US2363241A - Useful products and process of producing them - Google Patents

Description

Patented Nov. 21, .1944

Bobert' H..White,Jr., and Joseph A. Vaughan,

Atlanta,. Ga.,assiknors of one-half to said Harvey,Jr.,and one-half to Southern Wood Preserving Company, East Point, Ga., a corporation of Georgia l NoDrawing.

The instant invention relates to the production Applica oi "toxic oils employable as iungicides, insecti-r cides, and for any .otherservice to which toxic oils may be put. I

i More especially the instant inventi the production of toxic oils from mixtures of petroleum fractions characterized-wring structure content. Among such starting materialsmay he a onrelates to.

. mentioned mixtures of petroleum iractionscharance with consumer preference; ntion is the reforming, modifying, converting and/or? transiormingof the mixtures of hydrocarbonswhere byto induce toxicity.

provision of preservative ingyboiling ranges and residues in accordance" acterized by ring structure: content recovered from petroleum iractions by wellknown ,extraction methods including extractive distillation and azeotropic distillation. Also maybe jmentioned mixtures of petroleum fractions characterized by} ring, structure content as flowing from thermal and/or catalytic treatment oi certainpetroleum ample having ring structures induced J-in the fractions which includes rpetroleumj -fractions having ring structures induced in thecourseyof thermal and/or catalytic treatment, as {for texcourse of one or more thermal and/or. catalytic treatments ofunusual length, asi'or example, for I periods of from 1-10 hours or more,

An object or the instant inventiondsthe prothe aforenamed petroleumfractions or others whereby to'provide oils of the preservativetype, as for exa-m'piepreservati've wood impregnants conforming to speciflcations extant or acceptable to the mucus.

such oilmaterials.

duction of toxic ;oils from Another object of the instant invention is the with published specifications and/or in accord-' Anotherfobjector the instant inv sun another object of the instant invention is the induction of usable toxicity in the presence oifa gas or gaseous mixtures.

. :iAnother object or theinstant invention is the unveiling 0i latent toxicity in mixtures of pe- 1 troleum fractions havinginherentbut inhibited terial under treatment.

toxicity.w a *Yetanother object ,of the instant lnventionis the provision in the overall beneflc'iated materials or that percentage oi newly induced fractions .i-boiiing below 210 C. which is conduc'iveyto the induction of toxicity in other fractions of the ina- Another object of the instant invention .is a

coordination of process variables which will .pro-

vide in various fractional parts of the bneflciated material cyclic structures with specific gravities ifalling within the limits hereinafter stated. l

- Another object of the instant invention is the induction of toxicity in the presence of catalytic wood impre nahts havmaterials adaptedto favorably influencesaid toxicityinduction A o In the past wood preservative oils of the high temperature'coal tar". derived type have been em- .ployed in quantities greatly exceeding the total of all other wood preservative foils. From the.

- standpoint of javailabilityof said co'ai-tar as the parent productofwood preservativeoils, it is annually produced fin this country under normal conditions to. the extent otfive hundred milllon. to six hundred million gallons, This quantityi oi coal tar is capable of yielding an amount or high- 11y effective wood preservative oil which would 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 aresidue (pitch) which, at best, is a low pricedfproduct and which, at worst, is a seriously distress; product tothe end that at times itis placed in inventory rather than sold, this country cannot economicall producetits creosote a l needs. The current method of processing coal tar 1 leaves much to be desired. The net result of this situation obtaining is that the coal ta r distiller usually confines himself tothat distillation recover-y of creosote'which would correspond to the attending amount of pitch that he can market stta profit. Accordingly, over a period of years several hundred million gallons of creosote oil have been imported into this country. That such iasituation should obtainis apparently a paradox gin that we annuallyproduce a quantity of high temperaturecoaltar which if processed to yield creosote would make us self suiiicient in that requirement. A survey of thisparadoxis fully outlinedin an address given by no less an authority than S. 'P. Miller, technical director, The Barrett Company, f40"Rector Street,New York city,be-

fore, the Franklin Institute; Philadelphia, Pennsylvania,"in December 1932; 1 The economics of coal tar have not materially changed since that In view of the apparentinability 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 aromatic oils are produced by the petroleum industry,"and thehigh boiling oils of aromatic content produced by this industry havef for several years been tested for Jtheir wood"preservativeefliciencyb By the term p etroleum aromatic" as used herein and in the appended claims is meant'to include mixtures otpetroleuni fractionschari'icterized by cyclic content and include specifically various forms and types of naphthenes round in various mixtures of petroleum iractions, o

. F1aSh, C. O. C F

, s. F. vis. 77 F A. S. T. M. distillation:

as for example monocyclic and polycyclic thenes.

The so-called petroleum aromatics which includes the monocyclic and polycyclic naphthenes and unsaturated hydrocarbon fractions have in the past been produced in very large quantities.

naphence of an added protective gas or gases, to materials exhibiting a more pronounced toxicity than the parent feed stock. c

In former attempts to provide a wood preservative oil of petroleum origin by processes analogous to that of the'present invention, the feed stock However, very little work has been done on these materials. Such a fact is borne out on page 667,

Reactions of pure hydrocarbons, Gustav Egloff,

Reinhold Publishing Corporation, 330 West 42nd Street, New York city, which states: 1

Despite the fact that naphthenes or cycloparafllnes 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, com-1 paratively little work of a pyrolytic nature has" been performed on individual naphthene hydrocarbons or the cyclooleflns.

Several oils of cyclic content produced by the petroleum'industry have been inspected for their may be mentioned a high boiling oil of cyclic 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. C F 295 290 Fixed carbon per cent Pour point F B. S. & W per cent by volume S. U. vis. 100 F S. U. vis. 210 F Carbon res Per cent aromatics and unsaturates Sol. in CSz Loss 50 grams, 5 hours, 325 F Residue of 100 pene per cent I.B.P ..-F 518 rec. F.. 565 rec. F 589 rec. F 614 rec. F '637 rec. F 660 rec. "F 1 675 1 Maximum.

' toxicity to wood destroying fungi, among which.

utilized as starting material or the process adopted, or, both, were such as to provide an oil boiling 90% .at 270 C. or in another instance with only 0.6% residual matter at 315 C. These products have not been found acceptable in the art.

'One of the petroleum oils hydroformed in vapor phase above noted had the following distilla tion range: 1

I on,

Distillation cent Below 210 C 0.0 210-235 C q. 12. 0 235-270 C. 08. O 2703l5 C l9. 4 --Residuc ,0.6

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

Upon evaluatingthe foregoing oil for its toxicityto wood destroying fungi (Madison 517 it was found that this oil did not inhibit the growth of the fungi named at a concentration of up to and including 10%.

It is now discovered that the 011 above named -or other oils of cyclic content produced by the petroleum industry can be increased in toxicity in accordancewith the process of the instant invention.

, According to the instant invention oils of cyclic content produced by the petroleum industry are reformed, transformed, modified and/or converted to oils of a more toxic nature having characteristics acceptable to consumers of wood preservative impregnant and/or conforming to wood preservative specifications extant.

It is a specific object of the instant invention to reform, transform, modify and/or convert mixtures of petroleum fractions characterized by cyclic structures having inherent but-inhibited The oil above named after its impregnation into cellulosic materials to be preserved is entirely too volatile to provide an acceptable preservative impregnant. g 7

It is, therefore, an object of the instant invention to provide a vapor phase process carried on in the presence of added gas or gases, which yields a reformed petroleum oil characterized by induced toxic properties having at least about 10- 20% residual matter above 315 C. I

, By the expression. a reformed petroleum oil" as used herein and in the annexed claims: is

meant a beneficiated petroleum oil having induced toxicity as stemming from, among other things,,a changein molecular structure which occurs during the practice of the present process. Thus, a reformed petroleum oil? is a reformed, converted, transformed and/or"modi-' fled oil, and includes an oil reformed by' substitution and/or addition to the molecular structure, and/or subtraction from the molecular structure of the feed stock.

IWe-have discovered that some of the mixtures of petroleum fractions have very substantial residual matter above 355 C. and inherent toxic properties inhibited by the complexity of the structure which structure is inherently unstable. Taking advantage of the lack of stability of the complex structure of these relatively high boiling oils that have substantial residual matters above 315 C. or 355C, we are able by subjecting them to vapor phase reforming conditions in the presence of added gas or gases to simplify and stabilize the structure whilst providing in the finally beneficiated oil substantialresidual materials above 315 C. or 355 C.,'atthe same time unveiling the toxic qualities, and if the process is carried to an extent to provide specific gravities ofmaterials of cyclic structure content in fractional parts of the beneficiated material falling between the limits noted in the following tabular data:

toxic properties in the vapor phase in the pres 76 Fractions Low limit I High limit sic-235 0.913 I 1.0580 0.935 1 1.0756

2,363,241 1 and preferably carried to theextent to provide specific gravities of materials of cyclic structure content in the fractional parts of the beneflciated material as noted in the following tabular data:

, t 1 Fractions Low limit 1 High limit 1 commercial toxicity is secured. 13y stripping .fromjthe beneflciated'material the excess of 1 fractions boiling below 210 C. as required by commercial specifications, (or specifically, whateverother low boiling temperature is specified) we are able to use the residue as a commercial wood preservative impregnant with acceptable toxic properties. In the eventthis material has .too high a 'residue at 355 C. or has too high a coke residue for any particular service .the de sired preservative oil may be secured as an ex- .tract ordistillate havingno. excess of the desired materials at 355 C.1or an excess of coke residue.

The following examples will illustrate sev eralmodes of practicing the processof the in- 1stant invention. i t 1 Example 1.-A so-called petroleum aromatic sidue above 355 C., is subjected in the vapor phase in thepresence of hydrogen at atemperature of 510 C. whilst under a pressure of 1,000 pounds for such a length of time as to provide newly formed materials boiling below 1 210 C. and in fractional parts of the beneflciated I .oil materials of cyclic structure content having specific gravities falling between the limits noted Jinthe following tabular data; 1 1 t j Fractions Low limit High limit 2111-235 0.913 1.0580 sis-35sec... 1 t 1.027 1.1285

and preferably for such a length of time as to provide materials of cyclic structure content in fractional parts of the beneflciated oil having specific gravities falling between the following Operating under the conditions above named a period selected between the limits of oneand ture content in the fractions 210-235 C. and 3l5.-355 C. had specific gravities of 0.941 and 1.055, respectively. The residual matter above 355 C. in the beneilciation is about 34%.

Whenthe period of treatment has been com- .pleted the oil is condensed andinspected and three hours, say one hour and 15 minutes, will illustratively serve to. provide a. percentage of l ;newly induced materials boiling below1210- C. 1 and specific gravities of materialsof cyclic struc- 1 turecontent in fractlonalpartsof the overall beneflciation falling between the preferred limits noted above.

The beneficiated oil flowing from the treatment named above had 18.9% materials boiling isfound to require a smaller concentration for a given growth inhibition of wood destroying fungi (Madison 517). than the parent feed stock to such an extent as to be useful. as awood preservative. The induction and/or provision of ,the specific gravities of materials of cyclic structure content in the fractional parts of the beneficiated oilmentioned above is a valid test for the induction of toxicity in the overall fraction referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment Theoverall beneficiated material may be used as a preservative or for any other purpose to .overall beneficiated material of the instant proc-,

'ess, the following tabular data show several pub-'. lished specifications:

Woon PRESERVATIVE Imrnaomn'rs Specifications 1. American Wood Preservers Association 1 0. Up to 210 C., not more than 5% b. Up to 235 C., not more than 25% 2. American Wood Preservers Association a. Up to 210 C., not more than 1% 5. Up to 235 C., not more than 10% 0. Up to 355 C., not less than 3. American Wood Preservers Association 1 a. Up to 235 0., not more than I /2% 6. Up to 300, C., not more than Is /2% 0. Up to 355 C.,not less than45% 4. American Wood Preservers' Association a. Up to 210 C., not more than 8% b. Up to 235 C., not more than 35% American Wood Preservers Association 1 1 a; Up to 210 10., not more than 10%. 1 15. up to 235 C., not more than 40% American Wood Preservers Association. 1

1 0. Up to 210 C., not more than 5% 6. Up to 235 0., not more than 15%. 7. Prussian By. 1 i 1 1 a. Up to 150 C., not more than 3% b. Up to 200 C., not more than10% 0; Up to 235 0., not more than 25% 8. National Paint, Varnish & Lacquer Association #220 1 i 1 .1a, 5% at 1629 0.1 1 b. 97% at 270' C. 9. Southern pine shingle stain oil 1 a. 5% at 137 C. 1 1 b. at 257C. 10. Neville shingle stain oil.

,.a.I.B.P.,150'C.' 1

b. 5% at 205' C. 1 c. 95% at 292'. C.

below210 c., and the materials of cyclic struc- II '11. Carbolineum -=270' 0.1.3.1.

whilst under a pressure of1800 pounds. on the process for such a length of time asto Y iointly provide (1) newlyformed materials boiling below 210 C. and (2) in the fractions 235- By the nature of the process it is obvious that modifications of existing specifications, or other and more exacting specifications maybe met.

As mentioned in the foregoing, the process variables are illustratively so coordinated as to jointly provide newly formed fractions boiling below 210 C. and a preferred limit of specific gravities of materials of cyclic structure content in the fractions 210-235 C. and 3l5-355 C. of

the beneficiated oil.

} In lieu of jointly controlling the process as to provide the aforementioned specific gravities of materials of cyclic structure content in the 210-235" C. and 315-355 0. fractions of the beneficiated oil, the propercontrol may be evidenced in accordance with the following example: 1

Example 2.Select a material comparable in chemical analysis and boiling range to thefeed stock mentioned in Example 1, as for example aromatic extracts, flashed residuums, or the like. Subject same in 'vapor phase in the presence of hydrogen at a temperature of 500 C. a ry 270 C. and 315-355 C. materials of cyclic structure content having specific gravities falling'be- Operating under the conditions above named a period of about one hour and '15 minutes will illustratively serve toprovide apercentageof newly induced materials boiling below 210 C. and specificgravities of materials of cyclic structure content in the fractional parts of the beneficiated oil falling between the preferred limits noted above.

Atthe end of the named treatment period the oil is condensed and inspected, and is found to have induced toxic properties. The induction and/or provision of the specific gravities of materials of cyclic structure content in the fractional parts of the beneficiation stated in the presentexample is a valid test for the induction of. toxicity in the fraction referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment.

Example 3. -Select a liquid sulfur dioxide ex rials of cyclic structure content falling betwee the limits noted below:

Fractions Low limit High limit 270-315 0 0.973 rom- 315-355" 1.021 1.1285

and preferably between the following limitsz' Fractions Low limit High'llmit.

arc-315 c '1. 001 1.008: 1.055 1 11.1136

Operatingunder the conditions above named a period selectedbetween the limits of one and two hours will illustratively serve to jointly provide'a percentage 'of newly induced materialsboiiing below 210 C. and specific gravities of materials of cyclic structure content falling between the preferred limits in the fractional parts ofthe beneficiation as noted above.

When the period of treatment hasbeen comtional parts of the beneficiation "mentioned in the instant example is a valid test for the induction of toxicity in the fractions referred to, and

- further is an indication that toxicity has been materials of cyclic structure content falling befor such a period oftimeas-to jointly provideand/or induce 1) newly formed materials boiling below 210 C. and (2) in the fractions 270- induced in other fractions of the material under treatment.

Example 4.Select a furfural extract of a mixture of petroleum fractions, said extract boiling preponderantly above 250 C. and having substantial residual matter above 355 C. Subject same in vapor phase in the presence of hydrogen at a temperature of 515 C. whilst under a pressure of 1800 pounds. Carry on the process for such a length of time as to jointly provide ('1) newly formed materials boiling below 210 C., as for exampl l535%, and (2) in the fraction boiling between 315-355 C. a specific gravity of materials of cyclic structure content falling between the limits of 1.027 and 1.1285, and preferably between the limits of 1.055 and 1.1135.

Carrying on the'process under the conditions of theinstant example, a period of about one hour and 30 minutes will illustratively serve to provide a percentage of newly induced materials boiling below 210 C. and a specific gravity of tween the preferred limits in the"315-355 C. fraction of the reformed oil.

At the end of the processing period the oil is cooled, condensed and inspected. Find in the beneficiation a toxicityin excessof that of the parent feed stock. The induction and/or provision of the specific gravity of materials of cyclic structure content falling between the stated limits'in the materials boiling between 315-355 C.ls a valid test for the induction of toxicity in the fraction referred to, and further is an indie cation that toxicity has been induced in other fractions of the material under treatment.

As noted in the tabular data in the foregoing with carbon dioxide, as for .with nitrogen.

with a molybdenum oxide catalyst.

with a chromium oxide catalyst.

Example 14.-Practice the process of 2,363,241 giving boiling range specifications for oil wood preservatives, many preservative oils are possible of segregation from the beneficiated feedstock of induced toxicity. As for example, an oil boiling within the carbolineumpreservative range,

in which instance the segregation would have an initial boiling point of about 270 0., thefractions 270-315 C. and 315-355 C of which, would illustratively contain materials of cyclic structure content having specific gravities falling between thelimits Of1.001-1.078 3 and,1.055- -1.1 135, 1e

spectively.

Example 5.- Practicethe process of Example 1 with a hydrogen containing gas.

Example 6.- Practice the processor Exampleaemploying hydrogen derived from carbon monoxide and water.

Eaample 7.-1=fractice the process of Example 3 example with acombustion gas. I Example 8.--Practice the process of Example 4 Example 9. -Practice the process of Example 1 with water gas.

Example 10.-Pra.ctice the process of Example '2 Example 11.-Practicethe'process of Example 3 with a vanadiumoxidecatalyst.

Example 13.-Practice the process of Example 1 with a tin oxide catalyst.

Example 12.-Practice the process of Example 4 a Example2 with a molybdenum sulfide catalyst.

Ezample 15.Practice the process of Example 3 "with a chromium sulfide catalyst.

with coprecipitated alum Example 33.,Practice the process of Example 1 with a silicious material impregnated with a metallic oxide as catalytic material.

Example 34.-Practice the process of Example 2 with a silicious materialimpregnated with a metallic sulfide as catalyticmaterial.

Example 35.- -Practice the process or Example 3 ina and chromia hydrogels as catalytic materials. a r

Example 36.-Practice the process of Example 4 Y with a synthetic silica-alumina gel as catalytic material.

an the Examples 1-4 inclusive, instances have been cited wherein the feed stocks have very small percentages, if any, or materials boiling below 270 C. The "instantprocess, as illustrated by 1 Examples 1-4 inclusive, or others, is adaptedto petroleum, fractions thermally treatfin vapor phase in the presence of a protective gas of extraneous source, within the processing limits herein disclosedja mixture of characterized by relatively little toxicity, as for example the so-called aro- ,niatic extracts or other petroleum fractions of induced cyclic structures, having fractions boiling for a given growth inhibition 3 Example 16'. Practice theprocess of Example 4 d with a vanadium sulfide catalyst.

Example 17.- -Practicethe process of Example 1 with a tin sulfide catalyst.

Example Ill -Practice the process of Example 2 with the coprecipitated oxides of copper and chromium as catalytic materials. Example 19.--Practlce the process of Example 3 j 45 Example 20.-Practice the process of Example 4 r with aluminum chloride as catalytic material;

with tin chloride as catalytic material.

with bromine as catalytic material.

Ea'ample 26.-Practice the processof Example 2 with a hydrogen halid as catalytic material. Example27L-Practicethe process of Example3 with ammonium chloride as catalyticmaterial.

Example 28.Practice the process ,0: Example4 with pelletedbentonite clay as catalytic material. Example 29..Practice the processor Example 1 with activated Attapulgus clay as catalytic materiaL,

Example 30.-Practice the process of Exam ple 2 with a silica hydrogel as catalyticmaterial.

Example 31 .'Practice the process of Example 3 with a silica gel impregnated with an aluminum salt as catalytic material.

Example 32.--Practice the process of Example 4 with bentonite and an adsorptive clay ascatalytic materials.

within the wood preservative range andthereby providean overall treated oil or segregated fractions thereof requiringa smaller concentration of wood destroying fungi thanthe starting feed stock to such an ex tent as to be useful as a woodpreservative impregnant.

Various purposesappear to be accomplished by the vaporphase induction of toxicity. in the presence of ages or gases of extraneous source not accomplished by liquid phase treatment. Among the purposes accomplished may be mentioned the thermal protection of thematerial under treat ment whereby to preclude or minimize undersirable polymerization, and in theevent the gas or gases partake of, or in the reforming, action, additionalbenefits are noted. It has been determined thatvarious gases of extraneoussource provide these desired and beneficial results in 1 varying degrees. It has specificaly been determined that included among these beneficial gases are hydrogen, hydrogen containing gases and substantially inert gases containing carbon.

Also specifically employable are methane and its homologues, various refinery gases, carbon dioxide and nitrogen.

' 'I'he gases above mentionedmay be employed separatelyorinadmixture, and this provision, in

one mode oi. operation, is be specifically read into all examples. I

Various catalysts assist in the reformingtranstorming modifying and/or converting of. the, starting petroleum oil whereby to provide materialso f induced toxic properties. Many catalysts other than noted in the ioreg oing are also employable as eflective broadly, the oxides and sulfides of metals may substfiices. Viewed be used as well as the carbonates, sulfates and the metals themselves. Cellulosicmaterials and car- .bon, activated or otherwise, may be used with advantage. Especially effective as catalytic materialsare the oxides and sulfldes of metals,

silicious materials, halogens halidsand derlvatives thereof, including specificallyysubstitution .and addition products thereof, asfor example and specifically, substitution and addition products of said derivatives, say a hydrogen halid, employed in well known manner.

The catalysts employed inthe instant process arerei'orming" catalysts. By the expression a.

reforming catalyst is meant a catalyst adapted to favorably influence the reactions that are conducive to the induction of toxicity, be the reactions those of addition, substitution or subtraction.

The temperatures in the instant process may be selected over a wide range dependent upon the pressures employed. It is, of course, understood that when relatively low temperatures are employed the lower will be the pressure in order to provide vapor phase operation, and when operating at very low temperatures, pressures only slightly above atmospheric will suffice. Temperatures employable are selected between the limits of 400-850 C. and preferably between 425-550 C. v

Various pressures are employable, as for instance 10, 50, 100 atmospheres or higher, and

' these pressures are so coordinated as'to give total or substantially total vapor phase'operation.

If desired, instead of subjecting the entirety of the starting feed stock to a single toxicity intoxicity and a substantialv percentage of materials of ring structure content, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-650 C. whilst contacting a gas of extraneous source under superatmospheric pressure; unveilducing operation in the vapor phase in the presence of an extraneous gas or gases, the parent material may be divided into a plurality of cuts and these plurality of cuts separately subjected to separate vapor phase toxicity inducing operations wherein the temperatures in each instance are dissimilar, as for example, but not as a re- .strictiomlsubjectingthe highest boiling cut the lowest temperature, etc. The hydrogen partial pressure. or the partial pressure of the gas or gases employed, may vary over wide limits, as for example it may represent a'partialpressure of 5-50% or higher.

The time element is specifically selected so as to jointly provide and/or induce in the overall beneficiated material 1) newly formed materials boiling below 210 C. and (2) specific gravities of materials of cyclic structure content in thestated fractions falling between the stated limits, and preferably between the preferred limits. Using any given feed stock, a few trials will enable those skilled in the art to determine the correct period of treatment when employing definite selections of temperature and pressure.

The process of the instant invention may be practiced in an intermittent processing vessel or in a continuous manner as will become apparent to those skilled in the art after having read the foregoing disclosures.

In the examples shown in the foregoing, one or more phases, etc. of one example may be added to or substituted f or other phase or phases in another example where thesubstitution or addition is obviously workable.

The evaluation of the materials of cyclic structure content and/or aromatics referred to in the foregoing is secured by recourse to the method disclosed under the caption Neutral oils of coal toxicity benefits will flow therefrom. The examples given, and the catalyst and gas linked therewith are for the purposes of illustration only. Minor changes may be made within the scope of theappended claims without departing from ing toxicityin the material under treatment by carrying on the process for a period not substantially in excess of two hours, the period being so selected with reference to the chosen temperature and .pressure as to iointlylprovide newly formed materials boiling below 210' C. and materials of cyclic structure content in the fractions 210-235,C. and 315-355 C. of the beneficisted material having specific gravities falling between the limits of about 0913-10580 and LOW-1.1285, respectively; and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly between210 C. and 355' C., having at least 10-20% residual material boil ing above 315' C., and in thefractions 210-235 C. and 315-355 C. a specific gravity in the mate- 1 rials of cyclic structur content falling between the limits above named. Y

2. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, theprocess which comprises: subjecting said material in vapor phase to a temperatur selected between the limits of 400+650 C. whilst contacting a gas of extraneous source under superatmospheric pres-.

sure; unveilingtoxicity in the material under treatment by carrying on the process fora periOd not substantially in excess of two hours, the period being so selected with reference to the chosen temperature'and' pressure as to Jointly provide newly formed materials boiling" below .210 C. and materials of cyclic structure content in the fractions 235-270 C. and 315-355 C. of the beneficiated material having specific gravities falling between the limits of about 0.935-1.0756 and 1.027-1.1285, respectively; and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 0., having at least 10-20%.residual material boiling above 315 C., and in the fractions 235-270 C. and 315-355 C. a specific gravity in the materials of cyclic structure content falling between the limits above named.

3. In the induction of toxicity into a mixture of petroleum fractions boiling prep onderantly above 270 C., characterized by inherent but inhibited toxicity and a substantial percentage of materials of ring structure content, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-650 C. whilst contacting a 88s of.

extraneous source under superatmospheric pressure; unveiling toxicity in the material under treatment by carrying on the process for a period not substantially in excess of two hours, the period being so selected with reference to the chosubstitution and addition catalytic material.

sen. temperature andl pressure as to "Jointly:-pro vide newly formed material's boiling below 210 210 C. and 355 C. having at least 10-20% residual material boiling above 315" C.,and in the fractions 270-315 C. and. 315355 C. aspecific gravity in the materials .of cyclic structure content falling between the limits above named.

4. Theprocess of claim 1 wherein the gas. of

extraneous source is hydrogen.

5. The process of claim 1 wherein the gas of extraneous sourceis. a hydrogen containing gas.

structure content having *a specific gravity betWeen:about"0.963 and 1.0606; the fraction 270- 315 C. or whichcontains'materials of ring tion "of which-boilingbetween 315-355" C. constructure content'whose specific gravity falls between1about 1.'001 and 1.0783; and thefractains materials 01. ring structure content having 6. The process of claim 1 with inclusion of carrying on the process inrthe pre'senceof a reforming catalyst.

'7. The process of claim 2 with inclusion. ofacar rying on the process in the presence or a: re-, forming catalyst.

8. The process of claim 3 with inclusion of car rying on the process inthe presence of a reforming catalyst.

9. The process of claim 1 with inclusion of carrying onthe process in the presenceof a catalytic material selected from the groupiconsistirfg of oxides and sulfides of heavy metals.

10. The process of claim 2 with inclusion of carrying on the process in the presence of a catalytic material selected from the group consisting of oxides and sulfides of heavy metals.

11. The process of claim 3 with inclusion of, carrying on the process in the presence of a cata a specific gravity falling. between about 1.055 and 1.1135.

19. A petroleum derived. preservative wood impregnantconsisting of in its entirety a destructively cracked product of petroleum fractions, said preservative characterized by apreponderance of materials boiling between 210 C.

, and 355 C., and atleast about 10-20%.materials boiling above 315 C., the fraction 235-270 C.

of which contains materials of ring structure content having a specific gravity between about 01963. and 1.0606; the fraction 270-315 C. of which contains. materials of ring structure content whose specific gravity falls between about 1.001 and 1.0783; and the fraction of which boilins between 315-355 C. contains materials of ring structure content having, a specific gravity falling between about'1.055 and 1.1135.

20. A petroleum derived preservative wood impregnant consisting of in its entirety a dc structively cracked product of petroleum fractions, said preservative characterized by a preponderanceoi' materialsboiling between 210 C. and 355 C., and at least about 10-20% materials boiling above 315 C., the fraction 2704115 C. of which contains materials of ring structure lytlc material selected from the group consisting of oxides and sulfides ofheavy metals.

12. Theprocess of claim. 1 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including substitution and addition. products thereof, ascatalytic: material.

13.;The process of claim 2 with inclusion of carrying on the process. in the presence of a halogen, halid or derivative thereoi',- including substitution and addition products thereof, as

catalytic material.

14. The process of claim 3 with inclusion or carrying on the process in the presence of a.

halogen, halid or derivative thereof, including 15.The process. of claim 1 with inclusion of carrying on the process iii the presence 'of silicious material as catalytic agent.

16. The process of claim 2 with inclusion of carrying on the process in the presence of sill ciousmaterial as catalytic agent. l 17. The process of claim 3 with inclusion of carrying on the process in the presence of silicious material as catalytic agent- 18. A petroleum derived preservative wood impregnant consisting of in its entirety a destructively cracked product of petroleum fractions, said preservative characterized by a preponderance of materials boiling between 210 C. and 355 C.,.and at least about 10-20% materials boiling above 315 C., the fraction 210- 235 C. of which contains materials of ring structure content having a. specific gravity be-- tween about 0.94.1 and 1.0430; the fraction235- 270 C. of which contains materials of ring,

products thereof, as 1 content having a specific gravity falling between the limits of about 1.001 and 1.0783; and the fraction of which boiling between 315-355 C.

contains materials of ring structure content having a specific. gravity falling between about Y 1.055 and 1.1135.

21. The process of inducing toxicity into a petroleum derived material, which comprises: subjecting a mixture of petroleum fractions non-toxic materials boiling above 315 0., ring structure content and inherent but inhibited toxicity to vapor phase cracking conditions whilst contacting a gas of extraneous source at a temperature selected between the limits of about 400-600 C. and a pressure in excess of atmospheric; unveiling toxicity in the materials under treatment by continuing the named cracking operation for a period not substantially in excess of two hours, the period being so selected with reference to the chosen temperature and pressure as tojointly provide newly formed materials boiling below 210 C., andan overall beneficiated material having fractional parts tent having specific gravities falling substantially between the limits noted in the appended tabular data:

Fractions Low limit High limit 235-270 0 Q 0.963 1.0606 27o-s15 o 1. 001 1. 0753 3l5-355 o 1. 055 1.1135

whereby to provide a material of induced toxic properties; and segregating from the overall beneficiated material an oil of the wood preservative type characterized by induced toxic properties, boiling preponderantly between 210 C. and

boiling preponderantly above 270 0., character- "ized by a substantial percentage of relatively which contain materials of cyclic structure con- 355 C. and having at least about 10-20% residual 355 C. contains materials of-ring structure conmatter above 315 C., the fract1on.270-315 C. tent which have a specific gravity falling be of which contains materials of ring structure tween about 1.055 and 1.1135. r j content which have a specific gravity falling JACQUELIN E. HARVEY, JR. between the limits of about 1.001 and 1.0783, 5 ROBERT H, WHITE, J

and the fraction of which boiling between 315- 1 JOSEPH A. VAUGHAN.