US2433364A - Hydraocarbon reforming process and products thereof - Google Patents

Description

Patented Dec. 30, 1947 nYnn'ooAR oN REFORMING rnoonss AND PRoDUo'rs THEREOF Jacquelin E. Harvey, Jr., Washington, D. 0., and

Robert H. White, Jr., and-Joseph A. Vaughan; Atlanta, Ga, assignors of oneshalfito Jacquelin. E Harve J washin l l a D a d ne: half to Southern Wood Preserving ,Gompany East Point, (3a a corporation of Georgia lio lltfawing Application October 7 i944], SerialNo. 551,725

(cr es-62) l z claims. 1

The instant inventionrelates to the production o toxic a s emnlbyab as ungi des insecti ides a d f r ny her; s ow ich taxic oils may be put, and isa continuation in part of our application Serial No. 469,722 for Brocess of providing useful d t fil d Dec mb r 2.1 .9 2 ol-l pending herewith, and which is now abandoned, as to all matter common to the two applications,

More especially the instant invention relates to the production of toxic oils from mixtures of. petroleum fractions characterized by ring. struc: ture content. Among such start n materials may be mentioned. mixtures of. petroleum tions characterizedby ring structure. content re-t, covered from petroleum fractions. by well known extraction methods inclu in ext active distiller: tion and solvent extraction. Also may be men: tioned" mixtures of petroleum fractions characterized' by ring structure content as flowing from thermal andflor catalytic treatment of certain petroleum fractions which includes petroleum fractions having ring structures induced in the course of thermal and/or catalytic treatment, as or m e a n ng str t e nduc in the course of. one; or more thermal and/or data, lytic treatments; of unusual length, say for periods of from 1-10 hours or more, 3

An object of the instantiinvention is the pro.- duction of toxic oils from the aforenamed petroleum fractions or others whereby to provide oils of the preservative type, as for example preservative wood impregnants conforming to specifica tions extant-or acceptable to the trade consuming such oil materials.

Another object of the instant invention is the provision of preservative wood impregnants havingboiling ranges and residues inaccordance with published specifications and/or in accordance with consumer preference;

Another object of the instant invention is the cracking, reforming, modifying, converting and/or transforming of mixtures of hydrocarbons whereby to induce toxicity.

Still another object of the instant invention is the induction of commercially usable toxicity the presence of a gas or gaseous mixtures ofof. that percentage ofa newly induced fractions boiling below 210 which, in View of attendant reactions, is-conducive. to. the induction of toxicity in other fractionsof; the material, under treat-. ment.

Another objectofatheinstantinventionis the induction or additional toxicity into fractional mol u r s ru ur s-of cy lic. aqntsut s re r ed.

ma e i l tics a PQQ qnqun a xic value,

s ll an he Q is o he Presen n ti the conversion of substantiallynon-toxic lpetrozleurntype aromatics into materials more closely approaching the highly toxic coal. tar aromatic type, as more fully set forth in the following.

Still another object ofthe present invention is the conversion of petroleum type aromatic" ma,

terial of a relatively narrow boiling range into" material Of lati'vely wide boiling range more closely approaching the characteristics of coal:

a a matics by a roces ein he o tro s evidenced by; among Other'things, the percentage o newly f m d a omat s oun i er in ra tiou o h benefit, vc l ma er al- In the past woodpreservative oils of the high temperature coal tar derived type have been em-- played in quantities greatly exceeding the total of all other wood preservative oils. From the standpoint of availability of said coal tar as theparent product of wood preservative oils, it is annually produced in this country under normal conditions to the extent of five hundred million to six hundred million gallons; This quantity of 9, 1 tar is capable of yielding an amount of high:

ly effective wood preservative oil which wouldv make this country self sufficient in its wood preservative requirements. However, due to the fact that when a wood preservative. distillate (creosote) is recovered from coal tar there remains in the still a residue (pitch) which, at bQStQis a low priced product and which, at worst, is a seriously distress product to the end that at times it is placed in inventory rather than sold, the current method of processing coal tar leaves much to be des r d e ne su t of h s-s tuat n m;

ing is that the coal tar distiller usually confines himself to that distillation recovery of creosote which would correspond to the attending amount of pitch that he can market at a profit. Accordingly, over a period of years several hundred million gallons of creosote oil have been imported into this country. That such a situation should obtain is apparently a paradox in that we annually produce a quantity of high temperature coal tar which if processed to yield creosote would make us self sufiicient in that requirement. A survey of this paradox is fully outlined in an address given by no less an authority than S. P. Miller, technical director, The Barrett Company, 40 Rector Street, New York city, before the Franklin Institute, Philadelphia, Pennsylvania, in December, 1932. The economics of coal tar have not materially changed since that date.

In view of the apparent inability of the coal tar industry to provide national needs of wood preservative oils, a strong incentive is given to groups processing other types of oil to invade the lucrative wood preservative market. At the present time many types of so-called aromatic oils are produced by the petroleum industry, and the high boiling oils of aromatic content produced by this industry have for several years been tested for their wood preservative efficiency.

By the term petroleum aromatic as used herein and in the appended claims it is meant to include mixtures of petroleum fractions characterized by cyclic structure content and specifically various forms and types of naphthenes found in various mixtures of petroleum fractions, as for example monocyclic and polycyclic naphthenes.

The so-called petroleum aromatics which include the monocyclic and polycyclic naphthenes and unsaturated hydrocarbon have in the past been produced in very large quantities. However, very little work has been done on these materials. Such a fact is borne out on page 667, Reaction of pure hydrocarbons, Gustav Egloif, Reinhold Publishing Corporation, 330 West 42nd Street, New York city, which states:

Despite the fact that naphthenes or cycloparaffines are available in enormous quantities, as shown by an estimate of 100,000,000 barrels present in the 1,498,000,000 barrels of crude oil which was the worlds production in 1934, comparatively little work of a pyrolytic nature has been performed on individual naphthene hydrocarbons or the cycloolefins.

Several oils of cyclic structure content produced by the petroleum industry have been inspected for their toxicity to wood destroying fungi, among which may be mentioned a high boiling oil of cyclic structure content produced (1940) at the Wood River Refinery of the Shell Oil Company and which has the following inspection:

Gravity 10.8 Flash, P. M. C. 0., F 295 Flash, C. O. 0., F 290 Fixed carbon, percent 4.9 Pour point, F. -10 B. S. & W., percent by vol. 0.1 S. U. vis. 100 F. 151 S. U. vis. 210 F 41 S. F. vis. 77 F. 34.5 Carbon residue 6.8 Percent aromatics and unsaturates 82.4 Sol. in CS2 99.8 Loss 50 grams, 5 hours 325 F 8.9 Residue of 100 pene., percent 37.5

A. S. T. M. distillation:

I. B. P., F. 518 10% rec. F 565 20% rec. F 589 30% rec. "F 614 40% rec. F 637 rec. "F 660 rec. F. max. 675

In the foregoing tabular data P. M. C. C. means Pensky-Martin Closed Cup; C. O. C. means Cleveland Open Cup.

Upon evaluating the foregoing oil for its toxicity to wood destroying fungi (Madison 517), it was found that this oil did not totally inhibit thegrowth of the fungi named at a concentration of up to and including 10%. Madison 517 is a strain of the fungus Fomes annosus. It is now discovered that the oil above named or other oils of cyclic structure content produced by the petroleum industry can be increased in toxicity in accordance with the process of the instant invention.

According to the instant invention, oils of cyclic structure content produced by the petroleum industry are cracked, reformed, transformed, modified and/or converted to oils of a more toxic nature having characteristics more closely approaching those of high temperature coal tar oils. Stated in another manner, the end product of the instant invention is acceptable to consumers of preservative wood impregnants and/or conforms in boiling range or aromatic content to previously published wood preservative specifications.

We have discovered that if the starting materials are subjected to a thermal treatment in the presence of an extraneous gas at a temperature selected between the limits of about 350-600" C., the while controlling process variables as to provide in the materials of the end product boiling between 210 C. and 355 C. a percentage of aromatics not substantially less than about 70%, the

' reformed, cracked, converted, transformed and/ or modified oil boiling between about 210 C. and 355 C. will have a toxicity to wood destroying fungi closely approaching or equalling the toxicity of high temperature coal tar or its wood preservative derivatives, provided (1) the specific gravities of the overall fractions within the 210-355 C. out of the beneficiation fall about within the or (2) specific gravities of the aromatics in the overall fractions of the 210-355 C. out of the beneficiated material fall about within the limits shown in the appended tabular data:

Fractions Low Limit High Limit 210-235" C 0. 913 1.0430 235-270" C 0. 935 1. 0606 2703l5 C 0.973 1. 0033 315355 C 1.027 1. 1285 The following examples will serve to illustrate several modes of practicing the present invention.

Example 1.A mixture of petroleum fractions characterized by a substantial content of petroleum type aromatics" and having but slight r .inh bi iont wqo gde qria iee t. st examp e a p b ep p nderan. q er i o 3 :27 ?250r3l l 355 C. have; respectively the following specific -5 boiling above 315? C., amongpthers thatour new 'gravitiesi 0.9697, 0.9989 and 1.036 is charged to a high pressure autoclave under a cold pressure 1 aeriod o o hou ..Th P $-$i1rre i$a um a i 22. m an 11 a ein =h- Th .beneficiated material is cooled and inspectedand .matters showniin the appended ehai ghes than aromat y .bBtWGQI11235" C. and-g 355 0 P d b ij ydrq 'e fane rou a e temperature oi /1 95? Ctwhereflt is helds, rqa

is found to have .(1') newlyfformd materials lboiling below 210 C.,and' .(2)"an.{ov.erallf toxicity ane rzar-me 1rz aser ati e19 vwh hfiew 'ifi f i our ontrol dithermal rc mse i emes ne fa ex r neo sas as a ea a o 5-13% residue above 315 C. for it is on these materials .011 dependsrfor its permanency after impregnat-ii in QWP Thenaterials of induced toxicproperties as flowing-from the process carried out under the xii0 controls above "disclosed .have at times substantial residual matter above 355C. and may be used in totoas aw'ood preservative impregnant, Orin the event it isdesiredto provide a preservative impregnant ccmplying with specifications extant closely approachingfor equalling the toxicity 'Iof or of consumer-preference; a woodpreservative i certain hightemperature coal tar wood presery'atives.

Inspection of the beneficiated material. discloses Toxicity e v i nspecific i Total In- Percentage Fraction qravityof l. litliggl mgmatics ofAromatics 235270'C 0.010 0.9941 1 100. 270315 O- 0 500 1.0159 100.0 3l5355 C 5. 000 1.0546 100.0

' Entire fivefiractions app oached The total inhibition point (toxicity test) above noted is expressed as thepercentageof the preservative by weight of medium on which tested and required to totally inhibit the. growth of the fungus under test. This toxicity test is fully det scribed on page 34 et'sedof the 1933 Proceedings of the American Wood Preservers Association;

The starting material of the instant example has an unsatisfactory toxicity to wood destroying fungi conceivably due to certain portions;-of'the side chainsattachedto :thelingnuclei which probably lower Water solubility. 1We have-found by controlling the process variables as to provide in the 0-355 C. or 210r355 C. out of thebeneficiated material (1) specific gravities in. aromatics in fractional parts ofsaid cut'which fall between the limits previously stated, and/or specific gravities in overall fractions of thenarned out which fall between the limitsnamedin the foregoing, that thisjis aguar anteegof, and a test for, the induction of toxicity to wood destroying both, are practices by which sufficient side chains or fractional parts thereof may be removed from the highly toxic'ring nuclei to insure acceptable toxicity in the beneficiated material to the wood preservingindustry.

By processin the starting material of the ihstant example .in the presence of an extraneous gas as above described, a crudeuinaterialiwlio se toxicity to..'wood destroyin fungi .is not accept- .able to thewoodfpreserving industry jsat lea st partially converted into a material which closely approaches or equals the toxicity of conventional high temperature. coal tar -or certain of its oily wood preservative derivatives.

The beneficiatedlmaterial is fractionated by oil may be segregated from the overall beneficiated. material, as. a s abi i e residual, distinateo v extract, and in the event the extract has nonpermissible low boilin ends, the extract lmayl be 1 tabilized} jbd l the necessary extent by removal pf 2 9w.bailin ..efia ap .tbenre ervat ec imayb recovered from the extract asa distillate.

Asillustrative pf preservativewood impregna tsof the ,oil derived type that have met with {consumer accepta ce, andwhich may besegredistillationto recover as a distillate a preservative wood impregnant of indu'ced toxic propertieshaving 5% distilling below 2 10? C., more than;13 C and-less than 10% esidue 8 gated from the overall beneficiated material of the instant process thefollowing tabular, data show. several published Wood preservative specifications which have been accepted v by trade.

= Woon .PRESERVATIVE IMPREGNANTS $p ifi qfiqm n a a iwaqd Brese yers A sociation 'a. Up to 210510., not more thar' 5% 5. Up to 235 (2., not morethan 25% 2. American Wood Preservers' Association a. Up tQ 210 C., not more than 1% b. Up to 235? C., notfmore than 10% c. Up to 355 0, not less than 3. American Wood Preservers Association a. Up'to 235 0., not more than 1 /2.% b. Upto300 0., not more than 16 e. Upto 355? C., not less than 45% U 4. American Wood Preservers Association V a Up to 210 C., not more than 8% i b. Up' to 235 0., not more than 35% 5. I American; Wood Preservers Association a. Up to 210 C.,'not more than 10% V b; Up to 235 6., not more than 40% 6. American Wood Preservers Association a. Up to 210 C., not more than 5% 1). Up to 235 0., not more than 15% --7. Prussian Ry.

' a. Up to 150 C., not more than 3% i b. Up to 200 (3., not more than 10% V c.-;Up to 235 0., not more than 25% 8;- Natioznal Paint Varnish & LacquerAssociation 2 0 J a. 5% at 162C. b. 97% at 270C. 9; Southern Pine Shingle Stain Oil a; 5% at 137 C. b. at 257 C. 10.- Neville Shingle StainOil dpI; B. P., C;

bf 5% at 205C. -c.' 95% at 292--C. 11. Carboline'urn A 270 0., I. B. P.

Exa mpZe Z.-A petroleum aromatic. oil having 6% distilling below 235 C., and boiling preponderantly between 235 C. and 355 C.--ls charged to a high pressureautoclave under .a .cold hydrogen pressure of about 475 pounds and brought up to a temperature .of 490 0.; within Toxicity Overall Fraction (Total In- Specific Percentage hibition Gravity of oi Aromatics Point) Fraction All four fractions approx. 0.050.

The 210-355 C. fraction of the beneficiated raw material is segregated therefrom by fractional distillation to provide highly toxic preservative wood impregnant as a distillate.

By providing in the beneficiated material the overall specific gravities noted in fractional parts of the 210-355 C. out, a guarantee is secured that sufiicient reforming, cracking, modifying and/or converting has been accomplished to insure the materials in the beneficiation boiling between about 210 C. and 355 C. having a tox icity comparing favorably with that found in high temperature coal tar preservative impregnants.

Example 3.When processing the starting materials in the presence of an extraneous gas as disclosed in Examples 1 and 2, it is found that the materials boiling below and above 270 C.

have a relatively high and low toxicity, respectively. It is of importance that the reformed materials boiling above 270 C. have as high a toxicity as possible to wood destroying fungi for the reason that these materials have a toxicity blanketing effect on the lower boiling materials of highest toxicity. By retreating the once processed materials boiling above 270 C. we have discovered that additional toxicity may be induced. We outline hereinafter a typical practice of this phase of our invention.

The starting material is charged to an autoclave under a cold hydrogen pressure of 500 pounds per square inch. The temperature is then raised to 480 C. and there held for a period of 45 minutes. The partially beneficiated material is allowed to cool to atmospheric temperature, and out at 270 C. to provide a low boiling portion of relatively high toxicity and a high boiling portion of relatively low toxicity. The high boiling portion is charged back to the autoclave under a cold hydrogen pressure of 500 pounds. The contents of the autoclave are heated to a temperature of 475 C. and there held for a period of 30 minutes. The autoclave is allowed to reach atmospheric temperature and the contents discharged. The once and twice treated materials are commingled and are found to have in the materials boiling between 210 C. and 355 C. a percentage of aromatics in excess of 70%. The specific gravities of the aromatics in question fall between the limits shown in the foregoing tabular data, and the specific gravities of overall fractions in the 210-355 C. out fall within the limits previously noted.

A preservative wood impregnant boiling preponderantly between 210 C. and 355 C. and with 30% residue above 315 C. is segregated from the commingled beneficiation, and subsequent inspection reveals the fact that the segregation has a toxicity acceptable to the wood preserving industry, that is to say, a toxicity closely approaching that found in oily preservative derivatives of high temperature coal tar.

Instead of cutting the primary beneficiated oil at 270 C., the cut may be made at any other temperature, say at 285 0., 300 0., above or below, whereby to provide the low boiling portion as a material of relatively high toxicity and the high boiling cut as a material of relatively low toxicity. The high boiling portion is then treated at a temperature falling within the limits previously disclosed.

We have found when practicing our two-step process in the presence of an extraneous gas as disclosed in the instant example that by providing a total treatment period of not in excess of about two hours, acceptable toxicity closely approaching or equalling that of high temperature coal tar preservative products may be provided. As illustrative of this mode of practice, but without inferring treatment period limitations, a period not in excess of one hour may be employed in the primary step, and a period not in excess of 30 or 40 minutes, more or less, may be employed in the secondary step which retreats the higher boiling segregation. Such treatment periods have been found to give the desired results, although other periods of treatment for the two steps, the total of which falls below about two hours, may be practiced.

Example 4.A petroleum aromatic extract" distilling 30% below 315 C. and with 40% residue above 355 0., having an aromatic and unsaturated content of 70%, a specific gravity of aromatics of 1.01 in the 270-315 C. fraction and a specific gravity of aromatics of 1.02 in the 315-355 C. fraction is charged to a high pressure autoclave and propane is pumped in to an upper limit of 1000 pounds per square inch. The temperature is raised to 450 C. and held there for a period of one hour. Thereafter and without substantially lowering the temperature, the contents of the autoclave are discharged to a larger autoclave and held under a pressure of 400 pounds for a period of 30 minutes. At the end of the named second period the beneficiation is cooled and inspected, and is found to have in excess of 70% aromatics in the materials boiling between 210 C. and 355 C., and the fractional parts of the 210-355 C. out have aromatics whose specific gravities fall Within the limits noted in the tabular data previously shown.

The beneficiation which has newly induced fractions boiling below 210 C. is fractionally distilled to provide a distillate of the Wood preservative type boiling substantially between 210 C. and 355 C. Upon evaluation, the wood preservative type distillate reveals a toxicity to wood destroying fungi comparing favorably with that toxicity found in high temperature coal tar creosote.

In the two-step operation disclosed in the instant example we have found that a period of not in excess of about one hour is suitable for the primary step. Dependent upon the temperature selected within the range previously disclosed, periods of 20, 30 or 40 minutes, more or less, are acceptable. In the secondary step of this mode of practicing the instant invention, we have found ass-sass that a period not excess of about one hour is sufficient to induce the desired qualities and characteristics in allstar-ting feed stocks. With some feedstocks periods of20, 30 or 40 minutes-more or less, are satisfactory in the secondary step; When employing in thefirst stage'arelatively high temperature within: the range previously disclosed,"and'a relatively high pressure dropiin the second stage, a relatively short period of treatment in the second 'stagewill provide the desired percentage and specific 1 gravities of aromatics.

The relationship of the high and" low pressure steps may'vary over relatively broad limits; as for example; the first step maybe-carried out at very high pressures 'andthe second stepat a-pressure' only slightly above -atmospheric.-' Oh theother hand,if a relatively low press-ure is employed-in the first and highpressure-step, say a pressure-of about 400 pounds per'squ'areinch; then atmosa pheric or subatmospheric pressure mayice em ployed in the secondstepe Viewed broadly this phase of practice of our ill-i: vention is notcircumscribed by any'definit'epressures iri the high and low pressure steps, but rather turns on employing a relatively high pres sure in-the first stage and'a relatively low pressure in the second stage.

Example 5.-The-Shell aromatic oil noted previously is' chargedto a high pressure autoclave.-

Methane is pumped into an-upper pressure of 900 pounds per squarednoh; The contents of the autoclave areraised toatemperature of 465 C; and held atthat temperature for 40 minutes;

Thereafter thetemperature-is 'raisedto 500 C;

cates that only about 0.5%is' required for total: inhibition of growthof wood destroying fungi.-

We have found that when practicing our invention with a relatively low temperature step and a subsequent relatively: high temperature step, either and'preferably both steps-being carried out in the'presence of an-extraneous gas, the

temperatures in both steps being selected between the limits of about-350 600 C., optimum conditions are secured-by providinga treatment in each step of not inexcess of about one hour If'relatively high temperatures within the limits named are employedin the two-step process of dissimilar temperatures, relatively short periods'in the two steps are possible, and we have found'that under very severe thermal conditions within 'the limits named, periods of 10;-20'or- 30*minutes-in each step suffice to induce the desired. characteristics.

Viewed broadly, thisphase of I our invention is not circumscribed =by;-any -definite time period, otherthan the upperlimitabove stated-,but rather turns on the correct 'coordination' of-a relatively: low temperature step and a relatively high tem perature step, whereby to provide th'e desired per centageand specific gravity of aromatics and/or the desired percentaged aromatics and specific= gravity of overall' 'fraictions in the endproduct,

which thing or things in turn insure induction of toxicity closely approaching :or equaling that of high temperature coal tar preservative wood. -i rn pregnants:

10 a When treating-certain mixtures of petroleum fractions that have a relatively low petroleum aromatic content we have found the operational procedure as outlined in the following example of especial merit.

Example 6.-A recycle petroleum oil containing less than35%petroleum aromatics is subjected to the processing conditions disclosed in Example 1. Upon inspection of the beneficiated'material it is found that although the specific gravities of the aromatics "fall within 'the limits previously shown, the total of'aromatic content is less than 70% iri'the 210355 C. cut: The beneficiated material is then extracted with liquid sulfur dioxide and the raffinate discarded.- The extract is then stabilized" to provide a residual as an oil of the wood preservative type boiling preponderantly between 210-355 C., and which has an overall total inhibition point to the growth of wood destroying fungi of not-in excess of about 0.5%.

Although liquid sulfur dioxide is shown as the extracting agent, it is immediately obvious that other materials may be employed, as for example furfural or the like.

Instead 1 of practicing the process in a once throughfltreatment as disclosed in Example 1, especial toxicity induction benefits flow from dividing the beneficiation into a relatively low boiling portion and a're'lativelyhigh boiling portion,

and subsequently retreating separately the two fractions The two fractions may be treated at similar or dissimilar temperatures within the range previously disclosed. When the retreated fractions arecommingled, it will be found that they have a toxicity'inexcess of the once treated material.

In lieu of retreating both the high and low boiling portions, the low boiling portion may be retreated and then commingled with the once treated high boiling portion to provide a comminglement having a toxicity in excess of the once treated oil.

Another mode of'practicing our invention resides in treating the petroleum aromatic containing'oil in the presence of benzene; toluene, naphthalene'or their derivatives. As exemplifying this mode of practice, illustratively 50 parts of the-petroleum aromatic oil and 50 parts of benzene are commingled. The' comminglement is then; for example, treated'as-in Example 1,

The resultant alkylated benzene is then removed.

Uponinspection, it will be found that the petroleum aromatichas a percentage of aromatics not lower than70% and the specificgravities of the aromatics in fractional parts of the 210- 355 C. out fallbetween thelimits noted in the tabular data previouslyshown. The commingling of 50parts of the petroleum aromatic with 50 parts ofbenzene is for purposes of illustration only; other percentages may be used.

When the-feed stock consists of a petroleum oilhaving arelatively low percentage of patroleum aromatics and unsaturates, it'is advisable to first extract the oil and then treat the extract according to any of the modes of practicing our process;

Ewample 7.-'-We have discoveredgas previously disclosed, that thebasic reason why petroleum aromatics have relatively little toxicity is because of the relatively non-toxic materials (side chains or fractional parts thereof) attached to the ring nuclei which probably lower water solubil-ity. Our previously describedmodes of practiceof the instantinvention-increase toxicity by," among other things, raising the-specificgravitv of aromatics and/or overall fractions by controlled side chain elimination from the ring nuclei. However, we have discovered that when shortening or removing side chains from the ring nuclei, nascent radicles are formed which may, on the one hand, further alkylate the ring nuclei, or, on the other hand, polymerize to form high boiling chain structures which boil within the range of the reformed aromatics. In either instance this is not desired, and more especially the polymerization of the nascent radicles to form relatively high boiling chain structures is not desired for the reason that they dilute the toxicity of the reformed aromatics.

We have discovered that if we will shorten or remove side chains from the ring nuclei inaccordance with the instant process and within a relatively short period, and then shock cool the entire beneficiation, a certain degree of the said polymerization and/or alkylation is precluded, thus resulting in a toxicity in the cracked, transformed, reformed, modified and/or converted oil comparable to that of certain high temperature coal tar preservative oils.

When applying this mode of practice to our instant invention, we hold the treating period to not in excess of about two hours, and preferably not in excess of about one hour. When employing relatively high temperatures within the extreme upper limits of the range previously disclosed, periods of -30 minutes, or less, will suffice for the necessary reforming previously taught. Immediately thereafter the beneficiation is shock cooled to a temperature below about 250 C., and preferably below 200 C. by a relatively cool oil, which may be the preservative oil previously made by the process. The reformed oil is fractioned as shown above.

Example 8.A petroleum aromatic oil, as for example, the Shell oil previously described is pumped in closed circuit through an apparatus designed to withstand high pressures and high temperatures. The pressure is maintained at 3000 pounds per square inch and the temperature at 480 C. Water gas is continuously circulated in the closed circuit at a rate of 5000 cubic feet per barrel feed stock. The oil and gas in the closed circuit are kept in circulation. At the end of about one hour or one hour and 15 minutes, the heat treated'oil and water gas are continuously withdrawn with compensating admission of fresh feed oil and gas to the circuit. The withdrawal and admission of the oil and gas are regulated to provide the heat treating period above named, that is to say, about an hour or an hour and 15 minutes. Fresh water gas is pumped in with the new feed at a rate previously indicated. The withdrawn heat treated material, after separation of occluded gas, iscooled and inspected and is found to have a percentage and spec fic gravity of aromatics in the 2l0355 C. out falling within the limits previously disclosed. The specific gravities of overall fractional parts of the 210-355" C. out will also be found to fall within the limits previously shown, and the toxicity of the overall 210-355 C. out compares favorably with certain high temperature coal tar creosotes.

In previous examples, the overall feed stock has been shown as being treated. In lieu of this, the raw feed stock may be divided into two or more fractions and separately treated. As an example, the feed stock may be divided into a relatively low boiling fraction and a relatively high boiling fraction. The low boiling fraction is then treated at a relatively high temperature within the range disclosed, and the high boiling fraction is treated at a relatively low temperature within the stated range, the periods of treatment in this instance being the same as taught previously for high and low boiling cuts, beneficiated or otherwise. If three cuts of the raw feed are made, the lowest boiling fraction is treated at the highest temperature, the intermediate fraction at an intermediate temperature and the highest boiling fraction at the lowest temperature. This teaching applies to any number of cuts into which the feed may be divided.

Viewed broadly, the product of the instant process is a transformed, reformed, modified and/or converted petroleum oil boiling preponderantly between 210-355 C. with at least about 15-20% material boiling above 315 0., having at least about 70% aromatics in the materials boiling between 210 C. and 355 C., and in the fractional parts of the oil boiling between 2l0-355 C., certain specific gravities as taught in the foregoing.

The pressures in the present invention are in excess of atmospheric (with the possible exception of the second step of the mode of practice described in Example 4), and may be as high as practicable.

Either liquid or vapor phase may be practiced, and this disclosure is specifically to be read into all examples. Non-inventive skill will enable those acquainted with the art to coordinate temperatures within the range disclosed with relatively moderate pressures in order to provide vapor phase practice. When employing vapor phase operation and processing any of the feed stocks previously described, definite periods falling within the limits previously disclosed will provide specific gravities and aromatic percentages shown in the foregoing.

One phase or various phases of one example may be substituted for a phase Or various phases of another example where the substitution is obviously workable.

It is to be strictly understood that all temperatures, pressures and periods of treatment shown in the examples are for purposes of illustration only.

Intermittent or continuous operation, or a combination thereof, may be practiced in the instant process, and those skilled in the art can apply this to our invention without recourse to inventive skill.

The instant process is carried on in the presence of an extraneous gas. and certain toxicity induction benefits will flow from the employment of either a reactive or non-reactive gas. Among such gases may be mentioned hydrogen, water gas, carbon monoxide, carbon dioxide, methane and its homologues, various saturated and unsaturated gases resulting from the cracking of hydrocarbons, and nitrogen, separate or in admixture. The extraneous gas or gases employed may represent a partial pressure in the process varying over a very wide range. As an example, but not as a restriction, the partial pressure of the extraneous gas or gases may be 550%, but it is to be strictly understood that this statement is for purposes of illustration only.

Minor changes within the scope of the appended claims may be made without departing from the spirit of the invention.

We claim:

1. In the induction of toxicity to Wood destroying fungi into a mixture of petroleum fractions boiling prep nderantly above 270 0., characterized by inherent butinhibi-ted' toxicity 'and a substa'ritia-l percentage of'mat'erialsof ring structure content;-theprocess which comprises: subjecting said material at superatmospheric pressure in the presence of a' non-oxidizinggas of extraneous source to a' temperature selected between the limitsof-about350-500' 0.; unveiling toxicity-in-the material un'der treatment by carrying on the proce'ss fora period not subs'tantiallyin excess'of about two hours, the period being so selected with referenceto' the chosen temperature and pressure as to jointly provide in the beneficiation newly formed materials boiling below 210 C., a'percentage of aromatics in the fractions boiling between 210-355" C. notsubstantially less than about 70%,- and a specific gravity in the overall fractions of the material boiling between -355 C. falling between the'limits shown in the appended tabular data:

Fractions Low Limit High Limit 210-235? 0.9500 0. 9942 235-270" '11 n. 9941 1. 0245 arc-315 (1 1.0159 1. 0575 315-355" 0.... 1. 0546 1.1175

whereby to'provide a material having induced" toxicity to wood destroying fungi.

2. The process of claim 1 with inclusion of segregatingiromthe beneficiated material an oil of thewoodpreservative'type characterized by induce'd toxic propertiesmonin preponderantly be tween about 210-355 C. and having at'least about -20% residual material-boiling above 315 C.

3. In the induction oftoxicity to wood destroying fungi into-amixture of-petroleum fractions boiling preponderantly above 270 0., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, theprocess which comprises; partially unveiling toxicity in the named materials by subjecting same at superatmospheric pressure in the presence of a non-oxidizing gas of extraneous sourceto a temperature selected-between the 11m its of-about350-600" C.- whereby to provide an oViall-brneficiation-having relatively high and lo'w'toxicity in -the --materia1s boiling below and above 270 0., respectively; segregating at least a portion of the materials of relatively low toxicity boiling above 270 C. and subjecting same at'superatmo'sphericpressure to a temperature between the limits above named; securing induced toxicity in a relatively high degree in the materials undertreatment bycarrying on the process inboth periods of treatment for atotal time not in'excess of'about two hours, the'periods in each step beingiso'selected with reference to the chosen temperatures and pressures as toprovide newl'y form'edinaterials boiling.be1ov1210 "C., a percentage of aromatics in the fractions boiling between 210-355 C. not substantially less than 70%, and a specific gravity in the overall fractions of the material boiling between 2l0-355 C. falling between the limits shown in the appended tabular data:

whereby to provide materials having induced toxicity to wood destroying fungi; and commingling the segregations above named to providean were oil of menses-team properties; and tainingrraetions essentiarm ah acceptable-Me servativeimpregnantz" V 4. The process of claim 3 with inclusion of: segregating from the beneficiat'edmaterial an oil of the wood" preservative type characterized by induced toxic properties, having at least about 15-20% residual matter boilin above 315 C., and boiling preponderantly between about 210 C. and 355 C.

v 5. In the induction of toxicity to wood destroy mg fungi into a mixture of petroleum fractions-- boiling preponderantly above 270 0., character ized by inherent but inhibited toxicity-and a substantialpercentage ofmaterials of-ring struc ture content, the process which comprises: subjectin saidmaterial atarelatively high pressure in the presence" of a non-oxidizing gas of extraneous source to a temperature selected-be tween the'limits of about 350-500 C, for a period not in excessof about one hour; thereafter subjecting the heat treated material-substantially in entirety'to a relatively low pressure without a substantial reduction-intemperature for a'-period not in excessof about 30 minutes;- unveiling toxicity to a relatively high degree in the material under treatment by carrying on the two-stage process for periods falling within the limits above named, the periods being so selected with reference to the chosen-temperature andpressure as to jointly provide newly formed ma terials boiling below 210 C., a percentage of aromatics in the fractions boiling-between 210-355 0. not substantially less than about 70%, and a 5 specific gravity in the overall fractions-of the- Fractions Low Limit High Limit whereby-toprovidea "material of increased toxicity to wood destroyingfungi.

61 The process ofclaim 5 with inclusion of' segregating 'from'the beneficiated material an oil of the "wood'preservative type characterized by induced toxic properties, boiling preponderantly between210 C. and 355 C., and having at least about 15-20% "residual materials boiling above 7. In' theinduction of toxicity to wood destroy-" ing "fungi into a mixture of petroleum fractions boiling preponderantlyabove 270 0., characterized by inherent but inhibited toxicity and a sub-' stan'tialfpercentageof materials of ring structure content; the'proce'ss which comprises: subjecting said material at' superatm'ospheric pressure in' the presence of a non-oxidizin gas of extraneous source to a relatively low temperature selected between the limits of about 350-600 C. for a period not in excess of about one hour; thereafter subjecting the heat treated material substantially in entirety at superatmospheric pressure to a relatively high temperature for a period vnot substantially in excess of about one hour;

unveiling toxicity in the material under treatment by carrying on the two-stage process for periods falling within the limits above named, the periods being so selected with reference to the chosen temperatures and pressures in the two steps as to jointly provide newly formed ma- Fractions Low Limit High Limit whereby to provide a material of increased toxicity to wood destroying fungi.

8. The process of claim 7 with inclusion of segregating from the beneficiated material an oil of the wood preservative type characterized by induced toxic properties, boiling preponderantly between 210 C. and 355 C., and having at least about 15-20% residual materials boiling above 315 C.

9. As a wood preserving impregnant a hydrogenated petroleum oil having at least about 15-20% residual materials boiling above 315 C. and boiling preponderantly between 210-355 C. which contains not less than about 70% aromatics, the fraction 210-235 C. of which has a specific gravity falling between the limits of about 0.9506 and 0.9942, the 235-270 C. fraction of which has a, specific gravity falling between the limits of about 0.9941 and 1.0245, the fraction 270315 C. of which has a specific gravity falling between the limits of about 1.0159 and 1.0575, and the fraction 315-355" C. of which has a specific gravity falling between the'limits of about 1.0546 and 1.1175.

10. As a wood preserving impregnant a, hydrogenated petroleum oil having at least about 15-20% residual materials boiling above 315 C. and boiling preponderantly between 210-355 C. which contains not less than about 70% aromatics, the 235-270 C. fraction of which has a specific gravity falling between the limits of about 0.9941 and 1.0245, the fraction 270-315 C. of which has a specific gravity falling between the limits of about 1.0159 and 1.0575, and the fraction 315-355" C. of which has a specific gravity falling between the limits of about 1.0546 and 1.1175.

11. As a wood preserving impregnant a hydrogenated petroleum oil having at least about 15-20% residual materials boiling above 315 C.

and boiling preponderantly between 210-355 C.

which contains not less than about 70% aromatics, the fraction 270-315 C. of which has a specific gravity falling between the limits of about 1.0159 and 1.0575, and the fraction 315-355 C, of which has a specific gravity falling between the limits of about 1.0546 and 1.1175.

12. In the induction of toxicity to wood destroying fungi into a mixture of petroleum fractions boiling preponderantly above 270 0., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, the process which comprises: subjecting said material at superatmospheric pressure in the presence of a non-oxidizing gas of extraneous source to a temperature selected between the limits of about 350-600 C.; unveiling toxicity in the material under treatment by carrying on the process for a period not in excess of about one hour the period being so selected with reference to the chosen temperature and pressure as to jointly provide newly formed materials boiling below 210 C., a percentage of aromatics in the fractions boiling between 210- 355 C. not substantially less than about and a specific gravity in the overall fractions of the material boiling between 210-355 C. falling between the limits shown in the appended tabular data:

whereby to provide a, material of increased toxicity to wood destroying fungi; and protecting the induced toxicity by shock quenching the overall beneficiation.

JACQUELIN E. HARVEY, JR. ROBERT H. WHITE, JR. JOSEPH A. VAUGHAN.

REFERENCES CITED The following references are of record in the file of this patent:

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