Organic compound bond rupturing process

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3 contemplated. In the process involving treatment of liq ing the product of the bombardment from the neutron uid or solid hydrocarbons, both gaseous and liquid prod fieldDuring beforethis further breakdown can occur.

cracking operation or as a consequence ucts of bombardment are usually produced. In such a thereof some higher molecular weight products also are case the evolved hydrogen or gaseous hydrocarbons may secured. It seems entirely possible that these higher be separated easily from the liquid and/or solid products molecular weight products result from secondary reac and the non-gaseous residue may be fractionated or used tions involving polymerization of gaseous or liquid un as such. Moreover, the gaseous hydrogen or hydrocar Saturated products or combination of free radicals, after bons evolved may be mixed with additional solid or liquid their initial production, with each other, with the initial 10 hydrocarbons and again subjected to high energy neutron charge material, or with intermediate products. bombardment.

The exact nature of the reactions resulting is not known it witi be understood that where the bombardment is and it is not intended that any theoretical explanation conducted using neutrons having a wide band of energies, shall be binding. From a study of the effects secured mixtures of products may be secured and various types of as a result of exposure of the compositions herein con bonds ruptured. In accordance with a further embodi templated to the high energy irradiation which is present ment of the invention, a selective rupture of chemical in a neutronic reactor, it appears that the resulting re bonds may be secured by use of neutrons having specific actions are propagated by the breaking of carbon-hydro energies. For example, selective rupture of carbon-hy gen and/or carbon-carbon bonds. For example, when a drogen bonds without rupture of carbon-carbon bonds compound of the general structure CnH2n+2 is sub may be effected by conducting the bombardment using jected to high energy neutrons, collisions between the neu neutrons having energies of about 5 to 12 electrons volts, trons and the atomic nuclei of the compound may be ex and preferably 10-12 electron volts. Preferential rup pected. A neutron having an energy above about 5 elec ture of carbon-hydrogen bonds with only a small per tron volts colliding with a hydrogen atom in such a com centage rupture of carbon-carbon bonds may be effected pound may remove the hydrogen atom from the com with neutrons of somewhat higher energies. pound with the resulting production of a pair of free radi A wide range of compounds may be treated as herein cals according to the equation contemplated, particularly organic compounds which con tain carbon-carbon and carbon-hydrogen bonds. Thus saturated aliphatic hydrocarbons such as ethane, propane, the two radicals on the right hand side of the equation n-butane, isobutane, pentanes, octanes, nonanes, etc., or being free radicals. unsaturated aliphatics such as ethylene, vinylacetylene, Rearrangement of the free radical CnH (2n+1) may propylene, isobutylene, n-butylene, butadiene, etc., or cy tend to occur in accordance with one or all of the foll clic compounds including the aromatics and cycloparaf lowing equations fins such as benzene, toluene, naphthalene, diphenyl, an thracene, tetrahydronaphthalene, cyclohexane, p-cymene, 3.5 diphenyl methane, triphenyl methane, cyclohexene, etc., may be cracked by the present process. Moreover,

Moreover, the free radicals CnHg2n+1) and H and/or petroleum fractions such as kerosene, naphtha, gas oil, their reaction products may form other products by inter fuel oil, recycle oil, waxes, etc., may be treated by this action with molecules undisturbed by the bombardment process. In addition, substituted hydrocarbons such as as, for example, in accordance with the following equation 40 lauryl chloride, oleyl chloride, octyl chlorides, or similar halides or oxygen compounds such as oleic acid, oleyl alcohol, lauric acid, lauryl alcohol, salicyl alcohol, sali

The cracking process may be conducted at atmospher cylic acid, benzoic acid, benzyl alcohol or other alco ic pressure. Frequently it may be desirable to subject the hols, acids or halides may be cracked by means of fast compositions undergoing bombardment to pressures of or high energy neutrons. The following examples are the order of 100-300 pounds per square inch during the illustrative.

The cracking operation herein contemplated may be Example 1. carried out at room temperature. However, elevated Seventeen parts by volume of previously purified ben temperatures frequently expedite reaction and, therefore, 50 Zene were placed in an aluminum tube extending into a temperatures above 100 C., for example, 100-500 C. well which extends into the central portion of the deu may be used. An advantage of the present process arises terium oxide moderated neutronic reactor described in from the fact that it may be conducted at temperatures the above-mentioned Fermi-Szilard application. The substantially below the pyrolytic decomposition tempera benzene was disposed in the interior of the reactor and ture. Since the cracking may be conducted below those 55 was therefore exposed to the irradiation by neutrons temperatures required in pyrolytic cracking processes, ranging from about 0.03 to one or more million elec control of the process to secure desired results without tron volts as well as to beta and gamma irradiation. undesirable carbonization or tarring is more easily facili The exposure was continued for a period during which tated. A further advantage of this process over pure py the reactor released about 2.5 megawatt days and the rolytic cracking processes resides in the fact that in the 60 temperature of the reactor during this period did not bombardment of compounds with high energy neutrons exceed about 70° C.

at 100 to 500 C., chain reactions of greater length oc During bombardment 3.2 parts by volume (standard cur without undergoing a chain-terminating reaction than conditions) of gaseous products were evolved. Two occur in other processes. thirds of the gas formed was found to be hydrogen. The products of the bombardment may be removed 65 The remainder of the gas comprised a mixture of gaseous continuously or periodically from the product undergo aliphatic hydrocarbons. - ing bombardment. For example, a liquid or gaseous hy Following bombardment the liquid was distilled and drocarbon may be circulated through a neutronic reactor found to contain 0.8 per cent by weight (based upon the and the resulting products separated by fractionation and initial benzene treated) of a high molecular weight hydro the uncracked fractions with or without fresh products 70 carbon polymer. The liquid after distillation and con recycled to the reactor. Conventional cracking, frac amount densation was largely benzene together with a small tionating and distilling equipment wherein a neutronic re of liquid reaction product containing biphenyl, actor provided with passages for passage of the product and other polyphenyls. The liquid condensate had an to be cracked is substituted for the conventional pyrolytic index of refraction (ND20 c.) 1.5021 and a bromine num cracking coils may be used to effect the processes...herein 75 ber of 0.80. -

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Example 2 tion except insofar as included in the accompanying The process of Example 1 was repeated using purified claims.

cyclohexane, cyclohexene and tetralin in lieu of benzene What is claimed is: with the following results: A process for the preparation of hydrogen and a poly Liq. Product Polymer Pts by Percent

Comp. Bombarded

Pts.. . bby Secured formed, percent

Wol.

gaS

drocar

Wolume by wgt. formed drogen bOn in treated ND20 C. Bromine of initial (std. (i. ES ) gas (by

Cyclohexane.----------- 14.0 1,4280 2.3 2.4 68. 99

Cyclohexene.------------- 13.8 1.4480 205 2. 15. 90.3 9,7 Tetralin------------------ 1.5 54.25 1.5 1, 2 7. 97 3

In this example, rupture of both carbon-carbon and mer from cyclohexane which comprises introducing into carbon-hydrogen took place. However, selective rup a reactor cyclohexane whereby it is bombarded by neu ture of the carbon-hydrogen bonds, to produce still more trons having an energy level of about .03 to several mil unsaturated compounds, can be effected by conducting lion electron volts and hydrogen is evolved, maintain the bombardment using neutrons having energies of 5 to ing 20 the cyclohexane in the reactor at a maximum tem 12 electron volts.

In accordance with a further modification, the crack perature of 70° C. until the reactor containing the cyclo ing operation herein contemplated may be carried out in hexane released about 2.5 megawatt days of energy, re conjunction with other reactions for the purpose of pro covering the evolved hydrogen, removing from the re actor the neutron-irradiated cyclohexane product, and ducing other products. For example, the neutronic bom 25 fractionating bardment herein contemplated may be conducted using said product to obtain a polymer fraction. a mixture of the hydrocarbon or other compound such References Cited in the file of this patent as propane, isobutane, benzene, toluene, cyclopenta UNITED STATES PATENTS diene, kerosene, etc., and a halogenating agent such as

HCl, HBr, HF, Cle, Br2, I, F2, PCl3, PCls, COCl2, 30 1,627,938 Lingley ---------------- May 10, 1927 CHCl3, CCl4, etc. Such treatment may be effected by 2,344,900 Reeves et al. ---------- Mar. 21, 1944 bombarding a gaseous mixture of the reactants or where 2,405,935 Anderson -------------- Aug. 20, 1946 the hydrocarbon to be treated is liquid, a solution of the FOREIGN PATENTS halogenating agent in the liquid may be treated.

In addition irradiation of hydrocarbons may be effected 35 114,150 Australia --------------- May 2, 1940 in the presence of other types of agents capable of effect 233,011 Switzerland ------------- Oct. 2, 1944 ing a replacement of hydrogen or addition to an un OTHER REFERENCES saturated double bond. For example, the reaction may Science, "Direct Synthesis of Higher From Lower Hy be conducted in the presence of sulphuric or sulphurous acid, SO2 or sulphur, in amount sufficient to form substan 40 drocarbons'

tial quantities of sulphonates, sulphides, etc. Likewise, the Schoepfle et al.-Industrial & Eng. Chem. "Gaseous bombardment may be conducted in the presence of oxygen Products From Action of Cathode Rays of Hydrocar or a peroxy compound in amount sufficient to form alde bons,” vol. 23, No. 12, (December 1931) pp. 1396-1397. hydes, acids and/or alcohols depending upon the degree of oxidation desired. Additional hydrogen may be in 45 59-5, Lind et al.-The Electrochemical Society, preprint troduced particularly where aromatic compounds are "The Action of Electrical Discharge on Gaseous bombarded to facilitate formation of alkyl compounds. Hydrocarbons' (Apr. 27, 1931) pp. 33-40. Thus naphthalene may be bombarded in the presence of Dunning et al-Physical Review, "Interaction of Neu hydrogen under several atmospheres pressure to form, trons With Matter,' vol. 48 (Aug. 1, 1935) pp. 265-280.

for example, alkyl benzenes or alkyl cyclohexanes. 50

Although the present invention has been described with Nature, 143, pg. 640 (1939). particular reference to the specific details of certain em Power, pp. 56-59 (July 1940). bodiments thereof it is not intended that such details shall be regarded as limitations upon the scope of the inven