US1224787A - Process of transforming mineral oils. - Google Patents

Description

A. S. RAMAGE.

PROCESS OF TRANSFORMING MINERAL OILS.

APPLICATION FILED APR.27.1916.

, 1,224,787. Patented May 1, 191 7.

l C E w sum/"m VI I 6i v f sratrris PAT NT OFFICE.

awn 8. men, or izurraorr,v moment, nssrenon r ros'rm imam:-

- Be it known that I, Annxanonn' Sr Ramon,

' residing at Detroit, in the county of Wayne ING To all whom it may concern: I

a subject of the King of "Great Britain,

and State of Michigan, have invented certain' new and useful Improvements in Proc esses' of Transforming Mineral Oils, of

' which the following is a specification.

My invention is a process whereby hydrocarbons are transformed, by restricted oxidation efl'ected through the. agency of a suitable reducible metallic oxid, into other hydrocarbons containing proportionately pinene and limonene;

drocarbons of the benzol type. I Presumably" lesshydrogemwater being produced in the reaction. According to my invention I am enabled to'transfor'm paraflin hydrocarbons into olefins, as for example pentane into amylene, etc.; or into terpenes such ;as

the formation of olefins, terpenes and aromatic hydrocarbons represents the successive stages inthe restricted oxidation of a par aflin, so that each of these groups may con-.

veniently be regarded as derived from the precedinggroup richer in hydrogen, by res moval of a portion only'of this hydrogen.

.On this 'assum tion some of the reactions I involved might e thus expressed,us1ng gen- 80 eralized formulaazp (1) Conversion of a parafiin into anolefin (2) Conversion'of an olefin into a terpene i (3) Conversion of a ,terpene into an aro A matic hydrocarbon the intermediate reaction stages, if such O1 (5) Conversion of an olefin into an aromatic body 2lt+ n gn +3H O. v Similarly anequation. maybe written to each case an oxidation of a or into aromatic 'hy-' may with equal propriety be recourm, or nnrnorr, KICIIIGAN, a conroiwrron or imminent.

income or ramsronme man. ons.

Patented May 1, 1 917."

11 into a-terpene (6) 'C,,H,.,.,,' 1 30= C H 3H,O.. In the practice of my process, at least reflpreseat the direct transformation of a parwhen carried out under conditionssubstan tiaily as specified below, there is reason to believe that the reaction does in fact occur in successive stages, inasmuch as I usually find among the reaction products representa tlves of, most or all of the above-mentioned oups (olefins, "terpenes' and aromatic odies).

It will be observed that there occurs in ortion only of the hydro en component. 0 the hydrocarbon, Where y a hydrocarbon of any given series (paraflin, olefin" or terpene) is transformed or converted into a hydrocarbon or hydrocarbons of a series relatively poorer in hydrogen. Another product of this restricted oxidation is in each case water, and

J the amount of water produced, relative to' the amount of h drocarbon treated .is an accurate index 0 the extent to which the oxidation has progressed. Therefore by 001- lecting the water of oxidation and determining its quantity I am enabled definitely to control the reaction. I

I accomplish the results above set forth by subjecting a hydrocarbon, or usually a mixture, of hydrocarbons, torestricted oxidation by a reducible metallic oxid, under conditions of temperature and time which are carefully regulated according to the oxid used, the character of the hydrocarbon'to transformed, and the nature of the products desired. In the preferred embodiment of my invention, the hydrocarbon, in a stateof vapor, is caused to pass over or through a bed of reducible oxid contained in a tube,

v retort or other chamber which may be heated by a'burner or by means of an electric resistance coil. The temperature within the tube is maintained, by suitable regulating devices, at a point which is suflicient for the reduction of the oxid in question: and the I time and temperature are regulated with reference to the yield of water in order to produce the particular hydrocarbon or hydrocarbon mixture desired.

As reducible oxids suitable 'for my purnickel, cobalt and iron, the last mentioned poses, I may mention the oxids of copper, no

0.) and the reaction is extremely rapid and not readily controlled.

Using ferric oxid (Fe O a temperature range of 580-750 0. is suitable. Within these limits, provided a sufiicient excess of iron oxid be present, no appreciable separation of carbon has been observed. At higher temperatures, or if the reduction of the OXld is carried too far, crackin sets in and the reduced metal contains car on.

Ferric oxid employed as above undergoes successive reduction to F8 0,, FeO and metal. For the best operating conditions it is preferred to arrest the treatment when the charge in the tube or retort has been largely reduced to ferrous oxid FeO, containing usually some iron. The reduced charge may be regenerated by blasting it with steam while maintaining a temperature of approximately 750 0., without removing it from the tubes. generation hydrogen is produced, which may be collected and utilized for hydrogenation, or for other purposes. In case hydrogen is not desired the regeneration may be accomplished by means of air or a mixture of air and steam.

Between the approximate temperature limits above mentioned (580750 0.) I

. effect a careful adjustment between the temperature of the oxid and the boiling-point of the hydrocarbon to be transformed. Thus for a hydrocarbon fraction boiling between 150 and 200 0., the lower temperature ranges, say 580 to 625 0., are used; whereas for a fraction boiling between 250 and 300 0., the higher temperature ranges, say between 700 and 750 0., are used; the intermediate fractions requiring intermediate temperatures for the best results. In practice the boiling-point of the material under treatment is observed and the temperature of the oxid regulated accordingly:

or example, when treating an oil fraction of which the boiling-point 11SeS progressively, the temperature of the oxid is progressively and correspondingly increased.

It will be apparent from the foregoing that the precise working conditions of the process may vary within somewhat wide limits, according, to the character of the Hydrocarbon to e transformed, the nature of the product or products desired, and the specific reducible oxid used. I will therefore describe my invention by reference to one specific illustrative example thereof, it being understood that'the invention is not limited to the mani ulative features detailed in this example.

Example: The material treated was a complex hydrocarbon mixture consisting largely of olefins and containing constituents boiling all the way from 150 to 300 '0. The

reaction vessel consisted of a malleable iron tube three feet six inches long by four inches In the course of this re-- from which it is delivered by in diameter, electrically heated by nichrome Wire set in alundum cement, a rheostat being provided for accurate control of the temperature. The tube was'filled with a pure iron oxid of paint grade, prepared from copperas the tube being nearly filled with the unground material, in lump and powder form. The temperature was measured by means of a thermocouple on the outside of the tube which had previously been calibrated with a thermocouple in the center of the oxid, so that the temperatures mentioned are, internal.

The oil was vaporized, and the vapors carried through the tube and discharged into a condensing system. At the beginning of the operation the temperature reading was 580 0., for a boiling-point of the hydrocarbon introduced of 150 0., and this temperature was gradually increased in proportion to the rising boiling-point of the hydrocarbon to an ultimate temperature of 750 0. The pressure within the system was sufiicient only to maintain the regulated flow of the vapor therethrough. The condensate amounted to upward of ninety per cent. of the oil treated. Of the recovered product forty-seven per cent. boiled under 180 0. The remaining high-boiling material was refluxed to be again subjected to oxidation.

The material boiling 'under 180 C. was fractionated, yielding a series of fractions .as follows 7 Up to (3., about 7%, largely 'amyleue.

150 180 0., 25-30%, of which approximately v18% was llmonene, the balance largely olefins and aromatic hydrocarbone.

. Practically no paraflins were discoverable m the reactlon products, which are therefore very readily purified in order to. recover.

thelr-values. For the purpose for example of recovering benzol and toluol, it is merely necessary to remove the olefins by the usual treatment with sulfuric acid leaving the aromatic compounds in excellent condition for rectification.

A suitable apparatus for carrying out the process is diagrammatically shown in the accompanying. drawing, and comprises. a tank 1 for containing ,the starting material pipe 2 to a nozzle 3, by pressure upon the hquid in the tank 1 supplied b a suitable air-compressor 4. .The hydrocar on is thus injected into a series of connected tubes 6 containing the reducible oxid these tubes being mounted in a suitable furnace F and heated in the arrangement shown by a burner 7. From the tubes 6, a pipe 8 leads to a reflux condenser 9, maintamed at a suitable temperature From this condenser the residualthrough pipe 14 to the nozzle of an injector 15, supplied with wash-oil (which ma be some heavier paraflin oil or kerosene, oiling-point 180-200 0.), through the pipe sprayed into a chamber 18,

through trapped pipe to the collecting I main 21. The vapors and gases pass from chamber 18 through pipe 22to atower 23, provided with a series of perforated plates, the separated liquid passmg through pipe 24 to the main '21. The gases from tower 23 pass 'throu h pipe 25 to a fbell tower- 26, from-,whic the separated liquidspass through pipe 27 to main 21. The gases, princl ally hydrogen, pass through'ipipe 28, ed with a suitable gas meter G,vto a gas-holder 29, from which they may be carried to the burner? through the pipe 30.

The wash oils and condensates recovered from, main 21 may be re-used, preferably a after fractioning off the light products, and

' gressively raising the temperature .of the are returned'to tank 17.

The references in certain claims to the introduction of thehydrocarbon in-a state of vapor snbstantially'unmixed with reactive oxygen is intended to indicate that the hydrocarbon vapors entering the retorts are substantially undiluted by air, steam or oxygen in any other reactive form, whereby the oxidizing efl'ect to which the vapors are subjected is essentially or substantially that of the reducible metallic oxid. I

'action products hydroc-ar 1'. The process of transforming hydroe carbons into other hydrocarbons relatively poorer in h drogen, which consists in bringing the hy rocarbon to be transformed,'in a state of vapor substantially unmixed with reactive oxygen, into 'contact'with a reduci- 'ble metal oxid, andso regulating the temperature of said oxid and the time of .con-.

tact of the vapor therewith as 'to oxidize a part only of the hydrogen component of the hydrocarbon, producin ons relatively poorer in hydrogen, and steam. I

' 2. The process of transforming hydrocar-- hydrocarbons relatively.

bons into other poorer in hydrogen, which consists in bringing the hydrocarbon to be transformed, in a state of vapor substantially unmixed with reactive oxygen, into contact with iron oxid 'at a temperature of 580-750. C., and so regulating the time .of contact between the vapor and the oxid as to oxidize a portion the condensate being collected from' the tank 17. This wash oil is.

rovided withthe separated liquid passing and'olefins into terpenes, and aromatic hy- II 7 temperature of the oxid in correspon thereby as .re- I reduction of the oxid,

onlg laof the hydrogen component of the h'yd rbon, reducing thereby as reaction ngl ucts hy rocarbons relatively poorer in y rag in, and steam. v. 3. e process of transforming parafiins and olefins into terpenes and aromatic hy drpcarbons, which consists in sub'ecting said parafl'ms and olefins, in a state 0 vapor substantially unmixe'dwith reactive oxygen,

to restricted oxidation by means of .a reducible metal oxid maintained at asuitable temperature, producing thereby as reaction products hydrocarbons relatively hydrogen, and steam. I

4. The process of transforming paraflins poorer in drocarbons, which consists in sub'ecting' said parafiins and olefins, in a state 0 vapor substantially unmixed with reactive oxygen, to

I of subjecting mixtures. of hydrocarbons of differing boiling-point t o ducting the vaporsinto contact with "a re ducible metal oxid, at-a temperature above the reduction oint of said oxid, and'pro hydrocarbons of difierin boiling-point to restricted oxidation, which consists in prof I ,gresslvely vaporizing said mixtures, conox1d in correspondence with the rising boil- I restricted oxidation, whic consists in pro- .gressively vaporizing said mixtures, conducting the vapors. into contactwith ferric ox d at a temperature abovethe reduction point thereof, and progressivelyraising the ence with the risingboiling-poi'nt of the hydrof carbons. I 7. The rprocess of transforming hydrocarbons mto other hydrocarbons relatively oorer inhydrogen, which consists in bring mg the hydrocarbon to be transformed,'m a state of vapor substantially unmixed'with reactive oxygen, into contact with a reducible metal oxid, and, so regulating the temperature of said oxid and the time of contact of the vapor therewith as to oxidize a part only ofthe hydrogen component of the hydrocarbon, and toefi'ect incomplete reaction, roducts hy poorer in ydrogen, and steam, .while-avoi mg material separation of carbon.-

8. The process of transforming hydrooo'rer'in hy ogen, which consists in brin roducing thereby as; ocarbo'ns' relativeliy .125 carbons intoother hydrocarbons relatively ing the hydrocarbon to be transformed, m Y

a state of vapor substantially unmixed-with reactive oxygen, into contact with ironoxid at a temperature of 580'750 C., and so regulatin V vapor an .the oxid as to oxidize a. part only of the hydrogen component of the hydrocarbon, and to effect incomplete reduction of the oxid, producing thereby as reaction products hydrocarbons relatively poo rer in oxygen, to restricted oxidation by means of a reducible metal oxid maintained at a suitable temperature, producin thereby as reaction products hydrocar ons relatively poorer in hydrogen, and steam, while providing such excess of the reducible oxid as I to avoidmaterial separation of carbon.

10. The process of transforming paraifins and olefins into terpenes and aromatic hydrocarbons, which consists in subjecting said parafins and olefins, in a state of vapor substantially unmixed with reactive oxygen, to restricted oxidation by means of iron oxid maintained at a temperature of 580750 C. producing thereby as reaction products hydrocarbons relatively oorer in hydrogen, and steam, while provi ing such excess of the reducible oxid as to avoid material separation of carbon.

the time of contact between the' 11. The process of subjectin' mixtures of hydrocarbons of differing boi ingpoint to restricted oxidation, which consists in progressively vaporizing said mixtures, conducting the vapors into contact with a reducible metal oxid, at a temperature above the reduction point of said oxid, and progressively raising the temperaturejof the oxid in corres ondence with the rising boiling-point of t e hydrocarbon, While maintaining throughout the operation a sufiicient excess of oxid to avoid material separation of carbon.

12. The process of subjecti'n mixtures of hydrocarbons of differing boi ing-point to restricted oxidation, which consists in. progressively vaporizing said mixtures, conducting the vapors into contact with ferric oxid at a temperature above the reduction point thereof, and progressively raisin the temperature of the oxid in correspon ence with the rising boiling-point of the hydrocarbons, while maintaining throughout the operation a sufiicient excess of oxid to avoid material separation of carbon.

In testimon whereof I aflix my signature in presence'o two witnesses.

ALEXANDER S. RAMAGE.

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