BE550846A - - Google Patents

Description

       

   <Desc / Clms Page number 1>
 



   The present invention relates to the pyrolytic decomposition of hydrocarbons to gas and more particularly relates to a new and improved process for carrying out the conversion of normally liquid hydrocarbon oils, in a cyclic thermal regenerator system, in high yields. normally gaseous olefinic hydrocarbons.



   According to this invention there is provided a process for the conversion of normally liquid hydrocarbon oils to high yields of normally gaseous unsaturated hydrocarbons - particularly ethylene, propylene and higher unsaturated products - and valuable oils. aromatics and liquid tars, process' of the type in which two communicating chambers, each containing a heat-storage refractory material, are heated to a cracking temperature in the range of about 735 -1.095 C, by making there passing hot combustion gases and introducing into one of said heated chambers a normally liquid hydrocarbon oil;

  process characterized in that simultaneously steam is introduced - in an amount of 1.1-1.5 kilograms per 4 liters of oil - in direct contact with said oil undergoing vaporization and partial conversion in said heated chamber; the partially converted oil and water vapor are passed into and through the second heated chamber, so as to complete the conversion; the reaction products obtained are discharged from the second chamber and valuable, normally gaseous unsaturated hydrocarbons and liquid aromatic oils and tars are recovered.



   The demand for unsaturated hydrocarbons, especially ethylene and propylene as chemical materials in the manufacture of many chemicals such as -. polyethylene, glycols, ethylene oxide, propylene oxide cumene, acetone and alcohols, keeps growing.



  Petroleum, consisting of a mixture of hydrocarbons containing small amounts of other constituents, readily available in large quantities, inexpensive, easy to transport and store, would appear to be the almost ideal source of raw material for oil production. conversion to the desired olefin.



  Ethylene and propylene are produced to some extent as a byproduct of thermal and catalytic cracking of petroleum oils in gasoline refineries. However, the concentrations of ethylene and propylene in the petroleum gases constituting this by-product are low and require expensive separation to provide the high purity olefinic gases required in the manufacture of chemicals. Likewise, the difficulty of transporting and storing these gases limits their usefulness and increases their cost price.

   Ethylene has been made from ethyl alcohol, an expensive raw material, and also from gaseous hydrocarbons, but the latter process is limited by the fact that the operation is only economical. 'on a very large scale involving an investment of many millions in equipment and the continuous daily processing of hundreds of thousand cubic meters of gas. In practice, such operations are limited to a location near a large and continuous source of gaseous hydrocarbons and, perhaps more importantly, chemists using the ethylene produced by such a plant are forced - owing to the difficulty and expense of shipping - to build and operate their chemical plants very close to the source of ethylene.

   In addition, the chemical manufacturer depends for its supply of ethylene from a single large supplier, since a particular chemical manufacturer does not ordinarily require the vast quantities of ethylene produced by a manufacturer. such group.



   It has long been known in the art that the application of heat to liquid petroleum oils transforms these liquid oils into hydro-

 <Desc / Clms Page number 2>

 gaseous carbides suitable for use as gaseous fuel. Efficient processes for the manufacture of fuel gas in a cyclic thermal regenerative system are illustrated in U.S. Patents.



    2,605,176 and 2,605,177. The art has also recognized that the gases resulting from the decomposition of liquid hydrocarbons contain a certain amount of ethylene and propylene and sporadic attempts have been made to use these cyclic thermal regenerative processes for the production of ethylene. and propylene, but without significant commercial success.



   One of the objects of the present invention is to provide an efficient process for converting hydrocarbon oils into high yields of ethylene and propylene. Another object is to provide a process for economically converting petroleum oils to gaseous olefins at relatively low flow rates, in an operation which can be easily suspended and started, and in a material representing a relatively low capital outlay. Other objects and advantages of the present invention will become apparent from the description which follows and from the accompanying drawing.



   The present invention is particularly aimed at the manufacture of valuable unsaturated products from liquid petroleum hydrocarbons in a cyclic recirculating thermal regenerator system.



   In the conventional method of pyrolytic decomposition of oil in a cyclic thermal regenerator system in order to obtain mainly non-condensable fuel gas, the regenerator is heated up to the cracking temperature by "pulling" ( blasting), that is, by introducing air and fuel oil into the system where the oil is burnt and passing through the system the combustion gases obtained to achieve a heat transfer to the refractory products contained in the system, and then by "making", that is to say by introducing the manufacturing oil into the system where it decomposes and simultaneously introducing water vapor into the system for propelling the pyrolytic decomposition products through said system.

   In good practice, this amount of water vapor was kept to a minimum just sufficient to move the reaction products through the system because the water vapor tended to slow the rate of the reaction. cracking and also increase the cost of the operation.

   The reaction products varied slightly depending on the nature of the oil charged and the operating conditions, but generally produced a gas containing on average about 18 mole percent ethylene and about 6% propylene. And higher unsaturated products. , totaling 24 mole percent ethylene and propylene and higher unsaturated products; or, based on the manufacturing oil loaded into the system, they gave about 25% by weight of ethylene and propylene and higher unsaturated products.



   The value of the thermal regenerative pyrolytic process as a producer of chemicals from low quality oil depends to a large extent on the yield of valuable ethylene and propylene and any increase in this area enhances the value of the process. After extensive experiments in a thermal regenerator apparatus of industrial dimensions, the Applicant has found it possible to increase the quantity of ethylene and of higher unsaturated products in the gas by about 35%, that is to say. say to produce about 24 mole percent ethylene in the gas and about 11% propylene and higher unsaturated products, totaling about 35 mole percent, which on the basis of the oil loaded into the system, is equal to a yield of about 33% by weight of unsaturated and aromatic carburized products.

   Unsaturated products-compre-

 <Desc / Clms Page number 3>

 including butylene, isobutylene, butadiene, acetylene and aromatic carbides - represent about 3-5%. In addition to the gaseous hydrocarbons, liquid hydrocarbons are recovered, in the form of a light oil and a tar, in an amount equivalent to approximately 30% by volume of the feed oil and in which the light oil represents about 20% of the liquid recovered, while tar represents about 80%. This light oil is a very interesting product consisting mainly of aromatic carbides with predominance of benzene, toluene and xylene.

   The recovered tar does not have the usual characteristics of tar from oil cracking for the production of gasoline, but it does have the characteristics of coal tar - of which there is now insufficient supply - and it can be used. for the many uses of coal tar, i.e. as a saturant, for the production of activated carbon, carbon electrodes, special arms, etc. for which petroleum tars are not suitable.



  The remaining products, called waste gases and composed mainly of hydrogen and methane with a small amount of upper paraffins, can be advantageously burned as fuel.



   In the course of its research for the production of increased yields of interesting products by the pyrolytic decomposition of petroleum hydrocarbons in a cyclic regenerative system with alternating circulation, the Applicant has discovered that the presumed inert water vapor had, when used in excess of the amount considered suitable in the prior art, a profound influence on the yield and quality of reaction products, increasing the yield of ethylene and propylene and higher unsaturated products of 'about 35% compared to the conventional technique and giving a valuable light aromatic liquid oil and an interesting tar having the characteristics of coal tar.

   The amount of water vapor to be employed in the process of the present invention is in the range of 0.25 to 0.4 kg of water vapor per liter of feed oil, preferably in the range of. the interval of 0.28 to 0.32 Kgs of water vapor per liter of feed oil. In conventional practice, with thermal regenerative systems of this type, the quantity of water vapor seldom exceeds much more than 0.5 kg. Per liter of charge oil. Although she cannot explain why this large amount of water vapor exerts such a great influence on the yields and types of products, the applicant believes that this large amount of water vapor acts as a catalyst rather. as a reactant to induce selective cracking of the oil.

   In any case, she has found that water vapor is not inert or detrimental to the reaction, but on the contrary extremely beneficial, in that it controls the reaction to selectively produce high yields of the unsaturated compounds. desired.



   There is a possible explanation for how the use of water vapor in the correct proportion increases the concentration of ethylene (and other desirable unsaturated products) in manufacturing gases. It is commonly believed that, in the mechanism of the vapor phase cracking of hydrocarbons, the first stage is the breaking of carbon-carbon and carbon-hydrogen bonds to form free radicals consisting of species with one and two carbon atoms. These free radicals then combine or convert to ethylene and other olefins. If carefully controlled conditions - in particular an appropriate concentration of water vapor - are not maintained these olefins are hydrogenated to paraffins, the final stage being hydrogenation to methane.

   It is evident that the preferred conditions provided by the present invention hamper the hydrogenation phase and leave good yields of product.

 <Desc / Clms Page number 4>

 desirable unsaturated milk.



   Another explanation is that the proper amount of water vapor helps to establish the thermal current and balanced temperature gradients giving the maximum yield of desired chemicals. It is known that irregular heating of the beehive brick or any reversal of the temperature gradient in this brick results in unevenly cracked tar, which gives poor chemical results and difficulties in handling the tar as a result of
 EMI4.1
 elution formation.



   In accordance with the present invention normally liquid oils can be converted to high yields of normally gaseous hydrocarbons, in particular ethylene and propylene, and valuable aromatic oils and liquid tars, by heating two interconnecting chambers - each containing a heat storage refractory material - up to a cracking temperature in the range of about 732-1.093 C.

   and preferably 787-871 C., by passing through said hot combustion gas chambers, introducing oil at one end of said heated chambers and simultaneously introducing water vapor in an amount of 0.25 to 0.4 Kgs and preferably 0.28 to 0.32 Kgs per liter of oil in direct contact with said oil undergoing vaporization and partial conversion, by passing the partially converted oil and water vapor from the first chamber into and through a second heated chamber to complete the conversion and discharging from this second chamber the reaction products obtained.



   According to the appended drawing which shows a preferred embodiment of an apparatus for carrying out the invention, the air entering through line 1 flows through lines 2 and 3 through the burner ¯ 4 in the fixing chamber 5 where it burns the fuel entering through line ¯6 and passing through the burner 4 into said chamber 5, thus generating hot combustion gases which flow upwards through the reactor vacuum 7, the transverse passage 8, then downwards through the empty reactor 9, the fixing chamber 11 and the beehive brick 12 which the latter contains.

   This passage of hot combustion gases through the system, called "blasting", heats the refractory interior lining in the reactors and the fixing chamber to a temperature of about 732-10093 C. preferably in the range of 787-871 Co, the latter temperature range being about 37-93 ° C lower than that ordinarily employed in the conventional process for the conversion of oil to fuel gases. The combustion gases escape from the bottom of the fixing chamber 12 through the duct 13, rise through the lifting pipe 14 and exit at the top of this pipe into the chimney 15.

   The chimney valve 16 is held open during this "firing" period as the combustion gases rise through the riser pipe 14 and the twin chimney valve 17 is held in the closed position during this same period to cause the flue to flow. Hot combustion gases to descend through the reaction chamber 9 and the fixing chamber 11. If desired, additional heat can be imparted to the system, in particular to the fixing chamber ¯Il and to the beehive brick it contains, by the introduction of fuel and additional air entering through pipes 18 and 19 respectively and. discharging through the burner 21 into the fixing chamber 11.



   The apparatus for converting petroleum oils to unsaturated gaseous hydrocarbons may be analogous to that employed in the manufacture of high BTU fuel gases consisting of metal shells.

 <Desc / Clms Page number 5>

 twin pipes 22 and 23 joined at their tops by a transverse duct 8 which also has a metallic exterior wall 24. The shells 22 and 23 and the transverse duct 8 are lined on the inside with refractory brick, tile or other suitable refractory material. , refractory interior lining which absorbs heat and also protects the metal shell from the direct impact of hot gases.

   The shell 22 is divided into two sections, an empty upper reactor and a lower preheating or fixing chamber 5 containing beehive brick 25 to help store and lose heat. The shell 23 is similarly divided into an upper empty reaction chamber ± and a lower fixing chamber 11 containing beehive brick 12. The two sections in each shell 22 and 23 are preferably divided by orifices. 26 and 27 which help to mix the gases and impart high velocity to the gases entering the bottom of the reactors.

   Starting from the bottom of the fixing chamber 11 are the refractory pipe 13 and the vertical riser pipe 14 fitted with the flue valve 16 from which, when open, the combustion gases escape into the flue. 15. In the same way, the pipe 28 starts from the bottom of the fixing chamber 5 and connects to the lifting pipe 29 provided with the flue valve 17 and provided with the chimney 31o. The air entering through the pipe 1 can be sent by line ¯2 in the lifting pipe 29 or by the line ¯3 and the burner 4 in the clamping chamber 5 or by the line 32 in the lifting pipe 14 or by the line 19 and the burner 21 in the fixing chamber 11, or alternatively follow any combination of the above routes.

   The water vapor can be injected during the reaction, or, in order to purge through the line 33 in the lifting pipe 29 or else through the line 34 in the lifting pipe 14. The feed oil is introduced into the pipes. reactors 7 and 9 by oil sprayers 35 and 36 respectively, to aid in the atomization of the incoming feed oil. A conventional reversing valve 37, a bar kicker 38, a seal pot 39 and a gas outlet 41 are installed to receive the reaction products discharging from the riser pipe 14 through the conduit 42 or else from the riser pipe 29. through conduit 43.



   Once the device has been heated to cracking temperature by burning '. the oil entering through line 6 with the air entering through line 3 into chamber 5 by passing the hot combustion gases upwards through the reactor 7, the transverse pipe 8 and downwards through the reactor 9 and the fixing chamber or regenerator 11 and the beehive brick 12 therein, it is good to purge the system with water vapor entering through the nozzle 33, descending into the Elevator pipe 29, ascending into chambers 5 and 7, passing through transverse pipe 8, descending into chambers 9 and 11, and ascending into elevator pipe 14 to discharge through open valve 16.

   The inner liner of the riser pipe 29 and the beehive brick 25 can be heated at the start of the operation by a "shot" of combustion gas in the opposite direction, i.e. from the right to the left; To minimize the dilution of the reaction products by the flue gases, the reaction period for the conversion of the feed oil may merge with the purge period by continuing the flow of steam from the feed oil. water down through the riser pipe 29 where it is preheated by the refractory inner lining and from there through the conduit, 28 into the bottom of chamber 5, up through the hot beehive brick 25 where the steam d the water is superheated, then continues to flow upwards through the orifice 26 in the bottom of the empty reactor 7,

     The feed oil for this process can be any normally liquid hydrocarbon oil having a density as low as 7.5 A.P.I. at 45 AoPoI. or higher.The process may use oil

 <Desc / Clms Page number 6>

 heavy residual of poor quality when steam is used in the preferred ratio, thus allowing significant savings
The feed oil is sprayed through nozzle 35 against the flow of the rising water vapor in chamber 7, which achieves substantially complete vaporization of the entering feed oil. partial conversion of this oil into gaseous olefins.



  As repeated several times, it is important to carry out the conversion of the oil in the presence of a large amount of water vapor, that is to say an amount in the range of 33 to 65 %, and preferably in the range of 35-45% water vapor by weight based on the feed oil undergoing conversion. Water vapor in an amount of substantially less than 33% by weight of the feed oil causes material loss in yield of the valuable ethylene and propylene and fairly high carbon losses overall. An insufficient amount of steam results in an excessive residence time in the regenerators (fixing chambers) giving too much cracked tar.



  Steam in an amount much in excess of 65% by weight of the feed oil does not increase the yield of olefins and on the contrary is a disadvantage causing loss of capacity, insufficient cracking. , difficulty in maintaining a high temperature and increased operating costs. Too high a steam to oil ratio requires excessively high temperatures to achieve the proper depth of cracking for the production of gases containing high percentages of ethylene and higher unsaturated products.

   The partially converted oil vapor and water vapor are sent downward, via the cross pipe 8, into the reaction chamber 9 and the fixing chamber 12 where the conversion of the oil vapors is completed to give a maximum yield of gaseous unsaturated olefins. The reaction products are discharged from the bottom of the chamber 12 through the conduit 13 and the riser pipe 14 and from there through the discharge line 2 and the reversal valve 37 conventional in the conventional bubbler 38 and final- This is also achieved through the gas outlet 41 to conventional absorption and fractionation systems for the separation of the gas mixture into its individual gaseous components.

   Although this is not a preferred method of operation, the feed oil can be divided between chambers 7 and 9, a significant portion of this feed oil entering through the nozzle. 35 and a small portion penetrating through the nozzle 36.



   At the end of the conversion period, the introduction of feed oil through nozzles 35 and 36 is stopped, but the circulation of water vapor entering through line 33 is continued, with the double aim of to expel the reaction products contained in the system through line 42 and to recover them, and also to purge the system before the introduction of air during the heating period, which minimizes the risk of explosion. Heretofore, a heating or "firing" period has been described followed by a purge period to remove combustible gases from the system. In these operations, traffic is one-way from left to right and only constitutes a half cycle. To complete this cycle, the same series of operations is performed in reverse circulation, that is to say from right to left.

   More specifically, the reverse heating period is achieved by introducing air through lines 1, 32 and 19 and the burner 21 where it oxidizes the heating oil entering through line 18 to generate combustion gases. heat which flow upward through chamber 12, reactor 9 and cross pipe 8 and downward through chambers 7 and 5 heating the refractory interior lining and beehive brick therein. find.

   In the preferred method of performing the opera-

 <Desc / Clms Page number 7>

 tion of "firing" or heating, the applicant has found that it was good to divide the air flow by passing part of this air through line 19 and part through line ¯3¯, with little or no air passing through line 32, then down through riser pipe 14 and up through beehive brick 12, because the passage of a significant part of the air in riser pipe 14 and through the beehive brick 12 causes excessive cooling of the beehive brick 12 with a consequent lowering of the temperature - particularly at the bottom - and a greater temperature differential between this beehive brick and the reactor.

   By reducing the amount of air sent through the beehive brick 12 during the heating period and dividing the amount of air between chambers 11 and 5, it is possible to achieve more uniform temperatures in the section. beehive brick and a smaller temperature differential between this beehive brick and the superimposed reactor.



   In the reverse purge period, the water vapor entering through line 34 descends through lifting pipe 14, passes through connecting conduit 139 rises through chambers 12 and 9, passes through transverse conduit 8, descends through chambers 7 and 5 and is evacuated at their bottom through line 28 and elevator pipe 29 in chimney 31, thus expelling the combustion gases contained in the system.



  Before the start of the reverse period of manufacture, the chimney valve 17 is closed, the reversing valve connected to the pipe 43 is opened, and the feed oil is then introduced through the sprayer. 36 countercurrently with the continuing flow of superheated water vapor rising through beehive brick 12 into fixing chamber 11 and thence through port 27 to the top of reactor 23.



  The reaction products then descend through the cross line 8 through the reactor 7 and the fixing chamber 5 where the conversion of the oil is completed, and the resulting reaction products flow upward through the lifting pipe 29. and evacuate through line 43.



  The flow of feed oil to the sprayer 36 is stopped, but the circulation of water vapor is continued, thereby purging the system of combustible gases and completing a complete cycle. The operation is then repeated starting with the heating period with circulation from left to right, i.e. going up through chambers 5 and 7 and down through chambers 9 and there * A cycle can be completed in about 5-10 minutes, with a little less than half of this time devoted to heating the equipment and a little less than half to carrying out the oil conversion, the rest of the cycle time being taken by the system purge.



   Another method of operation which emphasizes the advantages to be derived from the preferable water vapor / oil ratio, which is higher than normal in fuel gas technology, is to operate in reverse after the heating operation or "shoot". This results in higher temperature water vapor during the manufacturing process, because the beehives have just been heated by the combustion gases.

   This way of operating can also decrease the severity of cracking at a given control temperature, because the beehive bricks have been soaked in some way by the passage of manufacturing steam before being used during processing. manufacture for heat recovery, gas extinction and gas scavenging, and that a suitable uniform temperature gradient is established in said bricks. However, the present invention is not limited to any particular cycle of operations and may operate in the order of "shoot", make, reverse, instead of cycle; manufacture, "shooting", inversion which has just been described.

 <Desc / Clms Page number 8>

 



   The examples which follow illustrate a method of carrying out the present invention.



   Petroleum oil is converted to saturated hydrocarbons in a recirculating thermal regenerative system, in an apparatus substantially as shown in the drawing and whose twin hulls 22 and 23 are each 396 centimeters in diameter and 10,586 centimeters in height. . The cycle consists of a heating period, a purge period to remove flue gases, a conversion period and a purge period to remove flue gases, followed by reverse periods of heating, purge to remove gases. combustion, conversion and purging to remove flue gases. Each cycle takes seven and a half minutes.

   The data and corresponding results of the operation are summarized below.
Characteristics of the oil used
 EMI8.1
 
<tb> Specific <SEP> weight <SEP> 0.9492
<tb>
<tb>
<tb>
<tb> Carbon <SEP> Conradson <SEP> - <SEP> Percentage <SEP> 6.2
<tb>
<tb>
<tb>
<tb> Thermal <SEP> data <SEP> - <SEP> 180900
<tb>
<tb>
<tb>
<tb> Carbon / hydrogen <SEP> ratio <SEP> 7.6
<tb>
<tb>
<tb>
<tb>
<tb> Temperature <SEP> of <SEP> distillation <SEP> - <SEP> <SEP> C <SEP>
<tb>
<tb>
<tb>
<tb>
<tb> a <SEP> third party <SEP> to <SEP> above <SEP> 368
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> <SEP> conditions for <SEP> gasification
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Cycles <SEP> per <SEP> hour <SEP> 8
<tb>
<tb>
<tb>
<tb>
<tb> Oil <SEP> from <SEP> manufacturing <SEP>:

   <SEP> liters <SEP> per <SEP> cycle <SEP> 1.444
<tb>
<tb>
<tb>
<tb>
<tb> liters <SEP> per <SEP> minute <SEP> 643
<tb>
<tb>
<tb>
<tb>
<tb> Temperature <SEP> C <SEP> 153
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Oil <SEP> for <SEP> heating <SEP>: <SEP> Liters <SEP> per <SEP> cycle <SEP> 116
<tb>
<tb>
<tb>
<tb>
<tb> temperature <SEP> @ <SEP> C.

   <SEP> 152
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Water vapor <SEP> <SEP> from <SEP> manufacturing <SEP> s
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Kilogs <SEP> per <SEP> minute <SEP> 167.2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Water vapor <SEP> <SEP> atomization <SEP> - <SEP>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Kilogs <SEP> per <SEP> minute <SEP> 20.1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Steam <SEP> of water <SEP> total <SEP> to <SEP> the <SEP> manufacture
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Kilogs <SEP> per <SEP> minute <SEP> 188,

  2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Kilogs <SEP> per <SEP> liter <SEP> of oil <SEP> from <SEP> manufacture <SEP> 29
<tb>
<tb>
<tb>
<tb>
<tb> Temperature <SEP> steam <SEP> of water <SEP> of <SEP> manufacturing <SEP> <SEP> C <SEP> 785
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Air <SEP> main <SEP> -meters <SEP> cubes <SEP> per <SEP> minute <SEP> 270
<tb>
<tb>
<tb>
<tb>
<tb> Air <SEP> burner <SEP> - cubic <SEP> meters <SEP> per <SEP> minute <SEP> 330
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Temperature <SEP> in <SEP> high <SEP> of the <SEP> bricks <SEP> of <SEP> ruchage
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> maximum <SEP> average <SEP> <SEP> C. <SEP> 871
<tb>
<tb>
<tb>
<tb>
<tb> minimum <SEP> medium <SEP> <SEP> C.

   <SEP> 753
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Analysis <SEP> of <SEP> gases <SEP> - <SEP> Molar percentage <SEP> <SEP> -
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ethylene <SEP> 23.8
<tb>
<tb>
<tb>
<tb>
<tb> Propylene <SEP> and <SEP> olefins <SEP> higher <SEP> Il, 4
<tb>
<tb>
<tb>
<tb> Isobutylene <SEP> 1.8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Aromatic <SEP> carbides <SEP> 0.9
<tb>
<tb>
<tb>
<tb> Acetylene <SEP> 0.9
<tb>
 

 <Desc / Clms Page number 9>

 
 EMI9.1
 
<tb> Total <SEP> of <SEP> constituents <SEP> above <SEP> or
<tb>
<tb>
<tb>
<tb> "unsaturated <SEP> hydrocarbon <SEP> gas" <SEP> 38.8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Hydrogen <SEP> 14.9
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Methane <SEP> 30.3
<tb>
<tb>
<tb>
<tb>
<tb> Ethane <SEP> 4,

  8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Methane <SEP> and <SEP> ethane <SEP> (or <SEP> total <SEP> of <SEP> paraffins) <SEP> 35.1
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Carbon dioxide <SEP> <SEP> 3.0
<tb>
<tb>
<tb>
<tb>
<tb> Oxygen <SEP> 0.3
<tb>
<tb>
<tb>
<tb>
<tb> Oxide <SEP> of <SEP> carbon <SEP> 1.4
<tb>
<tb>
<tb>
<tb>
<tb> Nitrogen <SEP> 6.5
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Total <SEP> CO2 <SEP> + <SEP> 02 <SEP> + <SEP> CO <SEP> + <SEP> N2 <SEP> Il, 2
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Percentage <SEP> of <SEP> true <SEP> gas <SEP> of oil <SEP> 88,

  8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Btu <SEP> per <SEP> dm3 <SEP> of <SEP> gas <SEP> total <SEP> 41
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Btu <SEP> per <SEP> dm3 <SEP> of <SEP> true <SEP> gas <SEP> of oil <SEP> 46
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Substances <SEP> by <SEP> MCF <SEP> of
<tb>
<tb>
<tb>
<tb>
<tb> "Unsaturated <SEP> hydrocarbon <SEP> gas"
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Btu <SEP> by <SEP> dm3 <SEP> of <SEP> "unsaturated <SEP> products" <SEP> 66
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Oil <SEP> from <SEP> manufacturing <SEP> - <SEP> Liters <SEP> 170
<tb>
<tb>
<tb>
<tb>
<tb> Heating <SEP> oil <SEP> <SEP> - <SEP> Liters <SEP> 17
<tb>
<tb>
<tb>
<tb> Oil <SEP> total <SEP> - <SEP> Liters <SEP> 186
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Light <SEP> oil <SEP> recovered <SEP> - <SEP> Liters <SEP> 10,

  4
<tb>
<tb>
<tb>
<tb>
<tb> Tar <SEP> product <SEP> - <SEP> Liters <SEP> 40.3
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Total <SEP> of <SEP> hydrocarbons <SEP> liquid <SEP> recovered
<tb>
<tb>
<tb>
<tb>
<tb> liters <SEP> 49.7
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Hydrocarbons <SEP> liquids <SEP> employed, <SEP> net-
<tb>
<tb>
<tb>
<tb>
<tb> Liters <SEP> 136.8
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Yields <SEP> per <SEP> liter <SEP> of <SEP> oil from <SEP> manufacture
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Ethylene <SEP> - <SEP> Kilogs <SEP> 0.118
<tb>
<tb>
<tb>
<tb>
<tb> Propylene <SEP> and <SEP> olefins <SEP> higher <SEP> 0.097
<tb>
<tb>
<tb>
<tb> Isobutylene <SEP> 0.018
<tb>
<tb>
<tb>
<tb>
<tb> Aromatic <SEP> carbides <SEP> 0.013
<tb>
<tb>
<tb>
<tb>
<tb> Acetylenes <SEP> 0,

  006
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Total <SEP> of <SEP> constituents <SEP> above
<tb>
<tb>
<tb>
<tb>
<tb> ("Gas <SEP> hydrocarbon <SEP> unsaturated") <SEP> Kilogs <SEP> 0.252
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb>
<tb> Light <SEP> oil <SEP> recovered <SEP> - <SEP> Liters <SEP> 0.27
<tb>
<tb>
<tb>
<tb>
<tb> Tar <SEP> obtained <SEP> - <SEP> Liters <SEP> 1.03
<tb>
<tb>
<tb>
<tb>
<tb> Fuel <SEP> value <SEP> from <SEP> methane, <SEP> from <SEP> ethane
<tb>
<tb>
<tb>
<tb>
<tb> of <SEP> hydrogen <SEP> and <SEP> of <SEP> oxide <SEP> of <SEP> carbon
<tb>
<tb>
<tb>
<tb>
<tb> Thermies <SEP> 0.297
<tb>
 
Although some preferred embodiments of the invention have been set forth for illustrative purposes,

   it is evident that various changes and modifications can be made thereto without departing from the scope and spirit of said invention.


    

Claims (1)

CLAIMS. 1. A process for the conversion of normally liquid hydrocarbon oils to high yields of normally gaseous unsaturated hydrocarbons, in particular ethylene, propylene and upper unsaturated products, and valuable aromatic oils and liquid tars. ceded of the type in which two communicating chambers are heated, each containing a refractory heat storage material, up to one EMI10.1 temperature ': # of ciacking- ompise in -1 '. interval. of about 1359 r. 12095 OC. by passing through said hot combustion gas chambers and the normally liquid hydrocarbon oil is introduced into one of the heated chambers, characterized in that, simultaneously, water vapor is introduced in an amount of 1.1 - 1.5 kilograms of water vapor per 4 liters of oil, in direct contact with the oil undergoing vaporization and partial conversion in the heated chamber, in that the partially converted oil and water vapor from the first chamber into and through the second heated chamber so as to complete the conversion, in that the obtained reaction products are discharged from the second chamber and in that valuable normally gaseous unsaturated hydrocarbons and aromatic oils and liquid tars are recovered. 2.- Method according to claim 1, characterized in that the cracking temperature is between 7900 and 8700 Co and the water vapor is introduced in the ratio of 1.25 to 1.45 kilograms for 4 liters of 'oil; 3.- Method according to claims 1 and 2, characterized in that the respective chambers are each divided into a lower portion containing a heat storage refractory material and an empty upper portion coated with refractory material, these portions being interconnected by a narrowed opening situated between them, in that fuel is burnt with air in the lower part of the first chamber, in that the hot gases are passed through the corresponding empty upper part to the other upper empty part and the other lower part of the second chamber and in that they are evacuated until that the temperature is reached, by passing water vapor in the same direction and in the same order so as to purge these combustion gases, by passing the oil through the upper part of the first chamber and simultaneously water vapor through the refractory material in the lower part of the first chamber and in its upper part where it mixes with the vaporized oil, in the proportion of 1 , 1 to 1.5 kilograms of water vapor per 4 liters of oil, in that the partially concealed oil is passed. vertie and water vapor from the empty upper part of the chamber into and through the upper and lower parts of the second chamber, the system being purged with water vapor and the above phases being repeated in direction reverse, the fuel burning in the lower part of the second chamber and all combustion gases, water vapor and oil vapors passing through the chambers and out in the same succession, but into the reverse order of the chambers to that indicated above, thus completing a two-stroke cycle. 4.- Method according to claim 3, characterized in that, after having passed the initial combustion gases in succession through the lower and upper parts of the first chamber and the upper and lower parts of the second chamber in order and after purging with water vapor, the oil is introduced into the upper part and the vapor into the lower part of the second chamber, and the va- <Desc / Clms Page number 11> fear of water and reacting gases pass in reverse order through the upper part of the second and the first chamber and are discharged through the lower part of the first chamber - so as to complete the first half cycle, the second water vapor purge is performed, and the second half-cycle comprises burning fuel in the lower part of the second chamber, passing hot combustion gases through the corresponding upper part, through the upper and lower parts of the first chamber and there their evacuation, in that one makes another purge with water vapor and the same phases are repeated in the same succession, but in the reverse order of the chambers, the fuel is burnt with air in the lower part of the second chamber, the combustion gases are sent through the upper part of the second chamber, the upper and lower parts of the first chamber are discharged from this last lower part, the system is purged with water vapor, oil and water vapor are introduced, respectively in the upper part and in the lower part of the first chamber, are sent through the upper and lower parts of the second chamber and are discharged from the latter part, and the system is purged with water vapor, completing thus a two-stroke cycle.