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Publication numberUS2564268 A
Publication typeGrant
Publication dateAug 14, 1951
Filing dateNov 10, 1947
Priority dateNov 10, 1947
Publication numberUS 2564268 A, US 2564268A, US-A-2564268, US2564268 A, US2564268A
InventorsHelmers Carl J, Mathy Eugene V
Original AssigneePhillips Petroleum Co
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Catalytic oil cracking
US 2564268 A
Abstract  available in
Previous page
Next page
Claims  available in
Description  (OCR text may contain errors)

Patented Aug. 14, 1 951 CATALYTIC OIL CRACKING Eugene V. Mathy and CarlJ. Helmers, Bartlesville, kla., assignors to Phillips Petroleum Company, a corporation of Delaware No Drawing. Application November 10, 1947,

.Serial No. 785,199

3 Claims. (01. 196 52) This invention relates to an improved process for the catalytic cracking of hydrocarbon oils to produce a high yield of high octane gasoline motor fuel. In another aspect it relates to a process for the catalytic cracking of hydrocarbon oils in which the yield of gaseous by-products is low. In another aspect it relates to such a process in which the amount of carbon deposition is low.

In still another aspect, it relates to an improved catalyst and a method ofpreparation of same.

In the production of gasoline motor fuel from petroleum, a small amount may be obtained by simple fractionation. Since gasoline motor fuel is the petroleum product in greatest demand, efforts are being constantly made to devise methods or processes to produce this gasoline motor fuel 7 800--1400 F., a good catalyst must be able to withstand exposure to high temperatures without serious impairment of efficiency. The process must allow a high throughput of high-boiling point oil and return a high yield of high octane gasoline. The amount of dry gas (propane and lighter hydrocarbons) formed should be low. As carbon from the cracking builds up on the catalyst, the catalytic activity drops, and'the catalyst must be taken out of service for regeneration when the activity drops to a certain predetermined level. Therefore, it is desirable that the rate of carbon deposition be as low as is consistent with economical operation of the process. However, the carbon deposition increases with an increase in the space velocity'at' constant conversion or with an increase in per cent conversion at constant space velocity, so an optimum balance between these important factors must be maintained. 7

We have found that catalysts having a high order of activity for converting high-boiling hydrocarbon oils into gasoline with'a superior octane rating may be prepared by impregnating a solid, absorbent, catalytically active material with a mixed B203 and P205 promoter.

The principal object of our invention is to provide an improved process for the catalytic conversion of high-boiling petroleum oils ,into high octane gasoline motor fuels at a high yield through the use of the catalyst comprising a major constituent selected from the group consisting of bauxite, fullers earth, acid treated montmorillonite clay, and the synthetically prepared alumina, silica, and silica-alumina gels supporting a minor proportion of boric oxide and phosphorus pentoxide.

Another object of our invention is to provide a process for the catalytic conversion of high-boiling point petroleum oils into high octane gasoline motor fuels at a high yield and without forming an unduly high amount of dry gas.

Another object of our invention is to provide a process for the catalytic conversion of highboiling point petroleum oils into high octane gasoline motor fuels at a high yield and without depositing an unduly high amount of carbon.

Another object of our invention is to provide a process for the catalytic conversion of highboiling point petroleum oils into high octane gasoline motor fuels, in which process, the catalyst is maintained at high activity and high efilciency for longer periods.

Another object is to provide a new and improved catalyst for the conversion of hydrocarbon oils into high octane gasoline.

Another object is to provide a method of preparing said catalyst.

Numerous other objects and advantages of our invention will be apparent to those skilled in the art upon reading the following specification and the accompanying claims.

OPERATIONS not as economical, we prefer to employ in this.

catalyst from 0.1 to 10% by weight of boric oxide and from 0.1 to 10% by weight of phosphorus pentoxide.

In its operation, the high-boiling point 011 is substantially vaporized in a preheater, passed into a catalytic reactor where it is contacted with the catalyst for the desired time, and then passed tirely. The charge is'vaporized and superheated with as little thermal decomposition as possible to a temperature in the range of 850-1100 F. A pressure of 10-300 pounds per square. inch gauge at the preheater outlet is preferred.

The vaporized petroleum oil' ispassedfrom the preheater into the catalytic reactor where it contacts the catalytic mass at a space velocityof from 01-10 liquid volumes ofpetroleum' oil per volume of catalytic mass per hour. The amount of conversion is partially controlled by the. length of time the oil is exposedto the catalyst. However, if the velocity is low, the process is uneconomical beeausethe total' product" will be low and the rate of carbon deposition increases: If

the initial high activity of the catalyst. It was calculated that the promoter content was 1.05 weight per cent of P205 and 1.05 per cent of B203.

A catalyst of bauxite containing P205 alone in the amount of 1.4 weight per cent and one containing B203 alone in the amount of 2.0 weight per cent were prepared in a similar manner.

EXAMPLE II The four catalysts prepared in Example I were tested in a fixed bed hydrocarbon cracking system charged with an oil having a boiling point essentially above that of gasoline. A catalyst temperature of 10i5 R, a pressure of 85 pounds per square inch gauge, and an operating period of 3 hours. were used. The space velocities, measured in terms of liquid volumes of oil per volume of catalyst per hour, were held constant for" all tests. The results are shown in Table I. The activity index is the comparison of the per cent conversion obtained with each catalyst compared with that of the original bauxite.

Table I e Bauxite Bauxite Bauxite 20% B203 not B2O3':O1-505%.

Space Velocity -l 1. 8 1.' 8 1. 8" 1. 8 Per Cent Conversion. 51. 2 53. 9 52. 3 56. 5 Dry Gas, wt. per cent 12. 9 13.4 12. 8- 14.1 Birtanes, vol. per cent 6. 2 7. 4 7. 8 8. 1 Carbon, wt. per cent 1.8 2. 0 2. 8 3. 4 Gasoline:

Yield, vol. per cent"..- 35. 0 36. 3' 34. 4 36. 2

ASTM Octane N0 75. 6 76. 6' 77. 2 76. 8

Bromine N o 91 96 88 81 Activity Index.. 100 105 102 110 silica-alumina gel which material has been im-- pregnated with a, minor proportion of boron trioxide and phosphorus pentoxideas a combination promoter ma be used.

The efiluent gases: from. thecatalytic reactor are led into a separator where the gasoline motor fuel, dry gas, and butanes are removed. If desired, the high-boiling fraction maybe recycled through the system by introducing it back into the preheater. The following examples serve to illus trate further the advantages of our invention.

EXAMPLE I Samples of our catalysts were prepared 'as-follows A portion of bauxitecontaining less than 3-per' cent of iron and having'a particle size of 844' mesh was calcined at a temperature of 700-900 for a period of about 10 hours to reducethe water content below 5 per cent.

A250 gram sampleof the calcined bauxite was soaked for 1 hour in 250 ml. or" solutioncontaining 10.1'grams of HSPO4 and 1L7 grams of I-Is'B'Os. The mass was then drained for "1 hour, air dried for 3 days, oven dried "at 482 F; for hours, and

heat-treated for"168*h0urs at1500 F.- to kill The bauxite impregnated with B203 and the bauxite impregnated with P205 catalyst has a higher activity indexthan the untreated bauxite. Thecatalytic efiect of our catalyst is more than the combined effect produced by B203 and P205 separately.

EXAMPLE III Another comparison was made using a. high grade bauxite'and the same bauxite impregnated with 3203' and P205 in minor'amounts for cracking a virgin gas oil. The octane numbers were run on the product gasoline clear and with 1 and 3 'ml. of tetraethyl lead per'gallon of gasoline; The operating conditions and results are" shown in Table II.

Table [I Bauxite Bauxite+B20 +PiO5 Pressure 85 Temperature, F 980 980 Conversion, Vol. Per Cent I 52' 54 Gasoline:.

Yield, Vol Per'Cent' 38.3 35 7 Bromine N o 74 70 Cycle Stock, VOL- 48.0 45. 4 Dry- Gasfwt; PerOent; 9. 8 11.5 Tests. for tetraethyl lead responsez. ASTM Octane-Numbers 0 ml. TEL pergal 74. 1 76:5 1 ml. TEL per gal 78. 5 80. 0 3 ml. TEL per gal 81.8 82. 7 ResearchOctane Numbers 0 mlJTEL per gel H. 82.3 86.3 1 ml. TEL per'gali- 88.7 92.0 3 m1. TEL per gal= 92. 4 94.1

The higher conversion obtained by using our catalyst more than'compen'sates for the'slightly lower gasoline yield. The superiority of our catalyst'is clearly shownin the higher'octane rating of the gasoline produced? From the foregoing examples, it is apparent that this process has many advantages. The catalytic activity is not impaired by prolonged exposure to high temperatures. When our catalyst is employed a gasoline of a high octane rat ing is produced. The low rate of carbon deposition means prolonged life of the catalyst at high activity. Due to the high catalytic activity as reflected in the high conversion ratio, our catalyst permits a higher space velocity or throughput than is possible with the other catalysts tested. This means that more high-boiling point petroleum oil may be processed in less time and with a high yield of high octane gasoline motor fuel.

In the practicing of this invention it is obvious that variations in the arrangement may be made without invention. For instance, instead of the fixed-bed catalyst described in the examples, a fluidized bed may be used. This invention embraces such other obvious variations and modifications as come within the scope thereof. This invention is limited only by the following claims.

Having fully described our invention, we claim:

1. A process for the conversion of hydrocarbon oils to produce a high octane gasoline which comprises passing said oil at a cracking temperature and pressure through a cracking zone containing an active catalyst comprising bauxite supporting impregnated on'its surface .1 to weight per cent of phosphorus pentoxide and boron trioxide as such and maintaining said hydrocarbon oil in contact with said catalyst for a period of time sufiicient to obtain the desired conversion thereof.

2. A process for cracking hydrocarbon oils which comprises contacting the said hydrocarbon oil at a temperature of 800 F. to 1400 F., a pressure between 10 and 300 pounds per square inch gauge, and a space velocity of from 0.1 to 10 volumes of liquid charge per volume of catalyst per hour with an active catalytic mass comprising bauxite as a major constituent supporting impregnated thereon as such 0.1 to 10 weight per cent of boron trioxide and 0,1 to 10 weight per cent of phosphorus pentoxide.

REFERENCE S CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,109,866 Moser Mar. 1, 1938 2,341,363 Connolly Feb. 8, 1944 2,398,819 Cook Apr. 23, 1946 2,441,493 Krug May 11, 1948 2,443,402 Schulze June 15, 1948 2,480,672 Plank Aug. 30, 1949 OTHER REFERENCES Mellor, Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 5, page 147.

Handbook of Chem. & Physics Hadgman and Lange, 16th edition, page 198.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2109866 *Aug 6, 1935Mar 1, 1938Shell DevTreating of motor fuels
US2341363 *Dec 27, 1940Feb 8, 1944Standard Oil Dev CoConversion of hydrocarbon oils
US2398819 *Mar 20, 1942Apr 23, 1946Texas CoConversion of hydrocarbons
US2441493 *Jun 10, 1947May 11, 1948Atlantic Refining CoDesulfurization of hydrocarbons with boron phosphate-alumina catalyst
US2443402 *Feb 10, 1942Jun 15, 1948Phillips Petroleum CoProcess for hydrocarbon conversion
US2480672 *Aug 12, 1944Aug 30, 1949Socony Vacuum Oil Co IncProcess for forming porous glass and composition thereof
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2938001 *Dec 13, 1956May 24, 1960Universal Oil Prod CoCatalyst composite
US3030300 *Dec 11, 1957Apr 17, 1962California Research CorpCatalytic cracking with an attrition resistant catalyst
US3261878 *Feb 5, 1962Jul 19, 1966 Autothermal cracking of liquid hydrocarbons
US3883442 *Dec 26, 1973May 13, 1975Union Oil CoNon-shrinking alumina-based catalyst compositions
US4295955 *Mar 10, 1980Oct 20, 1981Uop Inc.Attenuation of metal contaminants on cracking catalyst with a boron compound
US4334979 *Apr 11, 1980Jun 15, 1982Phillips Petroleum CompanyHydrocarbon cracking process using a catalyst containing germanium
US4386015 *Jun 22, 1981May 31, 1983Phillips Petroleum CompanyHydrocarbon cracking zeolitic catalyst
US4439536 *Dec 13, 1982Mar 27, 1984Phillips Petroleum CompanyHydrocarbon cracking catalyst
US4490476 *Jun 28, 1983Dec 25, 1984Rohm And Haas CompanyCatalyst for the preparation of α,β-unsaturated compounds
US5151394 *Jan 25, 1991Sep 29, 1992Mobil Oil CorporationCracking catalysts
US5300215 *Jul 15, 1992Apr 5, 1994Mobil Oil CorporationCatalytic cracking with a catalyst comprising a boron phosphate matrix
U.S. Classification208/114
International ClassificationC10G11/00, C10G11/04
Cooperative ClassificationC10G11/04
European ClassificationC10G11/04