DE1244764B - Method and device for the production of unsaturated hydrocarbons - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

C07c

German class: 12 ο -19/01

Number: 1244 764

File number: S 89219 IV b / 12 ο

Filing date: January 25, 1964

Opened on: July 20, 1967

The invention relates to a method and an apparatus for performing the thermal Decomposition of hydrocarbons for the purpose of pyrolysis into unsaturated hydrocarbons, such as acetylene and ethylene, under normal production conditions with improved effectiveness and particularly with a larger capacity device.

In these processes, gaseous fuels of any kind are burned with oxygen, to form heat and hot gases. In this saturated hydrocarbons, z. B. gasoline, injected into a mixture of acetylene and ethylene for pyrolysis. The invention relates to Pyrolysis reactions of the last-mentioned type, in particular those described in U.S. Patents 3,019,271 and 3,055,957 procedures described.

As indicated in these patents, a generally cylindrical furnace is provided, in the flows of a fuel gas and a combustion sustaining gas, e.g. B. Oxygen, through inlet devices at the top of the furnace. The inlet devices are mounted on concentric rings, and the axes of each pair of oxygen and Fuel gas inlet devices are at an angle of approximately 90 °. So with an oxygen and fuel supply with practically equal moments of motion in the furnace in the combustion zone a uniform ring of flames is formed, each flame practically parallel to the axis of the combustion chamber and pyrolysis zone is directed. These flames supply the hot gases in which the to pyrolysing hydrocarbon is injected later. As stated in the cited patents, An important point in this process is extremely rapid heating of the material to be pyrolyzed Gas to decomposition temperatures, preferably in the absence of free oxygen, if it is present, easily react with the hydrocarbons to be pyrolyzed and are undesirable Would form by-products that would lead to the ultimate conversion of the hydrocarbon into the desired, would reduce unsaturated products.

To achieve uniformity and effectiveness, it is also useful that the hot combustion gases extend practically uniformly over the entire pyrolysis chamber, in particular at the point of introduction of the hydrocarbon to be pyrolyzed. This entire filling of the chamber with hot combustion gases, however, is preferably carried out without directly impinging on the extremely methods and apparatus for producing
unsaturated hydrocarbons

Applicant:

Societe Beige de l'Azote et des Produits

Chimiques du Marly, Liège (Belgium)

Representative:

Dr. W. Schalk, Dipl.-Ing. P. Wirth,

Dipl.-Ing. G. E. M. Dannenberg

and Dr. V. Schmied-Kowarzik, patent attorneys,

Frankfurt / M., Große Eschenheimer Str. 39

Named as inventor:

Dr. Frederic Francois Albert Braconier,

Plainevaux;

Jean Joseph Lambert Eugene Riga,

Liege (Belgium)

Claimed priority:

V. St. v. America 11 February 1963 (257 591)

hot flames are achieved on the inner walls of the combustion chamber to waste the To avoid thermal efficiency for merely heating the walls of the combustion chamber and around the Life of the heat-resistant or other materials from which the chamber is made extend.

According to the above patent specifications, particularly satisfactory results are achieved when the ring, which forms the heat supplying flames, concentric with the cylindrical combustion chamber and has a diameter of about half the diameter of the combustion chamber.

For many reasons, especially when increasing the size and capacity of the combustion chamber, it may be appropriate to have the inlet device of fuel and oxygen on a circle a slightly larger diameter than half the diameter of the combustion chamber. In in this case means a sufficient expansion of the flame area to cover the whole Central part of the combustion chamber that a

709 617/569

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A substantial part of the flames are directly on the, whereby the gases hit with practically the same movement walls of the combustion chamber, are introduced in advance,
In the drawings, in which the same reference construction and numbers are used in the operation of the burner, the above information is used to denote the same parts. 5 game a form of a pyrolysis system for invention

According to the invention, the advantages of practical purposes are shown. It is a vertical and the same systems as described in the above patent-brought cylindrical combustion chamber 12, even with larger ones, which are in unrestricted flow connection with pyrolysis systems and / or systems in which a pyrolysis chamber 13 is located, whereby the combustion -Diameter of the flame ring is greater than the io voltage chamber 12 and pyrolysis chamber 13 is a half the diameter of the combustion chamber, compartment distributor 11 is connected upstream. Maintain the lines 14 in that the axis of the flame or 15 lead fuel and a gas no longer exactly parallel to the axis maintaining the combustion, such as oxygen, in the distributor of the combustion chamber. This takes place inven- 11, while the line 16 is to be pyrolyzed according to z. B. by adding the fuel and 15 hydrocarbon, e.g. B. gasoline (as described below using the combustion-maintaining gases separately) leads to the pyrolysis chamber 13. For and at high speed, but different- quenching the pyrolysis gases at their exit borrowed moments of motion through the Einlaßvorrich- from the pyrolysis chamber 13 is in a known manner introduces lines and / or the inlet devices a quenching device 17, z. B. a ring of or the separate gas streams in the flame ring in ao water spray nozzles, provided,
at an angle other than 45 ° to the axis of the manifold 11, which attaches to the combustion combustion chamber, etc. tion chamber 12 contains an annular

The invention relates to a method for the notch or groove 18 with a trapezoidal cross-section, Generation of unsaturated hydrocarbons that are concentric to the longitudinal axis of the pyrolysis furnace especially acetylene and ethylene, is attached by ther- 25. A ring of inlet openings or mix splitting of more saturated hydrocarbon feed nozzles 19, which with line 14 in Verstoffe in a stream of hot combustion gases, when bound, and a second concentric ring that for generating the hot combustion gases one of inlet openings or nozzles 20, the one with conduit gaseous fuel and a combustion 15 is in connection, lead fuel or maintaining gas by means of a multiplicity of oxygen into the chamber 12. The openings 19 and separated and opposite pairs of öff- 20 are, as shown, in the inclined, annular openings in the cylindrical combustion zone one side walls of the notch 18, practically perpendicular to is guided, the axes each facing these walls (in the device of FIG insertion openings lying opposite one another and and 2) attached, the axes of the openings with respect to the axis of the combustion chamber, 19 and 20 are perpendicular to one another and inclined in a direction and these openings are arranged on circles at approximately 45 ° to the longitudinal axis of the combustion network, which are inclined concentrically to the longitudinal axis of the compression chamber 12. The openings 19 and 20 Combustion chamber and their respective through-holes are symmetrically distributed around the notch 18, with diameter greater than half the diameter of a fuel inlet nozzle 19 of each oxygen combustion zone and in which the inlet nozzle 20 to be split 40 is adjacent; satisfactory results Hydrocarbons at the border between vermin were obtained according to the invention if each combustion zone and gap zone in the hot inlet nozzle 19 and 20 had such dimensions, Combustion gases are introduced, which means that for the so in the combustion chamber 12 is characterized by the fact that the moments of motion introduced oxygen and fuel are high of the gaseous fuel flows and the 45 nozzle head speed resulted, e.g. B. about 100 Combustion of entertaining gas and / or up to 200 m / sec.

Angle at which the currents meet, when operating, hydrogen or a water so adjusts the flames in the combustion fuel-enriched fuel gas and oxygen chamber to the axis of the combustion chamber by lines 14 and 15 and articulated therewith will. 50 nen rings of the inlet nozzles 19 and 20 in the

The invention is introduced in more detail by the combustion chamber 12 in the drawings. Which possibly pre-demonstrates meet heated, gaseous reactants

F i g. 1 is a somewhat diagrammatic longitudinal view as it enters through inlet nozzles 19 and 20

section of a pyrolysis furnace according to the invention; with an angle of about 90 ° and high linear

F i g. Figure 2 is a cross section of the device at 55 speed. This results in an effective,

Fi g. 1 along line 2-2; rapid local mixing with the formation of a short

F i g. 3 is a diagram showing an undesirable flaming ring, with the flames generally

The furnace works well with uniform insertion points along the combustion chamber 12.

tion of fuel and fuel gas with the same routes. Thus, in the particular one shown in FIG. 1 and 2

Shows moments of movement; 60 shows the actual flame

F i g. 4 is a diagram like FIG. 3, which, however, is formed at the meeting point of the gas flows from the inlet

shows the operation of the furnace according to the invention; nozzles 19 and 20 take place; there will be a small one

F i g. 5 is a vector diagram showing the distance from the bottom surface of the manifold 11 desired Working of the furnace according to the invention preserves and an actual contact with the same shows; 65 of the intense flame heat avoided. As below

F i g. 6 is a detail of one side of the fuel, which is intended to be achieved in this way

and fuel gas inlet devices which provide a relatively uniform front hotter for satisfactory combustion

According to the present invention, modified gases are formed in the upper end of the pyrolysis chamber 13

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be passed through the ring of inlet devices In a device in which the diameter

25 for the introduction of the carbon to be pyrolyzed the flame ring about half the diameter

Hydrogen is limited. of the combustion chamber 12, the

In the particular, in FIG. 1 and 2 so in the middle between the walls of the device can also be a curtain of water 5 of the combustion chamber 12 and the center of steam around the primary combustion ring of the flames, and the flames can easily be provided around the distributor 11 can be regulated in such a way as to keep the hot gas zone at a reasonably low temperature at the level of the injection nozzles 25 (which is hottest there and the inner walls of the combustion chamber against) to protect the combustion chamber 12 from completely over-heating. As indicated, it is achieved, but not directly on the walls, which calls for the formation of such a steam combustion chamber. If the notch 18 precedes the attachment of a steam chamber 21 from the inner walls of the combustion chamber centrally in the distributor 11 and a steam inlet 12 at a distance corresponding to a quarter 22. The water vapor of diameter "d" introduced through line 22 of the same, so is in can be used to preheat part of the 15 F i g. 1 the area of the circles with the diameter device 14 used fuel introduced; practically equal to the distance BC of the annular surface AB-CD, which the water vapor is from chamber 21 into the circle surrounds,
Combustion chamber 12 by an annular, however, if the furnace is inserted with a notched ring slot 23, which is seen to the longitudinal axis of the furnace, which has a diameter which is inclined larger at an angle of about 35 to 50 °. 20 as half the diameter of the combustion chamber is a second annular slot 24 around the periphery 12 (as is the case for many reasons, particularly with the combustion chamber 12, which is also inclined in an increase in the overall size and capacity of the pre-angles of about 35 to 50 ° , leads one direction may be appropriate), then the above other steam jet or curtain around what has been said does not apply. So become fuel and internal walls of the combustion chamber. 25 gas through the nozzles 19 and 20 with practically the same

As can be seen from the above explanations, some moments of motion are introduced, this being a flame ring around the notch 18 with such a choice that they form a flame front or intensity or amount of heat and fuel - a hot gas zone which forms the combustion that is a practically uniform, hot chamber 12 at the level of the injection nozzles 25 forms a full gas layer at the level of the device, where 30 constantly sweeps over, so the hot gas zone in front of the hydrocarbon injection nozzles 25 can be attached to the level of the injection nozzles 25, so that hit the hydrocarbon chamber wall to be pyrolyzed. In this case, as at this height of the device for almost instantaneous by line EK in FIG. 3 is shown, with practical and uniform mixing with a uniform equal moments of motion of the charge hot gas layer introduced 35 flows through the nozzles 25 and the angle at which the flows can be opened. After that, the hydrocarbon will meet in each other, a substantial part of the flames the desired components (e.g. mainly heat wasted.

Acetylene and ethylene when using gasoline. A preferred embodiment according to the invention is hydrocarbon) pyrolyzed. The form obtained is shown in FIG. 4 and in particular in FIG. 5 ge reaction and decomposition products are shown on 40, where working under the above conditions the end of the pyrolysis zone 13 is quenched by water spray nozzles (the special attachment of the nozzles 19 and 20 17. For a particularly improved can also be through other mechanical or operational effectiveness and because of the practically immediate conditions dictated), with the pyrolysis reaction and the gas flow rates the direct impact of the intense heat on the through the device, it is expedient to the hot 45 walls of the combustion chamber 12 (to avoid combustion gases at the height of the nozzles 25 avoiding unnecessary thermal decomposition of the maximum thermal temperatures and practically free of stable materials) and at the same time molecular oxygen (which is disadvantageously achieved with the pyrolytic zone of hot gas or sizing hydrocarbons under BiI- heat at the level of the injection nozzles 25 application unexpected Desired waste or by-products 50 becomes. Even if, therefore, the axes of the nozzles 19 could connect) and under conditions as adiabatic and 20 perpendicular to each other and at an angle as possible. Since high temperatures of 45 ° to the longitudinal axis of the combustion chamber are doors and intense flames are desired, 12 the injection moments of the distributor 11 and the walls of the fuel and fuel gas flow through the combustion chamber 12 nozzles inevitably become extremely high 55 19 or 20 changed and regulated so that a temperature is subjected; Although the use of vector moments EF at such an angle for the formation of materials for the device that forms such an axis of the combustion chamber 12 that the temperatures can withstand the point F at the level of the injection is definitely possible, it is more expedient to proceed in this way that nozzles 25 reached on a circle that the direct heating of the walls of the combustion chamber is reduced as much as possible from a distance of about a quarter of the diameter of the combustion chamber. This is the combustion chamber 12 from the walls which on the one hand conveniently stands for a longer length of the same.

Lifetime of heat-resistant metals or The direction of flame expansion will therefore

other materials used and, on the other hand, influenced by the relative moments of motion,

because of the fact that each directly affects the 65 with which the flows of fuel and

Walls of the combustion chamber or other parts of fuel gas after introduction into the combustion

the amount of heat impinging on the device practically hit chamber 12 through openings 19 and 20,

is lost. As in Fig. 5, the individual meet

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Gas flows of fuel and fuel gas from the diameter were 40 fuel gas openings 19 openings 19 and 20 at point E and are obtained through and 40 corresponding oxygen openings 20 the vectors EG and EH and a obtained Vek- borrowed to pairs in the notch 18 and with a perpendicular gate EF shows what depends on the axes of movement relative to one another and the angular moments of the separate gas flows. If 5 of 45 ° to the axis of the combustion chamber 12 are practically the same at these moments, then the values that were achieved run.

hold vector EF practically parallel to the axis of the order shown in FIG. 3 presented undesirable situations

Combustion chamber 12, and there will be un- tion to avoid, oxygen and combustion desires or deleterious results from FIG. 3 fuel gas with differently regulated speeds. If the special introduction speeds (see Fig. 5) are introduced that the obtained speeds of the separate fuel and fuel gas vector EF was inclined at such an angle that flows are selected so that they are of the order of magnitude of the point F are at a distance of about 65 mm of at most that indicated by EG and EH (ie d / A) from the walls of the combustion vectors, then the vector EF lies in a chamber 12. For this purpose, the various angles to the axis of the combustion chamber 12 were selected. Then the relative moments are selected at speeds of 900 m ³ / hour. Oxygen mixed with that the vector EF obtained in such an angle 700 kg of water vapor introduced at 650 °, which is an angle to the axis of the combustion chamber 12, total amount of 1987 kg through the inlet nozzles 20 that the point F from the outer walls approximately at a actual area of 88 mm ^{2 at} a distance of dlA as measured by the 20 made. At the same time, 630 m ^s / h. Fuel level of the injection openings 25 of the gas to be pyrolyzed mixed with 400 kg of water vapor at 650 ° C. for the hydrocarbon. through the inlet nozzles 19 with an actual

^{If the working area of 44.5 mm 2} shown in FIGS. 3 and 4 is introduced, which maintains an overall condition, the expansion amount of 940 kg is shown. Under these conditions of intensely hot flames and conditions, the ratio of the quantities of movement of hot gases within the combustion chamber to that of fuel gas and fuel was about 1.77, which deflected the center, and indeed in a controlled, radially inward bending manner that desired the heat is distributed uniformly across that of the flames or thermal expansion to the total area of the combustion chamber at the desired point of about d / 4 at the height defined by the height given by the inlet device 25, while a direct and useless or un - caused the combustion chamber 12,
Desired impingement of the heat directly on the results, albeit very satisfactory

Walls of the combustion chamber is avoided. Regulation of the corresponding moments of motion It is not only avoided that the walls of the combustion chamber 12 of the introduced fuel and fuel gas streams do not directly reach the intensely hot gases through the nozzles 19 and 20, which were so attached, before the point where they are practically at an angle of 90 ° heat of the same immediately for the pyrolysis of the hydrocarbon introduced through the met, satisfactory openings 25 can also be achieved. Results if the distributor 11 is turned according to, but the above fig . 6 is modified. Instead of the axes working further a more uniform, better 40 of the nozzles 19 and 20 vertically and each in a separate mixture of the hot combustion gases, at an angle of about 45 ° to the axis of the combustion, especially at the level where the pyrolysed chamber 12, the nozzles can also be arranged in such a way that hydrocarbon introduced through the openings 25 is arranged in such a way that the desired one is radially inward. directional bending of the vector EF is achieved,

As a further example of a device 45 and 45, even if fuel gas and fuel are introduced through them with the same working method to achieve moments of motion according to the invention, the use as in FIG. 1 and 2, the notch 28 is provided with an irregularly trapezoidal cross-section, in detail in U.S. Patent 3,019,271; Therefore, the axes of the is described, and for the production of 61 per day 50 fuel gas nozzles 29 and fuel gas nozzles 30 so an-acetylene and 121 per day ethylene brought from the pyrolysis that are considered in the combustion chamber 12 of petroleum naphtha are considered to be introduced Currents at a different angle than when this furnace meet the conditions than 90 °; the axes of the nozzles 29 and 30 are shown in FIG. 4 is operated. The diameter d furthermore have different angles with respect to that of the combustion chamber 12 of such a device 55 longitudinal axis of the combustion chamber 12.
tion is about 260 mm. Due to the high So an inward turn of the

Capacity of this device is achieved a large number of vector EF , even if the introduction of the openings 19 and 20 for fuel and fuel gases takes place with the same moments of motion, and gas required. In fact, that number is so high by varying the angles of the streams. Therefore, optimal results cannot be achieved or only with difficulty. Satisfactory results can be achieved according to the invention if the numerous openings in a large number of possible combinations do not have a notch 18 with a diameter of not identical. mm diameter of the (see. F i g. 6) can be achieved. Here, a combustion chamber 12 may be arranged. Further regulation is carried out in that the gas streams, which are separate for mechanical and other reasons and for 65, are used with different movement-effective functions of the furnace under the desired torques, so that the notch 18 possessed the given conditions, therefore a desired inner bending of the vector EF takes place Diameter of about 190 mm. With this larger and the direction of thermal expansion so far

is pushed that a practically complete and uniform heat front at the level of the hydrocarbon feed is obtained without the direct impact of the intense flame or gas heat the wall of the combustion chamber 12.

According to the invention, a device and method for achieving maximum effectiveness in a pyrolysis furnace are therefore claimed. The diameter of the notch 18 can be larger than the desired combustion conditions would allow if the flames forming the ring of flames around the notch 18 are parallel to the longitudinal axis of the combustion chamber and at a radially inwardly directed distance of a quarter of the diameter of the combustion chamber be attached to the walls. The advantages according to the invention can either be achieved by modifying the feed rates of the separate flows of fuel and fuel gas, so that unequal moments of motion are present which cause the vector EF obtained to bend internally; or the inlet nozzles themselves can be mounted other than perpendicular to each other; combinations of the above measures are also possible.

Claims (7)

Patent claims: 1. Process for the production of unsaturated hydrocarbons, especially acetylene and Ethylene, by thermal splitting of more saturated hydrocarbons in a stream hot combustion gases, in which a gaseous one is used to generate the hot combustion gases Fuel and a combustion sustaining gas by means of a plurality of separate ones and opposing pairs of openings are introduced into the cylindrical combustion zone is, the axes of opposite insertion openings against each other and are inclined with respect to the axis of the combustion chamber and these openings are arranged in circles are concentric to the longitudinal axis of the combustion chamber and their respective Diameter is greater than half the diameter of the combustion zone, and at that of the hydrocarbons to be cracked at the boundary between the combustion zone and the cracking zone are introduced into the hot combustion gases, characterized in that the moments of motion of the flows of the gaseous Fuel and the gas maintaining the combustion and / or the angles with which the currents impinge on each other so that the flames in the combustion chamber be deflected to the axis of the combustion chamber. 2. The method according to claim 1, characterized in that the angle, the two opposite Form gas streams, 90 °, the angle of the two gas streams to the longitudinal axis of the Combustion zone is 45 ° in each case and the moment of movement of the externally supplied Gas is increased so that the flames are directed accordingly. 3. The method according to claim 1 and 2, characterized in that the fuel gas at the further inside openings is introduced. 4. Apparatus for performing the method according to claim 1 to 3, consisting of a cylindrical combustion zone (12) for producing the hot combustion gases Burning a fuel and a fuel gas, a downstream pyrolysis zone (13), into which the hydrocarbons to be pyrolyzed are injected, and one to the combustion zone upstream (12) subsequent distributor (11), a plurality of separate, opposite one another Openings (29, 30) for introducing fuel gas and fuel gas streams into the combustion zone (12), the openings (29, 30) on one to the longitudinal axis of the combustion zone concentric circle, which is larger than half the diameter of the combustion zone, thereby characterized in that the axes of the openings opposite one another and opposite the longitudinal axis the combustion zone are inclined, with the outer openings being larger Angle to the longitudinal axis of the combustion zone forms as the inner opening. 5. Apparatus according to claim 4, characterized in that an annular groove (28) is provided is into which the openings for the fuel gas and fuel gas open at opposite points. 6. Apparatus according to claim 4 and 5, characterized in that the inner introduction opening serves for the fuel gas. 7. Apparatus according to claim 4 to 6, characterized in that the difference in the Angles of the openings (29, 30) is dimensioned so that the corresponding flame ring at the injection point (25) for the hydrocarbons is about a quarter of the diameter of the combustion zone from the outer wall. Considered publications:
German interpretative document No. 1 181 697. 1 sheet of drawings 709 617/569 7.67 © Bundesdruckerei Berlin