US2931765A - Process and apparatus for treating petroleum oils and solid fuels - Google Patents

Description

April 5, 1960 Filed Oct. 17, 1958 c. G LlNKA PROCESS AND APPARATUS FOR TREATING PETROLEUM OILS AND SOLID FUELS 4 Sheets-Sheet 1 Aprll 5, 1960 c. GLINKA 2,931,765

PROCESS AND APPARATUS FOR TREATING PETROLEUM OILS AND SOLID FUELS Filed Oct. 17, 1958 v 4 Sheets-Sheet 2 f" ll i H-H- III I I I I I E l l i hH-h'i' Inventor. 4a! WA .f. 119%.), A ffa April 5, 1960 2,931,765

C. GL INKA PROCESS AND APPARATUS FOR TREATING PETROLEUM OILS AND SOLID FUELS Filed 061;. 17, 1958 4 Sheets-Sheet 3 i'i' f'h i izifillhflfli t i IIHHH HI HHAHH M.

April 5, 1960 2,931,765

C. GLINKA PROCESS AND APPARATUS FOR TREATING PETROLEUM OILS AND SOLID FUELS Filed Oct. 17, 1958 4 Sheets-Sheet 4 cation of heat, such as oil shales or peat.

United States Patent PROCESS AND APPARAT US FOR TREATING PETROLEUM OILS AND SOLID FUELS The present invention relates to a process and apparatus for treating petroleum oils and solid fuels.

More particularly, this invention relates to a process for the treatment of petroleum oils which have a low content of low-boiling components, such as petroleum oils which accrue as the residue from the distillation of petroleum crudes at temperatures of between 250 and 400 C. The invention also relates to a process for the removal of water and preferably of bitumen from wet solid fuels, i.e. from solid fuels which contain water and which also contain substances convertible into bitumen by the appli- As will be seen further below, the treatment of such petroleum oils and of such solid fuels can be advantageously carried out in a single process and in a unitary apparatus.

It is frequently of great economic importance to reduce the molecular Weight of the hydrocarbons forming high boiling petroleum oils, so as to obtain high-grade lower molecular weight hydrocarbons. It is also of great economic importance to reduce o'reliminate the water content of water containing solid fuels prior to combustion of the fuel, and also to remove from the fuel bituminous substances which can be more economically utilized than would be the case by combustion as part of the solid fuel.

Various processes are known for the removal of water from, or the drying of, solid'water-containing fuels, and for the cracking, i.e. the reduction of the molecular weight of the constituents of high boiling petroleum oils, as well as for the extraction of bituminous substances'from solid fuel prior to utilization of the solid fuel as a source of heat.

However, all of these prio'r art methods for achieving one or the other of the above discussed results are relatively expensive, require a very high fixed investment, and are not capable of achieving all of the above results in a unitary process and apparatus.

In the context of the present application low boiling oils are understood to mean oils boiling at temperatures in the region below 250 C. The upper limit for oils regarded as low boiling within the meaning of the invention may depend upon various factors, such as the type of the crude, and especially the proportion of oils contained therein which boil above the specified limit, the processing method, and the final product required.

' Processes for refining such oils are already known which consist in converting the preheated oils into low boiling hydrocarbons whilst in contact with hot substances, especially substances known as catalysts. In these processes contacts which have no catalytic efiect merely serve as carrier means for the transfer of heat. Contacts which have a catalytic eftectfrequently employed in these processes in mixture with contacts that have no catalytic effect-favorably influence the process itself-for instance in that they permit the reaction temperature which in purely thermal processes may be about 600. C. to be ice reduced to say 500 C.as well as upon the yield, and the quality of the products obtained.

The efficiency of a catalyst depends to a considerable extent upon the size of its contacting surface. Lumpy catalysts of a porous nature have a very large surface. However, the surface formed by the pores is very inefiiciently utilized because the oil vapors evolved by the oil in contact with the hot catalyst cannot penetrate from the outside to'the interior and into the core of the catalyst since, when entering the pores of the very hot catalyst their temperature considerably rises, and they expand, the pressure set up expelling them again from the pores before they have penetrated into the catalyst very far. In practice use is therefore made of fine-grained or even dust-like catalysts. In any event, solid residues from the cracking reaction are soon deposited on the catalyst and reduce its catalytic efficiency: These deposits may be removed by a process of regeneration and the catalyst reheated again to its previous temperature. Nevertheless; repeated reheating causes catalytic efficiency to deterio: rate so that at certain intervals of time the catalyst must be renewed. V

It is, therefore, an object of the present invention to provide a simple and economical process and apparatus for the de-watering of water-containing solid fuels.

It is another object of the present invention to provide a simple and economical process and apparatus for the removal of bituminous substances from solid fuels con taining the same. A

It is a further object of the present invention to provide a simple and economical process and apparatus for refining, and for at least partially reducing the molecular weight of the constituents of petroleum oils containing only a relatively small fraction of low boiling constituents;

It is still another object of the present invention to provide a simple and economical process and apparatus for jo'intly achieving in a unitary manner two or all three of the objects described in the three immediately preceding paragraphs.

Other objects and advantages of the present invention will become apparent from a furtherreading of the description and the appended claims. 7

With the above and other objects in view, the present invention includes a process of treating a water-containing particulate solid carbonaceous fuel and a petroleum oil having a relatively low content of components boiling below 250 C. at normal pressure, comprising the steps of contacting the petroleum oil with the water-containing, particulate, solid carbonaceous fuel the same being ca pable to be partially converted into bitumen by application of heat, so as to form a mixture of the petroleum oil and the solid fuel, subjecting the mixture to a temperature of about 350 C. at an elevated pressure so chosen as to substantially prevent evaporation of oil from the mixture while allowing evaporation of water therefrom, thereby forming steam and filling pores ofthe solid' fuel with petroleum oil, withdrawing the thus :formed steam, raising the temperature of the thus; formed substantially water-free mixture to about 400 C. so asto convert a portion of the solid fuel into liquid bitumen, while maintaining a pressure sufficiently high to substantially prevent vaporization of the thus formed liquid bitumen, separating the oil-containing solid fuel from the remainder of the reaction mixture, subjecting the separated, oil-con,- taining solid fuel to a temperature of at least about 500 C. while maintaining a pressure of about between 0.5 and 5 atmospheres, so as to crack the oil within the pores of the solid fuel thereby transforming the oil at least partially into lower molecular hydrocarbons, and separating the thus fo'rmed lower molecular hydrocarbons from the solid fuel, whereby steam at relatively high pressure and temperature, a dry solid carbonaceous fuel biturnen and lower molecular hydrocarbons are formed from the petroleum oil and the water-containing carbonaceous Solid .f I. I; i J

The present invention also contemplates in anapparatus for simultaneously dewatering water-containing, solid, carbonaceous fuel,-and at least partially reducing the molecular-weight of higher-boiling petroleum oil and the like in combination, first reaction means for subjecting amixture of water-containing, carbonaceous, solid fuel and. petroleum oil to superatmospheric pressure and to an elevated temperature sufiiciently high to cause evaporation and steam formation of the water contained in the solid fuel while retaining the petroleum oil in unvolatilized condition, whereby petroleum oil will enter into the pores of the thus dewatered solid fuel, means for removing the formed steam from the first reaction means, hydrocyclone means operatively connected to and com municating with the first reaction means for separating free petroleum oil from the thus dewatered petroleum oil-containing solid fuel, conveying means communicating with the hydrocyclone means and with the first reaction means for conveying the free petroleum oil from the hydrocyclone means to the first reaction means, second reaction means operatively connected to the hydrocyclone means for receiving the dewatered petroleum oil-containing solid fuel and subjecting the same to a temperature sufiiciently high to cause at least partial transformation of the petroleum oil contained in the solid carbonaceous fuel into lower molecular hydrocarbons, and at a, pressuresuh'iciently low to volatilize the thusformed lower molecular weight hydrocarbons, and means operatively connected to the second reaction means for separating the thus-formed volatilized hydrocarbons and water-free, solid, carbonaceous fuel. I According to the invention it is proposed in the processing of the specified oils to replace such catalytically effective contact substances with solid fuels containing water and substances which are convertible at elevated temperature into bitumen. Such fuels are for example oil shales, brown coal, and peat. The treating oil is brought into contact with these fuels at a temperature at which, the bitumen produced by the solid fuel is liquid, but at pressures which are sufficiently high to prevent the bitumen from evaporating. However, the water contained in the solid fuels does evaporate and turn into steam which is removed. The treating oil now enters the pores in the solid fuel which had been previously filled with the water. The solid fuels are then separated from the remainder of the oil by mechanical means, for instance in a hydrocyclone, and at atmospheric pressure or a pressure which differs only slightly therefrom, for instance at a pressure between 0.5 and atmospheres, they are heated to a temperature, say 500 C. or more, at which the oil that has penetrated into the pores will be transformed into higher grade hydrocarbons by cracking. If desired, the water may be driven out of the pores of thesolid fuels before these are introduced into the oil, for example by previous desiccation until all their water has been expelled.

Fresh brown coal, peat, and oil shale all contain more or less appreciable quantities of water and bitumen-forming substances. By evaporating the water inside the pores a finely porous solid material results which has a very large surface of the kind synthetic catalysts are desired to have. 7

Analytical tests have disclosed that this finely solid material consists of silicic acid or of alumina, with oxides of iron, aluminum and magnesium embedded therein, in addition to traces of other elements, i.e. of substances which are known to have a catalytic effect.

It follows that when their water content has been evaporated and their bitumen-forming substances liquefied these solid fuels can serve as catalysts for processing oils. Their efficiency depends upon their content of catalytically active elements which may vary in quantity according to the natural deposits from which the fuels originate. On the average such solid fuels contain 10% oil and about 50 to water related to dry weight. The bitumen-forming substances contained in the fuels generally liquefy at temperatures of about 400 C. However, this liquid bitumen which has an oily consistency fillsonly a small proportion of the cavities in the fuels. Some of the treated oil enters the pores that had been filled with the water. After having been heated the pores of the fuels therefore contain an oily mixture consisting of the liquid. bitumen which is rich in hydrogen and the treated oil which contains little hydrogen. If now the solid fuels containing this oily mixture are separated from the remaining volume of oil and heated to about 500 C. under a pressure which permits the oils at this temperature to volatilize, then the oil that has penetrated into the pores will react with the liquid bitumen and form fresh compounds consisting of high-grade hydrocarbons.

The changes in the structure of the hydrocarbons that occur inside the pores of the solid'fuels proceed in conditions which in every respect favor the process of cracking. It may be assumed that the vaporized oil in the pores of the solid fuels is forced to travel through comparatively long channels, frequently changing its direction of flow, and that the buifeting it receives promotes the complete decomposition of the compounds which have already been loosened up by the high tempeartures that prevail.

Other conditions favoring the progress of the reaction are that the vapor that has been formed in the pores is in constant intimate contact with the embedded catalytically effective elements which present a large surface and that escape of the vapor from the system of pores is retarded by the frequent changes in its direction of flow.

In these excellentreaction conditions the high hydrogen content of the bitumens and of the oils and vapors which have already been formed and which evolve when the fuels are heated gives rise to the formation of high grade hydrocarbons without,the production of major quantities of solid carbon. In any event, any elementary carbon that does form will be deposited on the fuel. In the circumstances this has no disadvantageous effect, because the treated solid fuels pass only once through the process and the solid deposits are removed with the fuels.

Furthermore, it is important to note that the solid fuels have a comparatively high content of oxygen which in the temperature range of the process reacts with the carbon, and to some extent with the hydrogen. This is an exothermic reaction which at high temperatures proceeds at great speed so that the heat of reaction becomes fully available for promoting the process at the points where the solid fuels and the oil are required to have a temperature of about 500 C. and even higher. The heat liberated in these reactions is suificient not only to replace the consumption of heat by the endothermic cracking reaction but also to heat the fuels to the temperature level required for cracking.

The velocity of the reaction can be greatly accelerated by mixing the fuel at a temperature of about 400 C., before admitting it to the reactor, with a proportion of the fuel which leaves the reactor and which has already achieved a temperature of about 600 C. or even more. The oil-charged fuel will then rapidly attain a temperature of 500 C. or more, at which the exothermic and endothermic reactions proceed very quickly.

The reaction process may be performed in this way with especial advantage in cases in which the fuel employed has a low content of oxygen or of catalytically elfective components. I v

The oil vapor evolved in the process can be desulfurized with the aid of the treated fuels by cooling them after leavingthe process, submitting them to an ageing process by oxygenation to prevent self-ignition, and by-then contacting them with gases containing hydrogen sulfide. The hydrogen sulfide will then be adsorbed by the fuel and oxidized into sulfur which is then taken up by the fuel.

The gases thus purified can be used for refining the products of cracking.

In the described processing of residual oils functions are thus allocated to the solid fuels and to the liquid and gaseous components liberated therefrom which in existing plant are performed by products of which at least some must be produced in auxiliary plant. 1 In performing the method according tothe invention the possible advantage of controlling the course taken by the cracking reaction by the selection of the synthetic catalyst may be lost, but this advantage decreases materially in importance if localconditions are suitable for using the process, such as for instance the location of the solid fuels in relation to theoil, and the general nature of the solid fuels'that are available.

The method of the present invention permits exploitation of oil shale deposits which had hitherto been considered uneconomical to work, especially if the moisture content of the shale is fairly high and would consume a large proportion of the energy derived from the oil in evaporating the water.

Brown coal which, owing to its high content of water, has a low calorific value of only 2500 cal. is transformed into a high-grade fuel with a calorific value of about 7000 cal. by the ageing effect due to the withdrawal of oxygen and the removal of water during the process.

Peat can similarly be transformed into a high-grade low temperature carbonization coke.

Thus, besides high-grade hydrocarbons, the process yields valuable by-products.

The fact that two processes are combined into a unitary process l eads to a simplification of the entire plant and a consequent reduction in capital and maintenance cost.

Other advantages arise in connection with the thermal economy of the process. In this connection an important factor is the conversion of the moisture contained in the fuel into steam which is free from dust and leaves the process, free from oil vapor, at a pressure of about 30 atmospheres. In this condition it can be used in a power station of a capacity limited only by the volume of available steam, i.e. by the amount of water contained in the fuels, The high-pressure steam obtained without the use of a boiler should at least be sufiicient to generate all the power needed for operating the whole of the processing plant.

From the point of view of removing water and possibly bitumen from wet solid fuels, the present invention achieves the separation of the oil vapor of the steam evolved in the process in such a way that the steam will contain no oil and especially no oil vapors. Thus, a simple method of obtaining from the solid fuels an oil which contains absolutely no water is provided.

The heat contained in the vapors evolved in the process can be utilized for the generation of mechanical energy in an energy transforming plant, and more particularly, the steam which contains no oil and particularly no oil vapors can be used for the generation of mechanical energy in a conventional prime mover.

To this end the invention proposes to perform the process by treating the solid fuel in two consecutive temperature stages, namely in afirst treatment stage at a pressure above 12 atmospheres, for instance 30 atmospheres, performed at a temperature above the boiling point of water at the said pressure, and in a second stage at approximately the same pressure performed at atemperature above about 400 C. at which the bitumenforming substances will be released and the oils formed chamber.

being of a kind that will not begin to vaporize at the tem, perature or at the pressureused in the first stage. Y a 3 In the temperature range of the second stage exothermic reactions occur in the oxygen-carbon-hydrogen system of the solid fuels, which, as has been established by empirical tests, rapidly raise the temperature of the treating oil. This internal heating of the oil is an advantage for reasons of thermal economy. However, since it results in oil vapor formation the process proposed by the invention suppresses it in the stage in which the expulsion of the water takes place.

To permit the process to take full advantage of this internal heating effect of the treating oil Whilst at the same time in the stage in which the water contained in the solids evaporates definitely maintaining the temperature at ,a level at which the treating oil will not vaporize, the

invention divides the treatment of thesolid fuelsinto two separate temperature stages. In the first stagethei moisture contained in the solids is evaporated at a pressure such as 30 atmospheres and a temperature between say 250 and 350 C. conditions under which the treating oil will not form oil vapors. However, the steam re leased from the solids will'escape from the treating oil and can be withdrawn at the operational pressure of the plant. In the second stage the solid immersed in the oil is heated to about 400 C., a temperature at which the oil-forming substances in the solid will be released. These substances will change from the solid into the liquid state from which the light and middle oils can then escape in vapor form. The heavy oil fraction which has a boiling point equal to that of the treating oil remains in the solid fuel in liquid form and, after separation of the solids from the treating oil, this fraction will also be vaporized when the solids leave the operational pressure in the treating chamber'of 30 atmospheres and enter the lower pressure obtaining in a decompression In this second stage the exothermic reaction of the oxygen-carbon-hydrogen system of the solids can take full eifect. The heat absorbed by the oil may be usefully employed by returning the oil to the first stage.

Tests have shown that fuels with a higher content of moisture initially sink in the hot oil for a short period of time but then rise and float on the oil. This is due to the fact that the rapid increase in temperature causes intense evaporation of water in the pores of the particles of the fuel, giving rise to the formation of small bubbles. During their formation these bubbles adhere to the surface of the fuel and support it. As the generationof steam becomes less and fewer bubbles are formed the fuel sinks again in the treating oil.

' Allowance is made in the process of the present invention for the occurrence of this phenomenon in that the comminuted fuel is introduced into a-current of oil which circulates in a horizontal plane in this part of the plant. The smaller particles of fuel will then sink in the current of oil after having travelled a short distance along the circular path, whereas the larger ones travel a greater distance, and the largest ones circulate several times. They therefore enter the next' treating zone by the same route but at the end of different periods of dwell which depend upon the size of the particles. The treatment time may thus be adapted to grain size. In the following treating zone the oil travels frombelow in an upward direction at a velocity which transcends the sinking speed of the largest particles of-the fuel' so that the entrainment of the whole of the fuel will be assured. The particles of fuel are therefore conveyed up wards freely suspended in the current of oil, the period of dwell of the particles in the current of oil depending upon the size of the particles.

If it is desired to treat fresh peat by the process that has been described it must be remembered that the moisture content of wet peat amounts to something like by .the bitumen vaporize, the oil employed for this process .75 of its weight. It will therefore usually b e necessary to "enemas remove the greater part of the water prior to the processing of the peat. This may be effected by heating the peat under pressure to a temperature of about 180 C. At this temperature the major proportion of the colloidally bound water is released and can then be separated from the peat by mechanical means. The preliminary dewatering of the peat.can be combined advantageously with the main features of the present process. The crude peat .is pumped in a macerated condition from the bog to the plant and there passed through a treatment in a zone in which water iscirculated instead of oil at the operational pressure of the plant. At a pressure of f.i. 30 atmospheres, the water-peat mixture can be heated to 180 C. without the evolution of any substantial volume of steam since the boiling point of water at this pressure is at about 232 C. The small volume of steam and gas thatis formed in the course of this heating can be utiliied in the process. At the operational pressure. of the plarit the peat is. separated from the surplus waterand, together with the heat absorbed during this treatment, it is directly transferred to the process according to the invention. The surplus water whichis still at the operational pressure of the plant gives off its heat to the water-peat mixture that is pumped into the plant and may then be used for the wet excavation of the peat and for. washing it into the excavated bog in a .manner that is well understood.

..The novel features which are considered as characteristic for the invention are set forth in particular in the appended claims. The invention itself, however, both as to its construction and its method of operation, together with additional objects and advantages thereof, will .be best understood from the following description ofspecific. embodiments when read in connection with the. accompanying drawings, in which: I

, Fig. 1 is a schematic representation of plant for processing a residual oil with the aid of a previously dewateredbrowncoal; 3 r V Fig. 2 diagrammatically illustrates the course of the brown coal throughthe reactor;

Fig. 3 is a schematic representation of plant for the treatment of a residual oil with the aid of a brown coal which still contains water; r

Fig. 4 shows a plantfor dewatering said fuel, operating in two temperature stages; in the first stage the water and in the second stage those substances are removed which can be transformed by heating into oil or oily bitumen; and V Fig. 5 shows a plant for treating fresh peat. The apparatus illustrated in Fig. 1 comprises a riser pipe 7 of sufficient diameter to permit major quantities of lumpy solid material to be entrained by an ascending column of oil. The diameter of the pipe may be say 30 cms. and its height 600 cms. to deal with a through put or 2000 kg./h. At the foot of the riser 7 is a pipe 8 through which the oil enters the riser after having been pumped through the coil 10 ofa heater. 26 by pump means 9. The head of the riser 7 is connected with a container 11 fitted at the top with a steam outlet 12 and connected at the bottom with a pipe 13 which may have a diameter of perhaps 10 cms., and which leads to a hydroclone 14. I The liquid is discharged from the hydroclone 14 through a pipe 25 and returned to the suction side of pump 9. The oil is thus circulated by pump 9 through the riser pipe 7 and the pipelines .13, 25, 10 and 8. Thelower end ofriser pipe -7 is also v"connected with several pipes 6 which are all jointed at .the top into a common pipe ring 5. Another pipe 4 connects this ring with the coil 3 of a heater 27 which receives oil througha pipe 2 incorporating a pump 28. Pipe 4 contains a gate '1 through which comminuted solid fuel such as peat, oil shale, or brown coal, can enter pipe 4 in which the flowing oil is under a pressure of several atmospheresfor instance 30 atmospheres.

The,. dischargev of the solids from hydroclone is through a trap 15 through which the solid substances separated in the hydroclone which operatesat the above mentioned pressure of 30 atmospheres can be gated into a chamber 16, the reactor proper, in which a much lower pressure, for instance 0.5 atmosphere, is maintained. Rotatably arranged inside the rigid shell of the reactor 16 is a system comprising a plurality of annular plates 18 arranged one-above the other and provided with peripheral gaps 21 (Fig. 2) which are relatively angularly displaced from one plate to the next. The plates 18 therefore actually consist of annular segments. The annular segments 19 (Fig. 2) which constitute the top plate are therefore angularly displaced in relation to the annular segments 22 of the next plate below in such manner that the major proportion of solid material 17 dropping into the reactor through trap 15 will be intercepted by the segments 19 and the smaller remainder by segments 22. A stationary scraper 20 is arranged above each ofthe plates 18 so that when the plates 18 are rotated the solid fuel deposited on one of the segments will be dislodged and finally reach an outlet 23 at the foot of the reactor 16. This arrangement prolongs the dwellof the fuel inside the reactor. The lower portion 'of the reactor 16 is provided with a second shell 24.

The gases can rise in the gap between the two shells to be withdrawn. I

In this apparatus the process is performed as follows:

Through pipe 2 as much oil (oil residue) is pumped into the apparatus as is required to fill the tubes and pipes 6, 7, 8, 13, 25, and 10 completely. As it passes through the heater 27 the oil asumes a temperature of about 400 C., the pump generating a pressure in the tubes and pipes of about 30 atmospheres.

The oil is now circulated through the system by pump 9 and the temperature of the heater 26 is maintained at slightly over 400 C. At the same time pump 28 introduces as much residue oil through pipe 2 as is required to replace the amount discharged from the hydroclone 14 into the reactor 16. About 800 kg./h. of oil are thus introduced at a throughput of 2000 kg./h. of dry brown coal. The proportions of the processed quantity of oil to the quantity of fuel introduced varies since this will depend upon the pore volume of the fuel.

The brown coal which has been crushed to a grain size of 6 mm. and dried until free from Water is continuously introduced through gate 1 into pipe 4 and thence reaches the pipe ring 5. The upper portion of the ring fills with gas evolved by the fuel as its temperature'rises. The gas is discharged into the riser 7 through the pipes 29. The coal sinks in the stream of oil in pipe ring 5 and through pipes 6 reaches the foot of the riser 7 where it is entrained by the ascending column of oil delivered to the riser 7 by pump 9 to be carried upwards freely suspended in the current of oil. The velocity of the oil slightly exceeds the sinking speed of the coal. Assuming the velocity of descent of the coal to be 10 cms./sec., then the velocity of ascent of the oil would be 12 ems/sec. As it travels up the riser 7 the temperature of the brown coal increases to 400 C. and at this level the bitumen-forming substances in the coal liquefy. Oils may be formed which vaporize at this temperature. Any such light oil vapors are discharged through a valve 12. The pores of the brown coal which are emptied by this process of vaporization, and more particularly those pores in the brown coal which were formerly filled with water, now fill up with the circulated oil, i.e. the residue oil, as the coal gradually ascends up riser 7. At the head of the riser 7 the oil and the brown coal flow into container 11 whence they reach thehydroclone 14 via pipe 13. In the hydroclone the oil is separated from the oil-enriched brown coal.

The oil flows back to pump 9 through pipe 25 and, after having been reheated in heater 26, it is returned to the riser 7 The brown coal is gated through trap 15 into the reactor 16, whereat low pressure it is exposed to a temperature sufliciently'elevated to ensure that during its a sur s period of dwell, which is prolonged by the particular construction of the reactor, the required reactions of the oils contained in the pores of the coal will take place. The resultant desired hydrocarbon compounds are gaseous and can be withdrawn through the space between the two shells of the reactor. Part of the coal treated in the reactor is withdrawn through outlet 23. Another part enters pipe 50 where it is entrained by'a current of inert gas which is circulated through pipe 50 by a blower 51 and which delivers the coal into a cyclone 52. From there this part of the coal reaches a container 53 provided at its bottom end with a nozzle 54 through which air is blown by a second blower 55. The volume of air blown into container 53 is so controlled that it will burn as much coal as is needed to raise the temperature of the coal to 600 C; or to any desired higher level. The combustion gases can escape from the top of container 53 through an exhaust 56, whereas the coal thus'heated in the container is reintroduced into the reactor and mixed with the coal arriving from hydroclone 14 at about 400 C. and further raises the temperature of the latter to 500 C. or more.

Owing to the exothermic nature of the reactions which take place in the riser 7 and in pipe 13 at a temperature of 400 C. the oil returning through pipe 25may have a temperature that greatly exceeds the temperature the oil in riser 7 need possess, so that this oil need not be reheated in heater 26.

The plant illustrated in Fig. 3 differs from that shown in Fig. 1 principally in that two riser pipes are provided each constructed substantially like riser 7 shown in Fig. 1 and that the temperature in the riser firstentered by the solid lumpy fuel which in this instance still contains its natural Water, is not raised beyond the level at which the water will evaporate .without the simultaneous liquefaction of the bitumen-forming substances, whereas in the second riser, through which the mixture of oil and lumpy fuel then passes, the temperature level is such as to cause the bitumen-forming substances to be transformed into an oily bitumen or into oils, the evolving oil vapors being withdrawn. This plant therefore separately delivers water vapors containing no oil, and oil vapors containing no water.

In the plant illustrated in Fig. 3 the construction of the riser 7 as well as the arrangement of the associated pipe system is similar to that shown in Fig. 1. The reactor 16 and the trap 15 as well as the hydroclone correspond to the equivalent apparatus in Fig. 1.

The top of the riser 7 is connected by pipe 13 with a hydroclone 30. The outlet for solids .31 discharges into the bottom end 22 of the second riser 33. The head of the latter communicates with a -container 34 with a gas outlet 35. Pipe 36 connects container 34 with hydroclone 14. The liquid discharged from hydroclone 30 enters a pipe 37 which divides into two branches 38 and 39. Branch 38 leads to the suction side of pump 9, whereas branch 39 is connected through the heating coil 40 of a heater 41 with a pump 42.

Two streams'of oil circulate in the plant, the first incorporating pump 9. This pump forces the oil through riser 7 into container ll. From here the oil reaches hydroclone 30 through pipe 13 and, after elimination of the solids by the hydroclone, the oil returns through pipe 37 and branch 38, part being diverted into branch 39, to the suction side of pump 9.

The second circulatory oil system incorporates pump 42 which receives part of the oil from the first stream through branch 39. Pump 42 forces the oil which is heated in heater 41 to a temperature slightly over 400 C. through riser 33 into container 34. This oil then-flows through pipe 36 into hydroclone 14 and, after elimination of the solids contained therein, returns through pipe 25. to the suction side of pump -9,'to be thus recombined with-v the first circulatory oil system.

Before entering pump 9 the oil from the first circulatory,

system returning at a lower temperature of about 250-.C.- through; branch 38 is recombined at 43 with the oil returning at-a temperature of about 400 C. through pipe 25, the combined stream of oil being pumped by pump 9 back into riser 7 at a temperature of about 300 C.

At'the operational pressure of the plant, i.e. approximately 30 atmospheres, pump 2 delivers the volume of oil'that is to be treated, after having been preheated to about 350 C. in heater 27, to the circulating system from which a like volume including the fuel is Withdrawn and transferred to reactor 16.

The crushed brown coal in this plant is likewise introduced through a gate 1 into pipe 4. As soon as the brown coal in the pipe ring comes into contact with the hot oil, the greater part of the water contained in the coal will be rapidly converted to steam. So long as the brown coal still occludes an adequate volume of steam it will float in pipe ring 5. The upper part of pipe ring 5 fills with Steam at a pressure suflicient to force it through pipes 29 and upwards through riser pipe 7. When the greater proportion of the water has been driven out of the brown'coal; the latter will sink down pipe 6 to thefoot of riser 7, where it will be entrained by the rising. column of oil and conveyed upwards suspended in the ascending oil. In this stage the remaining steam is expelled. The steam is withdrawn through a steam outlet pipe 12. The oil pumped through the riser 7 heats up to a temperature which is sufficiently high to ensure that the water will vaporize at the pressure at which the plant operates, but not high enough to cause the liquefaction of the bitumen-forming substances in the coal. This temperature may be, for instance, in the range between 300 and 350 C., whereas the pressure may be between 20 and 30 atmospheres. The steam delivered through. out1et 12-1will then contain no oil whatsoever.

1 Therpores of the brown coal which are thus emptied of Water will'therefore fill with the residual oil.

The mixture of oil and brown coal enriched with residual oil will now flow through pipe 13 to the hydroclone 30 which separates the coal from the oil. The oil returns through pipe 37,.thence partly through branch 38 to riser pipel7, the remainder returning through branch 39 to pump 42'; During its course through this latter branch it is reheated in heater 41 to a temperature at which the bitumen-forming substances liquefy. The brown coal leaves the hydroclone 30 through the outlet 31 for the delivery of solids and enters the bottom 32 of riser 33 whenceit iscarried upwards by the oil that is forced byypuinp 42"into'the riser 33. As it ascends the riser the fuel is heated to about 400 C. so that the bitumen in the fuel is liquefied. The gases evolved by the coal duringithis process escape through the gas outlet 35. From container 34 the oil-coal mixture is taken through pipe 36 to hydroclone 14. From the hydroclone the oil returns to riser 7 through pipe 25 whereas the brown coal, enriched with the oil that is to be treated, is conducted through gate 15 into the reactor 16. The process performed in the reactor 16 corresponds with that already described by reference to the plant shown in Fig. 1.

. The apparatus illustrated in Fig. 4 comprises a riser pipe 1 of suflicient diameter to permit larger quantities of lumpy fuel to be carried upwards therein by an ascending column of oil. The velocity of the ascending oil slightly exceeds the sinking velocity of the fuel. For instance, if the fuel should sink in the oil at the rate of 10 cms./sec., then the velocity of ascent of the oil is arranged to be about 12 ems/sec. The diameter of the riser pipe maybe for instance 30 cms. and its height 600 cms; to'deal with a throughput of about 2000 kg. of fuel per houra .The foot of the riser communicates with aipipe 2 through which the admitted oil is pumped by apump 3. The upper extremity of the riser 1 is fitted with a header4" with a steam outlet 5 at the top and connected at the bottom with a pipe 6 which in the illus-v trated embodiment may have a diameter of 10 cms, and.

11 which descends to' a hydroclone 7.- The outlet 8 for the liquid discharged from the hydroclone is connected by a pipe 9 and a further pipe 10 with pump 3. In this part of the plant the oil is therefore circulated by pump 3 through the riser pipe 1 and the pipes 6 and 10.

A proportion of the circulated oil reaches a pump 13 through pipe 11 and a heater 12. This latter pump forces the oil through pipe 14 into a second riser pipe 15 which at its upper end likewise carries a header 16 with an oil vapor outlet 17. Through a pipe 18 the oil flows into a hydroclone 19 whence it is returned through pipe 20 to pump 3. Before reaching pump 3 the oil which has been heated to a temperature above 400' C. by the exothermic reaction occurring in the oxygencarbon-hydrogen system in this part of the plant, is recombined with the oil returning through pipe 10 which has a lower temperature, in the region of 250 C., so that pump 3 will force the recombined oil back into riser 1 at a temperature of about 300 C.

r A small proportion of the oil delivered by: pump 3 is heated to about 300 C. in a heater 21 and through pipe 22 enters a pipe ring 23 which communicates with riser 1 through pipes 24 and 25.

This plant operates as follows:

The pipe system of the plant is first filled through pipe 26 with a heavy oil fraction boiling between about 300 and 400 C., pumps 3 and 13 circulating this oil through the pipe system at a pressure of about 30 atmospheres in the manner that has been described.

The fuel which has been disintegrated to a grain size of about 6 mm. is continuously introduced into pipe 22 through a gate 27 and the oil in the pipe conveys it into the pipe ring 23. Contact between the fuel and the hot oil in the pipe ring quickly turns the water contained in the fuel into steam. The upper portion of the pipe ring 23 will therefore fill with steam under sufiicient pressure to force it through pipes into the interior of the riser pipe 1 in which it ascends to'the header 4. So long as a sufficient volume of steam is evolved by the fuel it will swim in the oil which flows through pipe ring 23 in a circular path as a result of its tangential introduction from pipe 22. When the major proportion of the Water has been expelled from the fuel the latter will sink in the oil in pipe ring 23 and descend through pipes 24 to the foot of the riser pipe 1. Particles of fuel of different sizes will sink at the end of different periods of time and therefore descend from the pipe ring through different pipes 24 to reach the foot of the riser 1. Consequently, larger lumps of fuel will undergo a longer period of. treatment .than small ones. At the foot of the riser the fuel is entrained by the current of oil entering the riser from pipe 2 and it is carried upwards freely suspended in the risingflcolumn of oil. During its ascent any residual moisture still contained in the fuel will be transformed into steam. The steam collects in the header tank 4 and is discharged through valve 5 at the operational pressure of the plant. The oil pumped through the riser 1 is heated to a temperature which is sufficiently high to ensure that at the prevailing pressure the water will evaporate but the bitumen-forming substances in the fuel will not yet be liquefied. At a pressure of between say 20 and atmospheres this temperature may befor instance 250 to 350 C. The steam evolved by the moist fuel in these operational conditions will therefore be free of oil.

The fuel from which the water has thus been removed is then taken, together with the oil, from the header tank 4 through pipe 6 into the hydryclone 7 where it is separated from the oil and discharged through the .outlet 28 for solids into pipe 14. In heater 12 the temperature. of the fuel is now raised to about 400 C. and the fuel is then entrained by the current of oil forced up the. riser pipe 15 by pump 13. In the course of its ascent up the riser the temperature of the fuel is established at about 400 C. and the bitumen-forming substances liquefy.

The lighter fractions evaporate from the liquid bitumen, whereas the heavier ones remain in the liquid state. The light oil vapors collect in the header tank 16, together with the gases evolved by the fuels in the course of their heat} ing and are discharged through valve 17. Through pipe 18 the fuel and the oil reach the hydroclone 19 where fuel' and oil are separated and the fuel enters a decompres'sion chamber 30 through a trap 29. The liquefied heavy oil remaining in the fuel is vaporized in this chamber, discharged at 31, and further processed in the conventional manner.

The plant shown in Fig. 5 differs from the plant illustrat'ed in Fig. 4 by the provision of an additional unit comprising a riser pipe 35 in which the colloidally bound water contained in the treated fresh peat, i.e. about water related to the wet weight of the peat, is released by heating the peat in hot water, and removed, leaving about 60% residual water.

This additional unit comprises a riser pipe 35 with a header tank 36 and a steam exhaust 37. A pipe 38 connects the bottom of the header tank 36 with a centrifuge 39 The outlet 40 for solids from the centrifuge discharges into a trap 27 connected with the main part of the plant which is constructed as already described by reference to Fig. 4. The outlet 41 for liquids from the centrifuge is connected with a pump 42 which forces part of the water removed from the crude peat in the centrifuge through pipe 43 and a heater 44 back into the riser pipe 35, and the remainder of the still hot water through a pipe 45 into a heat exchanger 46 where the heat contained in the water is transferred to the fresh incoming peat.

This plant operates as follows:

A pump not shown in the drawing pumps the fresh peat from the bog at the operational pressure of the plant, for instance at about 30 atmospheres, through pipe 47 and heat exchanger 46 into the riser pipe 35. In this riser pipe the peat is entrained by the hot current of Water which has been heated in heater 44 to a temperature of about 250 C. and conveyed in the upward direction. During its ascent the peat heats up to about C. at which temperature the colloidally bound water in the peat is released. The water-peat mixture then descends through pipe 38 into the centrifuge 39 where water and peat are separated. With the water content reduced to 60% the peat is now gated through trap 27 into pipe 22 and thus enters the pipe ring 23 from where it travels through the plant in the manner already de scribed in greater detail in connection with Fig. 4.

The following examples of the process according to 'thepresent invention are given as illustrative only, the present invention, however, not being limited to the specific details of the examples. 1

Example I A solid fuel, such as oil shale or brown coal, is crushed to an average grain size of about 6 mm; A fairly fine comminution is to be preferred to open up as much pore space as possible. forthe reception of oil, and hence to permit ;the.temperature of the fuels to be raised to the desired level .sufiiciently quickly.- The treated oil flows through the process in continuous cycle at a pressure of something like 30 atmospheres. At the beginning of the process the oil is heated to a temperature of about 300 C. The solid fuel is then introduced into the oil. First, the water contained therein is very rapidly turned into steam which is. Withdrawn and may be utilized for the generationof power. Despite the elevated temperature no oil vapors are as yet formed because of the high pressure-prevailing. In the further course of the process the oil is heated to over 400 C. so that the fuel assumes a temperature of about 400 C. At this temperature the bitumen forming substances in the solid fuels change into a liquid oily state. 'I'he solid fuels from the pores of which the water has been expelled and which have in stead been filled with the oil that is to be treated are then separated from. the remainder of the oil and conducted into a chamberwhere apressure of between 0.5 and" In this example, numerical data will be given pertaining to a specific manner of carrying out the dewatering of soft coal according to the present invention.

The apparatus used has an hourly capacity of 50,000 kg. of wet coal. The coal contains.60% water so that 20,000 kg. of dry coal substance, including or 2,000 kg. of oil or hydrocarbons are to be processed.

The temperature during the de-watering of the coal is about 230 C. The petroleum oil introduced together with the soft coal has a boiling point above 380", C. A pressure of 30 atmospheres is maintained.

In describing the dimensions, etc. of parts of the apparatus, reference is made to Fig. 4: i 1

Diameter of horizontal ring pipe 23 i.. m.. 0.65

Median diameter of pipe ring (23) m 5.0 Number of riser pipes (1) connected with pipe r n (23) 6 Height of riser pipes (1) m 6.0 Diameter of riser pipes 1) m 0.6 Lengths of descending pipes (24). m 3.0 Diameter of descending pipes (24) m 0.6 Time required for passage of soft coal through ring 4 p p 1 Time required for passage of soft coal through riser and descending pipe min 2% Quantity of circulating oil m. /h 720 Temperature of oil at inlet (2) C-.. 360 Temperature of oil at outlet point (10) C 240 Quantity of steam of '30 atmospheres produced k /h 30,000

The following data refer to the second step, i.e. the removal of bitumen from the de-watered soft coal:

Temperature About 400 C. Diameter of riser pipe 1.0 111.

Height of riser pipe 6.0 m.

Time required for passage of coal 2 min. Quantity of circulating oil 360 m. /h.

Temperature of heating oil at inlet (14) 400 C. Temperatureof heating oil at outlet 425 C. Quantity of oil contained in coal 2,000 kg./h.

Temperature in decompression chamber 425 C. Pressure in decompression chamber 1' atm. overpressure.

Thus,'pressure has been reduced from 30 atmospheres overpressure to 1 atmosphere overpressure. l V

. Therebythe oil in the pores of the coal and the oil adhering to the surface thereof are vaporized; The thus obtainedoilwapors are condensed and further processed in conventional manner.

14 A ,s mal l portionof the circulating petroleum oil which has been described as being introduced together with the soft coal, is converted into light oil during the process and is replaced by a portion of the heavy oil separated from the coal.

In this manner the following yields are obtained: In the firststep or stage of the process.-

Steam at 30 atmospheres kg./h 30,000

Useful mechanical energy kwh 7,000 In the second stage of the process- Low temperature coke kg./h 16,500

Light, medium and heavy oil ..kg./h 2,000

Low temperature coal gas kg./h 1,500

Example III Operating pressure atm 30 Temperature of heating water entering the apparatus C 232 Temperature of heating water leaving the apparatus C 180 Quantity of circulating heating water kg./h 115,000 Medium diameter of pipe ring m 5.0 Number of connected descending pipes 6 Number of connected riser pipes 6 Diameter of riser pipes m 0.6 Height of riser pipes ...m 6.0 Length of peat treatment min 3 Thereafter, the peat is separated from the previously colloidally bound water as described further above.

There remain:

Peat containing 60% water kg./h 50,000 Circulating heating Water at 180 C kg 115,000 Water removed from peat kg./h 150,000

The heat contained in the thus removed water is conveyed to fresh peat being introduced into the apparatus. After thus utilizing the heat content of the removed Water, the same may be disposed of in any desirable manner, for instance by being returned tot he peat pit.

The thus pre-dried peat is then further treated like the soft coal according to Example-II.

Example IV This example relates primarily to the treatment of petroleum oils containing only a small fraction of low boiling oils.

The treated oil has a boiling point above 380 C.

As carrier for the oil, -a soft coal containing 60% water is used.

The oil content of the soft coal amounts (on dry basis) to 10% and the oxygen content to 22%.

The analysis of the coal ash is as follows:

I Percent CaO 3 1 SiO; 12.9 1 F 0 10.8 A1 0 21.9 MgO 4.6 16.1

Due to the high calcium oxide content of the coal used according to the present example, which has a partially inhibiting effect on the catalytically active constituents, the process is adjusted so as to put relatively great weight i on thermal cracking at a temperature range around 600 C.

Capacity of the apparatus:

Wet soft coal kg./h 50,000 Water content of coal kg./h 30,000 5 Dry coal kg /h 20,000. Oil content of dry coal kg./h 2,000

The temperatureduring the first stage of the-process is maintained at about 230 C.

Circulating petroleum oil, boiling range C 380 Operating pressure atm 30 Steam temperature C 232 Diameter of horizontal (circular) treatment conduit m 5 Diameter of circular pipe 'm 0.65 Number of riser pipes (7) 6 Diameter of riser pipes m' 0.6 Length or height of riser pipes '.'m 6.0 Number of descending pipes 6 Diameter of descending pipes 'm 0.6" Length of descending pipes m 0.3 Coal treating time min 3 /2 The second stage of the process is carried out at about 425 C.

Diameter of riser pipe 1.0 m,

Height of riser pipe -2 6.0 m.

Coal treatingtime 2 min. Quantity of circulating oil About 360 111. h. Quantity of oil dissolved in coal 2,000 kg./h.

(A small portion thereof, light oil, is

separated in the second stage in the form of oil vapors.) i Coal gas produced 1,500 kg. Heat consumption in stages 1 and 2 About 32,500,0000

kcal./h.

Of this amount of heat about 5,600,000 kcal. are accounted for by the reaction between the oxygen, carbon and hydrogen of the coal. Altogether,.upon carrying out the process at great speed, about 400 kcal./kg. coal are released, or upon treatment of 20,000 kg. dry coal/h. 8,000,000 kcal.

The thus-formed coke is then separated from the circulating petroleum oil, and introduced into the second reaction means.

Of the originally introduced 20,000 kg. of dry coal/h,- 2.000 kg. represented oil and 1,500 kg. of coal gas were formed. Thus, 16,500 kg./h. of coke are introduced into the second reaction means together with.8,000 kg. of added oil and 2,000 kg. of originally dissolved oil, so that a total quantity of 10,000 kg. of oil/h. is now to be treated.

The pressure in the second reaction means is 5. atmos- 65 pheres, representing a pressure drop from 30 to 5 atmospheres.

Due to the thus reduced pressure, the oil adhering to the coke is vaporized. The coke and the oil in the pores of the same is then contacted with circulating coke having a temperature of about 700 C., and thereby heated to about 550 C.

The heat requirements for this step of the process, for heating coke and oil, vaporizing the oil and for marin taining endothermic cracking reactions, amount to about 4,200,000 kcal./h. During the reaction, about 2,400,000 kcaL/h. are liberated, and the missing balance of about 1,800,000 kcal./h. is supplied by the addition of coke heated to 700 C.

Quantity of circulating heated coke kg./h. 40,000 Dimensions of the reactor:

Diameter m T Height m 5.0 Reaction time min 12 In the first stage:

Steam at 30 atm kg./h 30,000

- and converted into mechanical energy kwh' 8,000

In the second stage: I

Low temperature coke ..kg./h 16,500

. Low temperature coal gas kg./h 1,500

Oil originally contained in coal kg./h 2,000

In the reactor or third stage:

8,000 kg. of heavy oil' introduced per hour and'2,000 kg. of oil contained in the coal are transformed into light and medium oils and coke. The latter is then removed together. with the coke obtained from the original soft coal. Additional combustible gases are formed from the coke during heating in the above described third stage, in addition to the combustible gases resulting from the oil cracking process. 7

Residual heavy oil is used for heating the apparatus.

Without further analysis, the foregoing will so fully reveal the gist of the present invention that others can by applying current knowledge readily adapt it for various applications without omitting features that, from the standpoint of prior art, fairly constitute essential characteristics of the generic orvspecific aspects of this inven-" tion and, therefore, such adaptations should and are intended to be comprehended within the meaning and range of equivalence of the following claims.

What is claimed as new and desired to be secured by Letters Patent is:

1. A process of treating a water-containing particulate solid carbonaceous fuel and a petroleum oil having a relatively low content of components boiling below 250 C. at normal pressure, comprising the steps of contacting said petroleum oil with said water-containing, particulate, soild carbonaceous fuel the same being capable to be partially converted into bitumen by application of heat, so as to form a mixture of said petroleum oil and said solid fuel; subjecting said mixture to a temperature of about 350 C. at an elevated pressure so chosen as to substantially prevent evaporation of oil from said mixture while allowing evaporation of water tthereform, thereby forming steam and filling pores of said solid fuel with petroleum oil; withdrawing the thus formed steam; raising the temperature of the thus formed substantially water-free mixture to about 400 C. so as "to. convert a portion of said solid fuel into liquid bitumen, while maintaining a pressure sufiiciently high to substantially prevent vaporization of the thus formed liquid bitumen; separating said oil-containing solid fuel from the remainder of the reaction mixture; subjecting said separated, oil-containing solid fuel to a temperature of at least about 500 C. while maintaining a pressure of about between 0.5 and 5 atmospheres, so as to crack the oil within the pores of said solid fuel thereby transforming said oil at least partially into lower molecular hydrocarbons; and separating the thus formed lower molecular hydrocarbons from the solid fuel, whereby steam at relatively high pressure and temperature, a dry solid carbonaceous fuel, bitumen and lower molecular hydrocarbons areformed from said petroleum oil and said water-containing carbonaceous solid fuel.

2. A process of treating a petroleum oil having a relatively low content of components boiling below 250 C, at normal pressure, such as the oily residue remaining after distillation of petroleum oils at temperatures of between 250 and 400" C., comprising the steps of contacting said petroleum oil with a substantially waterfree, particulate, soild, carbonaceous fuel including bituminous substances capable of being converted into liquid bitumen by application of heat, so as to form a mixture of said petroleum oil and said solid fuel; subjecting said mixture to a temperature at which the bitu- 17 men in said solid fuel will liquefy, while maintaining a pressure sufiiciently high to substantially prevent evaporation of said'liquefied bitumen, while the pores of said solid fuel are being filled with at least a portion of said petroleum oil; separating said oil-containing solid fuel from the remainder of the reaction mixture; subjecting said separated, oil-containing solid fuel to a temperature of at least about 500 C. while maintaining a pressure of about between 0.5 and atmospheres, so as to crack the oil within the pores of said solid fuel thereby transforming said oil at least partiallyinto lower molecular hydrocarbons; and separating the thus formed lower molecular hydrocarbons from the solid fuel, whereby a dry solid carbonaceous fuel, bitumen and lower molecular hydrocarbons are formed from said petroleum oil and said carbonaceous solid fuel.

3. A process of treating a petroleum oil having a relatively low content of components boiling below 250 C. at normal pressure, such as the oily residue remaining after distillation of petroleum oils at temperatures of between 250 and 400 C., comprising the steps of forming in said petroleum oil a suspension of a substantially water-free, particulate, solid, carbonaceous fuel including bituminous substances capable of being converted into liquid bitumen by application of heat; subjecting said suspension to a temperature at which the bitumen in said solid fuel will liquefy, while maintaining a pressure sufficiently high to substantially prevent evaporation of said liquefied bitumen, while the pores of said solid fuel are being filled with at least a portion of said petroleum oil; separating said oil-containing solid fuel from the remainder of the reaction mixture; subjecting said separated, oil-containing solid fuel to a temperature of at least about 500 C. while maintaining a pressure of about between 0.5 and 5 atmospheres, so as to crack the oil within the pores of said solid fuel thereby transforming said oil at least partially into lower molecular hydrocarbons; and separating the thus formed lower molecular hydrocarbons from the solid fuel, whereby a dry solid carbonaceous fuel, bitumen and lower molecular hydrocarbons are formed from said petroleum oil and said carbonaceous solid fuel.

4. A continuous process of treating a petroleum oil having a relatively low content of components boiling below 250 C. at normal pressure, such as the oily residue remaining after distillation of petroleum oils at temperatures of between 250 and 400 C., comprising the steps of forming a flowing stream of said petroleum oil and of a substantially water-free, particulate, solid, car-.

bonaceous fuel including bituminous substances capable of being converted into liquid bitumen by application of heat; subjecting said flowing suspension to a temperature at which the bitumen in said solid fuel will liquefy, while maintaining a pressure sufficiently high to substantially prevent evaporation of said liquefied bitumen, while the pores of said solid fuel are being filled with at least a portion of said petroleum oil; separating said oil-containing solid fuel from the remainder of the reaction mixture; subjecting said separated, oil-containing solid fuel to a temperature of at least about 500. C. while maintaining a pressure of about between 0.5 and 5 atmospheres; so as to crack the oil wthin the pores of said solid fuel thereby transforming said oil at least partially into lower molecular hydrocarbons; and separating the thus formed lower molecular. hydrocarbons from the solid fuel, whereby a dry solid carbonaceous fuel, bitumen and lower molecular hydrocarbons are formed in a continuous manner from said petroleum oil and said carbonaceous solid fuel.

5. A process of treating a petroleum oil as defined in claim 4, wherein the mixture of said petroleum oil and said liquid bitumen remaining after separation of theoil-containing solid fuel is heated to an elevated temperature and contacted with subsequent portions of said 18 substantially water-free, particulate, solid, carbonaceous fuel.

6. A process of treating a petroleum oil as defined in claim 1, wherein said remainder of the reaction mixture is used as said petroleum oil for contacting subsequent portions of said water-containing, particulate, solid, carbonaceous fuel.

' 7. A process of treating a solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of forming a mixture of said solid fuel and a petroleum oil; subjecting said mixture to an elevated pressure of at least 12 atmospheres while maintaining said mixture at a first elevated temperature above the boiling point of Water at said elevated pressure and below the vaporization point of said petroleum oil at said elevated pressure, so as to vaporize the water of said solid fuel; withdrawing the thus-formed steam; and subjecting the remainder of said mixture to a second elevated temperature higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and liquefy the same,

. thereby cracking at least a'portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thusformed petroleum oils.

8. A process of treating a solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of forming a mixture of said solid fuel and a petroleum oil; subjecting said mixture to an elevated pressure of about 30'atmospheres while maintaining said mixture at a first elevated temperature above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil at said elevated pressure,

so as to vaporize water of said solid fuel; withdrawing the thus-formed steam; subjecting the remainder of said mixture to a second elevated temperature of about 400,

C. being higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thus-formed petroleum oils; and separating said vaporized petroleum oils from the remainder of said solid fuel.

9. A process according to claim 8, wherein said mixture is formed of said separated petroleum oils and subsequent portions of said solid fuel.

10. A process of treating a solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of forming a mixture of said solid fuel in comminuted form and a petroleum oil; subjecting said mixture to an elevated pressure of at least 12 atmospheres while maintaining said mixture at a first elevated temperature above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil at said elevated pressure, so as to vaporize the water of said solid fuel; withdrawing the thus-formed steam; and subjecting the remainder of said mixture to a second elevated temperature higher than said first elevated temperature While maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and 'liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thus-formed petroleum oils.

11. A process of treating a solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of forming a suspension of said solid fuel in comminuted form in a petroleum oil; subjecting said suspension to an elevated pressure of at least 12 atmospheres while aasmse maintaining said suspension at a first elevated temperature above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil at said elevated pressure, so as to vaporize the water of said solid fuel; withdrawing the thus-formed steam; and subjecting the remainder of said suspension to a second elevated temperature higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thus-formed petroleum oils.

12. A continuous process according to claim 7, in which said petroleum oil is separated from the solid fuel having been treated as defined in claim 7; and the thusseparated petroleum oil is re-introduced into said process for forming a mixture with subsequent portions of said solid fuel, said petroleum oil thus conveying the solid fuel and flowing in a closed cycle.

13.- A process of treating a solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of contacting a substantially horizontally flowing stream of petroleum oil with particles of said solid fuel; subjecting the thus-formed stream of solid fuel-carrying petroleum oil to an elevated pressure of at least 12 atmospheres while maintaining a first elevated temperature being above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil, so as to vaporize at least the major portion of the water contained in said solid fuel, thereby causing said solid fuel upon loss of most of its water content to sink downwardly in said stream of horizontally flowing petroleum oil; thereafter directing said stream of petroleum oil conveying said fuel in an upward direction at least until substantially all of the remaining water of said solid fuel has evaporated so as to form a substantially water-free stream of flowing oil and solid fuel; subjecting said substantially water-free stream to a second elevated temperature higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thus-formed petroleum oils.

14. A process according to claim 13 in which the particles of said solid fuel contacting said stream of petroleum oil are of varying size, so as to sink downwardly in said horizontal oil stream at different points after being carried by the same varying distance corresponding to the size of the particles, respectively; and whereby said particles of solid fuel are thereafter carried upward y in one of a plurality of successively arranged upwardly flowing streams of said petro eum oil, each particle respectively being carried upwardly by a stream of petroleum oil emanating from said horizontally flowing petroleum oil at a point in the vicinity of sinking of said respective particle of solid fuel. v

15. A process of treating a solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of contacting a substantially horizontally flowing circular stream of petroleum oil with particles of said solid fuel; subjecting the thus-formed stream of solid fuel-carrymg petroleum oil to an elevated pressure of at least 12 atmospheres while maintaining a first elevated temperature being above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil, so as to vaporize at least the major portion of the water contained in said solid fuel, thereby causing said solid fuel upon loss of most of its water content to sink downwardly in said stream of horizontally flowmg petroleum oil; thereafter directing said stream of petroleum oil conveying said fuel in an upwarddirection at least until substantially all of the remaining water of said solid fuel has evaporated so as to form a substantially water-free stream of flowing oil and solid fuel; subjecting said substantially water-free stream to a second elevated temperature higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thus-formed petroleum oils.

16. A process of treating peat, comprising the steps of heating peat containing colloidally bound water, in water under pressure to a temperature sufficiently high to release the colloidally bound water of said peat; forming a mixture of the thus-treated peat and a petroleum oil; subjecting said mixture to an elevated pressure of at least 12 atmospheres while maintaining said mixture at a first elevated temperature above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil at said elevated pressure, so as to vaporize water contoined in said peat; withdrawing the thus-formed steam; and subjecting the remainder of said mixture to a second elevated temperature higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transform a portion of said peat into bitumen and liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporizing the thus-formed petroleum oils.

17. In on apparatus for simultaneously de-watering water-containing, solid, carbonaceous fuel, and at least partially reducing the molecular weight of higher-boiling petroleum oil and the like, in combination, first reaction means for subjecting a mixture of water-containing, carbonaceous, solid fuel and petroleum oil to superatmospheric pressure and to an elevated temperature sufficiently high to cause evaporation and steam formation of the water contained in said solid fuel while retaining said petroleum oil in unvolatilized conidtion, whereby petroleum oil will enter into the pores of the thus dewatered solid fuel; means for removing the formed steam from said first reaction means; hydrocyclone means operatively connected to and communicating with said first reaction means for separating free petroleum oil from the thus de-watered petroleum oil-containing solid fuel; conveying means communicating with said hydrocyclone means and with said first reaction means for conveying at least a portion of said free petroleum oil from said hydrocyclone means to said first reaction means; second reaction means operatively connected to said hydrocyclone means for receiving said de-watered petroleum oil-containing solid fuel and subjecting the same to a temperature sufliciently high to cause at least partial transformation of the petroleum oil contained in the solid carbonaceous fuel into lower molecular hydrocarbons, and at a pressure sufficiently low to volatilize the thus-formed lower molecular weight hydrocarbons; and means operatively connected to said second reaction means for separating the thus-formed volatilized hydrocarbons and water-free, solid, carbonaceous fuel.

18. In an apparatus for simultaneously de-watering water-containing, solid, carbonaceous fuel, and at least partially reducing the molecular weight of higher-boiling petroleum oil and the like, in combination, first reaction meons including a tubular, upwardly extending reaction vessel for subjecting a mixture of water-containing, carbonaceous, solid fuel and petroleum oil to superatmospheric pressure and to an'elevated temperature sulficiently high to cause evaporation and steam formation of the water contained in said solid fuel while retaining said petroleum oil in unvolatilized conidtion, whereby petroleum oil will enter into the pores of the thus dewatered solid fuel; means for removing the'thus formed steam from said first reaction means; hydrocyclone means operatively connected to and communicating with said first reaction means for separating free petroleum oil from the thus de-watered petroleum oil-containing solid fuel; separating and conveying means communicating with said hydrocyclone means and with said first reaction means for separating a portion of said free petroleum oil from said hydrocyclone means and for conveying the remaining portion to said first reaction means; second reaction means operatively connected to said hydrocyclone means for receiving said de-watered petroleum oil-containing solid fuel and subjecting the same to a temperature sufiiciently high to cause at least partial transformation of the petroleum oil contained in the solid carbonaceous fuel into lower molecular hydrocarbons, and to a pressure sufiiciently low to volatilize the thusformed lower molecular weight hydrocarbons; and means operatively connected to said second reaction means for separating the thus-formed volatilized hydrocarbons and water-free, solid, carbonaceous fuel.

19. Inan apparatus for simultaneously de-watering water-containing, solid, carbonaceous fuel, and at least partially reducing the molecular weight of higher-boiling petroleum oil and the like, in combination, first reaction means including a tubular, upwardly extending reaction vessel for subjecting a mixture of water-containing, carbonaceous, solid fuel and petroleum oil to superatmospheric pressure and to an elevated temperature sufficiently high to cause evaporation and steam formation of the water contained in said solid fuel while retaining said petroleum oil in unvo-latilized condition, whereby petroleum oil will enter into the pores of the thus de-watered solid fuel; means for removing the formed steam from said first reaction means; hydrocyclone means operatively connected to and communieating with said first reaction means for separating free petroleum oil from the thus de-watered petroleum oil-containing solid fuel; conveying a portion of means communicating with said hydrocyclone means and with said first reaction means for conveying said free petroleum oil from said hydrocyclone means to said first reaction means; second reaction means including a reaction chamber having arranged therein means for retarding the passage of solid, particulate fuel through said chamber and for displacing particles of said fuel relative to each other, operatively connected to said hydrocyclone means for receiving said de-watered petroleum oil containing solid fuel and subjecting the same toa temperature sufficiently high to cause at least partial transformation of the petroleum oil contained in the solid carbonaceous fuel into lower molecular hydrocarbons, and at a pressure sufliciently low to volatilize the thus-formed lower molecular weight hydrocarbons; and means operatively connected to said second reaction means for separating the thus-formed volatilized hydrocarbons and water-free, solid, carbonaceous fuel.

20. A process of treating of solid, carbonaceous fuel containing water and at least one substance convertible into bitumen by application of heat, comprising the steps of comminuting said solid fuel to a particle size of about 6 mm. forming a mixture of said comminuted solid fuel and a petroleum oil; subjecting said mixture to an elevated pressure of at least 12 atmospheres while maintaining said mixture at a first elevated temperature above the boiling point of water at said elevated pressure and below the vaporization point of said petroleum oil at said elevated pressure, so as to vaporize the water of said solid fuel; withdrawing the thus-formed steam; and subjecting the remainder of said mixture to a second elevated temperature higher than said first elevated temperature while maintaining substantially said elevated pressure, so as to transfer said convertible substances into bitumen and liquefy the same, thereby cracking at least a portion of the thus-formed bitumen in contact with said solid fuel under formation of petroleum oils and vaporization of the thus-formed petroleum oils.

References Cited in the file of this patent UNITED STATES PATENTS 1,881,968 Pier et a1. Oct. 11, 1932 2,637,683 Kassel May 5, 1953 2,714,086 Bluemner July 26, 1955 I FOREIGN PATENTS 1,022,728 Germany Jan. 16, 1958

Claims (1)

1. A PROCESS OF TREATING A WATER-CONTAINING PARTICULATE SOLID CARBONACEOUS FUEL AND A PETROLEUM OIL HAVING A RELATIVELY LOW CONTENT OF COMPONENTS BOILING BELOW 250*C. AT NORMAL PRESSURE, COMPRISING THE STEPS OF CONTACTING SAID PETROLEUM OIL WITH SAID WATER-CONTAINING, PARTICULATE, SOLID CARBONACEOUS FUEL THE SAME BEING CAPABLE TO BE PARTIALLY CONVERTED INTO BITUMEN BY APPLICATION OF HEAT, SO AS TO FORM A MIXTURE OF SAID PETROLEUM OIL AND SAID SOLID FUEL, SUBJECTING SAID MIXTURE TO A TEMPERATURE OF ABOUT 350*C. AT AN ELEVATED PRESURE SO CHOSEN AS TO SUBSTANTIALLY PREVENT EVAPORATION OF OIL FROM SAID MIXTURE WHILE ALLOWING EVAPORATION OF WATER THEREFORM, THEREBY FORMING STEAM AND FILLING PORES OF SAID SOLID FUEL WITH PETROLEUM OIL, WITHDRAWING THE THUS FORMED STEAM, RAISING THE TEMPERATURE OF THE THUS FORMED SUBSTANTIALLY WATER-FREE MIXTURE TO ABOUT 400*C. SO AS TO CONVERT A PORTION OF SAID SOLID FUEL INTO LIQUID BITUMEN, WHILE MAINTAINING A PRESSURE SUFFICIENTLY HIGH TO SUBSTANTTIALLY PREVENT VAPORIZATION OF THE THUS FORMED LIQUID BITUMEN, SEPARATING SAID OIL-CONTAINING SOLID FUEL FROM THE REMAINDER OF THE REACTION MIXTURE, SUBJECTING SAID SEPARATED, OIL-CONTAINING SOLID FUEL TO A TEMPERATURE OF AT LEAST ABOUT 500*C. WHILE MAINTAINING A PRESSURE OF ABOUT BETWEEN 0.5 AND 5 ATMOSPHERES, SO AS TO CRACK THE OIL WITHIN THE PORES OF SAID SOLID FUEL THEREBY TRANSFORMING SAID OIL AT LEAST PARTIALLY INTO LOWER MOLECULAR HYDROCARBONS, AND SEPARATING THE THUS FORMED LOWER MOLECULAR HYDROCARBONS FROM THE SOLID FUEL, WHEREBY STEAM AT RELATIVELY HIGH PRESSURE AND TEMPERATURE, A DRY SOLID CARBONACEOUS FUEL, BITUMEN AND LOWER MOLECULAR HYDROCARBONS ARE FORMED FROM SAID PETROLEUM OIL AND SAID WATER-CONTAINING CARBONACEOUS SOLID FUEL.

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