US1445040A - Process of treating petroleum - Google Patents

Description

Feb. 13, 1923. 1,445,040. L. c. READ.

PROCESS 0F TREATING PETROLEUM.

FILED APR. 4, I917.

- lnwntor Patented Feb. 13, 1923.

UNITED STATES PATENT OFFICE.

LANDON CABELL READ, OF LOS ANGELES, QCALIFORNIA; CLARA GENEVIEVE READ ADMINISTRATRIX OF SAID L. CABELL READ, DECEASED.

PROCESS OF TREATING PETROLEUM.

Application filed April 4,

T 0 all whom it may concern: I

Be it known that I, LANDON CABELL READ,

a citizen of the United States, residing at,

. of producing only hydrocarbons other than those in the original substances.

As applied to petroleum or other hydrocarbons this invention more particularly relates to processes for treating hydrocarbons whereby products are formed which do not exist in the original substance; that is, in contradistinction to merely separating different constituents of an original substance, this process is, in this specific case, one in which hydrocarbons of a character different from the original are produced. However, it will of course be understood that my process does not preclude the possibility of preliminarily extracting the desirable constltuents from the original substances; as it is not. an object to effect changes or transformation in all of the hydrocarbon constituents but only in those which maybe changed or transformed into more desirable substances.

. Thus I mav first separate the lighter and more desirable constituents by any ordinary separation means before proceeding to trans form the remaining constituents into more desirable substances.

It may be stated as a primary object of this invention to transform original hydrocarbons so as to produce the largest possible quantity of the most valuable product at the least cost; and for this purpose I provide a system of operation inwhich the control conditions may be varied to produce a maximum yieldof various desirable roducts and minimum. yields of undesirab e products; a system in which, the control of quantity and quality may be said to be separate and independent of each other so that each may be controlled for maximum results; and a 1917.- Serial N0. 159,705.

system of control in which the deposition of free carbon may be prevented as far as posslble, if not eliminated entirely.

In accomplishing my objects I operate upon the hydrocarbons in that state which allows of the greatest possible independent variation of control of the controlling factors of the reaction-in the vapor state. This state of the hydrocarbons not only allows me to lndepen ently vary the factors of control such as temperature and pressure, but allows me to obtain reactions which are pecullar to the gaseous state alone. As other controlling means, I may here mention the use of superheated water va or, to be partially disassociated for suppiying hydrogen to hydrocarbons and oxygen to the carbon whlch may be thrown out; the use of air, oxygen, carbon-dioxide or a mixture of any or all'of these with or without steam for the supply of oxygen to the carbon which may be thrown out. The carbon dioxide may be either pure or'mixed with other gases as in the products of combustion of various fuels. Such gases, either reactive or inert, may be used to vary the control factor of concentration, as hereinafter explained.

The action of superheated steam in my process includes (1) a physical effect in preventing overheating of the hydrocarbon gases, (2) a catalytic effect in accelerating the reaction taking place shortening the time of subjection of the vapors to high temperature, 3) a chemical action of oxidation of any free carbon thrown out of the hydrocarbons, (4) a liberation of hydrogen corresponding to the oxygen used by the carbon to form raw material for hydrogenating the unsaturated hydrocarbons; (5) variation in the mass action relationship; and (6) a diluting effect for reduction of the partial pressures of the hydrocarbons.- It may be well here to note that although the instant percentage of disassociation of the water va-,

por or carbondioxid at the temperatures used may be comparatively small, yet the using up of the decomposition products tends to produce further decomposition to restore equilibrium conditions; resulting in a continuous supply of the decomposition products in a comparatively large final amount.

Generally speaking, equilibrium conditions in a reaction system-the factors which control reaction, include the factors of time,

there is, as a matter of actualfact, very lit- I tle chance that any one'selected set of control factors will produce the optimum conditions. This is particularly true as ap lied to petroleum hydrocarbons. It is an o ect of my invention to provide a system wherein all four of these control factors may be controlled and varied independently each of the other, so that proper conditions may be imposed for the maximum (production ofthe most highly desirable. pro ucts.

It is my conception that the largest production of the most desirable and valuable product is not to beobtained by a s ngle operatiton or by the 1mpos1t1on of a single set of control co-nditionsupon the original hydrocarbons; that some at least, of the most desired products, are not produced d1- rectly from the original hydrocarbons, but from intermediate products; that the most highly desired products may be, to some extent at least, products which are made under different kinds of conditions in difi'erent chains or processes of reaction from those in which the intermediate products are made. The intermediate products are produced in greatest quantity and value by conditions which usually are, and as a matter of fact in'a great many" cases are, the very opposite of the best conditions for the production of the valuable final products. Consequently, in order to obtain maximum efficiency, in order to obtain maximum recovery of the highest quality, I operate in more than one stage of operation; typically, a stage or stages in which control conditions are held for maximum production of inter mediate products, and a setting, or fixing, of those intermediate products by a stopping of the reactions which would carry them on into undesirable products, and then a stage or stages in which the conditions are made best for transformation, conversion, etc., of the intermediate products to the final products desired. This statement may not be entirely or strictly true, as some minorreactions which are not desired may go on in any of the stages, and as there may be in any circumstance, certain-original substances, they are not transformed into the final products most desired.

But, speaking in a general way, I provide in my process a system of operation in which the control of one thing is not dependent upon the control of another thing; in which the variation of one control factor is not interfered with by variation in another control factor; and in which control to produce a certain desired intermediate or final result is not' interfered with by the necessity of control to produce some'other result; and in which the original substances are taken through a series of ste s in which the control conditions are in epend'ently manipulated, so that, once the desirable product is obtained, it is so to speak, set and held while another desired product is produced, or the course of reaction is changed for the purpose of producing a further desired product.

In setting or fixing the intermediate prod- ,uct I may of course accomplish the desired result by changing any one of the control factors, these being independently variable.

For instance, after'breaking down complex petroleum carbon at high temperature under vacuum, I may then apply pressure while still keeping a moderately high temperature. The original complex open chain hydrocarbons will not be reproduced because the conditions necessary for their reproductiton are not made. This operation I give merely as an illustration of whatmay be done to change the course of reaction or to fixor set the intermediate products, 'to keep them from from going on in their previous reaction, or on the other hand, to keep them from reverting back to their original state, even in the case of such reactions as may be reversible.

v I conceive that it is impracticable to impose all of the conditions hereinbefore stated at any one time or in a single stage, or in a single reaction space. My conception,therefore, is that only by working-in a plurality of stages, where the difi'erent control con- -d1tions, hereinabove illustrated, can be successively applied, can the maximum results be had. Conditions for maximum results at each of the stages may be more or less nearly approximated by calculation in advance, by reference to known reaction procedures, and generally by former experience.

With this general idea of my system of procedure in mind, I now proceed to the explanation of typical and actual processes and the results thereof. I illustrate with processes of only two stages; but the method ence.

In an actual process a small boiler 10 has been used for generating steam, provided with a coil 11 for super-heating the steam to a temperature of from (500 to 800 F. The oil to be treated is led in through a pipe l2 from any suitable source of supply and injected with the superheated steam into the upper end of a double coil of pipe 13 in a furnace 14. The apparatus at 15 may be in the formof any ordinary injector, for draw ing in and injecting oil, and for atomizing and thus facilitating the vaporizing of the oil at the point of injection. The oil is thus fed into the coil 13, with the-steam, practically in the form of vapor. An air compressor 20 draws the vapors from the coil 13 and compresses them to any desired de gree; at the same time keeping the desired pressure, either greater or less than atmospheric pressure, but preferably less, upon the coil 13. A gage is provided at 21 for noting the pressure in the coil 13; and a control valve at 22, in conjunction with those at 22 and 22, provides the means for regulating the pressure by regulating the suction action of the compressor 20 upon the coil 13. From the compressor the vapors are compressed into a condenser coil 25 wherein the desired pressure is maintained, under control of the discharge valve or valves 26 and 26 a gage being provided for observation of the pressure. At 28 I provide a separat; ing chamber from which the fixed gases may escape through the pipe 29 and from which the liquids may escape through a suitable trap outlet 30.. The gas outlet pipe 29 may be provided with a discharge control valve 26 and the liquid outlet 30 may have a discharge control valve 26; and the pressure maintained in the condenser coil and in the separating chamber may be controlled with one or both of these valves. For instance, the liquid may be discharged intermittently, but the valve 26 may be set to discharge the gases at such a rate as to hold the proper pressure upon the condenser coil and the separating chamber. I prefer to hold pressure upon the separating chamber as well as upon the condenser coil, rather than on the condenser coil alone, for the reason that the gases are then not permitted to expand in the presence of the condensates and consequently do not absorb and carry off so much of the liquids as they would do if allowed to expand in their pres- The time elements and pressures in the various parts of the system are regulable and controllable by the general design, capacity, etc. of the apparatus to suit it in the first place to some particular relation of the factors of capacity, pressure, time of passage of vapors, etc.; and then, in any constructed and organized apparatus, by the speed of operation of the compressor, and by the manipulation of the various valves.

The compressor may be operated to keep the desired pressure, preferably less than atmospheric, on the furnace coil, for the purpose of obtaining first those products which a low pressure would induce; ahd the outlet valve 26 or 20 on the condenser coil is then regulated to cause the desired pressure to be built up in the condenser coil.

In the particular cases, hereinafter described, the original gasolene contents of the oil had been removed by othermeans; and this will normally be done before the oils are subjected to my process, because there is nothing to be gained by subjecting the original, valuable and desirable contents of the oil to my process. The fact that the first step of my process takes place under partial vacuum facilitates the combination of my apparatus directly with a distilling apparatus, as shown in the drawing. I illustrate a still at 40 from which the vapors are drawn off through pipe 12 into the pipe 13 leading to coil 13. The line 13 conducts the resultant from the coil 13 to the compressor 20 and a pressure relief valve at 13 may be used to protect the apparatus against rise in pressure. The arrangement may otherwise be similar to that previously described; the only operating difference being that in using the still the oils are delivered in initially gaseous state to the heating coil 13. Vith this general combination of apparatus it is practical to first distill off the lighter desirable products from an original petroleum and then take off the heavier vapors to be treated according to my process. However, the general results are the same in either case herein described. It will of course be understood that the still may be of any form in which oil vapor may be generated either with or without admixtures of superheated steam, and the remaining steam needed may be mixed at the apparatus 15, as before.

As particular instances of my method of procedure, I now describe specific operations. In one particular case the initial oil used Was a 26 gravity fuel distillate from California oil. The furnace temperature was estimated to be about 2000 F. The temperature in the heating coil is designed to be sufiicient to cause oxidation of carbon by oxygen from dissociated Water vapor, and to cause hydrogenation of the hydrocarbons by the liberated hydrogen; this temperature being also 'suflicient to cause the rapid break down of the high boiling hydrocarbons to low boiling hydrocarbons at the reduced pressure. The time period during which the vapors were subjected to the heat in coil 13 is sufficient to allow this. break down to proceed to the desired extent; and further break down is then arrested by the immediate cooling of the gases when they pass through the pipe 13 to the compressor. In a small unit no special cooling means is necessary for this reduction of temperature. A vacuum of15" was maintained upon-the furnace coil. The pressure in the condenser coil was. in this case, atmospheric. The recovery was approximately 80% of the origioily products being separated, distilled and analyzed. it was found that 64% of the products was light distillates of boiling points between 132 and 320 F.; while 36% was naphthalene oils of boiling points 300 F to 406 F. and anthracene oils of boiling points 500 to 597 -F. and a. small amount of pitch and loss. In other words, treated in this particular manner (and it is not claimed that these particular conditions are the most efiicient for producing the proclucts finally evolved), approximately 51% of the original substance was recovered as light distillates of a quality useful as gasolene.

The foregoing described operation is one of a number carried on in the apparatus illustrated, in which different operations a number of different c0ntr0l' conditions were imposed. For instance, the following described operation illustrates results obtained by imposing conditions different from those imposed above. In this case, the oil was a 48 gravity engine distillate from a California oil and the total recovery was approximately 80% of the original. The temperature in the furnace coil was estimated to be approximately 1700to 2000 F. and a vacuum of 12 was maintained in the furnace coil. These control conditions were somewhat similar to those maintained be-,

fore; but a pressure of 100 pounds per square inc-h was maintained in the condenser coil. The quality of the recovered products is shown by the following tabu-. lated results of distillation:

Distillation.

Quantity taken, 300 CC.; 100%.

Total If)? It will be noted that the temperatures in 'in the original substance; but the substantial difference was between the final con,-

denser pressures. I find from a number of runs, and from varying the final condenser pressure, that a pressure between approx1- mately eighty and one hundred twenty five pounds per square inch (varying with different circumstances) is sufficient and desirable to cause the products obtained in the last described run. Examination of the 64% of light oils from the first described operation has shown that they contained a very large percentage of unsaturated hydrocarbons; while examination of the 47% of light oils from the second described operation indicated a content of from one-third to one-half of toluene, the remainder being principally saturated, with only a sliuht quantity of unsaturated hydrocarbons. Jxami'nation of the recovered oily products, of both the above described operations, showed the presence of easily separated pyridene bases and terpenoid hydrocarbons to a greater or less extent, whilst the recovered aqueous products showed the presence of alhedydic and other oxygenated hydrocarbon products to a small extent.

There was some difference.

In each of the above described specific I cases the weight of water vapor used was approximately one-half the weight of hydrocarbons. This amount of water vapor is not only sufficient for the purposes herein set forth, of oxidation, hydrogenation, catalytic action, etc., and for the purpose of influencing the'mass action by varying the concentration on account of its reactivity; but also for further variation of the mass action by influencing the concentration by virtue of its diluting effect. For varying the concentration and causing dilution. independently of the pressures and temperatures used, I' may introduce atotally inert fluid, as hereinbefore stated. The timeelements in each of the above described specific cases were uniformly very short. It is somewhat diflicult to state exactly what the time elements were, due to conditions of varying volumes, etc.; but it may be generally stated that the total time element from beginning to end of these processes was approximately five seconds, divided as follows: Approximately three seconds for subjection to the high temperature under low pressure, approximately one second for falling of temperature before compression, and approximately one second for compression and condensation. In both cases the temperature to which the vapors fell before compression, or at which they were compressed, did not exceed approximately 1200 F. In some cases it may be well to keep the gases, after compression, at their temperature of compression for a slight interval before cooling and physical condensation. so as to allow suflicient time forthe chemical reactions of condensation, etc. to be practically completed before the vapors are cooled below a temperature at which such reactions can go forward at suitable speed. However, I have. found that such necessary per-10d 1s, in fact. comparatively short. The final temperature at the d15- charge of the condenser was practically atmospheric. regardless of the pressure there maintained.

The above described specific operations are typical of others which have been carried out; all with the substantial result of obtainance of a comparatively large percentage of low boiling hydrocarbons; uniformly a percentage very much in excess of any percentage obtained by any known cracking system or system of distillation. And it will be seen how these specific in stances conform to the general statement of procedure I have hereinbefore made; how I first apply one set of controllable conditions. and then another, to the whole body, varying the conditions to suit circumstances and to suit the nature of the desired final products.

Considering the large number of combinations possible under such extreme flexibility of so many control conditions, it is quite impossible to state the final result for each particular combination. (Alnd I might here add that I have so far only been able to try a few of the-m.) But it is sufiicient to say in abroad way that, with primary temper atures around 1300 I. and at about atmosphere primary, and 1 atmosphere final, pressure the final product will contain considerable olefins, acetylenes, etc., and some benzene and other cyclic hydrocarbons; with temperatures up to 2300 and at about 7} atmosphere primary, and 10 atmospheres final, pressure, the o-lefines and acetylenes, etc., are considerably diminished and the benzenes and other cyclic hydrocarbons considerably increased. The distillation fraction of any of these products corresponding in boiling points with commercial gasolene can be used with advantage in place of that article; it is, moreover, an excellent solvent and can be worked up profitably for its large content of benzene, toluene and other valuable cyclic hydrocarbons, the content of any one of which cyclic hydrocarbons can be increased or diminished by special variations of control conditions to suit the particular case in hand.

It should be understood that I do not limit myself to the introduction of steam or other oxygen bearing vapors or'gases, or inert gases, which may be introduced either for the purpose of reacting with the free carbon or of forming addition or substitu-' tion products of the hydrocarbons themselves or for varying the concentration of the reacting substances, or for the mere purpose of dilutling the reacting system. For instance, any of the halogens, say, chlorine, may be used for reacting with the carbon and for obtaining different results along similar lines; and other gases, vapors or liquids either with or without steam, or other oxygen bearing gases, may be used to bring about specific effects due to their composition. I claim my invention is broad enough in scope to include any and all such applications of. it. I

\Vhile the theoretical basis of the explanations may not be fully correct, I have given them as my explanation of what actually occurs in my process, and in order to render my process fully intelligible in its workings and my invention fully intelligible in its scope. It will be obvious that the described operations, steps and applications of controlling factors may be applied to hydrocarbons, etc., and in situations, other 90 than herein specifically stated, and with various forms of apparatus; in fact, that many variations may be made Within the general scope and extent of my invention. I do not conceive of my invention as limited to any of the specific procedures herein stated, but rather to include those general procedures of which these particular procedures are specific instances. Accordingly I have not given the above descriptions in a limiting 100 sense, but in a sense typifying and indicating the invention and I do not limit myself to the specific procedures, etc., herein set forth excepting as particularized in the following claims. These claims are intended 105 to cover briefly and concisely the whole subject matter of my invention, generically and specifically, and whatever modifications, variations, etc., may lie between the most general and most specific claims.

Having described a preferred form of my invention, I claim:

1. The process of chemically converting hydrocarbons that embodies first subjecting them to a cracking temperature at a low 115 pressure to cause chemical conversion, then subjecting the resultant gases and vapors to reduction of temperature and to an increase of pressure to cause further chemical conversion. i

2. A process of chemically converting hydro-carbons, embodying first subjecting an original body of hydrocarbons to control conditions including a temperature of approximately 2000 F. and a pressure less 125 than atmospheric to cause chemical conversion, and then subjecting substantially the whole of the converted products to an increase in pressure to cause chemical conver= slon.

. hydro-carbons,

chemically converting hydro-carbons, embodying first subjecting an original body of hydro-carbons to control conditions includin a temperature of approximately 2000 and a pressure less than atmospheric to cause chemical conversion, fora certain time period in the presence of water vapor, and then subjecting the whole body of resultant vapors to an increase in pressure to cause further chemical conversion. 4. A .process of chemically converting hydro-carbons, embodying first subjecting them to relatively high temperature and to pressure substantially not more than atmospheric to cause chemical conversion, then subjecting the whole of theresultant gases and vapors to reduction of temperature and then to an increase of pressure to cause further chemical conversion and condensing the product.

5. A process .of

3. A process of chemically converting embodying first subjecting them substantially exclusively in 'vapor phase to relatively high temperature and to pressure substantially not more than atmospheric to cause chemical conversion, then subjecting the'resultantproducts to an increase in pressure to cause chemical conversion.

6. A' process of chemically converting hydro-carbons, embodying first subjecting them to relatively high temperature and to pressure substantially not more than atmospheric to cause chemical conversion, then subjecting the resultant products to a.

diminution of temperature and an increase in pressure to cause chemical conversion.

7. The herein described process of treating hydrocarbons, embodying first subjecting them substantially exclusively in vapor phase to a relatively high temperature at a low pressure in admixture with reactive and hydro-carbons and then v the presence of an inert gases whereby the controlling factors of temperature and pressure and concentration may be maintained independently of each other, to effect chemical change in such cooling the admixture ofvapors and subjecting the whole of thesame to an increase in pressure, to effect further chemical densing the product.

8. The herein' described process of treating hydrocarbons, embodying subjecting them to relatively highheat and pressure substantially not more than atmospheric in excess of water vapor, said water vapor being in excess of the amount required to supply hydrogen and oxygen, for reaction with the hydrocarbons and the e cessacting as an inert diluent by which the concentration of the hydrocarbon may be controlled independent of the pres-- sure. r

9. The herein described process of treat,

. taining these change and coning hydrocarbons,

embodying subjecting them in vapor phase substantially exclusively to relatively high temperature at a pressurev substantially not more than atgases being in excess of the amount re quired for reaction with the hydrocarbons and the excess acting as a controllable diluent by which the concentration of the hydrocarbons may be controlled independent of the pressure.

11. The herein described process of chemically converting hydrocarbons, embodying first subjecting an original body of the same to relatively high temperature and relatively low pressure and concentration and mainconditions each independent of each others by carrying on such subjection with the hydrocarbons,

cooling and condensing the resulting prod-.

ucts while under pressure,

12;. The herein described process of chemically converting hydrocarbons, first subjecting an original body of the same to relatively high temperature and relatively low pressure and concentration and maintaining those conditions each independent of each of the others by carrying on such subjection with the hydrocarbons substantially exclusively in the vapor phase and in admixture with water vapor in excess of the amount of water vapor that will react with the hydrocarbons at the temperature employed, the excess being controllable in amount and thus forming a controllable diluent to vary and control the concentration; and then somewhat cooling the resulting products and subjecting them to in creased pressure while still at a temperature considerably above atmospheric, and then cooling andcondensing the resulting products while under pressure.

13. The herein described process of chemically converting hydrocarbons, embodying first subjecting them-in the presence of water vap r to'a temperature sufiiciently high to substantially ex-' clusivelyin the vapor phase and. in ad- "mixture with a diluent controllable in embodying cause partial dissociationof the water vapor and oxidation of. carbon with the oxygen thus freed, under a pressure substantially not more than atmospheric,'then subjecting the whole of theresultant gases and vapors to increase of pressure, and condensing the product.

14. The herein described process of chemically converting hydrocarbons, embodying first subjecting an original body of hydrocarbons to control conditions including a relatively high temperature and a pressure substantially not more than atmospheric to cause chemical conversion, then subjecting substantially the Whole of the converted products to a diminution of temperature but still maintaining the temperature above at mospheric and to an increase of pressure while at that diminished high temperature, then to reduction of temperature to approximately atmospheric; and then finally'relieving the pressure to atmospheric pressure.

15. The herein described process of chemically converting hydrocarbons, embodying firstsubjecting them substantially exclusively in vapor phase to a relatively'high temperature at a pressure substantially not more than atmosphericin admixture with reactive and inert gases, whereby the controlling factors of temperature and pressure and concentrationmay be maintained independently of each other, then subjecting the resultant vapors to a, diminished high temperature without material change 1n pressure, then to an increase in pressure, then to decrease in pressure to approximately atmospheric pressure.

16.-A procem of treating hydrocarbons,

embodying subjecting them to a relatively high temperature in substantially exclusive vapor phase and in the presence of water vapor and under apressure substantially not more than atmospheric, then-reducing the temperature but still maintaining itabove normal atmospheric temperature and materially increasing the pressure, and then cooling the vapor while under increased pressure, and finally relieving the pressure.

17. A process of treating hydrocarbons,

' embodying first subjecting them to relatively high temperature and pressure substantially not more than atmospheric in the presence of an excess of Water vapor, said Water vapor being in excess of the amount required to supply hydrogen and oxygen for reactionwith the hydrocarbons and the excess acting as-an inert diluent by which the concentration of the hydrocarbons may be controlled independent of the pressure, and then subjecting the products to an increase of pressure. y In witness that'I claim the foregoing I have hereunto subscribed my name this 29th day of March, 1917.

4 o LICABELL READ. Witnesses:

Enwoon H, BARKELEW,

JAMES T. BARKELEW.

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