US3369996A - Petroleum binder oil from catalytic cracking - Google Patents

Description

Feb. 20, 1968 G. P. HAMNER 3,369,996

PETROLEUM BINDER OIL FROM CATALYTIC CRACKING Filed May 20, 1965 GASES PRODUCT 3\ ,/FRACTIQNATOR l8 [CATALYTIC CRACKING ZONE /l 12 2 FLASH /DISTILLATION 4\ ZONE HOPPER 'L 2s STEAM 26 ASPHALT Glen Porter Humner mm PATENT ATTORNEY United States Patent ()fiiee 3,3693% Patented Feb. 20, 1968 3,369,996 PETROLEUM BINDER OIL FROM CATALYTIC CRACKING Glen Porter Hamner, Baton Rouge, La., assignor to Esso Research and Engineering Company, a corporation of Delaware Filed May 20, 1965, Ser. No. 457,318 7 Claims. (Cl. 208120) This invention relates to an improved process for the preparation of carbonaceous binders suitable for use in carbon or graphite electrodes. More particularly, this invention relates to an improved process for the preparation of carbonaceous binders from catalytic fractions of coal tar, petroleum, or shale oil for use in carbon or graphite electrodes which are equal to or superior to those of the prior art.

Heretofore, carbon or graphite electrodes have generally been produced from a suitable hard carbonaceous material, usually calcined coke. However, inasmuch as the coke has no natural adhesiveness, it must be bound together in the desired shape or configuration with a suitably compatible material. Hence, when producing electrodes, the coke is usually ground, mixed with a binder material, molded, and subsequently baked so as to carbonize said binder material. It is well known in the art relative to electrode production that the nature and quality of the binder material used is extremely critical. For example, if pitch is employed as the binder material, such pitch must fall within a relatively narrow range of specifications in order to be suitable as a binder material.

It is also well known that the specifications of these binder materials are empirical in nature. A low hydrogen to carbon atomic ratio is required in order to minimize the development of porosity during the electrode operation. In addition, a high coking value is necessary. The coking value is a measure of the amount of coke residue produced by a pitch when decomposed by heating at 1200 F. for four hours. A softening point of 180 F. to 320 F. is also required. Softening points of less than 180 F. do not provide a sufiicient binding of the fabricated electrode and the formations tend to loose shape in the pre-calcination warm-up technique utilized. On the other hand, the materials possessing extremely high softening points, i.e. above 320 F., are not amenable to mixing with coke particles, they do not have enough plasticity for effective molding operation, and also possess other inherent disadvantageous characteristocs. Hence, the softening is preferably within the range of temperatures of from 180 to 320 F. The pitches softening in the lower portion of this range are designated as soft pitches, and those softening in the upper portion of said range are designated as hard pitches.

Inasmuch as the Conradson carbon value is a measure of coking properties, it is manifest that a high Conradson carbon content, at an accepted softening point, is desirable. Hence, the relationship between Conradson carbon and softening point values become a criterion in evaluating the pitch product.

In the past, coal tar pitch has been substantially exclusively employed as the binder material in the manufacture of carbon products, e.g. carbon electrodes, inasmuch as petroleum pitches generally did not meet the above specifications, for example, did not contain appreciable benzene and quinoline insolubles and, hence, were generally undesirable as binders. The petroleum pitches were found undesirable because of a plurality of reasons, such as, for example, the electrodes made therefrom were of uneven mechanical strength and varied in electrical conductivity. While highly aromatic tars resulting from cracking processes appeared potentially attractive, such tars failed to result in a production of a satisfactory pitch which was acceptable as a binder. For example, if the coking value and content of benzene and quinoline insoluble matter of the resulting binders were high enough to satisfy the desired specifications, then the softening point was found to be too high. Conversely, if the softening point was in the correct range, then the coking value and content of benzene and quinoline insoluble matter was too low. Further, white some processes in the prior art relating to petroleum pitches resulting in a binder material would satisfy the desired specifications, such processes had serious inherent disadvantages which made them commercially unattractive. One such disadvantage was the tendency to form insoluble fractions during processing which settled from the product in storage and/ or caused fouling in the process facilities utilized.

With regard to coal tar, as hereinbefore mentioned, pitch prepared from such coal tar has been almost universally employed as the binder material in the manufacture of carbon products. It thus follows, naturaly, that it is also desired to provide a process which produces such binder material in yields higher than those heretofore realized, while maintaining standards equal to or better than the specifications set forth.

It is an object of the present invention, therefore, to provide and improve binder material in yields superior to those heretofore realized. It is another object of the present invention to provide a process which will produce a superior binder material from coal tar or petroleum fractions in yields higher than those heretofore realized. It is still another object of this invention to provide a binder material from petroleum residue which will simulate the physical properties of a coal tar pitch binder. It is a further object of this invention to provide a process for the production of highly desirable binders from petroleum residues without incurring the disadvantages heretofore known in the related art. It is also an object of the present invention to provide a commercially feasible, continuous process for converting coal and petroleum tars to valuable electrode binder pitches. Other objects and advantages will become apparent from discussion and disclosure which follow.

The sole figure is a schematic flow diagram illustrating a preferred method for practicing the process in a continuous manner.

In accordance with the present invention, it has been found that the above objects can be accomplished by subjecting a suitable feedstock, e.g. mid-boiling fractions, i.e. gas oil (SOD-1050" F.) from crude petroleum, to catalytic cracking with a molecular sieve catalyst or a blend of said molecular sieve catalyst with silica, silica-alumina, alumina, activated carbon a high surface area binder, or the like. Said catalytic cracking is effected at a temperature in the range of 7501050 F. and under pressures of from 0 to 500 p.s.i.g. A catalyst to petroleum feed ratio of about 1:40 is employed and the reaction is generally efiected at flow rates of from 1 to 14 w./hr./w.

In accordance with the invention, it has also been found that an addition of a suitable carbonaceous material, e.g. carbon black, to the binder oil fraction, which has been preferably stripped to a softening point of 180 F. or more, may be made in order to advantageously control the fluidity of the binder oil, e.g. when employed in Soderberg-electrode production. Accordingly, it is contemplated to add such carbonaceous material in amounts ranging from about 2 to 10 wt. percent, preferably 2.5 to 5 wt. percent, based on the total binder oil fraction.

A petroleum bind'er oil produced in accordance with the process of the present invention is found to have a composition of desired components similar to those of coal tar pitch. Prebaked electrodes made from a petroleum binder oil having a minimum concentration of benzene and quinoline insolubles are found advantageously to equal to the standard coal tar products of the prior art.

More specifically, the processing sequence of the present invention involves treating the gas oil fractions of crude petroleum in the following manner:

FEED INSPECTIONS (1) Mid-boiling fractions, i.e. gas oil (5001l50 F.) from crude petroleum is introduced to a one-pass catalytic cracking in which the napthalenes and isoparaifins contained therein are largely converted to lighter boiling products, including gasoline and heating oils. Trace impurities such as nitrogen, sulfur, and metals may be reduced in this step through carbon deposition on the cracking catalyst.

(2) The mid-boiling fraction (590650 F.) from step (1) may, if desired, be sent to steam cracking at temperatures of about 1100 F. to 1500 F. in which the linear chain paraffins are substantially converted to olefins and diolefins which are preferred in the utilization as basic chemical raw materials.

(3) The higher boiling aromatic and condensation products (850 F.+) from step (1) are recovered as a catalytically-cracked material. This material is subsequently stripped to a softening point temperature of 180 F. or above. While said stripping operation is being effected it may be desirable to add a carbonaceous material as disclosed above.

The charge stock for the process of this invention may be any petroleum crude oil which ordinarily would be used for the preparation of petroleum products. The process is particularly valuable for the preparation of such products from naphthenic base crude oils such as those obtained from Southern Louisiana fields. Other charged stocks especially advantageous for use in the process of this invention include residual gas oils from propane/ butane deasphalted vacuum residuum, thermal gas oils, coal tar oils, and shale oils of equivalent boiling range previously disclosed.

The actual practice of this invention may be understood more readily by reference to FIGURE 1 attached herewith. In FIGURE 1, a topped crude oil from an atmospheric tower, not shown, in which for example, a furnace oil and lighter fractions have been removed, is delivered through line to vacuum tower 1. In accordance with the invention, the top crude oil introduced into tower 1 has a boiling point of above 600 F. and, preferably, a boiling range of 650 to 1150 F. Vacuum tower 1 is operated at a flash temperature corrected to atmospheric pressure above about 900 F., and may range up to a corrected equivalent temperature of about 1300 F. A distillate gas oil, that is, a heavy virgin gas oil, suitable for use as a catalytic cracking charge is discharged through line 12 from the top of vacuum tower 1 and a bottoms fraction containing virgin heavy residuum is delivered via line 14 from the bottom of the vacuum tower 1. Ordinarily steam is injected to a line into the bottoms of the vacuum tower to aid in the stripping of volatile components from the bottoms fraction, i.e. high a'sphaltenes or asphalt which are removed from the bottom of tower 1. Thus, in accordance with the invention the vacuum distillation effected in tower 1 may be defined as one adapted to remove a distillate, i.e., the heavy gas oil fraction having a boiling range of 500 to 1350 F. and preferably 650 to 1150 F.

The heavy virgin gas oil removed from the top of tower 1 via line 12 is introduced into catalytic cracking zone 2. The operation per se conducted in zone 2 constitutes a conventional type of once-through catalytic cracking operation. Hence, the catalytic cracking may constitute the fixed-bed type of. cracking, moving bed type of cracking or fluidized catalytic cracking. In accordance with the present invention, the cracking catalyst system employed in said catalytic cracking zone consists essentially of a molecular sieve catalyst, or a blend of said molecular sieve catalyst with silica, silica-alumina, alumina activated carbon or a high surface area binder. Accordingly, cracking conditions require maintenance of temperatures in the range of about 650 to 1150" F. and preferably 750 to 1050 F. and at pressures ranging from O p.s.i.g. to about 500 p.s.i.g. The catalytic cracking catalyst is employed in a catalyst to heavy virgin gas oil ratio of from 1:1 to 40:1 and preferably 4:1 to 20:1. The flow rate through said catalytic cracking zone is maintained at a rate of from 1 to 14 w./hr./w. preferably 1 to 4 w./hr./w. The catalytic agent employed is regenerated intermittently or continuously in order to restore or maintain the activity of the catalyst. The typical operation, catalytic cracking of the heavy virgin gas oil feed results in conversion of about 30 to 60% boiling in the gasoline boiling range and about 70 to to gasoline and lighter.

More specifically, the cracking catalysts which are employed in accordance with the process of this invention consists essentially of crystalline alumino-silicate zeolites, commonly referred to as molecular sieves or crystalline alumino-silicate zeolites blended with silica, silica-alumina, alumina activated carbon or a high surface area binder. Such crystalline alumino-silicate zeolite are well known in the art and they are characterized by their highly ordered crystalline structure and uniformly dimensioned pores. They are distinguishable from each other on the basis of composition, crystal structure, adsorption properties, and the like. The term molecular sieves is derived from the ability of these zeolite materials to selectively adsorb molecules on the basis of their size and form. The various types of molecular sieves may be classified according to the size of the molecules which will be rejected (i.e. not adsorbed) by a particular sieve. A number of these zeolite materials are described, for example, in U.S. Patent 3,013,982, wherein they are characterized by their composition and X-ray diffraction characteristics.

In general, the crystalline alumino-silicate zeolites within the purview of the present invention may be represented by the following formula, expressed in terms of moles:

wherein M is selected from the group consisting of metal cations and hydrogen, n is its valence, and X-is a number from about 1.5 to about 12. The value of X will vary with the particular zeolite in question. Among the wellknown natural zeolites are mordenite, faujasite, chabazite, gmelinite, analcite, erionite, etc. Such zeolites differ in structure, composition, and particularly in the ratio of silica to alumina contained in the crystal lattice structure; e.g. mordenite, having a ratio of about 8 to about 12; faujasite, having the ratio of about 2.5 to about 7; etc. Similarly, the various types of synthetic crystalline zeolites, e.g. faujasite, mordenite, etc., will also have varying silica to alumina ratios depending upon such variables as compositions of crystallization mixture, reaction conditions, etc. US. Patent Nos. 3,013,982-86 describe a number of synthetic zeolites, designated therein as zeolites A, D, L, R, S, T, X and Y.

The processes for producing such crystalline synthetic zeolites are also well known in the art. Typically, they involve crystallization from reaction mixtures containing: A1 0 as sodium aluminate, alumina sol and the like; SiO as sodium silicate and/ or silica gel and/ or silica sol; alkali metal oxide, e.g. sodium hydroxide, either free or in combination with the above components; and water. Careful control is kept over the alkali metal oxide concentration of the mixture, the proportions of silica to alumina in alkali metal oxide to silica, the crystallization period, etc., to obtain the desired product.

The zeolite which will be most preferred in the present invention is the synthetic faujasite variety, wherein X in the above formula is about 2.5 to 7, preferably 3 to 6, most preferably 4 to 5.5. Itwill usually have an average pore diameter of about 6 to 15, preferably 8 to 13, A. A conventional scheme for preparing synthetic sodium faujasite is as follows:

Colloidal silica or silica hydrosol is mixed with a solution of sodium hydroxide and sodium aluminate at ambient temperature. Suitable reactant molar ratios fall within the following ranges: Na O/SiO 0.28 to 0.80; SiO Al O 4 to 40; H O/Na O, 15 to 60. The reaction mixture is preferably allowed to digest at ambient temperature for up to 40 hours or more, preferably 1 to 15 hours, or cooled to below about 80 F., in order to aid crystallization, and then heated to and held at about 180 to 250 F., e.g. 200 to 220 F., for a sufficient period to crystallize the product and to achieve maximum crystallinity, e.g. 24 to 200 hours or more, typically 50 to 100 hours. A crystalline hydrated sodium alumino-silicate zeolite having a faujasite structure is the separated from the aqueous mother liquor by decantation or filtration, washed, and dried to recover a crystalline product. It is then calcined at temperatures up to about 1000 F. in order to remove the water of hydration and thereby form interstitial channels which confer adsorptive and catalytic properties.

The crystalline alumino-silicate zeolites which are used as catalytic agents in the cracking step of the instant process must be subjected to cation exchange to reduce their alkali metal oxide (e.g. Na O) content to less than about 10 wt. percent, preferably less than about 6 wt. percent since alkali metal oxides do not effectively promote the desired cracking reactions. Accordingly, the alkali metal oxide content is customarily reduced by ion exchange treatment with solutions of ammonium salts, or salts of metals in Groups I to VIII or the rare earth metals, preferably metals in Groups II, III, IV, V, V-I-B, VII-B, VIII and rare earth metals. Specific examples of suitable metals include magnesium, calcium, boron aluminum, nickel, cobalt, yttrium, cerium, platinum, iron, copper, zinc, manganese, palladium and lanthanum. The alkaline earth metals will be preferred, with magnesium being particularly preferred. The ion exchange can be simply accomplished by slurrying the zeolite product with an aqueous solution of the desired cation at temperatures of about 60 to 180 F. to replace the alkali metal, and washing the resulting base-exchange material free of soluble ion prior to drying. Suitable salt solutions include, for example, magnesium sulfate, calcium chloride, barium chloride, iron sulfate, ammonium hydroxide, ammonium chloride, etc. Magnesium ion has been found to be especially valuable informing a superior cracking catalyst.

With regard to the use of crystalline zeolites as catalytic cracking catalysts, it has been found that the extremely fine size crystals which are usually produced in their manufacture have generally proved unsuitable in moving or fluidized bed operations because of excessive carryover losses. Additionally, these crystalline zeolites are frequently unsuitable for direct use as catalysts because 6 of their extremely high activities which often lead to over conversion and undesirable product selectivity. Accordingly, it has been discovered that an improved form of crystalline alumino-silicate zeolite, which is usitable for moving or fluidized bed operations can be produced by distributing the crystalline zeolite throughout a siliceous gel or cogel matrix. The terms gel and cogel as used herein are intended to include gelatinous precipitates, hydrosols, or hydrogels of silica' and/or admixtures of silica and one or more oxides of metals selected from Groups II-A, III-A and IV-B of the Periodic Table, e.g. alumina, magnesia, zirconia, titania, etc. The silica content of the gel may range from about 55 to wt. percent. The term siliceous as used herein is thus intended to include silica per so as well as silica in combination with one or more of the above metal oxides. Silica-alumina cogel is especially preferred. The resulting composite,

which consists of crystalline zeolite distributed throughout a siliceous gel or cogel matrix, has been found to exhibit improved catalytic selectivity, stability and fluidization properties.

A relatively simple means of incorporating the crystalline alumino-silicate zeolite into the siliceous matrix is to add pre-formed zeolite crystals to a suitable hydrogel such as silica-alumina hydrogel, and homogenize the resulting mixture by passage through a blending apparatus, such as a colloid mill, ball mill, and the like. The homogenized slurry is then formed into particles of a size range desired for fluidized bed operations. This may be conveniently accomplished by any rapid drying technique, such as spray drying, although other methods may be employed. For the catalytic cracking purposes, of this invention, the final composite catalyst will typically contain about 4 to 12 wt. percent crystalline zeolite. The water content of the hydrogel or gelatinous precipitate before spray drying is adjusted to within the range of about 88 to 96 wt. percent, and the crystalline aluminosilicate zeolite is added in sufficient amount to produce the aforementioned compositions. The resulting slurry is mixed well and is then formed into fluidizable particles by spray drying.

In accordance with the invention, the alumino-silicate composition utilizable herein may be suitably blended with other materials having catalytic properties for the treatment of petroleum oils. Suitable materials include, for example, silica or silica and one or more metallic oxides, such as, alumina, magnesia, zirconia, beryllia, boria, and the like. These catalysts are generally prepared from silica hydrogel or hydrosol, then mixed with a suitable metallic oxide, preferably alumina. A standard catalytic agent is one containing about 13% alumina and 87% silica.

In addition to foregoing co-agents, activated carbon may also be blended with the alumina-silicate catalytic agents of this invention.

The blends of co-catalytic agents with the aluminosilicates of this invention may be used in powdered, granula, or molded state formed into spheres or pellets or finely divided particles having a particle size of 2 to 500 mesh. The catalytic blend is then preferably pre-calcined in an inert atmosphere near the temperature contemplated for cracking but may be calcined initially during use in the cracking operation. Generally the catalyst blend is dry between F. and 600 F. and thereafter calcined in air or in inert atmosphere of nitrogen, hydrogen, helium, flue gas or other inert gas at temperatures ranging from about 500 F. to about 1500 F. for periods of time ranging from 1 to 48 hours or more.

Referring again to FIGURE 1, the products of the once-through catalytic cracking operation are removed from the catalytic cracking zone 2 through line 16 for introduction to a product fractionator 3 which may constitute one or more distillation zones. Distillation zone may be operated to permit removal of like portions of the catalytically cracked product through an overhead line; to permit the removal of gasoline, furnace oil, and the like through one or more side stream controls, and; to permit heavier fractions of the catalytically cracked products, for example, light catalytic cycle oil (LCCO) and heavy catalytic cycle oil (HCCO) from the lower portions of the said fractionator 3. Thus, a light catalytic cycle oil (LCCO) fraction boiling above about 400 F. and boiling up to about 600 F. may be removed from a lower side stream Withdrawal 18. Similarly, a heavy catalytic cycle oil (HCCO) fraction boiling above about 590 F. and boiling up to about 850 F. may be removed from a lower side stream withdrawal 20. In accordance with the present invention, heavy residual fractions of the catalytically cracked products are removed from the bottom of fractionator through line 22. The bottoms withdrawal stream 22 will include hydrocarbons boiling about 850 F. and boiling up to about 1200 F. or higher. In the event that a powdered catalyst is employed in the catalytic cracking zone 2, some catalysts will be entrained in the bottoms withdrawal. In this case, the product of line 22 may be subjected to a clarification or filtration operation in order to segregate the hydrocarbons from cracking catalysts, and the product of this operation is commonly called clarified oil.

The bottoms withdrawal stream, in line 22 from product fractionator 3, comprising catalytically cracked product is delivered through said line 22 into an atmospheric flash distillation tower 4. Fractions boiling at 900 F. and lower temperatures are removed as distillate products from tower 4 via line 24 and a petroleum binder oil product is discharged as a bottoms product through line 26. The flash temperature in tower 4 is controlled such that the overhead vapors range from about 800 F. up to about 950 F. The maximum flash temperature in the tower is critical in accordance with this invention since it is employed to obtain the desired specific softening point, e.g. 180 F. or more, in the final binder oil product.

In an embodiment of the present process, the carbonaceous material may be added to the binder oil fraction for controlling the fludity of the binder oil when used for Soderberg-type electrode production, e.g. in amounts of from 2 to 10 wt. percent, preferably 2.5 to 5 wt. percent, based on the total binder oil fraction. Accordingly, said carbonaceous material may be added prior to or subsequent to subjection to vacuum distillation in the zone 4. As illustrated in FIGURE 1 said carbonaceous material is added from hopper or bin 5 via line 28 into the final binder oil product. The carbonaceous materials which find utility in the manufacture of the petroleum binder oil compositions of this invention are those carbonaceous materials which are amorphous in nature. Representative carbonaceous materials can be employed out of those materials which are found in their natural state or derived from material wherein carbon is constituent as in coal, petroleum, gas or oil and asphalt materials. Carbon obtained artifically, in varying degrees of purity, as carbon black, lamp black, activated carbon, charcoal and coke are suitable sources which can be employed to obtain carbon in the manufacture of the catalytic compositions of this invention.

As mentioned, the attractive advantage of this invention is increased binder oil yields and the increased Conradson carbon values for binder oils of given softening points as compared with binder oils produced by other processes of the art. The production of a marked increase in benzene/quinoline insoluble components Without the formation of coke is also a unique feature of the process. As employed herein, the Conradson Carbon value is defined as wt. percent carbon residue after evaporation by destructive distillation (ASTM D189 Procedure). The softening point is defined as that temperature at which a steel ball drops through a specific quantity of sample suspended in glycerine (ASTM D36-62T).

In order to illustrate the unique features and advantages of the process hereinbefore described, references made to exemplary data attained in evaluating the process of this invention.

Example I Part APreparati0n of Sodium Form of Crystalline Alumina-Silicate Ze0lite.-The sodium form of a crystalline aluminosilicate zeolite having a silica to alumina mole ratio of about 5.1 was prepared by the following typical procedure.

A solution of 30.0 kilograms of NaOH and 8.5 kilograms of sodium aluminate in 107.5 liters of water was added with stirring to 193.0 kilograms of low soda Ludox (30 wt. percent silica hydrosol supplied by E. I. duPont de Nemours & Co.) contained in a 200 gallon steam jacketed vessel. Mixing was conducted at ambient temperatures. Stirring was continued until the mixture was homogeneous. The mixture was then heated to 210 to 215 F. and maintained at said temperature for 5 /2 days to eifect crystallization. The crystals were removed from the liquor by filtration and water washed until the wash water showed a pH of 9.0 to 9.5. On drying, the crystalline alumino-silicate analyzed 13.9% Na O, 64.0% SiO and 21.2% A1 0 On a mole basis, this corresponds to: 1.08 Na O:1.0 Al O :5.l SiO The zeolite exhibited a typical faujasite structure as determined by X-ray analysis.

Part B-Preparati0n 0 Magnesium Form 0 Crystalline Alumina-Silicate Ze0lite.T-he above sodium form of crystalline alumino-silicate zeolite was converted to the magnesium form by the following procedure.

Twenty kilograms of the dried sodium-zeolite were added to 50 gallons of a 6% by weight solution of MgSO The slurry was stirred at ambient temperatures (70 to F.) for 3 hours. Stirring was stopped, the solids were allowed to settle, and the supernatant liquor was removed by decantation. This exchange procedure was repeated two more times using fresh 6% MgSO solutions each time. The solids were finally water washed until the wash water gave a negative test for sulfates with barium chloride. On analysis the zeolite contained 5% MgO and 3.85% Na O.

Part CPreparati0n of Magnesium Form of Catalyst in Siliceous Matrix.-The above magnesium form of the crystalline alumino-silicate zeolite was modified by slurrying the above-described magnesium form of the zeolite in an unwashed silica-alumina hydrogel containing 25 wt. percent alumina which was prepared by a procedure similar to that described above. After mixing and spray drying at about 600 F., the product was slurried in a 1.2 wt. percent ammonium carbonate solution in an amount sufficient to yield 13.5 equivalents of ammonium ion per equivalent of sodium ion in the zeolite. After stirring for 1 hour, the slurry was filtered, washed with water, and the ammonium-exchange treatment was repeated with fresh ammonium carbonate solution, filtered, and rinsed on the filter. The filter cake was then reslurried in fresh magnesium nitrate solution containing 1.4 wt. percent salt. The amount of magnesium nitrate solution used provided 10 equivalents of magnesium ions per sodium and ammonium ion in the zeolite. After stirring for about 1 hour, the slurry was filtered, washed with water, and water, and dried. The final catalyst comprised 5 wt. percent magnesium form zeolite embedded in wt. percent EXAMPLE II.-Catalytic Cracking The catalyst of Example I referred to above was initially calcined at 1000 F. and then steamed at 1400 F. and 0 p.s.i.g. pressure for 16 hours. The calcined catalyst was then employed in a batchwise fluidized bed type cracking operation. The feedstock was a gas oil having a boiling range of 600800 F., a sulfur content of 1.14 wt. percent, and a gravity of 269 API. The run was conducted at atmospheric pressure and 960 F., using a 3- minute cycle time. The results of this run with the above catalyst are summarized in Table I.

TABLE I.CATALYTIC CRACKING OF 600800 F. VIRGIN GAS OIL [Temperature, 960 F.; pressure, atm.; cycle time, 3 min] Catalyst description and preparation Preformed Mg-zeolite embedded in unwashed 75% silica- 25% alumina hydrogel; spray dried; ammonium exchanged; magnesium exchanged; washed and dried. Conversion to 430 F., wt. percent 77. Carbon, wt. percent 7. Ca-Dry Gas, wt. percent- 10. Ct to 430 F., wt. percent 50.

As shown in the above table, the catalyst of the present invention demonstrated more than twice the activity of a conventional cracking catalyst. The catalyst of the invention is shown to be substantially superior for catalytic cracking of gas oil feeds to naphtha product. It is to be noted that, in this example, the silica and alumina contents of the hydrogel matrix in the catalyst of the present invention was the same as that of a standard silica-alumina cracking catalyst.

Example III This example presents a comparison of a binder containing no extraneous carbonaceous material, i.e. a straight binder with a binder containing 2.5 Wt. percent of a carbonaceous material, i.e. carbon black.

ELECTRODE BINDER OIL INSPECTIONS It is obvious from the comparative data that addition of suitable amounts of carbonaceous material has a beneficial efiect on the physical properties of a binder oil.

Example IV This example serves to illustrate the excellent electrodes which may be prepared by utilizing the binder oils of this invention.

ELECTRODE EVALUATION-PREBAKED Source Coal Tar 1 Catalytic Petroleum Binder Electrode Mix:

Percent Binder 23 23 Delayed Coke...- 77 77 Density 1.66 1. 64 Baked Electrode:

Percent Shrinkage 1.82 -1. 22 Percent Wt. Loss. 9. 3 8. 5 Density 1. 49 1. 50 Compressive Strength. 7,000 8, 200 Resistivity 2. 77 2. 73

1 Coal tar inspections: Softening point of 212 F., Conradson Carbon contlent of 53% and contained 28% benzene insolubles and 9.1% quinoline inso ubles.

ELECTRODE EVALUATION.SODERBERG TYPE Percent From the foregoing data it is readily apparent that the results issuing from the practice of the present invention differ with conventional practice, not in degree, but in kind. Inspections show extreme differences in softening points and in Conradson Carbon values as Well as in benzene and quinoline insolubles. Further, the electrodes made from the binder materials Were then the instant invention equal and surpass minimum quality specifications.

It is to be understood that this invention is not limited to the specific examples which have been offered merely as illustrations and that modifications may be made without departing from the spirit of the invention.

What is claimed is:

l. A process for the preparation of binder oils from a feed consisting essentially of a distillate gas oil fraction having a boiling range of about 650 to 1150" R, which consists essentially of, catalytically cracking said feed in a one-pass catalytic cracking zone, said catalytically cracking zone containing an alumino-silicate zeolite having an average pore diameter of about 6 to 15 A and catalytically cracking said feed at a temperature of about 650 to 1150 F., a pressure of from 0 to 500 p.s.i.g., catalyst to gas oil ratio of about 1:1 to 40:1 and at a flow rate of 1 to 14 w./hr./w., distilling the catalytically cracked resulting product to separate lighter fractions from a bottoms fraction boiling above about 850 F. passing said bottoms fraction to a distillation zone and therein stripping said bottoms of substantially all of the volatile products boiling over about 900 F. to produce a binder oil product.

2. The process of claim 1 in which said zeolite has been base-exchanged with a cation selected from the group consisting of hydrogen containing cations and cations of metals in Groups II, III, IV, V, VIB, VII-B,-

VIII and the rare earth metals.

3. The process of claim 1 wherein said alumino-silicate zeolite has been base-exchanged with magnesium.

4. A process for the preparation of binder oils from petroleum crude oil which consists essentially of flashing a topped crude oil under vacuum and at flash temperature above about 900 F. (atmospheric), recovering a product consisting essentially of a distillate gas oil fraction having a boiling range of about 650 to 1150 F., catalytically cracking said gas oil fraction in a one-pass catalytic cracking zone, said catalytically cracking zone containing an alumino-silicate zeolite having an average pore diameter .of about 8 to 13 A and catalytically cracking said gas oil fraction at a temperature of about 750 to 1050 F., a pressure of from 0 to 500 p.s.i.g., a catalyst to gas oil ratio of 4:1 to 20.1 and at a flow rate of 1 to 4 w./hr./w., adding from about 2 to 10 Wt. percent of a carbon black material prior to or after distilling the catalytically cracked resulting product to separate lighter fractions from a bottoms fraction boiling above about 850 F. passing said bottoms fraction to a distillation zone and therein stripping said bottoms of substantially all of the volatile products boiling over about 900 F. to produce a binder oil product.

5. The process of claim 4 in which said alumnio-silicate zeolite has been base-exchanged with a cation selected Baked Electrode Data, kg./cm.

Binder Source Binder, wt.

percent Elongation Compressive Density Percent 1 Strength Coal Tar 31 274 1. 44 Goal Tar+2.5 wt. percent Vulcan 6 31 32 360 l. 45 Catalytic Petroleum Binder +2.5 Vulcan 6 31 62 383 1. 45 Minimum Desired Specification Optimum 60-80 320 1 43 1 High temperature flow properties.

from the group consisting of hydrogen containing cations References Cited and cations of metals in Groups H, HI, 1V, V, VI-B, UNITED STATES PATENTS VIIB, VIII and the rare earth metals.

6. The process of claim 4 wherein said alumino-silicate i mp hree 2O8 55 lite has been base-exchan ed with ma nesium and is 5 atch 208-83 9 g g 3,140,248 7/1964 Bell et al s mlxed Wlth mamx- 3,140,251 7/1964 Plank et a1. 208

7. The process of claim 4 in which said carbon black is added in amounts of from about 2.5 to 5.0 Wt. percent. ABRAHAM RIMENS, Primary Examiner.

Claims (1)

1. A PROCESS FOR THE PREPARATION OF BINDER OILS FROM A FEED CONSISTING ESSENTIALLY OF A DISTILLATE GAS OIL FRACTION HAVING A BOILING RANGE OF ABOUT 650* TO 1150*F., WHICH CONSISTS ESSENTIALLY OF, CATALYTICALLY CRACKING SAID FEED IN A ONE-PASS CATALYTIC CRACKING ZONE, SAID CATALYTICALLY CRACKING ZONE CONTAINING AN ALUMINO-SILICATE ZEOITE HAVING AN AVERAGE PORE DIAMETER OF ABOUT 6 TO 15 A AND CATALYTICALLY CRACKING SAID FEED AT A TEMPERATURE OF ABOUT 650* TO 1150*F., A PRESSURE OF FROM 0 TO 500 P.S.I.G., CATALYST TO GAS OIL RATIO OF ABOUT 1:1 TO 40:1 AND AT A FLOW RATE OF 1 TO 14 W./HR./W., DISTILLING THE CATALYTICALLY CRACKED RESULTING PRODUCT TO SEPARATE LIGHTER FRACTIONS FROM A BOTTOMS FRACTION BOILING ABOVE ABOUT 850*F. PASSING SAID BOTTOMS FRACTION TO A DISTILLATION ZONE AND THEREIN STRIPPING SAID BOTTOMS OF SUBSTANTIALLY ALL OF THE VOLATILE PRODUCTS BOILING OVER ABOUT 900*F. TO PRODUCE A BINDER OIL PRODUCT.

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