US2296796A - Manufacture of acetylene - Google Patents

Manufacture of acetylene Download PDF

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US2296796A
US2296796A US252640A US25264039A US2296796A US 2296796 A US2296796 A US 2296796A US 252640 A US252640 A US 252640A US 25264039 A US25264039 A US 25264039A US 2296796 A US2296796 A US 2296796A
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steam
oxygen
vapors
oil
acetylene
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Floyd J Metzger
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Airco Inc
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Air Reduction Co Inc
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00Aliphatic unsaturated hydrocarbons
    • C07C11/22Aliphatic unsaturated hydrocarbons containing carbon-to-carbon triple bonds
    • C07C11/24Acetylene
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/34Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours

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  • This invention relates to improvements and apparatus for the production of acetylene; and more particularly to improvements in apparatus for the production of acetylene ⁇ from normally liquid hydrocarbons by a cracking or conversion operation in which the heat required for the cracking or conversion is obtained by the combustion vor reaction with oxygen of a portion of the hydrocarbons being cracked or converted.
  • 'I'he apparatus of the invention is intended and adapted for the commercial production of acetylene from normally liquid hydrocarbons in a continuous manner, is of simple construction and permits the practice of a process of economical operation such that the production can be Divided and this application 24, 1939, Serial No. 252,640
  • the apparatus of the invention includes, when needed, asuitable vaporizer, which, when heavy oils are used, is advantageously a countercurrent vaporizer, in which steam and preheated liquid oil iiow countercurrently, and inwhich the steam aids in the vaporization of the oil and in which substantially more complete vaporization of the oil is obtainable Without objectionable cracking or coking than is obtainable with other types of vaporizers, in combination with a suitable superheater and a suitable reaction chamber or vessel.
  • the invention includes u i apparatus for the production of acetylene by a cracking or conversion operation, in which vapors of normally liquid hydrocarbons, in admixture ywith steam, are subjected to combustion or reaction with a regulated amount of oxygen.
  • the mixture of hydrocarbon vapor and steam is introduced V into the cracking or reaction apparatus in the form of a large number of individual jets.
  • the large number of individual separate jets of ad*- mixed hydrocarbon vapors and steam and the large number of separate individual jets of oxygen are brought together to accomplish the local'- ized combustion of a part of the hydrogen vapors in 'a large number of localized individual zones merging intoa'flame zone to accomplish the completion of the conversion or cracking operation.
  • combustion products are continually merging into the composite flame zone and such that the products of the completed reactions are continuously removed and immediately cooled or quenched and subsequently treated for the recovery of acetylene therefrom.
  • the present apparatus is an advantageous one for use in the cracking or conversion ofrelatively heavy liquid hydrocarbons; and crude oil or even heavy residuum oil, if suitably vaporized and admixed with steam, can advantageously be utilized in the apparatus of the present invention for the production of acetylene therefrom.
  • special precautions should be taken to insure complete vaporization of the hydrocarbons or of such portions of the hydrocarbons as are supplied tov the cracking or reaction zone in admixture with the steam.
  • the amount of steam which is used in admixture with the vapors of liquid hydrocarbons may vary within more or less Wide limits, depending somewhat on the particular oil vaporized. It should be suicient to prevent the accumulation of carbon in the reaction chamber, but not suflicient to cause the production of too much carbon dioxide in the exit gases, or to prevent the temperature attained in the reaction chamber from being sufficiently high to accomplish the desired production of acetylene.
  • the amount (i. el weight) of steam may be less than or about the same as the amount of oil or may be in excess of the amount of oil, e. g. up to about twice as much steam as oil.
  • the amount of steam required increases with heavier oils, and with an East Texas crude oil, for example, of which about 90% is vaporized, about 150 pounds of steam may be used with 87 pounds of the vaporized oil.
  • the temperatures which are used in the reaction chamber are considerably in excess of those used. in ordinary cracking operations' for the production of gasoline or pressure distillate, and considerably in excess of those used in the various cracking processes which have been proposed for the production of ethylene. While the temperatures attained at the .zone where the localized combustion of the oxygen and hydrocarbon jets takes place are difficult to measure, the temperature of the walls of the reaction chamber may be as high as 900 C. or 1020 C. or higher on the outside, with the temperature on the inside of the wall somewhat higher.
  • yIt is advantageous to preheat the vapors fed to the reaction chamber.
  • the oil should be vaporized and supplied in vapor form admixed with steam, and it is-advantageous to preheat the admixed oil vapors and steam to around 400 C. or 500 C. to prevent the condensation of any of the vapors and to avoid feeding to the reaction chamber any of the hydrocarbon in liquid form.
  • This cylinder may be provided atl one end with a head of suitable metal having a large number of directed jets arranged in pairs, or as concentric jets, or otherwise. When the jets are arranged in pairs one jet of each pair is used for hydrocarbon vapors and steam, and the other jet is used for the supply of oxygen.
  • the head may thus be provided with 20 or 30 pairs of impinging or concentric jets; and for larger scale operation, using cylinders or reaction chambers 12 or 18 inches in diameter, the head may be provided with two or three hundred pairs of jets, although a much smaller or larger number of jets may be used, depending on the size of the apparatus, the size of the jets, etc.
  • the jets instead of arranging the jets in pairs, there maybe provided a plurality of jets of oxygen for each jet of hydrocarbon vapor and steam or vice versa, as long as the arrangement is such as to give the intense localized combustion followed by a further combustion or reaction in a composite combustion or reaction zone which is advantageously used in the process.
  • the apparatus is provided with suitable means for vaporizing and preheating the liquid hydrocarbon feed, and with means for the regulation and control of the hydrocarbon and oxygen fed to the apparatus, and with means for admixing the hydrocarbon vapors with steam.
  • suitable scrubbers for the exit gases, to remove entrained tar and carbon therefrom, and suitable means for recovering the acetylene from the gases, or for converting the acetylene into other useful products, such as acetaldehyde.
  • Fig. 1 is a ilow sheet or schematic representation of an apparatus suitable for the production of acetylene from normally liquid hydrocarbons;
  • Fig. 2 illustrates in a somewhat conventional and diagrammatic manner a reaction 'chamber and head which may be used
  • FIG. 3 shows conventionally and in somewhat greater detail the arrangement of one of the lpairs of jets used in the head illustrated in Fig. 2;
  • Fig. 4 is a sectional view of the head shown in Fig. 2;
  • Fig. 5 is a somewhat conventional sectional view of a modified head which may be used with advantage.
  • the oxygen used in the process is advantageously supplied from an oxygen plant I 9, e. g. a liquefaction plant, inwhich it is produced from air as required.
  • the various preheating and superheating coils (which are used for the preheating and superheating of the hydrocarbon, the steam and the oxygen) are advantageously placed within a single furnace 8; but instead of this arrangement, the preheating of the liquid oil and the superheatin'g of the steam to be used in vaporizing it may be carried out in a separate preheater, with the oil vapors and ad-v mixed steam, and the oxygen, being suitably superheated in a separate furnace (not shown).
  • a suitable reaction tube 25a which may be advantageously made of car- .borundum or other refractory material, or may be made of metal, with provision .ffor causing a stream of Water to iiow down its interior surface to protect the metal and keep it clean, surrounded by suitable insulation 2B, in casing 21.
  • a head 28 into which is introduced the admixed superheated oil and steam vapors through pipe I8, and the oxygen separately through pipe 23.
  • 'I'he oil vapors and admixed steam enter the upper chamber 29, while the oxygen enters the lower chamber 30, both .provided within the head.
  • This head is advantageously made in three sections, a lower section 3l Iprovided with holes for the nozzles, an upper section 32, and a middle section 33, which is provided with openings for the nozzles and which is formed 'with central recesses on both sides so that the chambers 29 and 30 are formed whenvthe upper and lower plates are fastened to it.
  • the head 28 is provided, as shown with a number of nozzles or jets through which the hydrocarbon vapors and admixed steam and the oxygen separately flow into the tube 25a.
  • nozzles or jets through which the hydrocarbon vapors and admixed steam and the oxygen separately flow into the tube 25a.
  • the construction of these nozzles is illustrated in Fig. 3.
  • Each nozzle includes a tube 34 which extends from ⁇ the the ⁇ top of the plate, andthe tubes 34 are square in shape where they fit into the upper part of the openings, so that they are properly centered in the openings, while leaving suitable passageways for the iiow of oxygen down past the tubes 34 into the tube 25.
  • This method of centering the tubes 34 is illustrated in Fig. 4, which shows how the square portions of the tubes' 34 correctly center the tubes in the openings 36 while leaving spaces for the iiow of the jets of oxygen.
  • the number of such nozzles may vary; but in the apparatus illustrated, with a tube about 4 inches by 12 inches and intended for the production of five to ten thousand cubic -feet of acetylene per day, about 19 such nozzles may be used, each, e. g., with the diameter of the openings for Vthe flow of hydrocarbon about three-sixteenths of an inch, and with the area of the annular space through which the oxygen flows about equal to that of the three-sixteenths inh opening.
  • the number of nozzles may be increased about as the cross-sectional area of the tube, so that 200 or more such nozzles may be provided; although with the larger scale apparatus, the size of the nozzles may be somewhat increased, and their number may be somewhat less than the number which would be provided if the apparatus were simply enlarged to scale; so as to reduce the back pressure and the resistance to ow of the vapors and gases.
  • the number may be as 10W as 50 or less, or as high as 300 or more, depending on the size of the apparatus, the
  • FIG. 5 A modified arrangement of the head which may also be used with advantage is illustrated in Fig. 5.
  • a plate 31 whichhas a number of obliquely cut holes 38, about one-eighth inch in diameter, arranged in concentric circles. These openings are arranged in pairs so that they produce directed jets of hydrocarbon vapors and admixed steam and oxygen in pairs, the jets of eachpair impinging as they comeinto the reaction tube.
  • a box 39 with separate chambers into which the hydrocarbon vapors and admixed steam are introduced through line I3, and the oxygen through line 23.
  • the hydrocarbon and admixed steam thus ilowvinto the chambers 40 while the oxygen flows into the chambers 4I. 'I'he oxygen thus passes through the openings aaa, while the hydrocarbon and admixed steam flow through the vopenings bbb.
  • the openings in the plate 3l are made somewhat smaller at the bottom of the plate than at area of the reaction tube is increased.
  • a metal tube 42 through which the exit gases ow.
  • 'Ilhis tube is kept coolv by a stream of Water which ows down its inner surfaces, the water entering the annular chamber 43 from pipe 44 and flowing over the upper portionof the tube 42 and down the inner surface of the tube.
  • This stream of Water not only serves to keep the tube 42 cool, but also serves to prevent the deposition of car- 'bon thereon.
  • the vapors and gases and water from the nozzle 46 may be passed through a separator, in which the greater part of the water ls removed, and then led to an oil scrubber.
  • a water scrubber it is advantageous to provide a water scrubber, as the gases, even after the separation of entrained water from the nozzle 46, contain a good deal of Water vapor, and if they are cooled to any great degree in an oil scrubber or tar scrubber, tend to condense out water which forms an emulsion.
  • the gases and vapors, after having been scrubbed with water in the scrubber 4 8, are led by pipe 53 to a tar separator 54.
  • This separator which may be of the bubble plate type, is shown of usual construction, and is provided with a tank 55 and a circulating pump 56 so that the scrubbing oil used may be circulated through the separator.
  • entrained tar and oil which the gases and vapors carry is removed.
  • the vapors and gases then pass through a centrifugal separator 5l and through pipe 58 to the vessel 59, in which the hydrogen suliide is removed by iron oxide.
  • the gases and vapors pass to a suitable bubble plate column 60 in which the lightoils such as benzol are ,removed by scrubbing with a suitable absorbent, such as straw oil.
  • a suitable absorbent such as straw oil.
  • These purified gases which contain e. g. from 7 to 8% of acetylene, may be treated directly for the production of acetaldehyde from the acetylene, or they may be passed into contact with a suitable solvent for acetylene for the recovery of the acetylene in more concentrated form.
  • the gases may be brought into contact, as in a suitable scrubbing tower, with diethyl carbonate, which preferentially dissolves the acetylene as described in my Patent No. 1,900,655.
  • the concentration of acetylene may be increased to as much as 60% or more, and by one or more repetitions of the treatment may be increased to above 90%.
  • the concentrated acetylene-containing gases may be advantageously used for the production of acetaldehyde, or may be used in other ways or for other purposes.
  • the apparatus can advan- 'tageously be operated at pressures around atmospherlc, or such that the gases emerge from the purifying apparatus at about atmospheric pressure. That is, the pressure in the various parts of the apparatus subsequent to the combustion or reaction chamber may be only suflciently above atmospheric to provide for the ow of the gases and vapors through these subsequent parts of the apparatus.
  • the pressure drop through the jets and the pressure required to force the oxygen and hydrocarbon through the jets with suicient velocity will vary somewhat with the size and construction of the jets and may be e. g. around 8 or 10 pounds per square inch for the steam and admixed oil vapors and around 3 pounds per square inch for the oxygen.
  • the pressure drop throughout the subsequent parts of the apparatus will vary with the construction and arrangement of the apparatus but may be, for example, around 2 or 3 pounds or more per square inch.
  • the neces-l sary pressure of the oxygen and of the admixed hydrocarbon vapor and steam is readily obtained by providing suitable means for supplying the same under the necessary pressure to the respective large number of jets.
  • the preheated gases and vapors are supplied at a sufficient pressure to provide the necessary flow and velocity through the jets and the apparatus, the oil vapors and admixed steam being at a gauge pressure of e. g. about 11 pounds, and the oxygen at a gauge pressure of about 6 pounds.
  • the oil vapors and admixed steam, and the oxygen are introduced into the reaction chamber through separate nozzles in such a manner that there are a number of directed jets of oxygen and a number of directed jets of oil vapor and steam, each jet of oxygen coming into contact with, or implnging upon, a jet of admixed oil vapor and steam,
  • each jet of oxygen coming into contact with, or implnging upon, a jet of admixed oil vapor and steam
  • the gases asthey flow from the bottom of the i exit gases tol be about ⁇ 1,000 C., over 27,000 cubicfeet of gas and vapor leave the reaction chamber per hour. After the removal of water from the gases, and their cooling to room temperature, there may be obtained e. g. about 3,100- cubic feet of dry gas per hour.
  • the gas so produced had the following composition:
  • EXAMPLE II -Acetylene from range oit-Range oil (approx. kerosene) is vaporized at the rate of aboutv 110 pounds per hour, and with the va.- pors are admixed about 67 pounds of steam per hour.
  • the mixture is superheated to about 330 C., and fed to a 4-inch carborundum reaction vessel, provided with a head of the type illustrated in Fig. 5.
  • About 1020 cubic feet of oxygen, preheated to about 360- C., are. also supplied (through separate jets) to the reaction vessel per hour.
  • Example II a reaction vessel similar to that of Example I, along with about 1020 cubic feet of oxygen, preheated to about 380 C.
  • an exit gas containing about 6.0% of acetylene was obtained.
  • EXAMPLE IV -Acetylene from Darst Creek crude ail- Darst Creek crude oil is supplied to the countercurrent vaporizer at a rate of about 126 pounds per hour, along with about 77 pounds Per cent C2H2 7,6 COz 11.0 C2H4 5.2 v O2 0.0 CO 31.6 H2 38.8 CH4. and higher 5.8
  • EXAMPLE V Acetylene from Darst Creek crude oil.-Darst Creek crude oil is supplied to the countercurrent vaporizer at the rate of about 126 pounds per hour,v along with about 58 pounds of steam. About 88.8% oi the oil was vaporized' and about 93 pounds of steam per hour are admixed with the mixture of oil vapors and steam. The resulting mixture is superheated to about 435' C., and fed to a reaction vessel similar to that'of Example II along with about 1060 cubic feet of oxygen, preheated to about 400 C., per In one case, about 3400 cubicfeet of exit gas (measured dry, at room temperature and pressure) were obtained per hour.
  • the gas had the following composition:
  • EXAMPLE VI -Acetylene from Darst Creek crude cih-Darst Creek crude oil is supplied to the countercurrent vaporizer at the rate of about 126 pounds per hour, along with about 60 pounds of steam. About 88% of the oil is vaporized, and about 60 pounds of steam are admixed with the vapors per hour. The resulting mixture is superheated to about 425 C., and supplied to a reaction chamber similar to that of Example II, along with about 1120 cubic feet of oxygen,
  • the new and improved apparatus of the present invention includes the vaporizer, and particularly the countercurrent vaporizer, adapted for the production of a mixture of oil vapors and steam, in combination with a suitable superheater and reaction chamber', adapted for the cracking or conversion of the hydrocarbon vapors with the production of substantial amounts of acetylene, and for the treatment of large quantinecting said outlet of said vaporizer with the inother gases which are produced as by-products.
  • Apparatus as in claim 1 heater for preheating a gas such,as oxygen, said preheater being connected with that inlet of the reaction chamber which is adapted to introduce oxygen into the chamber.
  • Apparatus as in claim 1 in which the vaporizer is a countercurrent heated vaporizer in which heavy oil can be eil'ectively vaporized.

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Description

Sept. 22, 1942. F. J. METZGER MANUFCTURE OF ACETYLENE 2 Sheets-Sheet l Original Filedl July 18, 1956 il..." b.- l
Patented Sept. 2.2, 1942 MANUFACTURE oF ACETYLENE Floyd J. Metzger, New York, N. Y., assignor to AAir Reduction Company, Incorporated, New
York, N. Y., a corporation of New York Original application July 18, 1936, Serial No.
Claims.
This invention relates to improvements and apparatus for the production of acetylene; and more particularly to improvements in apparatus for the production of acetylene `from normally liquid hydrocarbons by a cracking or conversion operation in which the heat required for the cracking or conversion is obtained by the combustion vor reaction with oxygen of a portion of the hydrocarbons being cracked or converted.
'I'he apparatus of the invention is intended and adapted for the commercial production of acetylene from normally liquid hydrocarbons in a continuous manner, is of simple construction and permits the practice of a process of economical operation such that the production can be Divided and this application 24, 1939, Serial No. 252,640
January -the liquid hydrocarbon in producing the composite mixture of hydrocarbon vapors and steam whchare utilized in the carrying out of the process. The apparatus of the invention includes, when needed, asuitable vaporizer, which, when heavy oils are used, is advantageously a countercurrent vaporizer, in which steam and preheated liquid oil iiow countercurrently, and inwhich the steam aids in the vaporization of the oil and in which substantially more complete vaporization of the oil is obtainable Without objectionable cracking or coking than is obtainable with other types of vaporizers, in combination with a suitable superheater and a suitable reaction chamber or vessel.
The introduction of the large number of separate individual jets of a mixture of hydrocarbon vapors and steam and of oxygen is eiected as directed jets such that effective localized intense combustion is obtained followed by blending of the gases in thecomposite ame zone which is continuously changing in the sense that the large i' number of individual high velocity jets and their In its broader aspects, the invention includes u i apparatus for the production of acetylene by a cracking or conversion operation, in which vapors of normally liquid hydrocarbons, in admixture ywith steam, are subjected to combustion or reaction with a regulated amount of oxygen.l
admixed with steam in proper proportion so that a composite admixture of hydrocarbon vapor and steam is subjected to reaction or combination with the oxygen. It is important to admix the steam with the hydrocarbon vapor and not with the oxygen.
Advantageously, the mixture of hydrocarbon vapor and steam is introduced V into the cracking or reaction apparatus in the form of a large number of individual jets. -In 4such cases the large number of individual separate jets of ad*- mixed hydrocarbon vapors and steam and the large number of separate individual jets of oxygen are brought together to accomplish the local'- ized combustion of a part of the hydrogen vapors in 'a large number of localized individual zones merging intoa'flame zone to accomplish the completion of the conversion or cracking operation.
combustion products are continually merging into the composite flame zone and such that the products of the completed reactions are continuously removed and immediately cooled or quenched and subsequently treated for the recovery of acetylene therefrom. i
In order to obtain the large number of directed .jets of high velocity of both the hydrocarbon vapors and admixed steam and the oxygen it is important to supply both the hydrocarbon vapors and admixed steam and the oxygen to the individual jets under a sufliciently high pressure to give the directed jets of high velocity. When these directed jets are discharged into the large combustion and reaction chamber the jets rst lintermingle with each other locally with expanw sion of the jets as they emerge at high velocity into the zone of lower pressure-in the combustion and reaction chamber and with decrease in velocity of the jets, and contact or intermingling of the jets locally followed by inter-mingling or mixing or blending` in the large combustion chamber. Moreover, a large volume of hydrocarbon vapor, steam and oxygends thus introduced with rapid and intense combustion in a relatively short time, usually a very small fraction of a second, and with a high velocityvof the gases and vapors, and of the products ofcombustion and reaction, through the large chamber.
In this process, the presence of the steam admixed with the vapors of liquid hydrocarbons seems to be important both in its effect on the 1ocalized combustion brought about in the zones Where the high velocity jets are initially admixed, and in its effect on the subsequent composite combustion or reaction and in reducing or preventing the accumulation of coke or carbon in the large combustion or reaction chamber. This steam may also be advantageously used, as above pointed out, for assisting in vaporizing the liquid hydrocarbon.
The present apparatus is an advantageous one for use in the cracking or conversion ofrelatively heavy liquid hydrocarbons; and crude oil or even heavy residuum oil, if suitably vaporized and admixed with steam, can advantageously be utilized in the apparatus of the present invention for the production of acetylene therefrom. With such heavy hydrocarbons special precautions should be taken to insure complete vaporization of the hydrocarbons or of such portions of the hydrocarbons as are supplied tov the cracking or reaction zone in admixture with the steam.
The amount of steam which is used in admixture with the vapors of liquid hydrocarbons, may vary within more or less Wide limits, depending somewhat on the particular oil vaporized. It should be suicient to prevent the accumulation of carbon in the reaction chamber, but not suflicient to cause the production of too much carbon dioxide in the exit gases, or to prevent the temperature attained in the reaction chamber from being sufficiently high to accomplish the desired production of acetylene. With various oils, the amount (i. el weight) of steam may be less than or about the same as the amount of oil or may be in excess of the amount of oil, e. g. up to about twice as much steam as oil. The amount of steam required increases with heavier oils, and with an East Texas crude oil, for example, of which about 90% is vaporized, about 150 pounds of steam may be used with 87 pounds of the vaporized oil.
The temperatures which are used in the reaction chamber are considerably in excess of those used. in ordinary cracking operations' for the production of gasoline or pressure distillate, and considerably in excess of those used in the various cracking processes which have been proposed for the production of ethylene. While the temperatures attained at the .zone where the localized combustion of the oxygen and hydrocarbon jets takes place are difficult to measure, the temperature of the walls of the reaction chamber may be as high as 900 C. or 1020 C. or higher on the outside, with the temperature on the inside of the wall somewhat higher.
yIt is advantageous to preheat the vapors fed to the reaction chamber. The oil should be vaporized and supplied in vapor form admixed with steam, and it is-advantageous to preheat the admixed oil vapors and steam to around 400 C. or 500 C. to prevent the condensation of any of the vapors and to avoid feeding to the reaction chamber any of the hydrocarbon in liquid form. It is also desirable to preheat the oxygen, to increase carborundum tube about 4 inches 'in diameter and about 12 inches long can be advantageously used. This cylinder may be provided atl one end with a head of suitable metal having a large number of directed jets arranged in pairs, or as concentric jets, or otherwise. When the jets are arranged in pairs one jet of each pair is used for hydrocarbon vapors and steam, and the other jet is used for the supply of oxygen.
For an operation such as just referred to, and with a cylinder or reaction chamber about 4 inches in diameter, the head may thus be provided with 20 or 30 pairs of impinging or concentric jets; and for larger scale operation, using cylinders or reaction chambers 12 or 18 inches in diameter, the head may be provided with two or three hundred pairs of jets, although a much smaller or larger number of jets may be used, depending on the size of the apparatus, the size of the jets, etc. Instead of arranging the jets in pairs, there maybe provided a plurality of jets of oxygen for each jet of hydrocarbon vapor and steam or vice versa, as long as the arrangement is such as to give the intense localized combustion followed by a further combustion or reaction in a composite combustion or reaction zone which is advantageously used in the process.
At the other end of the cylinder, through which the exit gases ow, there is advantageously provided a water spray which .aids in the removal of tar or carbon from the exit gases and quenches and rapidly cools these gases.
The apparatus is provided with suitable means for vaporizing and preheating the liquid hydrocarbon feed, and with means for the regulation and control of the hydrocarbon and oxygen fed to the apparatus, and with means for admixing the hydrocarbon vapors with steam. There are also provided suitable scrubbers for the exit gases, to remove entrained tar and carbon therefrom, and suitable means for recovering the acetylene from the gases, or for converting the acetylene into other useful products, such as acetaldehyde.
The invention will be further illustrated |by the accompanying drawings, but it will be understood that the invention is not limited thereto.
In the drawings:
Fig. 1 is a ilow sheet or schematic representation of an apparatus suitable for the production of acetylene from normally liquid hydrocarbons;
Fig. 2 illustrates in a somewhat conventional and diagrammatic manner a reaction 'chamber and head which may be used;
Fig. 3 shows conventionally and in somewhat greater detail the arrangement of one of the lpairs of jets used in the head illustrated in Fig. 2;
Fig. 4 is a sectional view of the head shown in Fig. 2; and
Fig. 5 is a somewhat conventional sectional view of a modified head which may be used with advantage. f
In the apparatus illustrated in Fig. 1, which is .adapted for the production of acetylene from steam, which is supplied to a. preheater I I through Ipipe I2, and -which after being preheated enters the countercurrent vaporizer 9 at the bottom through pipe I3. The admixed hydrocarbon ya- .pors and steam pass from the top of the vaporizer -9 through pipe I4 to superheater I5. A connection I6 from the superheated steam line I3 to the vapor line I4 is provided for the introduction of more superheated steam to the mixture of hydrocarbon vapor and steam, where the amount of steam required or'utilized in the countercurrent vaporizer is less than that which is desirable for use in admixture with the oil vapors. The residue from the vaporizeris drawn off through outlet I1 and may be used as fuel. From the superheating coil I the admixed hydrocarbon vapors and steam are led to the reaction chamber 25 by pipe I 8.
The oxygen used in the process is advantageously supplied from an oxygen plant I 9, e. g. a liquefaction plant, inwhich it is produced from air as required. The oxygen is compressed in compressor 20 and passes through pipe 2l to heating coils22, in which it is preheated, and from 'which it passes through pipe 23 to the reaction cham- =ber 25.
In the rarrangement shown, the various preheating and superheating coils (which are used for the preheating and superheating of the hydrocarbon, the steam and the oxygen) are advantageously placed within a single furnace 8; but instead of this arrangement, the preheating of the liquid oil and the superheatin'g of the steam to be used in vaporizing it may be carried out in a separate preheater, with the oil vapors and ad-v mixed steam, and the oxygen, being suitably superheated in a separate furnace (not shown).
The construction oi the reaction chamber, and the attached head and the means for quenching the exit gases -from the chamber are illustrated,
in a more or less conventional fashion, in Figs.
In Fig. 2, there is shown a suitable reaction tube 25a, which may be advantageously made of car- .borundum or other refractory material, or may be made of metal, with provision .ffor causing a stream of Water to iiow down its interior surface to protect the metal and keep it clean, surrounded by suitable insulation 2B, in casing 21. At the top of this tube 4is provided a head 28 into which is introduced the admixed superheated oil and steam vapors through pipe I8, and the oxygen separately through pipe 23. 'I'he oil vapors and admixed steam enter the upper chamber 29, while the oxygen enters the lower chamber 30, both .provided within the head. This head is advantageously made in three sections, a lower section 3l Iprovided with holes for the nozzles, an upper section 32, and a middle section 33, which is provided with openings for the nozzles and which is formed 'with central recesses on both sides so that the chambers 29 and 30 are formed whenvthe upper and lower plates are fastened to it.
The head 28 is provided, as shown with a number of nozzles or jets through which the hydrocarbon vapors and admixed steam and the oxygen separately flow into the tube 25a. The construction of these nozzles is illustrated in Fig. 3. Each nozzle includes a tube 34 which extends from\the the` top of the plate, andthe tubes 34 are square in shape where they fit into the upper part of the openings, so that they are properly centered in the openings, while leaving suitable passageways for the iiow of oxygen down past the tubes 34 into the tube 25. This method of centering the tubes 34 is illustrated in Fig. 4, which shows how the square portions of the tubes' 34 correctly center the tubes in the openings 36 while leaving spaces for the iiow of the jets of oxygen.
The number of such nozzles, each of which provides a jet of hydrocarbon vapor admixed with steam through the central opening with an annular jet of oxygen surrounding it, may vary; but in the apparatus illustrated, with a tube about 4 inches by 12 inches and intended for the production of five to ten thousand cubic -feet of acetylene per day, about 19 such nozzles may be used, each, e. g., with the diameter of the openings for Vthe flow of hydrocarbon about three-sixteenths of an inch, and with the area of the annular space through which the oxygen flows about equal to that of the three-sixteenths inh opening.
' Where the apparatus is intended for a larger scale operation, and the reaction chamber is made of a tube 12 to 18 inches in diameter, and 3 or 4 feet long, the number of nozzles may be increased about as the cross-sectional area of the tube, so that 200 or more such nozzles may be provided; although with the larger scale apparatus, the size of the nozzles may be somewhat increased, and their number may be somewhat less than the number which would be provided if the apparatus were simply enlarged to scale; so as to reduce the back pressure and the resistance to ow of the vapors and gases. The number may be as 10W as 50 or less, or as high as 300 or more, depending on the size of the apparatus, the
size and -shape of the nozzles, etc.
A modified arrangement of the head which may also be used with advantage is illustrated in Fig. 5. In` this head, there is provided a plate 31, Whichhas a number of obliquely cut holes 38, about one-eighth inch in diameter, arranged in concentric circles. These openings are arranged in pairs so that they produce directed jets of hydrocarbon vapors and admixed steam and oxygen in pairs, the jets of eachpair impinging as they comeinto the reaction tube. Above thisv plate is a box 39 with separate chambers into which the hydrocarbon vapors and admixed steam are introduced through line I3, and the oxygen through line 23. The hydrocarbon and admixed steam thus ilowvinto the chambers 40 while the oxygen flows into the chambers 4I. 'I'he oxygen thus passes through the openings aaa, while the hydrocarbon and admixed steam flow through the vopenings bbb. With this head,
when used with a combustion tube such as shown number of openings provided may be increased,
-' in about the ,same ratio as the cross-sectional plate 33 through an opening 3B in the plate 3l, j
forming a passageway from chamber 29 to thev interior of the tube 25a. The openings 36 in the plate 3| through which these tubes pass are somewhat larger than the outer diameter of the tubes 34 as shown, so that there is an annular passageway around each of the tubes from the chamber 30 to the interior of the tube 25a.
The openings in the plate 3l are made somewhat smaller at the bottom of the plate than at area of the reaction tube is increased.
Below the reaction tube 25 there is provided a metal tube 42 through which the exit gases ow. 'Ilhis tube is kept coolv by a stream of Water which ows down its inner surfaces, the water entering the annular chamber 43 from pipe 44 and flowing over the upper portionof the tube 42 and down the inner surface of the tube. This stream of Water not only serves to keep the tube 42 cool, but also serves to prevent the deposition of car- 'bon thereon.
'I'he exit gases flow'through this tube 42 into the chamber 45- where they are quenched and cooled by a water spray from nozzle 46. -The amount of water which is sprayed into the gases Y which may be provided with baflie plates 49, the
gases and vapors are brought into contact with water introduced through pipe 50. This washer, together with the Water spray, removes a large part of the tar and carbon from the gases. The water from ,the Washer, and the excess water sprayed into the gases by nozzle 46, ows into the Water seal 5| and then into a settling basin 50 in which oil and tar is separated.
Instead of providing a water lWasher for the exit gases, the vapors and gases and water from the nozzle 46 may be passed through a separator, in which the greater part of the water ls removed, and then led to an oil scrubber. However, it is advantageous to provide a water scrubber, as the gases, even after the separation of entrained water from the nozzle 46, contain a good deal of Water vapor, and if they are cooled to any great degree in an oil scrubber or tar scrubber, tend to condense out water which forms an emulsion.
The gases and vapors, after having been scrubbed with water in the scrubber 4 8, are led by pipe 53 to a tar separator 54. This separator, which may be of the bubble plate type, is shown of usual construction, and is provided with a tank 55 and a circulating pump 56 so that the scrubbing oil used may be circulated through the separator. In this separator, entrained tar and oil which the gases and vapors carry is removed. The vapors and gases then pass through a centrifugal separator 5l and through pipe 58 to the vessel 59, in which the hydrogen suliide is removed by iron oxide. After the removal of hydrogen sulfide in this vessel, the gases and vapors pass to a suitable bubble plate column 60 in which the lightoils such as benzol are ,removed by scrubbing with a suitable absorbent, such as straw oil. Fr'om this tower, the gases and vapors, which n ow contain e. g. about 7 to 8% of acetylene, pass through pipe 6I to be treated for the recovery or use of the acetylene. y
These purified gases, which contain e. g. from 7 to 8% of acetylene, may be treated directly for the production of acetaldehyde from the acetylene, or they may be passed into contact with a suitable solvent for acetylene for the recovery of the acetylene in more concentrated form. For example, the gases may be brought into contact, as in a suitable scrubbing tower, with diethyl carbonate, which preferentially dissolves the acetylene as described in my Patent No. 1,900,655. By bringing the gases while under pressure into contact with diethylv carbonate, and then boiling the acetylene oif from the diethyl carbonate, the concentration of acetylene may be increased to as much as 60% or more, and by one or more repetitions of the treatment may be increased to above 90%. The concentrated acetylene-containing gases may be advantageously used for the production of acetaldehyde, or may be used in other ways or for other purposes.
It is one advantage of the apparatus of the present invention that high super-atmospheric pressures are not required; nor is the use of a vacuum required. The apparatus can advan- 'tageously be operated at pressures around atmospherlc, or such that the gases emerge from the purifying apparatus at about atmospheric pressure. That is, the pressure in the various parts of the apparatus subsequent to the combustion or reaction chamber may be only suflciently above atmospheric to provide for the ow of the gases and vapors through these subsequent parts of the apparatus.
It is, however, important in those parts of the apparatus whichA precede the combustion or reaction chamber to have a suilicient pressure to insure introduction of the hydrocarbon' vapors and admixed steam and of the oxygen through the jets to give directed jets of both the oxygen and the hydrocarbon vapors and admixed steam; and, where the exit gases from the purifying apparatus are at atmospheric pressure, it is also important that the pressure of the oxygen and the hydrocarbon vapors and admixed steam suflicient to insure oW of the gases through the apparatus from the reaction or combustion chamber to the purier.
The pressure drop through the jets and the pressure required to force the oxygen and hydrocarbon through the jets with suicient velocity will vary somewhat with the size and construction of the jets and may be e. g. around 8 or 10 pounds per square inch for the steam and admixed oil vapors and around 3 pounds per square inch for the oxygen. The pressure drop throughout the subsequent parts of the apparatus will vary with the construction and arrangement of the apparatus but may be, for example, around 2 or 3 pounds or more per square inch. The neces-l sary pressure of the oxygen and of the admixed hydrocarbon vapor and steam is readily obtained by providing suitable means for supplying the same under the necessary pressure to the respective large number of jets.
The operation of the apparatus will be further illustrated by the following specific examples, but it is not limited thereto.
EXAMPLE I.-Acetylene from East Texas crude oil.-East Texas crude oil is supplied to the counter-current vaporizer at such a ratethat about 87 pounds of oil is Vaporized per hour, about 60 pounds of steam being supplied to the vaporizer per hour to assist in the vaporization. About 90 pounds of additional steam are admixed with the oil vapors and steam, and the resulting mixture is superheated, e. g., to about 450 C. These vapors are fed to a 4-inch reaction vessel, provided with a head such as is illustrated in Fig. 2. About 952 cubicfeet of oxygen, measured at atmospheric temperature and pressure, are supplied per hour, preheated to about 400 C.
The preheated gases and vapors are supplied at a sufficient pressure to provide the necessary flow and velocity through the jets and the apparatus, the oil vapors and admixed steam being at a gauge pressure of e. g. about 11 pounds, and the oxygen at a gauge pressure of about 6 pounds.
The oil vapors and admixed steam, and the oxygen, are introduced into the reaction chamber through separate nozzles in such a manner that there are a number of directed jets of oxygen and a number of directed jets of oil vapor and steam, each jet of oxygen coming into contact with, or implnging upon, a jet of admixed oil vapor and steam, As a result, there is an immediate localized combustion of the oxygen with the oil vapors, with the formation of a large number of separate flames and the production of steam per hour. About 89.5% of the oil is of a large number of localized high temperature zones. The gases and vapors as they continue to pass down the reaction tube intermingle and intersperse in a composite ilame zone, and the reaction continues or goes to completion.
The gases asthey flow from the bottom of the i exit gases tol be about\1,000 C., over 27,000 cubicfeet of gas and vapor leave the reaction chamber per hour. After the removal of water from the gases, and their cooling to room temperature, there may be obtained e. g. about 3,100- cubic feet of dry gas per hour. In one case the gas so produced had the following composition:
Per cent C2H2 7.8 C21-I4 5.3 CH4 6.2 H2 38.6 CO 31.3
In this case, about 240 cubic feet of acetylene were produced per hour, vor about 1 pound of acetylene for each gallon of oil. vThe gas after the removal of the acetylene contained about 42% hydrogen, about 34% carbon monoxide, and
about 12% of saturated hydrocarbons, and was suitable for use as a fuel gas or for the production of synthetic methanol.
EXAMPLE II.-Acetylene from range oit-Range oil (approx. kerosene) is vaporized at the rate of aboutv 110 pounds per hour, and with the va.- pors are admixed about 67 pounds of steam per hour. The mixture is superheated to about 330 C., and fed to a 4-inch carborundum reaction vessel, provided with a head of the type illustrated in Fig. 5. About 1020 cubic feet of oxygen, preheated to about 360- C., are. also supplied (through separate jets) to the reaction vessel per hour.
In one case, about 3320 cubic feet of exit gas, measured dry and at room temperatures and pressure, were obtained. The gas had the following composition: v
EXAMPLE Il'L-Acetylenefrom naphtha bottoms.-A mixture containing about 123 pounds of naphtha bottom vapors and 71 pounds of steam, the steam being added to the naphtha bottom vapors, superheated to about 365 C. is
-supplied per hour to a reaction vessel similar to that of Example I, along with about 1020 cubic feet of oxygen, preheated to about 380 C. In one case, an exit gas containing about 6.0% of acetylene was obtained.
EXAMPLE IV.-Acetylene from Darst Creek crude ail- Darst Creek crude oil is supplied to the countercurrent vaporizer at a rate of about 126 pounds per hour, along with about 77 pounds Per cent C2H2 7,6 COz 11.0 C2H4 5.2 v O2 0.0 CO 31.6 H2 38.8 CH4. and higher 5.8
' hour.
vaporized, and the mixture o'f oil vapors and steam is superheated to about 377 C., and supplied to a reaction chamber similar to that of Example II, along with 950 cubic feetvof oxygen, preheated to about 373 C. per hour. In one case, about 3000 cubic feet of exit gas (measured dry, at-room temperature and pressure) were obtained per hour. 'I'he gas had the following composition:
Per cent C2H2 8.3 CO2 7.2
C2H4 3.3 Oz 0.2
H2 37.8 CH4 and higher 7.0 lN2 (by diierence) 2.2
EXAMPLE V.- Acetylene from Darst Creek crude oil.-Darst Creek crude oil is supplied to the countercurrent vaporizer at the rate of about 126 pounds per hour,v along with about 58 pounds of steam. About 88.8% oi the oil was vaporized' and about 93 pounds of steam per hour are admixed with the mixture of oil vapors and steam. The resulting mixture is superheated to about 435' C., and fed to a reaction vessel similar to that'of Example II along with about 1060 cubic feet of oxygen, preheated to about 400 C., per In one case, about 3400 cubicfeet of exit gas (measured dry, at room temperature and pressure) were obtained per hour. The gas had the following composition:
EXAMPLE VI.-Acetylene from Darst Creek crude cih-Darst Creek crude oil is supplied to the countercurrent vaporizer at the rate of about 126 pounds per hour, along with about 60 pounds of steam. About 88% of the oil is vaporized, and about 60 pounds of steam are admixed with the vapors per hour. The resulting mixture is superheated to about 425 C., and supplied to a reaction chamber similar to that of Example II, along with about 1120 cubic feet of oxygen,
r.preheated to about 400 C. per hour. In one case,
an exit gas containing 8.4% of acetylene was obtained.
In the process as described, using a liquid hydrocarbon such as crude oil, it is important, as previously pointed out, to admix the oil vapors with steam, both for the prevention of objectionable coking and for modication of the reaction. The-oxygen should be used without an excess of diluent or it will not produce the localized high temperature combustion required in the DIOCSSS- i It will thus be seen that by the present invention I .provide a new and improved apparatus in which acetylene may be produced from normally liquid hydrocarbons in large quantities and which can be run for long periods of time can be advantageously used for fuel or for the manufacture of such products as synthetic alcohols.
The new and improved apparatus of the present invention includes the vaporizer, and particularly the countercurrent vaporizer, adapted for the production of a mixture of oil vapors and steam, in combination with a suitable superheater and reaction chamber', adapted for the cracking or conversion of the hydrocarbon vapors with the production of substantial amounts of acetylene, and for the treatment of large quantinecting said outlet of said vaporizer with the inother gases which are produced as by-products.
let of the superheater whereby mixed steam and hydrocarbon vapors from the vaporizer may be superheated in said superheater, a reaction vessel or chamber having two inlets, means connecting the outlet of said superheater with one of said reaction vessel inlets whereby superheated hydrocarbon vapors and admixed steam may be introduced into the reaction chamber, the other of said inlets being adapted to introduce oxygen to the reaction chamber. l
2. Apparatus as in claim 1 in which the means connecting the outlet of the vaporizer with the inlet of the superheater is provided with an inlet adapted to introduce steam into said connecting means.
3. Apparatus as in claim 1 in which the reaction vessel is connected with rapid cooling means whereby exit gases from the reaction chamber may be rapidly cooled.
4. Apparatus as in claim 1 heater for preheating a gas such,as oxygen, said preheater being connected with that inlet of the reaction chamber which is adapted to introduce oxygen into the chamber.
5. Apparatus as in claim 1 in which the vaporizer is a countercurrent heated vaporizer in which heavy oil can be eil'ectively vaporized.
FLOYD J. METZGER.
including a pre-
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