US1644736A - Process of carrying out chemical reactions with liquids - Google Patents

Description

- 3 Get. 11,192? E. LESUS'ET AL 9 PROCESS OF CARRYING OUT CHEMICA L REACTIONS WITH LIQUIDS Filed Sept, 4. 1920 2 Sheets-Sheet 1 Oct. 11 19 27 E. H. LESLIE ET AL PROCESS OF CARRYING OUT CHEMICAL REACTIONS WITH LIQUIDS 2 Sheets-Sheet 2 Filed Sept. 4 1920 .INVENTUR ATTORNEYS Patented ill,

EUGENE HENDRICKS LESLIE, GE Alil'l l ABBQR, MEGHIGAN, AND IBERZQ'ELL Bl, TUNISQE,

- 033 NEW Yfiltfi ldl Y.

PBGGESS OIi GAEEYIHG EU? CEEQIICAL' FEAGTIQNS WITH LIQUES.

Application filed September a, 1920. Serial No. %08,288.

Our invention relates toa process tor carrying out chemical reactions of various kinds, but relates especially to a process ttor carrying out reactions whereby hydrocarbons 5 of a comparatively low boiling point may be derived from hydrocarbon liquids having a higher boiling point. r

The object of our invention is to provide a process by means of which chemical reac tions of various kinds may be carried out in an advantageous manner, but the object of our invention is especially to provide a process whereby solvents or fuels of a com paratively low boiling point may be'derived from hydrocarbon liquids having a higher boiling point. In general, our invention relates to a process of subjecting organic liquids of various kinds, such as alcohols, ket-ones, ethers, esters, aldehydcs, amines, acids, anhydrides, halogen derivatives, phenols, and nitro-compounds todissociation or decomposition, so as to form various produets, but it relates more particularly to the dissociation or decomposition ofhydrocarbons, particularly hydrocarbons obtained from or contained in petroleum oils, coal tar oils, distillates, or those derived from shales. The object of our invention is, furthermore, to provide a process by means of which the influences of surfaces of liquids may-be utilised to the fullest extent, so as to bring about reactions in one or more '01 several liquics, the surfaces of which are adjacent to one another. While the theory upon which the process operates to bring about the reactions in question due to the presence of said surfaces is not known to the fullest extent, we do know that these reactions are brought about by reason of the presence of the surfaces-of the respective liquids in positions adjacent to one another, and it would seem, furthermore, that at least two of the active causes in starting these reactions are the surface enegy which acts as a stress in displacing the chemical equilibria of a liquid system, and the chemical or structural orientation of the molecules of substances in liquid form, which is known to .ex'ist in the surfaces of the liquids. Furthermore, in our process changes in temperature and concentration of the reacting molecules are utilized in the furtherance of the reactions, as these two stresses are also v active in displacing the chemical equilibria of the liquid system. Changes in pressure have very little effect in carrying out our process, so far as causing the reactions is concerned, inasmuch as changes in pressure have little or no eli'ect upon liquids, which are only slightly compressible. In accordance with the law relating to liquid systems to the eliect that, when a stress is brought to bear upon a system in equilibrium by process such a stress is applied by the extension or thesurtace or Lneliquid system. lrurthermorc, our process operates in such a manner as to tend to undo the effect of this stress by the production of compounds having a smaller surl'ace tension than the compounds troni which they were derived.

in most cases in carrying out our process,"

the production oi compounds having low molecular weights is favored. Another stress which is applied in our process is a change in temperature, and in accordance with the law of liquid systems, above referred to, the result in our process is to bring about reactions which are endothermic, as our process involves the application of an increase in temperature. We, however,

avoid unduly high temperatures, so as to provide fuel economy, and avoid as much as possible wear and tear on the apparatus. Furthermore, in this way, we obviate undesirable secondary reaetions which would occur it higher temperatures were I used. Again, in our process the efi'ect of changes in concentration is utilized, inasmuch as the desired reactions are carried out Without the disadvantage of interruption, owing to the fact that the reaction products are continually removed from the liquid system. Our process, therefore, provides a means whereby reactions may be brought about in liquid systems without depending upon the utilization of high temperatures, while at the same time the advantages of moder in he concentrac utilized to 'oracticai stand e, our iuvon on is especially in that, by its use, chemicai equilibria iplaced. with production of desircu rechanges general, our process comprises a moth-1 cu iich. may, if desired, be ca ried cu Va'o" ,geousiy by allowing dross or a. a 3 W obi iued as a resuit oi the a i oi uriace tension descent. sire or cyiindcrs of said liquid to fail onto be carried into a second liouid which a s slash ras-v Bus second dium a source of heat, liquid may or may not be soaubie in the first iiquid. Furthermore, W the chemical change is taking place in 4 first liquid, there is a vabor phase con molecules of said two liquids, as Weli a of the prod ucts formed is a result of the reaction. Preferably, the drops of liquid should be at least one-thirty sccoud of an in h is diameter in order to produce a proper uoroenoiu iowever, When'worlii J rapid increase of temperature and frequent renewal of the surface, the drops would preferably be larger and at least one-six teenth of an inch in diameter. If the drops were of a much smaller size, there would be a correspondingly great loss of the liquid by vaporization and mechanical removal before it reaches the splash medium, Furthermore, the extent of the splash. piicuozfi'enon is dependent on the momentum of the drop, which is influenced by the velocity of the vapor above the splash medium. The ex tent and nature of the splash phenomenon is further influenced by the surface tensions of the two liquids, liquids, and in general, bythc nature of the iiquids, The effect of an extensive proi'ioimced splash phenomenon to c y greatly extend the adjacent surfacesoif the iiquids in question, and this effect i uated if the drop of the as into ihe splash o1 1 heat" v icuilt of the violent disr' i ed into a large so cropiets W1 l i the same In c particular drop docs not'eutirely penctrate the splash medium, it will at least form a. distinct impression in thesurface of the splash medium, will then rebound upwardly and oscillate back and forth in this Way uutii it finally comes to rest on the surface of 511c solash medium. In either of these cases, the drop of liquid may, of course, become partly absorbed by the splash medium, part-- iy evaporated, and in partciianged chemically owing to the positions of the liquid surby the viscosities of said.-

zoo-sauce faces adjacent to one another, and to the heat transferred from the splash medium thereto, Similar results are also not only obtained while the liquid is in the form. of drops, but, also in the quantity of the liquid which spreads out upon the surface or" the splash medium, and which may acquire there a this layer covering the entire body of said spiash medium, In any case, the result of the process is every great extension of the surfaces of both liquids and of the surface oi contact between them inasmuch as the reactions taking place at the surfaces of the liquids eudoeuergetic, and also that there -Z vaporization of liquids, there consequently a continual. a-bsor otiou of heat. Because of the thin bodies of iiquids to which heatis to "er. 5. from the spiash medium, the absorption of heat is eiiccoive. iiiiowever, such transfer of heat very much faciiiiated by providing agiiatiou for the liquids. This may be done me anicaiiy iii any desired mane-er, or by utilizin splash medium ba ring a. temperatore that wili bring about a continua gentle cbuilitioiu thereof. Again it is desirable to renew the heated surface from time to time in order to furnish a soiash medium A having the pro z er surface energy and: proper molecular orientation, and this may he done by stopping the introductionofthc liquid drops for certain intervals of time, or by agitation or ebullition, as above indicated. For example, the drops of liquid may be introduced for periods of three minutes, 300 and the supply of liquid may be discontinued in the intervening periods of one minute. If the process were not carried out'in this way, but the drops of liquid were introduced continuously, there Wouid result a substantial equilibrium between the rate of heat introduction into, and the rate ofhcat abstract-ion from the surface of the splash medium. This would necessitate a higher temperature for the splash medium 10 in order to maintain the surface thereof at thedesired temperature, than is the case when the drops of liquid are supplied intermittently. Due to the utilization of the surface for reaction, there may have been a fur- 5 their surfacc'moditication such as change of molecular position in addition to tempera-- ture change. By the intermittent supply of. o the drops of liquid, therefore, the splash medium may be maintained at a lower temperature and proper surface condition.

Owing to the great increase in the demand for motor fuels and the limited supply of petroleum, which. is coi'itinualiy becoming less able to fur ish the desired quantity of motor fuel, We nave appiied our process esgeciaily to the production of motor fuels strom petroleum products which are heavier than the products which are ordinarily contained motor fuels used in internal comm l devices in. which masses ion engines. ZFor this purpose, we have died the heavy oils, such as the residuums,

tars, fuelfoiis, end the like.

In former urocess a number oi formation or high boilnx comp: s carbon, and g Ulefins have the easily osidized, pounds ughich will n? th were ol'itained rining con p mechanical. the fuel .tnsde therefrom is both the olefin end aromatic hydrocarbons produce large quentities'of carbon in internal combustion enutilized. Furthermore,

gines. In such previous processes ordinarily, furthermore, in which the yield obtained in a single processing amounted to 15%. of low boiling products which may be called gasoline the low boiling products so obtained contained at least 20% and in the majority of cases 30% of olefins. Also, such gasoline would have a gravity approximately 5 B.- lower than u distillate of similar boiling range obtained by the distillation of crude oil. In accordance with our process, we obtain 20% of gasoline and less than 15% of oleiins. Furthermore, the gravity thereof is substantially the same as a distillate of tlie same boiling range obtained from crude oil. Besides, these results are obtained by utilizing temperatures between 650 and 750 l1, although the temperature may, if desired, be considerably below or above these figures. Also, with our process no pressure is necessary. In our process, in contrast With previous processes, products such as residuurns, tars, fuel oils, and all similar heavy oils aresuccesstully treated, and are preferred raw materials, although, if desired, lighter distillutes, such as gas oils or kerosene may be treated together with said residuums, tars, fuel oils, and heavy oils.

Further objects of our invention will up pear from the detailed description thereof contained hereinafter.

While our invention is capable of embodiment in many dillerent forms, for the purpose of illustration we shall describe certain forms of the same hereinafter, and

connection with many different types of apparatus, we have shown only one type of apparatus in the accompanying drawings, in which;

Fig. 1 is a diagrammatic vertical section of an apparatus which may be used in accordance with our invention.

Figs. 2 to 9' are a series of diagrammatic while it is capable or being carried out inviews of the action of the drops upon the surface of the liquid in the still, and

Figs. to 3 aresnn lar series of views showing the action'of the drops when entering a. body of the liquid. For example, n carrying out ournventlon, a heavy oil, such for instance as a residuum having a specific gravity offromis to 162 B., i s'introduced into a horizontal cylindrical still 1 heated by means of a fire box. 2 provided with an air or steam blast oil burner 23, and having a stack 1- to carry of: the products of combustion. in the fire box 2, there is located an elevation 41* to bring the heated gases nearer the still at the rear thereof. Said heavy oil is introduced into the still through a pipe 5. At the top of the still there are two ventilating manholes and 5* and a steam pipe 5 for purging, At the bottom of the still, there is a manhole 6 for cleaning out the carbon and carbonaceous residues from the still, and at the bottom there is also provided a drawoii' pipe 7 the discharge from which is controlled by a hand valve 7* to conduct away the heavy tar to a Water-cooled cooler 8 adapted to discharge into a tank 9 having a valved draw-oil pipe 10 and a valved inlet pipe 11 for the introduction of any lighter products, when desired. The temperature in thb still 1 is gradually raised until the boiling 'point of the heavy oil is reached which may be from 600 to 700 F. The vapor coming from the heavy oil is carried through a pipe 12 having lugging 18 to a Water-cooled. dcphlegmut'or 14 having a hand hole 14, and provided with lagging 15, and

coil 15), and a valved outlet pipe 20, which may be also enclosed in the lagging 21 that surrounds the tank 17. The oil is then alloued'to run from the tank 17 back into the still, preferably through a plurality of alternately operable filters 22 and 22, a meter 23, a stop cock 23", as well as a check valve 24: undo preheating coil 24?, the liquid being discharged intothe still from a series of horizontal pipes 25 having overflow outlets 25, and supported by turnbuckle straps 25', said pipes 25 having perforations 26 adapted to form cylinders 27 of discharged oil which will break into drops 28. These drops 28 upon striking the surface of the enter the same and oscillate back and forth, as indicated in the series of diagrams contained in Fig. 2. If, however they do enter the body of said liquid and become separated from the surface of the same, the action of the drops within the body of liquid in the still is then indicated in the series of diagrams appearing in Fig. The pi s will thus provide a uniform (llStIlblltlOH of the drops over the surface of the liquid in the still 1. If desired, furthermore, the

ipe 20 may contain an intermittent supplying device 29 to supply the liquid for exainple at every alternate three'ininutes. This may be comprised of a rotating valve 29 having a gear 29, and driven by a gear 29 on an electric motor 529.

Reactions of the type above referred to, will then take place between the surfaces of the drops and the body of liquid in the still, as well asnany accumulation of the liquid from the drops on the surface of the liquid in the still, and the ebullition of the liquid in. the still will provide the desired agitation hcreinahove referred to. It is desirable to have the oil which returns to the still maintain its temperature as far as possible when leaving the still, in order to makepossible more accurate temperature control and to avoid using up unnecessarily the heat in the surface of the body oi: oil in the still; and for this purpose, the pipe 1.3, the dephlegmator 14, the tank 17, and the return pipe 20 are provided with leggings. The resulting vapor issuing from the still will now be composed of low boiling and higher boiling hydrocarbons, and'the dephleginator will remove the higher boiling hydrocarbons While allowing .the low boiling hydrocarbons to pass out by a valved pipe 30 to a water:

cooled condenser 31 having water inlet and outlet P1136331 and 31?. and a discharge ire 32 a'ovided with a si ht box 32 lead- P l T a ing to a tank 33 having a valved outlet pipe Connected to the lower portion of the condenser 31 and the outlet pipe 32, there is a gastakeoll 346. If it is desired during the operation of the process, any other distillate. such fpr example as gas oil or kerosene. iua hciutroduccd into the tank 17 through thc' pipe 18. I

' The process as described is continued for an number of hours desired but ordinarily for a period of about sivteen hours. the tein 'uerature of the heavy oil in the still being gradually raisel in order to keep up the gentle ehullition therein. At the end of this period, a heavv tar will be left in the still which is runthrough the cooler 8 into the tank 9. whereit may be thinned by adding any desired quantity of a heavy petroleum distillate through the pipe 11 to make a fuel oil. or otherheavy product. After making a few runs in this manner it will be found that a certain amount of carbon or very such as to e heavy tarry material left on walls of the still, and

then be necessary to erase ti tion of the same, allow it.

the inner and ti be thoroughly thro' I am here If; 6 With the aid of the ventilat 5 and 5 It will be found that as a the process on the basis at the ori l as the quantitieset the several products 3's obtained are approximately as follows:

If desired, as a modification of our invention, gas oil may he used in ll. trill l but inasi'nuch as the liquid woz'zld boil a' at temperatures below the Working temp. atures of the process in the Qlll-illftly oocu ation otthe same, the valve in. the pipe would be partly closed in order to ha. back pressure on the stilhand under these conditions the boiling point oi? the liquid 95 would be raised su'fficiently to prevent it boiling away below the desired teinpcramrc. Infthe event or" operating the process in this 37857., the parts of the pparatus would he made suiiioiently strong to Withstand pressures up to several atmospher r example 150 pounds per square inch. in .las use at this modification of our proce oi is can lie-cracked. more quickly than the a; of previous proces and with increased yields.

Another modification of our invention which are so viscous that the};

transported satisfactorily, either or tank car. in accordance h on i zosiy at these oil. cor he handled, While at the same the. producing enough gasoline to pay for the conduct of the process.

While we have described our invention above in detail, e Wish it to be under-- stood that many changes may be made there in without departing from the spirit of our invention.

e claim:

l. The process of converting liquid hydro: carbons into products of lower boiling point which comprises bringing together surfaces of liquid bodies oi? hydrocarbons at a con verting temperature at least as high as the boiling point of one there one of said weaves 2. The process on converting liquid hydro carbons into products otlower boiling point 'whi ch comprises bringing together surfaces- 7 of liquid bodies ofhydrocarbons at-a'converting temperature at least as high as the loboiling point of one of them, one of said bodies of liquid. being uniformly distributed over the surface of the other irvthe form of drops and being intermittently supplied thereto the temperature of the other body of tributed body of liquid.

I 3. The: rocess of converting liquid hydrocarbons nto products of lower boiling point which comprises bringing together surfaces 0 of liquid bodies of hydrocarbons at a con:

drops h'avin verting temperature at least as high as the boiling point of oneof them, one of said bodies of liquid being uniformly distributed over the surface of the other iii the form of a diameter of at least onethirty-secon of an inch and being intermittently supplied thereto, the temperature of the other body of liquid being higher than that of such distributed body of liquid.

4. The process of converting liquid hydrocarbons into products of lower boiling point which comprises heating a body of liquid hydrocarbons to conversion temperature to distil vapors therefrom, condensing relative- ,ly high boiling compounds from said vapors,

filtering the condensate and returning the same to said body of liquid hydrocarbons undergoing distillation, said condensate being intermittently supplied to said body.

5. The process of converting liquid hydrocarbons into products of lower which comprises heating a body of liquid hydrocarbons to conversion temperature to dis til vapors therefiom, condensing relatively high boiling compounds from said vapors,

boiling point i filtering the condensate and returning the" same to said body of liquid hydrocarbons in such manner as to eliect distributed contact thereof with the surface of said body.

6. The process of converting liquid hydrocarbons into products of lower boiling point which comprises heating a body of liquid hydroc'arbons to conversion temperature to d1stil vapors therefrom, condensing relatively highboiling com ounds from said vapors, filtering the con ensate and returning the same to said body of liquid hydrocarbons in the form of drops distributed over andcon- .tacting Withthe surface of said body.

16' liquid being higher than that of such dis- 7. Theprocess of converting mineral oil into proucts of lower boiling point which comprises heating a body of mineral oil to conversion temperature to distil vapors therefrom condensin a relat-ivel hi h boilin 7 c y g portion of said vapors, and refluxing the condensate tosaid body ot' oil undergoing distillation in such manner vas to-efi'ect distributed contact thereof with the surface of said body, said condensate being intermittently supplied to said body.

8. The process of converting mineral oil into products of lower boiling point which comprises heating a body of mineral-oil to conversion temperature to disti'l vapors therefrom, condensing a relatively high boiling portion of said vapors, and refluxing the condensate to said body of. oi}. undergoin distillation in the form of drops showered upon the surface of said body, said condeniatae being intermittently supplied to said to y- In testimony that I claim. the fore oing,

I have hereunto set royhand this 211 day of August, 1920, y I 1 EUGENE numerous LESLIE claim the foregoing, ll hand this 6th day oi unnatural n. run'isoit-

Images