US2689824A - Catalytic process and apparatus for the conversion of mineral oil residues - Google Patents

Description

Sept. 21, 1954 2,689,824

G. GOLL CATALYTIC PROCESS AND APPARATUS FOR THE CONVERSION OF MINERAL OIL RESIDUES Filed Sept. 9, 1949 INVENTDR 6115 few 6o// ATTCI RNEYS 5 Sheets-Sheet 1 Sept. 21, 1954 s. sou. 2,689,824

CATALYTIC PROCESS AND APPARATUS FOR THE CONVERSION OF MINERAL OIL RESIDUES Filed Sept. 9, 1949 3 Sheets-Sheet 2 H I- I Q T 45 a 15 b q if 2 J0 4 INVENTCIR BY Gus/a V0 50// ATTD Sept. 21, 1954 GQLL 2,689,824

CATALYTIC PROCESS AND APPARATUS FOR THE CQNVERSION OF MINERAL OIL RESIDUES Filed SQPt. 9, 1949 3 Sheets-Sheet 3 lig J65 J59 J60 16} 1 J16 Y J04 J69 J59 E-= J99 26,3 168/ 10b J11 /J59 INVENTDR Gus fan/o Gol/ ATTORNEYS Patented Sept. 21,1954

CATALYTIC PROCESS AND APPARATUS FOR THE CONVERSION OF MINERAL OIL RESI- DUE Gustavo Goll, Wilde, Argentina Application September 9, 1949, Serial No. 114,875

2 Claims. 1

The present invention refers to improvements in catalytic processes, and more particularly in processes for the catalytic treatment of hydrocarbons such as cracking and other conversions, the catalytic transforming and reforming and the catalytic synthesis of hydrocarbons.

One of the objects of the invention is to provide a process for catalytically treating even those hydrocarbons which contain only a small proportion of hydrogen atoms in the molecule and which are solid at room temperature under normal pressure, soas to obtain therefrom hydrocarbons richer in hydrogen without the formation of a substantial amount of normally gaseous products.

Another object of the invention is to provide a process permitting the exact control of the catalytic transforming, conversion or synthesis reaction.

Another object of the invention is to provide a process of the kind referred to in which substantially no undesirable by-products and residues are produced so that practically all the starting material is converted into .the desired final products, consisting of valuable fuels, particularly such as gasoline, kerosene and gas oil, this last mentioned product being specially suitable, on account of its high cetane number, for use in high speed diesel engines.

An additional object of the invention is to provide a process of the kind referred to which may be carried out at low temperatures (that is, at temperatures below the boiling point of the starting materials) and consequently without pressure and also continuously.

A further object of the invention consists in providing a process of the kind referred to, in which there is no necessity of discontinuing the process for the purpose of regenerating the catalyst or removing the coke deposited thereon.

Another object of the invention is to provide a process of the kind referred to in which only electric energy is used whilst preheating and previous vaporization of the feed materials are avoided.

A further object of the invention is to provide new apparatus for carrying out the catalytic conversion, reforming and synthesis, particularly the cracking of hydrocarbons.

A further object of the invention consists in providing an improved process for obtaining valuable products such as gasoline, kerosene and a high cetane number gas oil in addition to coke and hard asphalt, or asphalt only; and in the products obtained.

In order to achieve these objects and others which will become evident from the following detailed description of the invention, the process for the catalytic conversion, reformation or synthesis of hydrocarbons, in which the starting material is contacted with a catalyst constituted by one or more electrically conductive solid substances, comprises, according to the invention, the step of subjecting the catalytic mass to the action of an electric current so as to cause the mass to become catalytically active to the desired extent or so as to control in a desired manner said catalytic activity. According to another feature of the present invention, the coke deposited during the process on the catalyst is continuously removed therefrom by means of an electrically insulated scraper or by means of a scraper made of insulating material.

According to another feature of the invention, the apparatus for carrying out the invention comprises a reaction chamber, a member made of catalytic material and arranged within said chamber in contact with the feed material therein, and means for applying a given wattage to each unit of the catalytic surface of said member.

Further features of the invention will be evident from the following detailed description of the invention, in which reference will be made to the accompanying drawings which show schematically and by way of example several embodiments of the apparatus of the present invention. In said drawings:

Figure l is a longitudinal cross-section of an apparatus suitable for carrying out the invention.

Figure 2 is a flow diagram of a process in which the apparatus of Figure 1 is used;

Figure 3 shows a tube connection, with parts broken away, as used in the apparatus of Figure 1;

Figure 4 shows in longitudinal cross-section another embodiment of the apparatus suitable for carrying out the invention; and

Figure 5 is a perspective view, with parts broken away, of a further embodiment of an apparatus suitable for use in carrying out the invention.

In accordance with the above, the present invention is based on the discovery that it is possible to use electric current in order to induce and control in a desired manner the catalytic activity of catalytic material.

The catalyst used in accordance with. the present invention may consist of any known catalytic material provided it be electrically conductive to such an extent that a given wattage may be applied to each square unit of catalytic surface.

When selecting the catalyst for use in connection with the present invention, consideration should be given not only to the greater or smaller catalytic activity in connection with the desired reaction but also its conductivity and furthermore its temperature coenicient. As appropriate materials there may be regarded most of the metals known as catalysts such as tungsten, molybdenum, tantalum and especially the noble metals such as silver and platinum. Particularly suitable catalysts for use in connection with the present invention may consist of alloys of appropriate metals, particularly alloys containing at least one catalytic metal. These alloys should have, in addition to the desired catalytic activity and electric conductivity, the property of not greatly increasing resistance when heated.

In accordance with the present invention the catalyst is arranged within a suitable reaction chamber in such a manner that a predetermined surface be exposed, so that the hydrocarbons or other reagents may be contacted therewith after they have been introduced in said chamber either in batches or continuously. The catalyst may be separated from the walls of the chamber or may constitute said walls or an interior coating thereon, or it may be arranged in several layers or in any other form which may be convenient. In any case, however, the catalyst will be located in such manner that an electric current can be passed through the same or in such a way that the catalyst may be subjected to the action of ultrafrequent currents.

The desired wattage per square unit of catalytic surface may be adjusted either by controlling the voltage of the current or by shortening or extending the path of the current through the catalyst. According to such adjustment the conversion or transformation of the hydrocarbons will be influenced so that a greater proportion of light, medium or heavy hydrocarbons may be formed as principal product.

The process may be carried out in the liquid phase and under atmospheric pressure so that the reaction chambers may be of a light and relatively simple construction.

As starting materials there can be employed heavy crude oils which may be cracked by means of the process of the present invention without any previous treatment such as distillation, etc. Alternatively, as starting material there may be used those hydrocarbons which are obtained as undesirable by-products from distillation, selective solvent refining or thermal or catalytic cracking treatments. These by-products, including even soft asphalts or bitumens, can be converted by means of the process of the present invention into more valuable commercial hydrocarbons such as gasoline, kerosene and high cetane gas oil. It is also possible to treat hydrocarbons and residues consisting of naphthenic and parailinic mixtures in order to obtain as only products fuels such as gasoline, kerosene and gas oil including diesel oil and hard asphalt having a high softening index. Thus, from soft asphalts, or bitumens, or from asphaltite, or from coal or charcoal tars and the like, a hard asphalt of excellent quality may be obtained together with the above mentioned products such as gasoline, kerosene and a high octane number gas oil.

Several embodiments of the invention will now be further explained with reference to the accompanying drawings, in which Figure 2 shows an embodiment of the present invention as applied, to the cracking of residues obtained from ordinary refining, selective solvent refining, vacuum distillation or cracking processes. Reference numeral I designates a topping vacuum or cracking tower of known construction to which hydrocarbons are fed through line 2. The residues leave this tower I through line 3 and are charged through pump 4 to a storing container 5, in which a heat exchange coil 6 is mounted so that the en tering fresh material, which mainly consists of heavy hydrocarbons (for instance soft asphalt, soft bitumen, heavy fuel oil or the like), is undergoing a heat exchange with the material already stored in order to heat the same.

The material to be cracked, which is maintained in liquid state is withdrawn from the storage space 5 through line i by means of a pump 8 and through line 9 it is led to the cracking or conversion space I ll. The conduit ll comprises two branches 9a and 91) through which the feed material may be passed alternatively into the right hand portion or left hand portion of charm ber ill.

Below the chamber ll) there are two coke receiving chambers Ila and Ill), in which the coke formed during the process, is recollected. From said coke receiving'chambers, the coke may be removed and discharged into wagons i2.

The cracked or converted material is with drawn through lines its. and ltib and introduced in a fractionating column Hi, from which the desired final products are discharged through lines i5. Products desired to be subjected to further treatment may be recycled through line l6 provided with a suitable control valve i! (Fig. 1).

The cracking or conversion chamber iii has been illustrated with greater detail in Figure l, in which it is shown as comprising a horizontal cylinder 29 made of catalytic material, for instance an alloy of one or more noble metals, and surrounded by an external layer it made of thermally and electrically insulating material, such as glass wool, rock wool or mineral wool. Figure 1 also shows the above mentioned feed line 1, pump 8, feed line 9 and its branches ta and 8b, coke chambers Ila and Ill), discharge conduits Ida and [3b, fractionating tower I i, the outlet lines 15 therefrom and conduit it which permits recycling of material if desired. The fresh feed supply conduit 7 is provided with a one way valve it by means of which the pressure of the material fed into cylinder 20 may be adjusted to a predetermined value for which purpose a returnconduit 2! and a similar pressure control valve 19 therein are provided. Branches 9a and ill) are each provided with one way or clack valves 22a and 2279 respectively which enable the associated branch to be closed or opened so as to feed the fresh material or the mixture of fresh and recycled material alternatively to one or the other end of cylinder 20.

Within cylinder 2?] a piston 23 is housed which is fixed to a rod 24. Said rod extends longitudinally through the full length of cylinder 20 and the lateral cylindrical extensions 25a and 25b thereof, and is supported for sliding movement by means of ball bearings (not shown) or the like in openings 26a and 25b in the lateral walls 21a and 21b, respectively of extensions 25a and 2%.

One end of the rod 2 is connected eccentrically to a driving wheel 28, driven from an electrical motor (not shown) or the like so that the rotation of wheel 28 will reciprocate rod 24 and piston 23. The peripheral wall of piston 23 is in close contact with the inner wall of cylinder and due to its reciprocal movement the piston will wipe from said inner wall 20 any solid matter such as coke deposited thereon during the treatment.

In accordance with the above, below the reaction chamber I 0, there are two coke receiving chambers I la and Ill) into which the solid material scraped by piston 23 from walls 20 is discharged. These chambers are normally closed by the closure members 29a and 2% which are slidable on piston rod 24. Normally they are urged by springs 43 against abutments 44 so that during the reciprocal movement of the rod and piston, said members 2 9a and 2% remain in their sealing position shown in Figure 1. The rod 24 is provided with disk-like members 30a, 30b integral therewith. When piston 23 approaches one of the lateral ends of cylinder 20, said disks 30a, 30b will push the respective closure member 29a, 29b out of its sealing position and displace the same into the respective cylindrical or tubular extension 25a, 251) against the action of spring 43. The solid material, which is being pushed forward by piston '23 as the same advances, is then discharged into the upper mouth of containers Ha, I lb, which are provided with cooling sleeves 3| to which a cooling medium such as water, may be supplied through conduits 32 from a suitable source (not shown). The lower ends of chambers I 6a, lBb are closed by suitable valves 33a, 33b, which permit intermittent discharge of the solid material.

In accordance with the invention the catalyst is to be subjected to the action of electric current. For this purpose a transformer 34 is provided, which has several positive and negative terminals 35a, b, 36a, b and 37a, b. A slide switch 38 is adapted to connect any pair of terminals to the rail conductors 39a, 3922. By means of slide switches 40 these rails may be connected with terminals 41a, 4|b, so as to apply electric current to the cylinder wall 20. It will be understood that by means of the switches and connections shown it will be possible to adjust the wattage to the desired value per square unit of catalytic surface.

The discharge conduits [3a and |3b are provided with suitable closure valves 42a, 42b, respectively which are alternatively opened and closed in accordance with the reciprocal movement of piston 23. Automatic, electrical or mechanical devices may be provided in order to open and close these valves in the requisite timed relationship with the reciprocal movement of piston 23, and in the same way the operation of valves 22a, 22b may be automatic, or it may be electrically or mechanically controlled.

During operation, feed material is admitted through valve 22a into the left hand end of cylinder 20. Valves 22b and 42a are closed Whilst valve 42?) is open. Piston 23 moves from the left to the right, and while that portion of cylinder 20 which lies behind the piston 23 is being filled, the material which had been introduced through valve 22b during the preceding stroke into the right hand portion of cylinder 20, is now being displaced towards end 21b by the movement of piston 23. The vapours formed leave through valve 42b and conduit I3?) and are treated in fractionating tower l4. The solid material formed is pushed forward by piston 23 towards end 21?), and such solid material which may be adhering to the walls of cylinder 20, is scraped.

oif and falls to the bottom and is pushed forward by piston 23. The tension of spring 43 must be stronger than the resistance offered by valve 42b to the vapours formed, and the speed of the movement of piston 23 is adjusted in such a manner that all the material in the right hand portion of cylinder 20 has been converted into the desired hydrocarbons and coke and that all the hydrocarbon vapours formed have left through valve 42b by the time disk 3% engages closure member 29b and displaces it from its seat in the mouth of container Ilb. The piston now discharges all the coke from the batch into chamber [lb and then starts travelling back towards the left hand side. Due to the effect of suction thus produced, valve 422: closes. Under the pressure of pump 8, valve 22b opens and as pressure is built up in the left hand portion of cylinder 20, valve 22a closes whilst valve 42a opens. The material previously introduced into the space at the left hand side of piston 23 through valve 22a is converted into vapours and coke and removed from cylinder 20 in the manner already described.

it will be understood that it is possible to have the whole system operate automatically and for this purpose valves 22a and 2212 may be double seat valves offering a greater surface to the pressure originated within cylinder 2|] by piston 23 than to the pressure of pump 8 adjusted by valves i8, I 3. Valves 22a, 22b will then open only when the piston travels away from them whilst they will close at once when the piston 23 travels towards them. Alternatively, electrical or mechanical connections may be provided to effect the opening and closing of valves 22 and 42 whenever piston 23 reaches a given position, for instance one end of cylinder 20.

It will be clear that the piston rod 24 may be reciprocated by any suitable means. Whilst I have shown an eccentric connection to a 28 (Figure 2) it may be advisable to use instead of this arrangement a shaft driven by an electric motor alternatively in a clockwise and anti-clockwise direction. A cable connected to the end of rod 24 is wound on this shaft so that the same is moved toward with said shaft. At the opposite end a similar shaft is arranged and driven in unison with the first shaft so that when shafts start rotating in an opposite direction the piston rod is moved towards the second shaft on which a cable connected to the opposite end of rod 24 is wound up. In this case piston 23 is fastened to rod 24 so as to move together with the same.

It will be understood that, since during the whole process electric current from transformer 34 is applied to cylinder 20, piston 23 must be electrically insulated because it is in contact with the cylinder wall 20. For this purpose insulation 45 is provided at each side of piston 23. This insulation is shown in detail in Figure 3 and comprises flanges 46, one flange being provided at either side of piston 24. Each flange 46 has two or more perforations 41 through which bolt 48 of a screw 49 passes. The stem of bolt 4:8 is longitudinally insulated from opening 47 by insulating layers, for instance porcelain or steatite or the like. Similarly, the flanges are separated one from another by two rings 5| of packing material and a ring 52 made of mica or the like inserted between said packing rings. Similarly, the head of screw 49 is separated from flange 4 6 by two packing washers 53 and a mica washer 54 inserted between these. Finally, nut 55 is separated from flange 46 by a washer 56. The connection described provides a perfect insulation of heat resistant materials.

In order to avoid short circuits when piston 23 arrives at one end of cylinder 20 and enters one of the tubular extensions 25a 25b, similar insulations are provided between cylinder 20 and extensions 25. It will be noted that two insulations are arranged at each lateral end and they must be spaced one from another a distance greater than the width of piston 23 so that the piston be unable to bridge the space between the inner and outer insulations 51.

It will be understood that the whole apparatus has to be sealed and especially in the openings 25a and 26b packing glands may be used. However, the cracking or other catalytic conversion may be effected at relatively low, pressure and preferably at substantially atmospheric pressure.

In order to apply the desired electric current one transformer may be employed. in association with a number of chambers In, for example three and these can be connected to form a star or Y-connected system. The voltage, wattage, etc., will have to depend on the nature of the feed material, the electric and thermal properties of cylinder 2% and the duration of the treatment. Also, the speed of the travel of piston 23 should be adjusted accordingly. For this purpose a re duction gear may be included in the driving means for rod 24.

Figure 4 shows another example of an apparatus for carrying the present invention into practice. This embodiment comprises a horizontal reaction chamber I I0, of generally cylindrical shape. The feed material is introduced through inlet line Hi9 controlled by suitable valve means (not shown) The vapours formed are withdrawn through line I I3 to fractionating tower I I4, from which material may be recycled, if desired, through line H5. Below chamber IID there is one or more coke receiving vessels I I I.

The required electric current is supplied from transformer I345 over rails I38. Switches (not shown) similar to those in Figure 1 will be provided.

Within chamber IIIl there is a cylinder I20 made of catalytic material and supported on a bar i528 connected outside the chamber IIO to rails E39 over which electric current may be supplied to cylinder I20.

coke deposited on cylinder I It is removed by a rotary scraper comprising a rotary frame I59 on which scraper blades I50 are mounted. These blades are fixed to the frame by means of screws it! which are insulated in a similar way as screws it in Figure 3. To completely insulate blades use from frame I59, insulating plates I62 are interposed. It will be noted that the blades on. the upper arm of frame I59 are in staggered relationship with the blades on the lower arm of frame It!) so that, when frame I59 revolves, each blade 565i travels over a different path on the surface of cylinder I20. If the frame consists of more than two arms, a corresponding arrange ment will be employed.

The arms of frame I59 are connected at each lateral end to a sleeve I63 adapted to rotate on bar I58. If desired, antifriction devices such as roller bearing or the like may be employed. Also, insulating tubes I64 are interposed between supporting bar I58 and sleeves I63.

One of the sleeves I63 is fixed at its outer end to a gear wheel I65 adapted to mesh with another gear I65 driven by driving shaft IB'I which in turn is driven from a suitable power source, e. g., and electric motor (not shown).

The operation of the device of Figure 4 is as follows: Feed material is.- admitted into chamber III) until cylinder I20 is completely below the level of the liquid. Current is then applied tocylinder I20 and the scraper is slowly rotated. Coke and other deposits scraped from cylinder I20 by means of blades I60, drop to coke receiving bottom III where they are collected in containers I68 slidable on rails I69. The containers are intermittently removed from portion II of chamber I ID to discharge the coke, and then reintroduced. Such discharge is elfected only when there is no liquid in chamber H0.

In this embodiment it will be evident that instead of providing a rotary scraper, cylinder I20 may be rotary and the scraper stationary. There must be relative movement, however, between these two parts.

A further embodiment is shown schematically in Figure 5. This embodiment comprises two reaction chambers 2H3 connected by lines 238 to a fractionating tower 2M. The hydrocarbons ob tained may thus be discharged into said tower 2.

Within each chamber m a number of axially extending tubes or bars of catalytic material 228 are located. These tubes or bars are separated from the walls of chambers 2H] and connected to a source of electric current (not shown) so that electric current may be passed through said tubes or bars.

A scraper plate 259 is arranged within each chamber 2IEl and is provided with holes 26!! through each of which one of tubes or bars 220 passes. The plate 259 is of electrically insulating material such as porcelain or steatite, or alter natively each hole 260 may be lined with such material (at 216) and the holes or linings, respectively, tightly fit around the respective tubes or bars passing therethrough.

Below the scraper plate 253 there is a coke receiving vessel Z68 adapted to slide on rails 259.

During operation, liquid feed material is first admitted through a feed line and suitable valves (not shown) into one of the chambers Zit until the same is filled up to a level above the uppermost tube or bar 220. Electric current is then applied to each of said tubes or bars. 22%.

The batch of feed material is converted into the desired gaseous products and coke which deposits on bars or tubes 22c and is continuously scraped off by plate 259 so that it falls into the box 268. This is removed from the chamber by sliding it outwardly on rails 259 and the coke is discharged therefrom. While this is being done, the second chamber 2H3 is operated in a similar way.

It will be evident that a number of changes may be introduced in the details described and shown without departing from the essence of the invention as defined in the annexed claims.

What I claim is:

1. A process for converting mineral oil residues and natural products of similar nature, such as natural asphalts or the like, into liquid fuels of the group comprising gasoline, kerosene and gas oil, and into hard asphalt and coke, without formation of any other kind of residues, which comprises feeding the material to be converted in the liquid phase through inlet openings, into a reaction chamber the inner space of which comprises at least one body consisting of electrically conductive and catalytically active metal, containing at least one catalytically highly active non-ferrous metal; passing electric current through said body and controlling the power of said current so as to produce without any additional supply of heat the desired high degree of catalytic activity of said body; actuating an electrically insulated piston in said chamber for simultaneously removing through an outlet opening the vapors formed in said chamber, introducing additional material to be converted into said chamber through one of said inlet openings; removing from said body solid deposits such as coke, and moving closure members for disposing of said coke into receiving chambers.

2. Apparatus for converting mineral oil residues and natural products of similar nature, such as natural asphalts or the like, into liquid fuels of the group comprising gasoline, kerosene and gas oil, and into hard asphalt and coke, without formation of any other kind of residues, which comprises a horizontal cylindrical reaction chamber, the inner space of which comprises at least one body made of a catalytically highly active, electrically conductive metal, containing at least one non-ferrous metal; a transformer provided with switches and connections for passing a controlled supply of current through said body; discharge openings for vapors formed in said chamber disposed at each end of said chamber; dis- 10 charge openings for solids formed in said chamber disposed at each end of said chamber; coke receiving chambers communicating with said discharge openings for solids; an electrically insulated piston arranged for reciprocal movement within said chamber between said openings at one end and said openings at the other end in frictional contact with said body; a piston rod secured to said piston for causing movement thereof; closure members slidably positioned on said piston rod; and means secured to said piston rod adapted to contact said closure members for moving said closure members out of engagement with said discharge openings for solids, thereby providing for the discharge of solids formed in said chamber.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,324,213 Stapp Dec. 9, 1919 1,386,484 Adsit Aug, 2, 1921 1,616,515 Swoboda et a1. Feb. 8, 1927 2,533,945 Legatski Dec. 12, 1950

Claims (1)

1. A PROCESS FOR CONVERTING MINERAL OIL RESIDUES AND NATURAL PRODUCTS OF SIMILAR NATURE SUCH AS NATURAL ASPHALTS OR THE LIKE, INTO LIQUID FUELS OF THE GROUP COMPRISING GASOLINE, KEROSENE AND GAS OIL, AND INTO HARD ASPHALT AND COKE, WITHOUT FORMATION OF ANY OTHER KIND OF RESIDUES, WHICH COMPRISES FEEDING THE MATERIAL TO BE CONVERTED IN THE LIQUID PHASES THROUGH INLET OPENINGS INTO A REACTION CHAMBER THE INNER SPACE OF WHICH COMPRISES AT LEAST ONE BODY CONSISTING OF ELECTRICALLY CONDUCTIVE AND CATALYTICALLY ACTIVE METAL, CONTAINING AT LEAST ONE CATALYTICALLY HIGHLY ACTIVE NON-FERROUS METAL; PASSING ELECTRIC CURRENT THROUGH SAID BODY AND CONTROLLING THE POWER OF SAID CURRENT SO AS TO PRODUCE WITHOUT ANY ADDITIONAL SUPPLY OF HEAT THE DESIRED HIGH DEGREE OF CATALYTIC ACTIVITY OF SAID BODY; ACTUATING AN ELECTRICALLY INSULATED PISTON IN SAID CHAMBER FOR SIMULTANEOUSLY REMOVING THROUGH AN OUTLET OPENING THE VAPORS FORMED IN SAID CHAMBER, INTRODUCING ADDITIONAL MATERIAL TO BE CONVERTED INTO SAID CHAMBER THROUGH ONE OF SAID INLET OPENINGS; REMOVING FROM SAID BODY SOLID DEPOSITS SUCH AS COKE, AND MOVING CLOSURE MEMBERS FOR DISPOSING OF SAID COKE INTO RECEIVING CHAMBERS.

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