all of the steam and / or air is over the combustion zone 4 is introduced, it is preheated in a corresponding manner. In any case, all the substances involved in the reaction absorb heat and become practical preheated to reaction temperatures until they enter the catalyst zone 5. During the gas generation part of the cycle, the vent valve 9 is closed.

During the passage through the catalyst zone 5, it becomes the reaction coming hydrocarbons first in permanent hydrocarbon gases such as methane, Ethylene, propylene, and hydrogen and carbon split. By implementing between Some hydrogen and carbon monoxide are also formed from this carbon and vapor. The gas leaving the catalyst zone in this way is a stable, flammable gas certain composition, consisting of gaseous hydrocarbons, hydrogen and carbon monoxide.

Before the temperature of the catalyst zone dropped by more than 55 ° C is, as described, the feed of the hydrocarbon coming to the reaction through line 10 and steam through line 11 and / or 19 and all air through Line 12 and / or 7 interrupted and the apparatus is heated again and the catalyst regenerated.

Of course, you can avoid the system in the usual way Free gases that can contaminate the generated gas or desired residual gases press into the storage container. This cleaning can be done by supplying steam through line 19 are carried out. Except for a two-chamber apparatus Apparatuses with a single or three chambers can of course also be used may be applied, the procedure following the same general as described above Principles can be operated. Although in a similar way the Kataly satorzone is specified as a single layer or mass, the catalyst can of course also in the form of two or more separate layers, including layers in different chambers.

Example It is a piece of equipment of the technical extent in the The type shown in the drawing, which consists of a combustion chamber and a vertical, The chamber is lined with refractory bricks and has an internal diameter of 3 m. The catalyst is arranged as a layer in the last-mentioned chamber and is supported by the arches of refractory material. Circular processes lasting 2 minutes are used, with the gas generation stage making up 38 to 42% of the cycle. The gas generation stage is followed by steam cleaning, which is 1 to 2% of the cycle and then bare air is introduced, which makes up 1 to 2% of the cycle. Fuel is then burned if there is excess air; the resulting oxygen Combustion products containing are passed through the catalyst zone. That takes up 45 to 51% of the cycle. After completing this stage, that is Nickel in oxidized form. After brief air and steam cleanings, the 3 to 11 or 1 to 31 / a of the cycle, is the gas generation stage repeated. The first hydrocarbon additions to be implemented, which up to are split into hydrogen, the oxidized nickel should reduce to metal.

The catalyst comes in two different sizes in two superimposed Layers arranged. A layer with a thickness of 7.5 cm consists of pebbles, which have a diameter of 1.25 cm, and the other layer, which is a thickness of 35.5 cm, consists of pebbles with a diameter of 2.5 cm. In both catalyst sizes, the amount in the outer surface is 0.8 mm The nickel contained 0.075 kg / m2 and the mass of the entire catalyst 8.3 kg / m2 Surface.

During the gas generation stage, luminous oil is vaporized and through the Catalyst zone passed at a rate that 22 kg of carbon per hour corresponds to per m 'of catalyst surface, or 280 kg of carbon per hour per kg available nickel (in the outer 0.8 mm of the layer).

The resulting gas has a calorific value of around 7460 kcal / m3 (N2-free Basis), and 77.2% of the carbon in the luminous oil appears in the gases, 63.5% as gaseous hydrocarbons and 13.5% as carbon monoxide plus hydrogen.

Claims (6)

P 1 TENTANSP UCHE: 1. Circular process for the production of an oil gas rich flammable gas, in which in the gas generating part of the process a vaporized, normally liquid petroleum hydrocarbon and water vapor in contact with a heated nickel-containing catalyst are passed, the stream from the hydrocarbon and water vapor during the heating and regeneration part of the circular process is interrupted, characterized in that during the gas generation part of the cycle process the evaporated hydrocarbon and the water vapor through a Catalyst zone are passed, which does not exceed a temperature gradient of 55 ° C possesses and has nickel-containing refractory bodies whose mass is between about 4.7 and 50 kg / m2 surface area, and which has a nickel concentration in the outer 0.8 mm of the surface have between about 0.07 and 0.15 kg / m2 surface, namely at a rate that has a value between 2 and 6 for the prevention of the Amount of hydrocarbon feed (kg C / hr) to the catalyst surface (m2) X Ni concentration (kg / m2 surface) results, where that from the hydrocarbon and water vapor existing gas flow is interrupted before the temperature in the Catalyst zone drops by noticeably more than 55 ° C. 2. The method according to claim 1, characterized in that the above ratio is between 3 and 5. 3. Procedure according to claim 1 or 2, characterized in that the concentration of nickel in the outer 0.8 mm of the catalyst surface 0.1 to 0.15 kg / m2 of the catalyst surface amounts to. 4. The method according to any one of claims 1 to 3, characterized in that that the catalyst bodies have a porosity between 10 and 20%. 5. Procedure according to one of claims 1 to 4, characterized in that in the heating-regeneration part of the cycle process free oxygen is used, after which on the catalyst body an oxidizable gas is passed, with all the heat in this part of the cycle causes a temperature gradient in the catalyst zone of not more than 55 ° C. 6. The method according to any one of claims 1 to 5, characterized in that the heating-regeneration part of the cycle is continued at least until the gases emerging from the catalyst zone are at least practically free of sulfur. Documents considered: French Patent No. 1017 896.