US2441142A - Cracking hydrocarbons in the presence of bromine-containing terpenic compounds - Google Patents

Description

Patented May 11, 1948 UNITED STATES PATENT OFFICE 2,441,142 V CRACKING nrnaocaanons IN THE PRES- ENCE F PENIC COMPOUNDS Hillis 0. Folkins, Skokie, 111., assignor to The Pure Oil Company, Chicago, Ill, a corporation of Ohio BROMlNE-CONTAINI'N G TER- No Drawing. Application December 14, 1944, Serial No. 568,197

14 Claims. (ca. 196-52) of hydrocarbons when mixed in small amounts with the hydrocarbons undergoing decomposition.

One of the objects of this invention is to provide an improved method for converting hydrocarbons into lower boiling hydrocarbons and/or into hydrocarbons of less saturation.

Another object of the invention is to accelerate the rate of cracking of hydrocarbons.

Still another object of the invention is to provide a method for increasing the yield of cracked hydrocarbons in conventional type cracking operations.

Still a further object of the invention is to produce motor fuel of increased octane number.

Other objects of the invention will become manifest from the following description.

In accordance with my invention, hydrocarbons are mixed with a small amount of a terpene or camphor or a mixture thereof having one or more halogen atoms in the molecule. Compounds having more than one halogen atom in the molecule are preferred. As examples of halogenated terpenes and camphor type compounds which may be used in the invention are:

d-Limonene tetrabromide Dlpentene tetrabromide Bromo-menthone 1,4,8 trlbromo p-menthane d-Carvone hydrobromide d-Bromocamphor 2-bromocamphane-3 carboxylic acid u-bromocamphene Bromoienchone Bromoepicamphor Bromonitrocamphane Born'yl bromide Chlorobromocamphane Plnene dibromide In addition to the halogenated terpenes and camphors, halogenated derivatives thereof such as esters, ethers and amino, nltro, alkyl, aryl and aralkyl derivatives in which the aforesaid groups are substituted for one or more hydrogen atoms in the molecule may be used. The brominated terpenes and camphors and derivatives thereof give good results when used in amounts of approximately .05 to 5% by weight of hydrocarbons' undergoing cracking, although smaller amounts may be used. I prefer not to use in 8X";

cess of 3% by weight, since amounts below 3% provide satisfactory acceleration of the cracking reaction without causing the presence of ob jectlonable amounts of undesirable compounds in the resulting product. Generally speaking, 1%

or less of the brominated compound is adequate.-

Instead of using pure halogenated terpenes and camphors, or derivatives thereof, I may .use substances rlch 131- any of the aforesaid compounds and halogenatc the substances. As an example, brominated turpentine provides a satisfactory sensitizer since turpentine is largely alpha and beta, pinene.

Although the aforesaid sensitizers are primarily useful in cracking hydrocarbon oils boiling above the gasoline boiling range, in order to produce gasoline, or in cracking gasoline-boiling range hydrocarbons to produce gasoline of higher antiknock value, the invention is directed also to the cracking of hydrocarbon gases such as propane or butane in order to produce unsaturated hydrocarbons.

Sensitizers, in accordance with my invention, are useful in conventional thermal cracking processes at atmospheric, sub-atmospheric or superatmospheric pressure. Cracking of hydrocarbon oils and gases may becarried out within the t'emperature range of apfirbximately 650 to 2000 F., depending on the nature of the charging stock and the type of product desired. Where cracking of hydrocarbon oils to gasoline is practiced, the temperature may range from approximately 650 to 1200 F. When cracking gases or oils in order to form aromatics, temperatures of approximately 1000-1500 F. may be resorted to. Where it is desired to crack hydrocarbon oils and gases to butadiene, a temperature of approximately 1300 to 1600" F. may be used. Where cracking of oils or gases to low molecular weight gaseous hydrocarbons is desired, temperatures of the order of 1500 to 2000 F. may be used.

From the table it will be seen that without any sensitizer being present (run No. 24-G) the yield of gasoline (liquid below 400 F.) was 11.2% and the total yield of products below 400 F. was 16.7%.

When 0.1% by weight of bromine was present (run No. 28-G), the yield of gasoline was 13.1% and the total yield of products boiling below 400 F. was 21.6

Run No. 23-G made with 0.1% by weight of d-bromocamphor as sensitizer gave a gasoline yield of 14.8% and a total yield of products boiling below 400 F. of 22.2%. Thus, d-bromocamphor not only excels bromine on a weight for weight basis, but considering the small amount of bromine present in the compound, the compound is remarkably effective.

Run No. 22-G made with 0.5% by weight of l d-bromocamphor produced a gasoline yield of 17.2% by weight, and run No. 21-G using 1.0% by weight of d-bromocamphor produced a gasoline yield of 22.3%, almost twice the yield obtained without any sensitizer. Likewise the yield of total products boiling below 400 F., with 1.0% by weight of d-bromocamphor was 33.9, whereas it was 16.7% without any sensitizer.

Another series of runs was made using Pennsylvania gas-oil as charging stock under a pressure of 500 pounds per square inch in which the temperature was kept at approximately 887 F. during each run. The results on these runs are tabulated in Table II.

In practicing the invention, the halogenated Table II cyclic terpenes, camphors, or derivatives thereof. R N may be mixed with the hydrocarbons to be 2 3 4 5 6 charged to the process prior to entrance thereof R t a F the rem! zone or the miller may be 5 pfttr'.f$7s.:..1::::::::::: 333 583 233 $5 flash-injected directly into the reaction zone, hm sglbalhr 6.800 6.2 361 can sets case after heating sumclenuy to either melt vapor" fiifiiiitfii; wfl'fier'rifi 025 022 4 905 ize the sensitizer. Where flash-injection is pracgiquid products, 1m /hr 6.453 6.711 6.532 0.511 6.588 tlced, care should be exercised n to heat the 033: .a.::::::::::" 333 313i? i1??? i333? Hi3 sensitizer above its decomposition temperature Materlal'balame 0.986 1.024 0.997 0.992 1.001 prior to its injection into the reaction zone. hm "mm-Mien In order to demonstrate the effectiveness of 1*" m w 'wo g ggl n rs l l fi Seuss l l 1 gr's and lighter 2.6 3.0 2.8 2.3 2.6 me e g ennsy va a gas-o as c arg ng 4' 0.8 1.0 0.8 0. 0.8

i i i, 1 r. stock in a continuous laboratory cracking opera- $31, 3 mud 2.3 3} tion. The runs were carried out at a tempera- J n a-agav ioozr 7 .9 1 .1 71. gig 13.2 ture of approximately 977 F. and at atmospheric g g gg ft m gi R y 2 pressure. In three of the runs d-bromocamphor gg l fl 60.8 59.7 00.0 was used as sensitizer in diflerent amounts, A flon)H 5'cc TEL/ga1' r 63.7 6&5 6&2 blank run was made in order to form a basis of gt g fi s i g g fi; 64 8 66 4 66 4 66 2 comparison and a run was made with bromine in f+ 1% b g g fi g f ion cc. ga 6 .6 '1. order to show the effectiveness of d bromocam octane No. (1004000 F w I phor asasensltizer. tion)+3.0 cc. TEL/gal.. 12.1 73.6 was 73.4

The results of the several runs are given in the following table: I d-Bromo camphor.

Table I Run No. 24-6 Run No. 28-G Run No. 21-0 Run No 22-G Run No. 23-6 'Tcmperature,F s17 971 919 971 979.

Premurefin atm atm atm. Charge gins. 165.2 164.8 164.0. Sensitlzer d-bromo-camphor d-bromo-camphor d-bromo-camphor (1.0% by wt). (0.6% by wt.). (0.1% by wt). Liquid Products, gins/hr 145.2 148.4- 152.0. Gas Products, gins/hr 19.0 15.7 12.1. Liguir' z it rigucts below 400 F., For

-81! 0 urge:

Vol Wt Liquid Products above 400 F., Per

Cent 01 Charge:

Vol t Gas Produced, Wt. Per Cent of Charge. Specific Gravity of Gas It is apparent from Table II that even when 4 as little as .05% by weight of d-bromocamphor was used, an increase of approximately 18% in yield of liquid hydrocarbons boiling up to 400 F. was obtained. It is also evident from Table II that the liquid product boiling within the gasoline boiling range obtained, using d-bromocamphor as sensitizer, is higher than the octane number of the gasoline obtained without sensitizer. Thus, not only do sensitizers within the scope of the invention produce more gasoline than can be produced without sensitizer under similar cracking conditions, but they also produce gasoline of higher octane rating.

Although my invention is applicable to all known types of therma1 hydrocarbon cracking processes, including catalytic and purely thermal, it is particularly adapted for use in connection .with thermal operations in which no solid catalyst is used. The invention may be used in present types of thermal cracking processes and apparatus without modifying such processes or the apparatus in which they are conducted, except to the extent necessary to provide for the introduction of the sensitizer at some point in the operation prior to the time the products leave the reaction zone.

It is to be understood that my invention is directed to the use of brominated terpenes and camphor type compounds, regardless of whether groups or elements other than bromine are attached to the terpene or camphor rings. and is more particularly directed to brominated polycyclic terpenes, camphors and their derivatives.

It is claimed:

1. The method-of cracking hydrocarbons comprising subjecting said hydrocarbons to suitable cracking conditions in the presence of a small amount of a substance selected from the group consisting of bromine-containing terpenes, camphors, their esters and ethers, and amino, nitro, alkyl, aryl, or aralkyl derivatives thereof.

2. The method of cracking hydrocarbons comprising subjecting said hydrocarbons to temperatures of approximately 650 to 2000 F. in the presence of a small amount of a substance selected from the group consisting of bromine-containing terpenes, camphors, their esters and ethers, and amino, nitro, alkyl, aryl or aralkyl derivatives thereof.

3. The method of cracking hydrocarbons containing a major proportion of propane comprising, subjecting said hydrocarbons to temperatures of approximately 650 to 2000 F. in the presence of a small amount of a substance select ed from the group consisting of bromine-containing terpenes and camphors, their esters, ethers, and amino, nitro, alkyl, aryl, or aralkyl derivatives thereof.

4. The method of cracking hydrocarbons boiling above the gasoline boiling range comprising, subjecting said hydrocarbons to temperatures of approximately 650 to 2000 F. in the presence of a small amount of a susbtance selected from the group consisting of bromine-containing terpenes and camphcrs, their esters, ethers, and amino, nitro, alkyl, aryl, or aralkyl derivatives thereof.

5. The method of cracking higher boiling hydrocarbon oils to hydrocarbons within the gasoline boiling range comprising subjecting said oils to cracking at temperatures of approximately 650 to 1200 F. in the presence of approximately .05 to 3% by weight of a substance selected from the group consisting of bromine-containing terpenes, camphors, their esters and ethers, and amino, nitro, alkyl, aryl, or aralkyl derivatives thereof.

6. The method of cracking higher boiling hydrocarbon oils to hydrocarbons within the gasoline boiling range comprising, subjecting said oils to cracking at temperatures of approximately 650 to 1200 F. in the presence of approximately 0.05 to 3 per cent by weight 01 a bromo-camphor.

7. The method of cracking higher boiling hydrocarbon oils to hydrocarbons within the caseline boiling range comprising, subjecting said oils to temperatures of approximately 650 to 1200 F. in the presence oi approximately 0.05 to 3 per cent by weight or d-bromocamphor.

8. The method of cracking higher boiling hydrocarbon oils to hydrocarbons within the gasoline boiling range comprising, subjecting said oils to temperatures of approximately 650 to 1200 F. in the presence of approximately 0.05 to 3 per cent by weight of dibromocamphor.

9. The method of cracking hydrocarbon oil boiling above the gasoline range comprising subjecting said oil to a temperature of approximately 977 F. in the presence of approximately .1 to 1% by weight of d-bromocamphor for a period of time suitable for cracking a substantial portion of said oil to gasoline boiling hydrocarbons.

10. The method of cracking hydrocarbons comprising, subjecting said hydrocarbons to suitable cracking conditions in the presence of a small amount at a bromine-containing cyclic terpene.

11. The method of cracking hydrocarbons comprising. subjecting said hydrocarbons to temperatures of approximately 650 to 2000 F. in the presence, of a small amount of a bromine-containing cyclic terpene. h 12. The method of cracking higher boiling hydrocarbon oils to hydrocarbons within the gasoline boiling range comprising, subjecting said oils to temperatures of approximately 650 to 1200 F. in the presence of approximately 0.05 to 3 per cent by weight of a bicyclic terpene containing at least one bromine-atom in the molecule.

13. The method of cracking hydrocarbons comprising, subjecting said hydrocarbons to suitable cracking conditions in the presence of a small amount of a bromine-containing camphor.

14. The method of cracking hydrocarbons comprising, subjecting said hydrocarbons to suitable cracking conditions in the presence of a small amount of a bromine-containing polycyclic ter-' 'pene.

HILLIS O. FOLKINS.

REFERENCES CITED The following references are bi record in the file of this patent:

UNITED STATES PATENTS