US3409695A

US3409695A - Process and apparatus for cracking hydrocarbons with an electric arc

Info

Publication number: US3409695A
Application number: US476422A
Authority: US
Inventors: Sennewald Kurt; Bender Ludwig; Gehrmann Klaus; Schallus Erich; Strie Lothar
Original assignee: Knapsack AG
Current assignee: Knapsack AG
Priority date: 1964-08-05
Filing date: 1965-08-02
Publication date: 1968-11-05
Anticipated expiration: 1985-11-05
Also published as: BE667918A; US3514264A; CH482822A; GB1107589A; DE1468159A1; NL6510214A; AT269087B; AT257551B; NO115873B; SE305212B

Description

NOV. 5, 1968 SENNEWALD ET AL PROCESS AND APPARATUS FOR CRACKING HYDROCARBO WITH AN ELECTRIC ARC Filed Aug. 2, 1965 2 Sheets-Sheet 1 NOV. 5, 1968 SENNEWALD ET AL 3,409,695

PROCESS AND APPARATUS FOR CRACKING HYDROCARBONS WITH AN ELECTRIC ARC Filed Aug. 2, 1965 2 Sheets-Sheet 2 Patent No. 160,519, Reichspatentamt, Zweigstelle Oesterreich, which describes an improved method of utilizing calorific energy in excess available in the reaction chamber for cracking purposes, and in Belgian Patent No. 544,124 which describes the manner of circulating the feed hydrocarbon and gaseous heat carrier in the reaction chamber.

United States Patent 3,409 695 PROCESS AND APPARATUS FOR CRACKING HYDROCARBONS WITH AN ELECTRIC ARC Kurt Sennewald, Knapsack, near Cologne, Ludwig Bender,

Bruhl, near Cologne, Klaus Gehrmann, Knapsack, near 5 Cologne, Erich Schallus, Cologne, Hans-Werner Stephan, Cologne-Klettenberg, and Lothar Strie, Knapsack, near Cologne, Germany, assignors to Knapsack Aktiengesellschaft, Knapsack, near Cologne, Germany, a corporation of Germany Filed Aug. 2, 1965, Ser. No. 476,422 Claims priority, application Germany, Aug. 5, 1964, K 53 671 9 Claims. 0. 260-679) i ABSTRACT OF THE DISCLOSURE Feed hydrocarbon, in vapor form, is injected near the inflow end of a reaction zone, co-currently to hot hydrogen, which travels therethrough. The reaction mixture travelling at a continuously increasing velocity through the reaction zone towards the discharge end. A further quantity of feed hydrocarbon is introduced near the inflow end of a post-reaction zone in vapor form transversely into the hot reaction mixture, and the reaction mixture or cracked product leaving the reaction zone is ultimately quenched in conventional manner.

Apparatus comprises in coaxial arrangement a conventional arc chamber, an axially symmetrical reaction chamber with the larger diameter thereof facing the arc chamber and with the smaller diameter thereof facing a postreaction chamber following the reaction chamber, and a quenching zone following the post-reaction chamber and serving to quench cracked product.

The present invention provides a process and apparatus for cracking hydrocarbons with the aid of hydrogen heated in an electric arc, so as to obtain acetylene, ethylene, methane and hydrogen.

Various processes for cracking hydrocarbons with the In the process described in German Patent No. 587,129,

the arc is also allowed to burn in an atmosphere consisting essentially of hydrogen, but the inside walls of the reaction chamber are rinsed with liquid feed hydrocarbon.

As taught in German Patent No. 1,064,945, the inside Wall of the reaction chamber is rinsed with water or heavy oil which is continuously supplied, and calorific energy necessary to achieve the endothermal cracking reaction is produced by subjecting the feed hydrocarbon to partial combustion in the reaction chamber, or it is produced by supplying hot gases from the outside.

Further prior art processes have been disclosed in Still further processes have been disclosed in German Patents Nos. 1,175,224 and 1,168,419. In the first of these 3,409,695 Patented Nov. 5, 1968 two processes, a rotating, thin and continuously renewing film of liquid feed hydrocarbon is exposed to the simultaneous action of hydrogen heated in the electric arc and to the radiation emitted by the are. In the second of these two processes, hydrogen heated in the arc zone is contacted in a reaction zone following that are zone with feed hydrocarbon which is used in gas or vapor form, the feed hydrocarbon being supplied tangentially with respect to the reaction zone at the remote end thereof and being caused to flow in a helical line along the walls of the reaction zone counter-currently to hot hydrogen. At the other end of the reaction zone, the direction of motion of the reaction mixture is reversed and the reaction mixture is caused to flow along the center axis of an axially symmetrical reaction zone and with increasing flow speed into a post-reaction zone to be ultimately quenched. In this latter process, a first partial stream of hydrogen is supplied at the upper rim portion of the arc zone tangentially thereinto, and further partial streams of hydrogen are introduced into the zone along the electrodes so as uniformly to envelop the electrodes. The present invention also uses this method of introducing and heating the hydrogen.

The process of the present invention comprises injecting feed hydrocarbon in vapor form, near the inflow end of a reaction zone, co-currently to hot hydrogen travelling therethrough, causing reaction mixture to travel at a continuously increasing velocity through the reaction zone towards the discharge end thereof, thereafter introducing, near the inflow end of a post-reaction zone immediately following the reaction zone, a further quantity of feed hydrocarbon in vapor form into the hot reaction mixture travelling henceforth at a substantially uniform velocity of flow, said further feed hydrocarbon being introduced in a direction transverse to the direction of motion of the reaction mixture, and ultimately quenching in conventional manner the reaction mixture or cracked product leaving the reaction zone.

A modified mode of executing the present process co-mprises conveying the flowing hot reaction mixture from the first reaction zone into a second reaction zone immediately following the first zone, introducing, near the inflow end of that second reaction zone, a further quantity of feed hydrocarbon in vapor form into the reaction mixture co-currently thereto, continuously increasing the velocity of flow of the reaction mixture, and ultimately quenching in conventional manner the reaction mixture or cracked product leaving that second reaction zone. No post-reaction zone need be used when two or more series-com nected reaction zones are employed.

The velocity of flow of the reaction mixture within the reaction zone is steadily increased by allowing guide forces to act upon the reaction mixture which reduce the cross-sectional area of the flowing material.

Two to seven, preferably two to five, kwhr. are used per cubic meter (N.T.P.) hydrogen to heat the hydrogen supplied in partial streams to the electric arc.

The hot hydrogen is conveniently introduced into the first reaction zone with a velocity of flow of about 40-400 m./ second, preferably 60 m./second.

The feed hydrocarbon in vapor form is introduced into the reaction zone at a velocity of flow of about 20 400 m./second. Hydrocarbons of low molecular weight, e.g. methane, are supplied at a velocity of flow of about to 400 m./ second and petroleum hydrocarbons having the mean composition C H are supplied at a velocity of flow of about 50 to m./second.

An apparatus suitable for use in carrying out the process of the present invention comprises in coaxial arrangement a conventional arc chamber, an axially symmetrical reaction chamber with the larger diameter thereof facing the arc chamber and with the smaller diameter thereof facing a post-reaction chamber following the reaction chamber, and a quenching Zone following the post reaction chamber and serving to quench cracked product.

The constructional elements forming the arc chamber have been described in German Patent No. 1,168,419, and essential parts thereof are used herein unchanged. The are chamber comprises a cooled chamber of circular cylindrical design having an open bottom portion and a covered top portion with openings to receive and means to hold electrodes. Near its upper rim portion, the arc chamber has inlet openings for supplying hydrogen to be heated in the are chamber, and the electrodes are passed through special sleeves which enable further partial streams of hydrogen to be introduced along the electrodes into the arc chamber.

The upper rim portions of reaction chamber and postreaction chamber have annular slits of special design attached thereto, which serve to supply feed hydrocarbon in vapor form.

A sectional view of the apparatus taken along its meridian plane indicates that the directrix of the reaction chamber has an upper portion which is concave and a lower portion following a point of inflection which is convex with respect to the axis of rotation. In the extreme case, i.e. with radii of curvature infinitely large, the directrix of a truncated cone is ultimately obtained. The reaction chamber so shaped enables the feed hydrocarbon in vapor form, which is introduced near the upper rim portion of the reaction chamber through an annular slit in tangential relationship with respect to the generated surface of the reaction chamber, to be subjected while travelling through the reaction chamber to the action of guide forces acting in the direction of the axis of rotation, which steadily reduce the cross-sectional area of flowing material while increasing its velocity of flow until the reaction mixture ultimately leaves the reaction chamber. Every element of volume forming part of the reaction mixture travels substantially on a meridian of the reaction chamber.

In order to achieve an especially uniform degree of distribution of feed hydrocarbon in vapor form across the wall of the reaction chamber, it may be convenient to convey the feed hydrocarbon leaving the annular slit, e.g. by means of a guide vane, in a direction deviating from the meridian lines through an angle of to 30.

The outlet opening of the reaction chamber has a diameter smaller than that of the following post-reaction chamber which in turn has a diameter smaller than that of the following quenching chamber.

In a modified form of construction of the apparatus of the present invention, the first reaction chamber is series-connected to one or more further reaction chambers which in turn are connected to the following quenching chamber. All reaction chambers, except the reaction chamber located immediately before the quenching chamber, comprise no more than the directrix portion which is concave with respect to the axis of rotation.

The inlet opening of each reaction chamber is surrounded by an annular slit which is situated in a plan perpendicular with respect to the axis of rotation and through which feed hydrocarbon in vapor form is supplied. The annular slit is surrounded by a lip disposed near the reaction chamber and near the annular slit walls first contacted with flowing hydrogen or flowing reaction mixture, the lip pointing in the direction of flow to deflect the jet of feed hydrocarbon in vapor form. The lip forces hydrocarbon entering into the reaction chamber through the annular slit to run closely down the walls of the reaction chamber and thus prevents carbon from depositing thereon.

No post-reaction chamber is necessary when two or more reaction chambers are series-connected to one another. In other words, the last reaction chamber communicates directly with the quenching chamber.

The post-reaction chamber and quenching chamber both have an annular slit disposed near their inlet openings which lies in a plane perpendicular to the axis of rotation and through which a further quantity of feed hydro carbon in vapor form is introduced into flowing hot reaction mixture or through which quenching agent is introduced into flowing hot cracked product radially with respect to the axis of rotation and in the plane of that annular slit.

An apparatus suitable for use in carrying out the process of the present invention is shown diagrammatically in the accompanying drawings, wherein FIGURE 1 represents a meridian sectional view of an apparatus comprising an arc chamber, reaction chamber, post-reaction chamber and quenching chamber;

FIGURE 2 represents a meridian sectional view of an apparatus comprising a first and a second reaction chamber and a quenching chamber connected thereto.

In FIGURE 1, the arc chamber 1 is substantially limited by the cylindrical bore of spacer 9, which e.g. may be made of copper, spacer 9 being provided with an annular channel 10 to introduce a coolant, e.g. water, and with a water feed line 11 and a water outlet pipe 12.

The top portion of arc chamber 1 is covered by cover 2 which has openings to receive and means to hold electrodes 3. Each electrode 3 is surrounded by an annular inflow channel 4 supplying hydrogen so as to flow around the electrodes into arc chamber 1.

A distributor ring 5 having an annular channel 6 and serving to introduce further quantities of hydrogen is disposed between cover 2 and spacer 9. Annular channel 6 communicates through feed line 7 with a hydrogen source and communicates with arc chamber 1 through a plurality of outflow openings 8 distributed on a circle line and projecting tangentially into are chamber .1.

Are chamber 1 communicates in the direction of flow of hot hydrogen partial streams with annular slits 13 through which evapoarted feed hydrocarbon is introduced into reaction chamber 16. The wall 14 of annular slit 13 first contacted with flowing hot hydrogen is surrounded near the side facing the reaction chamber 16 with a lip 15 which deflects the stream of evaporated feed hydrocarbon 17 issuing through annular slit 13 so as to form a thin layer of hydrogen on the inside wall of reaction chamber 16. The shape conferred upon that inside wall ensures that this thin layer, except those portions thereof which undergo chemical transformation, is substantially preserved until the reaction mixture ultimately leaves the reaction chamber to flow into the following post-reaction chamber 20.

Inclined guide vanes 28 may be mounted in annular slit 13 when it is desired to introduced feed hydrocarbon into reaction chamber 16 of FIGURE 1 in a direction of flow other than parallel to the meridian lines.

Reaction chamber 16 is located in reactor structure 18, which e.g. may consist of graphite and is cooled from the outside.

The same applies to post-reaction chamber 20 located in reactor structure 19. The post-reaction chamber 20 has a circular cylindrical shape and its inflow side is surrounded by an annular slit 21 through which a further quantity of feed hydrocarbon in vapor form is introduced substantially in radial relationship with respect to flowing hot reaction mixture travelling in the direction of the axis of rotation. The feed hydrocarbon in vapor form can also be introduced in tangential relationship. In this case, the annular slit 21 can be replaced with means similar to structures 5, 6, 7 and 8 which are used for the tangential supply of hydrogen.

Post-reaction chamber 20 communicates in the direction of flow with quenching chamber 23 of circular cylindrical design located in quenching structure 22, the quenching chamber 23 being surrounded near its opening portion by an annular slit 24 through which a quenching agent is introduced radially with respect to hot cracked product flowing into the quenching chamber.

Quenched cracked product leaves the quenching chamber in the direction indicated by arrow 27 to be worked up in conventional manner.

The apparatus shown in FIGURE 2 differs from that shown in FIGURE 1 in that the post-reaction chamber is replaced with a second reaction chamber 25 which is located in reactor structure 26 and provided with an annular slit 14 for the tangential supply of evaporated feed hydrocarbon. Reaction chamber 25 comprises no more than that portion of the meridian section which is conca've with respect to the axis of rotation.

In the embodiment shown in FIGURE 2, feed hydrocarbon such as introduced into reaction chamber 25 primarily serves to produce a protective layer on the walls thereof, while intimate mixing of feed hydrocarbon in vapor form with hot hydrogen takes place when the mixture enters into the second reaction chamber 16. In other words, slightly varying functions are assigned to

rea'ction chambers

25 and 16. In this embodiment of the present invention it is advantageous to allow feed hydrocarbon to enter into reaction chamber 25 at a velocity of flow approximately the same as that used for supplying hot hydrogen.

For the sake of greater clearness, FIGURES 1 and 2, respectively, have been drawn to show two instead of three electrodes such as employed in a conventional threephase system. The process of the present invention is also applicable when other current supply sources are used which call for an apparatus designed for operation with a different number of electrodes.

EXAMPLE 6 and distributor ring 5 and ultimately through outlet openings 8 into arc chamber 1.

The heated and partially dissociated hydrogen entered into reaction chamber 16 at a mean velocity of flow of about 60 m./second. 2000 kg. gasoline in vapor form boiling at 40'-l30 C. were then introduced through cooled annular slit 13 into reaction chamber 16 at a velocity of flow of about 80 m./ second. Lip 15 surrounding the annular slit 13 and the shape conferred upon reaction chamber 16 forced the gasoline in vapor form 17 while travelling through reaction chamber 16 to run closely down the walls thereof and thus uniformly to rinse reaction chamber 16 in a manner similar to the hydrogen.

The reaction mixture travelled from reaction chamber 16 into post-reaction chamber 20 into which a further 200 kg. gasoline in vapor form were introduced near the inflow end of chamber 20 through annular slit 21.

Cracked product was quenched in quenching chamber 23 provided near its inflow end with an annular slit 24 spraying 80 cubic meters/hr. of a parafiinic oil boiling at 180350 C. into the quenching chamber.

3590 cubic meters (N.T.P.) crack gas containing 15.5% by volume acetylene and 7.7% by volume ethylene were obtained per hour. This corresponded to a yield of 651 kg. acetylene and 345 kg. ethylene per hour. Methane, hydrogen and rather small amounts of higher acetylenes, which could be recycled into the process, were also obtained.

No deposition of carbon black and coke in the reaction chamber or on the electrodes was observed even after prolonged operation.

We claim:

1. In the production of acetylene and ethylene by the thermal cracking of gaseous and vaporizable hydrocarbons by means of hydrogen introduced in partial streams into an arc zone, heated therein and conveyed into a reaction zone locally spaced from but immediately following the arc zone, the improvement which comprises injecting feed hydrocarbon in vapor form, near the inflow end of the reaction zone, co-currently to hot hydrogen travelling therethrough, conveying reaction mixture at an increasing velocity through the reaction zone towards the discharge end thereof, thereafter introducing, near the inflow end of a post-reaction zone immediately following the reaction zone, a further quantity of feed hydrocarbon in vapor form into the hot reaction mixture travelling henceforth at a substantially uniform velocity of flow, said further feed hydrocarbon being introduced in a direction traverse to the direction of motion of the reaction mixture, and ultimately quenching in conventional manner resulting cracked products leaving the reaction zone.

2. A process as claimed in claim 1, which comprises conveying the flowing hot reaction mixture from the first reaction zone into a second reaction zone immediately following the first reaction zone, introducing, near the inflow end of that second reaction zone, a further quantity of feed hydrocarbon in vapor form into the reaction mixture cocurrently thereto, continuously increasing the velocity of flow of the reaction mixture, and ultimately quenching in conventional manner the reaction mixture leaving that second reaction zone.

3. A process as claimed in claim 1, which comprises conveying the reaction mixture through a reaction zone tapered and bell-shaped towards the quenching zone, whereby the velocity of flow of the reaction mixture is steadily increased on being passed through that tapered and bell-shaped portion of the reaction zone.

4. A process as claimed in claim 1, wherein two to seven kwhr. are used per cubic meter (N.T.P.) hydrogen to heat the hydrogen in the arc.

5. A process as claimed in claim 1, wherein hot hydrogen is introduced into the first reaction zone with a velocity of flow of about to 400 m./second.

6. A process as claimed in claim 5, wherein the hydrogen is introduced into the first reaction zone with a velocity of flow of about m./second.

7. A process as claimed in claim 1, wherein the feed hydrocarbon in vapor form is introduced into the reaction zone at a velocity of flow of about 20 to 400 m./ second, hydrocarbons of low molecular weight being supplied at a velocity of flow of about to 400 m./second and petroleum hydrocarbons having the mean composition C H being supplied at a velocity of flow of about 50 to m./second.

8. A process as claimed in claim 7, wherein methane is used as the hydrocarbon of low molecular weight.

9. A process as claimed in claim 1, wherein a parafiinbasic oil is used as the quenching agent.

References Cited UNITED STATES PATENTS 3,217,056 11/1965 Sennewald et al. 260679 FOREIGN PATENTS 1,064,945 3/1958 Germany.

DELBERT E. GANTZ, Primary Examiner.

I. D. MYERS, Assistant Examiner.