US 1864687 A
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June' 28, 1932. J. D. FIELDS TREATMENT OF iETROLEUM MATERIALS Fiied sept. 24. 1951 w mi @y ww. @Rw ww, w..
Patented June 28, 1932 JOHN n. FIELDS, or Los PATENT oF FlcE j ANGELES, CALIFORNIA ,TREATMENT or PETROLEUM aluminum .Application iled September 24, 1931, Serial No. 564,944, and in* Canada, Venezuela, and Iexioo after v v l .August 1, 1931.
This invention relates to a method of ref ining hydrocarbons and particularly pertalns to the treatment of any kind of petroleum Oil, either crude or 4distillates or topped 011 or distillation residues or crackingresldues, to produce various products therefrom. The oil may be of parailin base or asphalt base or mixed base and may contain sulfur or not. The 'residues referred to may be freely l1qu1d vor nearly. solid or may contain greater or smaller proportions of constituents of a petak rolatum-like consistency at ordlnary at- ,mospheric temperature. The starting material also may be a mixture of two or more of the above mentioned materials, but -should contain some fractions less volatile than` ordinary kerosene (say 40 B.). The mak `terial to be treated will hereina er be termed petroleum which term is to be understood in the broad sense here referred to.
The primary object of the invention is to provide a process whereby any petroleum may be treated to produce any one or more of a number of the products of distillation or cracking at the will of the operator from anypetroleum available for treatment3 and at the same time to effect the production of a hard, dry, commercial coke from the residuum, andl also to effect the removal and recovery of resinous and other gummy con- -stituents whichv if left in the product, would result in discoloration of the distillates and to enable its ready removal from the distilling apparatus and also have pro erties -imparted thereto which will render 1t valuable as a carbon or coke product suitable for use in metallurgical and other operations.
Another object of the invention is to provide a method for purifying the distillates to effect the production of a sweet smelling, water white, absolutely stable distillate product of great brilliancy, and whereby resinous compounds and other gummy im.
purities, sulfur compounds and otherQimpurities, held in solution in the distillates may be removed in a usable condition, without Adestroying the benzol equivalent and octane number constituents of the distillate, whereby these latter constituents are conserved sol as to produce a high grade product which when used as fuel in an internal combustion engine, will not form. gummy or resinous deposits.
Another object of the invention is the proy vision of a methodwhereby theA distillates may be refined without material loss thereof thus enabling the roduction of a greater volume of the puri ed product from a given volume of distillates under treatment than is obtained byghhe refining processeslhereto- Vfore used.
purifyalkalies, filtering media and other substances which are lost `n the usual treatment of distillates by the acid and alkali treating processes, thereby obviatin the expense/in-A cident to the use of such su stances and thus resulting in a process for refining distillates 'which is of great economicvalue.
The invention resides generally in distilling any petroleum hydrocarbon together with a vegetable substance, with or without the addition offiron ore accordingv to the character of coke product desired, effecting such distillation, with any predetermined amount of cracking, all at predetermined temperatures and pressures. according to the fractions desired thereby producing oil vapors, condensing such vapors, and finally treating the condensed distillates to remove and recover resinous and other impurisubjecting the impurities in the condensates to the action of a catalytic agent of a charac'- ter such that it will act on the impurities and vties therefrom; the invention further re- "a siding in eii'ecting. the last named step by y cause same to separate from the distillate while the latter still retains the benzol and octane number components of the distillates in a manner which will permit ready re-V plishing the objects and advantages as may subsequently appear' further resides in the i and features hdreinafter more fully descrlbed and claimed and illustrated by way of example in the'accompanying drawing in perforated catalyzer supports 22, 23 and-24 which are spaced from the bottoms of the tanks and are here shown as composed of wire netting. The spaces 25,26 and 27 above the supports 22, 23 and 24 constitute catalyzing chambers within which are contained catalytic bodiesy I, J, andK `carried von the supports, which bodies are'formed of, solid alkali Vmetal, such as sodium, potassium, lithium or mixtures thereof. Metallic sodium is preferred.
The catalytic bodies are so sha ed and so arranged within the catalyzing c ambers as to permit the flow ofdistillates through said chambers yet cause the flowing distillates to be deflected into numerous small streams'A which .flow through the interstices between adjacent catalytic bodies in such manner that by the time a volumeof distillate has passed through a catalyzing chamber the major prwhich the figure is a diagrammatic view ofa tion thereof will havebeen brought into a refining apparatus embodying associated instrumentallties employed in producing the results sought.
In referring to the drawing A indicates generally a1 still' for initially distilling the petroleum'to formffdistillates and coke, and whichlembodies a' tank or boiler 3 arranged over a. tire box 4 in'which heat is generated,
' as by an oil or burner 5 or in any other manner. The is fitted at its ends with normally closed' manholes 6 and 7 for clean out purposes and through which coke residuum isremoved, and fitted with one or.
more domes or towers 8 connecting to a vapor discharge conduit 9 leading to a condenser B preferably operated under pressure. A low .pressure condenserB is preferably also provided; A pressure gauge ,10,is' provided on the tank and a pressure relief valve 11 is provided in the conduit 9, which pressure relief valve is adjustable to regulate the preure in with or without nely comminuted iron ore the still. A temperaturev indicatork 12 is mounted on the conduit 9 between the still t and the pressure relief valve and preferably near the latter to indicate the temperature of vaporswithin the conduit. A feed pipe 14 leads to the tank from an oil storage reser-v voir C or lother suitable source of petroleum supply, .through which the materials to be treated'are directed ton the still to charge the latter as occasion requires, and connecting with the feed pipe 14 is a conduit 1'5leading 'from amixer 16 to which comminuted vegetable matter is delivered from a' hopper D fed to the mixer 16 from a hopper E; the feed of materials from the hoppers D -and E belng controlled by valves or gates 17 and 18.
The feed pipes 14 'and 15 are tittedf'respecl tively with cut-off valve 19 and a valve or gate 2o.
The apparatus as shown in the 'drawing' also embodies a series of catalyzer containing tanks F, G and H within which are'mounted superficial contact with or in close proximity to a considerable area of the surfaces of the catalytic bodies. 'QFor this' purpose the -catalyzers may be shaped Vin the form of spheres, blocks or bars. They are placed within the tanks as by introducing them through man-holes with which the latter are other separable`V foreign contents of the distil-r lates are collected and these may be drawn off from time to time through drain-cocks 34,
and 36 fitted in drain pipes 37, 38 and-39 leading from the bottom portions of the tanks to suitable points of discharge.
41 and 42 which lead downwardly from the upper ends of the tanks through the catalyzer supports and open to the settling chambers beneath the supports in spaced relation to the lower ends of the tanks.
A conduit 44 leads from the liquid discharge en'd of the condenser B into the'upper yThe tanks are fitted with depending tubular bullies 40,
end portion of the baille 40 intank F; a conduit 45 leads from the upperend portion` of tank F into ,the upper end portion of` baiile 41 in tank G; a conduit 46 leads from the upper end portion of tank G to the upper end portion of baile 42 in tank H; and a conduit 47 may lead from the upper end portion4 of tank H to a finishing still L, -or to a filter, as illustrated.` The colduits 44, 45, 46 andV 47 are each fitted with cut-off valves 48, 49, 50 and 51 respectively, and leading from the conduits 45, 46 andi-47 are pipes 52, 53 and 54 leading to a conduit 55 connecting ing the catalyzer, after the latter has become.
so coated as to render such treatment necessary or advisable.
tanks F, G and H are pipes 60, 61 and 62 fitted with cut-olf valves 64, 65 and 66, which pipes connect with a pipe 67 leading to the upper portion of the tank N. The pump M and its connections affords a means for circulating acleaning liquid such as a mixture of benzene andalcohol through the tanks F, G and H separately or collectively when effectin cleansing thereof, as will be later described. A
A conduit 68 fitted with a cut-olf valve .6g leads from conduit 55 to/ the conduit 17 through which therpurifying liquid may be directed from the tank N to the still L.
Preferably I provide a battery of stills 3, for example I may employ six of these stills, four being in operation in different st a fifth bein cleaned out, while a sixth isaing recharger?. A manifold 71 connects the vapor outlets 9-from the several stills 3. A low pressure condenser 72 `-may be connectedto the pipes 9,- through valved by-passes 7 3,' and during a portion of the run, say during the distillation of the last six or eight per cent of the recoverable oil, the vapors may go into this low pressure condenser, and the condensate may be drawn oil' separately through valved pipe 74, or it may pas: through valved pipe 75 into the main condensate line 44.
There may also be rovided a branch of pipe 44 into'a dewatermg device, thence into balile 40.
It is also advisableA to have thermometers or thermocouples (pyrometers) at "any suitable placein the still, as shown at 84, to sho the temperatures in-the body of oil mixture.
In carrying out the invention by means of the apparatus here shown, a liquid petroleum is delivered to the still AA through the conduit 14 from the reservoir C together with a quanv tity of ground or comminuted moist vegetable matter, to which vegetable matter is added,
and if required, a quantity of finely comminuted iron ore; the iron ore being added where it is desired to produce a ferruginous coke of'hard character and being omitted where it is desired to `produce a soft, dry
, coke. Instead of gravity iow, the mixture of oil, vegetable matter and iron ore (if the latter is used) can be pumped into the still, and this mixture is readily pumpable at any temperature at which the oil is liquid.
As -is well known there is a difference in the quality and character of the two kindsfof coke referred to (hard coke and soft coke),
and that such cokes have distinctive properties which render them suitable for use `for different purposes, for example, soft coke is more valuable than a hard coke in the manufacture of carbon articles, and as a fuel in certain types of stoves or furnaces, while the hard coke with an iron content is useful in blast furnaces and metallurgical operations where the use of soft coke is not practical. Leading from the lower endportions of ther p The petroleum to be treatedl maybe of any character; the invention, however, being particularly applicable to the treatment of petroleum of either asphalt or paralin base having a high initial boiling point, for example, of approximately 650 degrees Fahrenheit. Such products are, at present, obtainable at very small cost, being practically unutilizable by the methods heretofore known, except as fuel, and then only when mixed with thinner oils.
The vegetable matter emplo ed is preferably of `such character as to he capable of giving, when strongly heated, alcohol, acetic acid, acetone, phenols and 'terpeneav As examples of such vegetable matter suitable for the purpose, are mentioned, saw dust, kelp, extracted beet pulp, sugar cane bagasse, and other substances of similar nature, but any vegetable matter which is substantially free of proteins, and capable of being converted into charcoal may be used. 'Vegetable matter in a green or natural state A(i. e. containing a considerable percentage of moisture) is preferably employed. When dry vvegetable matter is to be used, I preferably wet the same with water, before use. Y
The iron ore may consist of any ore which is subject to being reduced to metallic iron,
s and before being added to the other silbstanc is comminuted to such state offpulverizyation or iinene'ss that when addedV to said substances will be held in suspension by,4 the vegetable matter. Iron oxide or carbonate ore reduced to a fineness of from 150 to 250" mesh has been found satisfactory. The ore obviously should not contain a high percentage of sulfur. f The vegetable matter, iron ore and hydrocarbon may be combined in various proportions depending on the characteristics of said substances and the nature ofthe products thereof desired, but the hydrocarbon is employed in suicient quantity relative to the quantity of the vegetable matter as to form a liquid owable, pumpable mass, when at a temperature at which' the oil is freely liquid. An example of a specific proportion of the substances, found to be satisfactory, is 3 vto 10.
parts of vegetable matter, 2 to 10 partsv of iron ore and 80 to 97 parts' of a liquid petroleum hydrocarbon. As stated, the iron ore is sometimes omitted.
The mixture of substances placed in the stillis subjected to the combined actionof a temperature and pressure suiicient to effect destructive distillation of the vegetable matter, and thereby drive olf alcohols, pyroligneous acid, essential oils and other vaporized constituents from wthe vegetable matter, to separate any low boiling fractions from the petroleum used,` yto produce the desired amount of cracking ofthe oil, andto reduce the residuum to a dry coke. A temperature of from 350 to 650 degrees Fahrenheit (150 to 343 C.) has been found highly satisfactory, valthough Ahigher temperatures up to say 750 F., (400 C.) may be employed as where heavier fractions are to be produced; -it being evident that the higher the temperature to which the materials are subjected in the still the Vgreater separation of the heavier fractions from the hydrocarbons under treatment will result. Y
While" a wide range of pressures may be employed in the still during the distilling operation, it has been found ln'pra'ctice that by subjecting the material under treatment vto`a pressure of approximately 1004 pounds vwith a temperature of approximately 650 degrees Fahrenheit, a maximum of carbon is produced with ar maximum of low boiling j fractions, although variations of the pressure and' temperature are resorted to as occasionmay require.
The pressures in the still A are indicated by tures of the outgoing vapors a e shown by .the temperature indicator 12. he desired pressure and variations thereof is obtained by adj the 'pressure control valve 11, and the desired .temperature and variations thereof is obtained by controlling the heat i generated in the tire box 4 as by regulating the burner 5. v 1A reduction of temperature in the still may be effected by feeding addi- ."tional liquid'hydrocarbon with or without additional vegetablevmatter to the 'charge contained in the still. A
articular-ly effective mode of operate still in treating petroleum already conta' Y content o vegetable matter (and optionally iron ore) is to -initially heat the contents of the still (without superatmospheric pressure) through the conduit 9, have a temperature of 400 F., or thereabout; this temperature being maintained for a suitable period to distill off vthe gasoline content of the hydrocarbon 11nraised to 650 degrees or thereabout, which temperature is maintained until all high boiling fractions are vaporized, and may be continued until the residuum in the still is dried out, but the temperature may be increased to the pressure gauge 10 and the tempera.-L
a gasoline fraction with its added until the distillate vapors, which pass off Vsay 750 degrees where it is desired to hasten the drying action. -At some point after increasing the temperature to 650 degrees or thereabout, that is when the volatilesare suficiently driven off to the extent of about 90 to 95% of the recoverable oil, the pressure control valve 11 or the valve in pipe 73, is adjusted to open under lnormal atmospheric pressure'and is thereafter maintained open so as to relieve the still of internal pressures during the drying out operation, and steam may be blown'through the still to hasten this latter result. An important feature of the invention resides in the fact that the distillation of all except the last 6-10% of the recoverable oil may be completed at temperatures not substantially exceeding 650 F., due "to the expulsion of the volatile content of the of heat required during distillation under pressure in converting petroleum into gasoline and other distillates.
- l About to 94% of the recoverable oil in the charge is volatilized and passes from the still, while the liquid and solid matter in the still is at the selectedtemperature or temperatures between about 580 and 650 F., and while under superatmospheric pressure, leaving in the still ;only about 6% to 10% of the recoverable oil, together with the charcoal produced from the vegetable matter intimately mixed with the carbon (coke) which has been formed by decomposition of a part ofthe l oilvused. The pressure will then begin toV drop l rapidly, and the relief valve 11 or the valve in pipe 73 is then opened wide. The temgerature may then be raised to not over -7 50 driving off atleast 5 to 9% ofthe oil, leavin not substantially over 1%: of oil-in the co ve residue. Hence it is not necessary to use Aany special coke refining still, such as has generally been used heretofore, for refining petroleum coke.
A' hin layer of the forced into contact with the' walls of the still woody material being 1.10
is reduced to charcoal before the Aformation of any mineral carbon or petroleum coke takes place and this results inthe depositing of aA very thin-layer of the charcoal on the inner amount of mineral'carbon or coke is formed in the still so that when such mineral carbon or jcoke is subsequently formed it is largely deposited on, the layer of charcoal and accordfingly no accumulation of the mineral carbon or coke directly on the metallic walls of the still takespplace. Where iron ore is added,
the vegetable matter will hold most of Vthe' latter in suspension so as to prevent its precipitation torthe bottomof theV mass duringy the initial stages of .the distilling operation, and the fine ore remains thoroughly admixed with the vegetable matter 'and hardens the coke as the latter 'forms'near the walls of the still, thus rendering the formed coke highly surface of theistill before 'any appreciableconductive of heat so that it will serve to protect the walls of the still against burning out during the nal stages of drying out the coke and also serves to hasten the driving olf of the final volatiles from the coke residuum. The coke (which contains iron) also acts as a conductor of heat from the bottom of the still throughout the mass under treatment. However, Where the ore is not used, the charcoal will in like manner form a protective coating on the walls of the still, but this does not adhere to the Walls of the still as does petroleum coke in the usual `coking still and cracking still processes.
When the batch under treatment has been subjected to the distillation temperatures as abovestated until the desired fractions have been driven off and the charcoal and coke body has been formed, the temperature may then be raised to 7 50 degrees or thereabout if desired so as to more rapidly drive 0E the residual oil in vapor form and hasten drying of the coke and charcoal residuum as before stated; the resultant vapors on being condensed forming a high grade lubricating oil. This'higher temperature is rendered ossible by the heat-conductive action of the ody of charcoal and ferruginous matter in the coke on the walls of the still.
In this manner the petroleum distillates are completely removed and the residue of coke dried out. This coke will consist of an admixture ofvegetable carbon or charcoal and mineral carbon together with such other solid substances as may result from distillation of theA materials under treatment, it including in its composition mineral carbon derived from the petroleum together with charcoal or organic carbon derived from the vegetable matter. If iron ore has been used, the coke'will be ferruginous.
After the drying out stage has been effected, the carbon or coke body formed in the still is easily removed lfrom the latter .requiring only a rough breaking up with bars,
rakes or the like, without the vneed of the Workmen getting into the stills with chisels, to scale the walls: The coke can be raked out, through the man-holes 6 and 7 which operation is easily accomplished because the charcoal layer formed ou the Walls of the still is easily separable therefrom; the charcoal having no tendency to tenaciously adhere to the metallic surface ofthe still but only to rest thereon. This is highly advantageous as the mineral carbon v-(coke) resulting from the-distillation of petroleum without the use of vegetable matter, as in the common practice heretofore, sticks tenaciously to the heated metal of the still, usually iron, which adhesion of the carbon to the metal renders its removal very difficult and time-consumin y Furthermore the finished coke product o tained bymy process will contain, inmany cases, not to exceed one per cent volatile mat' ter whereas ordinary cracking still coke contains eight to eleven per cent volatiles, and accordingly the coke product thus obtained Will require no further treatment, but is in n commercial form as it comes from the still and is in condition for use. Again, the coke product is hard and firm, with practically no fines and is characterized by a high carbon content. When the iron ore is not used, the coke can be produced with an average of ninety-five per cent fixed carbon.
The coke made according to my process is very low in sulphur content, since the vegetable matter with which the petroleum is distilled converts the sulphur originally in the petroleum into compounds which are removed from the coke residue.
lhe vegetable matter Ialso serves a useful purpose in that it absorbs a portion of the oil, consequently during the distilling action, moisture and volatile constitutents from the vegetable matter and the lower boiling asy hydrocarbons from the petroleum are produced together. Furthermore, the charcoal residuum resulting from the decomposition of a portion of the vegetable matter, in depositing lon the bottomof the still insures a greatly desired uniformity of temperature throughout the walls of the still and this effect is 'further enhanced by the addition of the iron ore.
The still is charged with a batch of the substances (from time to time, in some cases), the materials subjected to the desired temperatures and pressures, and the accumulated coke removed, and the operations repeated as often as desired Without the need yof manual labor to chisel the petroleum coke from the bottom and sidewalls of the still.
During the' distilling operation, the operator by regulating the temperatures and pressures can takc 0H the desired distillates such as gasoline, kerosene, engine distillate or Diesel engine oil, lubricating oil and kindred products in vapor form, which products are delivered to the cndenser B and there condensed in the usual manner. By controlling the temperatures and pressures 1n the still, kerosene orgasoline or other desired distillatev or cracked product, may be produced alone, if desired.
. The condensed distillates contain certain objectionable impurities which fact necessltates refinement of the distillates to effect removal of such impurities.
- The preferred amounts of the green or wet sawdust, (iron ore, if used) and petroleum, to
give 'bestxresults in any particular case will depend on the character of the petroleum to be used and the proportions desired in the product.
Example 1 (Parts are by weight in the examples) For making gasoline of about 63 B., from fornia petroleum having an initial boiling point of 650 F. This residue would form about 18% 'of carbon or Iactual coke, by crackingthe same in Ia. coking'still. I may use 100parts 'of the said oil l(fed in at about 200 to 220 F.) mixed with 8 to 10 parts of green sawdust and about' 10 parts of iron oxide ore. The still contents would be heated to about 580o F., the pressure in'the'still kept at about 100 lbs. above atmospheric and the temperature shown at 12 kept at about 300 .F., (these factors being controlled by control of the fire at burner 5 and adjustment of pressure valve 11) during the major part of the run, until about 7 0-7 3 parts of gasoline have been distilled over, and la mass of fer- A ruginous coky materialA containing oil carbon ferentfrom petroleum coke in that it does not rigidly adhere to the walls of the still, and is a very good conductor of heat. By this time the temperature in the still has risen gradually (after the sawdust hasbe'en converted into charcoal) to about 650 F. The pressure then will begin to drop, andthe valve'll may then beropened wide, or the valve in pipe 73 opened wide into the low pressure condenser 72, and the last portion o f the oildistilled out at about atmospheric ressure, or under a partial vacuum, suction emg applied through pipe 74, or steam is blown t rough the stlll to aid in carrying off the vapors. The oils coming over during this last or dryin out' stage may ,be kept separate, these o' being heaver than water and of excellent lubricating character, and espeeially suitable for lubricating bearings under water, such as the propeller shafts ofrvessels.
These 4oils also are preferably purified by treatment with sodium, as herein described, 1n a separate small unit of apparatus.` The lmain bulk of the distillate from this run p from condenser B, through pipe 4.4 into and willconsist' very largely of gaso- 10o pares of high gravity California rude .'of aboutj22 B., which does not contain :my
gasoline fraction wasthe oil'treate'd, which 011 would give 8` to 10% of coke, 4 to 5 'parts wetisawdust, f3 to lparts iron oxide ore, arev used. The sawdust and rore arel mixed,
andthe ofthis with the'oilis perform-y u o'r co d, say atnot over'150 F. f* The y -reandtbeoutletvalvellaresoregulated parts of thick" residual oil. This layer is however quite difshown at 84 will rise from 580 to 650F.
The product (after purification)` will be a mixture of about equal parts of gasoline, kerosene and Diesel engine oil, which can be separated in the still L, into these separate fractions.
l A Example 3 The original oil is a relatively light California'crude, at' about 35 B., containing a substantial fraction (around 35%) of gasoline. The material fed to thestill may conveniently be 100 parts 'of such oil, about 5 parts of chopped up air dry kelp and about 3 parts of iron oxide ore. The still is first filled with the mixture, and at about atmospheric pressure, heated to about 350 to 400 F., to Ydistill off run gasoline. Then more of the samev oil is fed into the still to again fill the same,while continuing the dis-v tillation of gasoline at about atmospheric pressure. The still may even be filled up a third time and gasoline distilled therefrom at atmospheric pressure. Or the feed of the oil can be continuous, while the tempera ture is kept M350-400 F. Then the valve 11 is adjusted to give a still pressure of about 100 lbs., a still temperature of about 580 F. and a temperature at 12 of about 350 F.,
-which conditions are maintained until a mass to 650 F., at which temperature it will remain until about 94% of the recoverable oil has distilled off. The pressure can be dropped to about atmospheric and the valve in pipe 73 opened, and the still temperature then raised to about 750 F., to drive off most of the oil, leaving not substantially over 1% of volatile matter in the coke.
In this modication of the process we get three distilled products, the first 'run (or straight run) gasoline, distilled at about atmospheric pressure, a second run o f asoline by `cracking process and a third or al cut of lubricating' oil during the last part of the run, collected from condenser 72. The coke product left in the still be sold directly to smelters without further treatment.
The above examples are merely a few illus- VVtrations of details of operation showing the results WhichcanY be secured. By properl adjusting the factors governing.y (a) temperature (fb) still 'pressure(c) vapor temperature in line 9, mountof vegetable matter, AI `am led to Lget the bulk of 't he' product at'.an`y"desired. gravity. and boxlmgpointrangqortogetmixtures of any desired final fractions, in the proportions desired, these results being secured from any petroleum oil which is available.
A special feature of the process is that the temperatures at different parts of the still 3 are alike, in Which point the process differs from all ordinary cracking processes. Thus (a) the temperature of the inner surface of the still bottom, (b) the temperature of the oil in the bottom of the still, adjacentthe bottom plates, (c) the temperature in the upper stratum of the oil in the still and (d) the temperature in the vapor above the oil in the still are all. the same or at least within two or three degrees of each other. This condition exists as long as the mixture inthe still is a freely owing mass.
-While little is definitely known as to the components of distillates of the character above referred to, particularly as to the exact nature of the undesired impurities formed therein, it'is generally recognized that the' distillates may contain impurities of a resinous an'd gummy character, or gum-forming constituents, sulfur compounds, nitrogen bases, and acid compounds and perhapsv others.' It has heretofore been the practice to effect removal of the impurities present in oil distillates generally, by first treating the distillates with sulfuric or other acids. settling and removing acid sludge; then (if desired) vwater-Washing the acid treated distillates to remove the larger part of the acids that remain in the distillates; washing the.
distillates with an alkali wash embodying caustic soda, sodium carbonate, or sodium plumbite, to further remove impurities and to neutralize acids; then (if desired) passing the distillates through a filter of clay or diatomaceous earth, and in some cases, finally redistilling the distillates.
This practice results in a large waste of the distillates under treatment caused in part by evaporation of the lighter fractions during handlingthereof and also results in the loss of the removed valuable constituents and/or impurities which by reason of the acid and alkali treatments are removed and rendered unfit for use,'and further entails the loss of the acids, alkalies, and filter media employed inthe process. Furthermore, the acid acts to destroy a part of the benzol equivalent and octaine number components of the distillates, which if preserved in the refined product would render it of higher grade and of superior quality particularly in the ease of gasoline to `be used as motor fuel as the benzol.
equivalent and octane number constituents impart to the products greatly desired antiknock properties.
The distillates, as produced in the main part of my process, While in liquid form are accordingly directed through conduit 44 into the upper end portion of the tubular baffle 40 of tank F, and directeddownwardly through ing indicated by a gauge P with which the tank F is equipped. Water can also be removed in a separator inserted in the line 44, if desired.
The distillates flowing through conduit 45 are fed into the upper portion of the tubular bafile 41 in tank G and are thence directed through the spaces between the catalyzers J in the latter in the manner described with reference to tank F; the ldistillates then being delivered from tank G through conduit 46 into the tubular baffle 42 in tank H where the distillates are directed through spaces between the catalyzers K in said tank in a like manner and passed to discharge through the conduit 47 leading from the upper end of `tank H.
` In this fashion the distillates are directed through any suitable number of tanks as occasion may require to subject the resinous and gummy or other impurities of the distillates to the action of the catalyzers a sufficient length of time to effect coagulation of such impurities into a flocculent form; the dura' tion of time being varied according to/the character of the distillates under' treatment.
In practice it has been found that by main-l taining the liquid distillates in juxtaposition with the catalyzers for a period of from three to live hours at ordinary atmospheric temperatures of the liquid will give highly satisfactory results. Y
The coagulated or flocculent impurities resulting from the action of the catalyzers collect in part on the catalyzer bodies, and a portion of such impurities are suspended-in the distillates a major part of which settles in the tanks G and H and are separated from the distillates in these tanks by drawing ofi' through the drain-cocks 35 and 36 from time to time as occasion may require together with such other separable foreign matter as may accumulate in the settling chambers.
Such portions of the flocculent impurities as do not settle and remain in suspension in the distillates can readily be removed from '-.the distillates by redistilling the latter in the still L to which the distillates are delivered from the end tank H through the conduit 47, or may, if desired,be recovered by filtration lof the treated distillates-in a usual manner.
moval of impurities from thehydrocarbon oil, nevertheless it should be stated in' the interest of clarity that the alkali metal probabily acts to accelerate a condensing and coagulating action of the impurities in the hydrocarbon, some of which impurities adhere to the surface of the alkali metal while other portions thereof are merely iocculated and remain in suspension. In other words, the alkali metal merely hastens an action that would undoubtedly occur if suiiicient time were allowed, and hence I have referred to the action of the alkali metal as a catalytic action.
There is apparently no chemical action of the impurities of the oil, or the oil itself upon the alkali metal butthe said metal remains as such, although it becomes coated with impurities separated fromthe oil, lthese being generally of a gummy nature. When the amount of such precipitated gummy impurities on the sodium has partly filled up'the interstices of the mass, the accumulated impurities are removed by giving the sodium (in situ) a wash with a proper solvent such asa mixture of a benzolic liquid with a little alcohol, say 4 to 8 parts of benzol (benzene) and one part of alcohol.
The distillates after having been treated in the tanks are finally filtered or preferably redistilled; the subsequent treatment of the distillates depending on the character of the treated distillates and the results desired. For example, first run gasoline does not ordinarily require' redistilling but in some cases may be benefited thereby. Where the treated distillates embrace light and heavy fractions they are fractionally distilled to sepa-I rate the same into desired fractions such as gasoline, kerosene, engine distillate and Diesel engine oil.
The catalyzing apparatus as here shown is designed for continuous operation, that is, for a continuous run until conditions necessitate a shut down, and is also designed to facilitate a cleaning out operation to eiect recovery of the coagulated impurities as will presently be described, but manifestlyY any suitable catalyzing apparatus may be employed to carry out .the process.
Inthe course of a protracted run of the distillates through the catalyzing chambers the catalyzers will become coated with agummy 'resinousmassconsisting of the impurities before referred to, which coating while not interfering with the catalytic action must be removed in order to obviate clogging of the catalyzing tanks and also-to eil'ect recovery of the substances constituting such coating. This isaccomplishedby discontinuing flow of the distillates through the cat-alyzing tanks, draining Athe fluids from the tanks, then the tanks with a solvent of the separated impurities. For this pur- Cl pose, benzene is used as a solvent to vwhich Leases? is added a quantity of alcohol for the purpose of activating the catalyzers. volume of alcohol of from three to ten per cent of that f the benzene is ordinarily employed, but any suitable proportion of alcohol may be used as occasionV may nire. A roportion of one part of absolute denature al'- cohol with twenty to twenty-live parts of benzol or its homologues gives very satisfactoryresults.
The solvent is directed through one or more of the catalyzing tanks from the tank N by means of the pump M and the pipes leading pumpVV M'the solvent will be directed through l the tank F, or by closing valves 49 and-50 and opening valves 57 and 65 the solvent will be directed through tank G, or by closing valves 50 and 5l and opening valves 58 and 66 the solvent will be directed through the tank H.
To direct the solvent through the series of tanks the valves 48 and 51 are closed and valves 5 8 and 64 opened while valves 56, 57, Aand 66 are maintained closed. When it is desired to redistill the solvent benzene and .and the bath is removed from the tanks with the dissolved impurities held in solution therein and isV distilled insilch manner as to alcohol, to separate it from the dissolved nio effect separation and recovery of the benzol A and alcohol and the previously dissolved substances contained therein.V v By employing alcohol in the benzol solvent a slight amount of chemical action ma take place on the alkali metal bodies. Suc action leaves-'the surface "of the metal bright and will hasten the formation of the occulent gummy resinous matter when the metal is' again contacted withthe oil distillate the tendency of the gummy. matter to the surfaces of the bodies, and also ren ers the separation of the coa fromthe bodies more rapid and thorough. It is therefore desirable to also subject `the alkali metal bodies to an alcohol containing bath (e. g. this same benzol-alcohol miktu're)before initially employing alkali ,metal bodies in the treatment of the distillates.
VVAfter having thus washed the catalyzers with the benpzol-alcohol bath and cleansed the holes or windows may tanks of the solvent, the apparatus is thereby conditioned in readiness for another run of the distillates to be treated. This treatment with the solvent bath requires a short period, sayl 10-15 minutes, andthe benzolalcohol mixture is removed from contact with the alkali metal as soon as the llatter is cleaned up, in order to prevent any further action of the alcohol on the alkali metal, which would of course use up and waste the alkali metal.
For observing the alkali metal, glass peep be .provided in the walls of the tanks F, Gr and H. The removed impurities are of resinous or l gummy character and as recovered are in the form of a gum -or Wax, whichsubstances possess valuable qualities and may be emtraneous heat, and also that the entire vpuri- `ficat1on may be carried on atnormal atmospheric pressures. Temperatures much above 125 F. should be avoided in this step, otherwise a hard coky coating will' form, on the surface of the alkali metal, which coating would be dili'icult to remove from'th'e surface of the pieces of said alkali lmetal, and furthermore at any temperatures substantially above 100 F., there appears to be some y chemical action of some'of the impurities of the oil, on thealkali metal whereby a portion of the latter is consumed. Preferably I treat the oil distillate with the alkali .metal as the latter leavesl the condenser, when at about to 70 F., but for treating gasoline'received in tank cars, oi-l barges, from pipe lines, etc., the material can be first cooled to to 70 F., if refrigerating equipment is available, orocag be treated at any temperature below l0 As is well known, commercial gasoline .shows a tendency toform gums and to turn yellow or somewhat brownish in color, in storage, whether exposed to the light or not. Alsothe odor of the gasoline Generally gets bad during storage. Other oil istillates such as petroleum ether, naphtha, kerosene, Die sel engine oil, show this tendency to a greater or less extent. l Distillates which have so deteriorated can be treated by flowing 1 through the tanks containin the alkali meta1, to be thereby broughtbac to water white oreven to 30 Saybolt color, and are therecracked distillates by rendered stable. Dye in the oil so treated is usually also removed by this treatment. This refining here referred to may be applied to gasoline and other distillates made y previously known straight run or cracking processes and lpurified by the conventional processes, and (if desired) afterwards blended with other gasolines, petroleum distillates, benzol, etc. While purification is thereby accomplished to a wholly satisfactory degree, my catalytic purification process` obviously does not add anti-knock constituentswhich have been .removed in any acid' treating process towhich the distillates have been subjected'. Such anti-knock constituents as are well known in the art can of course b'e subsequently (or even previously) added,
The crude distillates produced in my proc# ess are'generally muc-h purer than the crude (produced in any of the commonly employe cracking processes with which I' amfamiliar. Thus the first distillate produced in Example l, maybe a pale yellow distillate having a rather sweet odor, even when the original oil contains a substantial percentage of sulphur.
tive :distillation ofl the woodl sawdust have -reacted with the sulphur compounds of the oil inthe still A .and in the reuxing domes (ortowers).. This distillate could be purified by treatment with sulphuric acid and soda by the conventional method, requiring less acidthan gasoline made bythe other well known high temperature cracking processes.' However the acid would destroy It is'my belief that some-.of the products of destruca substantial amountof the anti-knock constituents of the distillate hence the sodium treatment is far preferablel and produces from this distillate a better refined product produced by any other process than could be known to me.
In the. tank C may be provided a steam:
coil for warming up the oil, especially if the oil is very thick and viscous.
I have above referred to sodium as the' most economical of the alkali metals. Also potassium, lithium, calcium, strontium and barium (in the metallic state) could be employed, if desired. These metals I refer to vhereinafter as alkali metal.
I have above referred to sawdust and kelp in the examples. Other kinds of vegetable matter are comminuted corn cobs, peat, other comminuted wood, or woody material, preferably such as do not contain any substantial percentage of sulfur or large amounts of protein. Straw, chaff, comminuted bark (e. g; spent tan) if available, could be used although they might increase -thesilica content of the coke somewhat.
This application is a continuation in part of my copendingapplication, ySerial No; 549,862 led July 10, 1931,. j
I claim 1. A process of relining a distillate produced by distillation of a mixture of 80 to 1 95 parts of petroleum hydrocarbons, 3 to 1() parts of solid comminuted vegetable matter 5 rich in carbohydrates, and 2 to 10 parts of comminuted ironv ore, whereby at leasta part of the hydrocarbons are cracked and vaporized, and condensing the evolved vapors, which process comprises subjecting such condensed distillate to prolonged Contact with an alkali metal in a free state, at atmospheric pressure but not above 125 F., until at least some of the impurities in the distillate are coagulated, 'and separating the coagulated impurities.
2. A process of refining a cracked distillate produced by heating petroleum mixedl with a few per cent of its weight of a solid carbonizable vegetable lmatter consisting largel of carbohydrates, to a temperature capab e of causing destructive distillation of said vegetable matter and capable of causing cracking and distillation of said petroleum and condensing the vapors thereby liberated,
which process comprises subjecting such condensed distillate in a liquid state to prolonged contact with an alkali metal'in the free state,
while at atmospheric temperature but below 125 F., until some at least of the impurities` ing the coagulated impurities' from the distillate.
. 3. A process of refining a cracked distillate produced by heating petroleum mixed with a few percent of its weight of sawdust,
to a temperature capable of causing destructive distillation of said sawdust and capable of causing cracking and distillation of said petroleum Aand condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a li uid state to prolonged contact with an al ali metal in the free state, while at atmospheric temperature but below 125 F., until some at least of the im urities in the distillate are coagulated, an separating the coagulated impurities from the distillate.
4. A Process of refining a cracked distillate produced by heating petroleum mixed with a few per cent of its weight of kelp, to
a temperature capable of causing destructive distillation of said kelp and capable of causing cracking-and distillation of said petroleum and condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a liquid state to prolonged contact With-an alkali metal in the free state, while at atmospheric temperature -11111: below 125 F., until some at least of the impuritiesin the distillate are coagulated.
5. A process of refining a crackeddistillate produced by heating petroleum mixed with a few per cent of its weight of moist M solid carbonizable vegetable matter consistfree state, while at about 55 to 100 F ing largely' of carbohydrates, to a temperature capable of causing destructive distillation of said vegetable matter and capable of causing cracking and distillation of said petroleum and condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a liquid state'to prolonged contact with an alkali metal in the free state, while at atmospheric temperature but below 125 F.,until some at least of the impurities in the distillate are coagulated, and separating the coagulated process comprises subjecting such condensed distillate in a liquid state to prolonged contact with an alkali metal in the free state, while at atmosphericl temperature but below 125 F., until some at least ofthe impurities in the distillate are coagulated, and separating the coagulated impurities from the distillate. v
' 7 A process of refining a cracked distillate produced by heating petroleum mixed with a few per cent of its weight of a solid carbonizable vegetable matter consisting largely o'f carbohydrates, to a temperature capable of causing destructive distillation of said vegetable matter and capable of causing cracking and distillation of said petroleum and condensing the vapors thereby liberated, which processcomprises subjecting such condensed distillate in a liquid state to prolonged contact, with an alkali metal in the 'a until some at least of the impurities in the distillate are coagulated, and separating the coagulated impurities from the distillate.
8. A process of reflning a cracked distillate produced by heating petroleum mixed with a few per cent of its weight of a solid carbonizable vegetable matter consisting largely of carbohydrates, while under a superatmospheric pressure of several atmospheres, to a temperature capable of causing destructive distillation of said vegetable matter and capable of causing cracking and distillation ofsaid petroleum and condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a liquid state to prolonged contact with an alkali metal in the free state, while at atmospheric temperature but below 125 F., until some -at least of the impurities in the distillate are coagulated, and separating' the coagulated impurities from the distillate.
9. A process of refining a craked distillate sen tive distillation of said vegetable matter andproduced by heating petroleum mixed with a few er cent of its weight of a solid car'- boniza le vegetable matter consisting largely of carbohydrates, while under a superatmospheric pressure not substantially exceeding 100 lbs., during most of the heating, to a temperature capable of causing destructive distillation of said vegetable matter and capable of causing cracking -anddistillation of said petroleum and condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a liquid state to prolonged contact with an alkali metal in the free state, while at atmospheric temperature but below 125 F., until some at least of the impurities in the distillate are coagulated, and separating thecoagulated impurities from the distillate.
10. A process of refining a cracked distillate produced by heating petroleum mixed with a few per cent of its weight of a solid carbonizable vegetable matter v consisting largely of carbohydrates, to a temperature capable of causing destructive distillation of said vegetable matter and capable of causing cracking and distillation of said petroleum and Vcondensing the vapors thereby'liberated, which process comprises subjecting such condensed distillate in a liquid state and' while at substantially atmospheric pressure, to pro` longed contact with an alkali metal in the free state, while at atmospheric temperature but below 125 F., until some at least of the im urities in the distillate are coagulated,
an from the distillate. l
11. A process of refining a cracked distillate produced by heating .petroleum mixed with a few percent of its weight of a solid carbonizable vegetable matter -consistinglargely of carbohydrates, and line iron ore, to a temperature capable of causing destruccapable of causing cracking and distillation of said petroleum and condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a liquid state-to prolonged contact, with an alkali metal' in the free state, while at atmospheric temperature but below 125 F., until some at least of the impurities in the distillate are coagulated, and separating the coagulated impurities from the distillate.
.12. A process of refining .a cracked distillate produced by heating petroleum mixed with a few per cent of its weight of a solid carbonizable vegetable matter consisting largely of carbohydrates, to a temperature capable of causing destructive distillation of said vegetable 'matter-and capable of causing cracking and distillation of said petroleum and condensing the vapors thereby liberated, which process comprises subjecting such condensed distillate in a liquid state to contact for several hours with an alkali metal in separating the2 coagulated impurities i the free state, while at atmospheric temperature but below 125 F., unt1l some at least of the impuritiesin the distillate are coagulated, and separating the coagulated impurities from the distillate. y 13. A process of reinin a distillate produced by cracking and lstillation of pe troleum mixed with a few'per cent of com-- minuted vegetable carbohydrate matterl of' the type of wood, kelp, straw, and bagasse,
which is of such a size of particle as to be' signature.