US2363245A - Conversion of materials - Google Patents

Description

Patented Nov. 21, 1944 CONVERSION OF MATERIALS Jacquelin 1!. Harvey, Jr., Washington, D. 0., and

Robert H- Whlte, In, and Joseph A. Vaughan,

Atlanta, Ga., assitnors of one-half to said Harvey, Jr., and one-half to Southern Wood Preservin ration of Georgia I Company, East Point, 6a., a corpo- No Drawing. Application December 1, 1943, Serial lie. 512,515

Claims.

The instant invention relates to the production of toxic oils employable as fungicides, insecticides, and for any other service to which toxic oils may be put.

More especially the instant invention relates to the production of toxic oils from mixtures of petroleum fractions characterized by ring structure content. Among such starting materials may be mentioned mixtures of petroleum fractions characterized by ring structure content recovered from petroleum fractions by well known extraction methods including extractive distillation and azeotropic distillation. Also may be mentioned mixtures of petroleum fractions characterized by ring structure content as flowing from thermal and/or catalytic treatment of certain petroleum fractions which includes petroleum fractions having ring structures induced in the course of thermal and/or catalytic treatment, as for example having ring structures induced in the course of one or more thermal and/or catalytic treatments of unusual length, as for example, for periods of from 1-10 hours or more.

An object of the instant invention is the production 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 specifications extant or acceptable to the trade consuming such oil materials.

Another object of the instant invention is the provision of preservative wood impregnants having boiling ranges and residues in accordance with published specifications and/or in accordance with consumer preference.

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

Another object of the instant invention is the unveiling of latent toxicity in mixtures of petroleum fractions having inherent but inhibited toxicity.

Another object of the instant invention is the coordination of process variables so as to provide specific gravities within definite limits in various fractions of the beneficiated material.

Another object of the instant invention is th induction of toxicity in the presence of catalytic materials adapted to favorably influence said toxicity induction.

In the past wood preservative oils of the high temperature coal tar derived type have been employed in quantities greatly exceeding the total of all other wood preservative oils. From the standpoint of availability of said coal tar as the parent product ofvvood preservative oils, it is annuall produced in this country under normal conditions to the extent of five hundred million to six hundred million gallons. This quantity of coal tar is capable of yielding an amount of highly 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 a residue (pitch) which, at best, is 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 distilling tar leaving much to be desired. The net result of this situation obtaining 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 sufficient 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 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 efllciency.

By the term "petroleum aromatic" as used herein and in the appended claims is meant to include mixtures of petroleum fractions characterized by cyclic content and include 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 includes the monocyclic and polycyclic naphthenes and unsaturated hydrocarbon fractions 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, Reactions of pure hydrocarbons" Gustav Eglofl, Reinhold Publishing Corporation, 330 West 42nd Street, New York city, which states:

"Despite the fact that naphthenes or cycloparaiiines 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 world's production in 1934. comparatively little work of a pyrolytic nature has been performed on individual naphthene hydrocarbons or the cycloolefins."

Several oils of cyclic 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 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 Flash, 0, O. C F 290 Fixed carbon per cent 4.9 Pour point F 10 B. S. 8: W -per cent by volume 0.1 S. U, vis. 100 F 151 s. U. vis. 210 F 41 s. F, vis. (a) 77 F 34.5 Carbon residue 6.8 Per cent aromatics and unsaturates 82.4 Sol. in CS: 99.8 Loss 50 grams. hours, 325 F 8.9 Residue of 100 pene per cent 37.5 A. S. 'I. M. distillation:

I. B. P F 518 10% rec. (d) F 51B rec. F 589 rec. (d "F 614 rec. (17 "F 637 rec. "F 660 rec. "F 675 Maximum.

In the foreaoing tabular data P. M. C. 0. means Pensky- Martin Closed Cup: C. O. C. means Cleveland Open Cup.

Upon evaluat n the foregoing oil for its toxicity to wood destroying fungi (Madison 517), it was found that this oil did not inhibit the growth of the fun i named at a concentration of up to and including 10%.

It is now discovered that the oil above named or other oils of cyclic 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 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 toxic properties in the vapor phase, with or without catalysts, to materials exhibiting a more pronounced toxicity than the parent feed stock.

In former attempts to provide a wood Preservative oil of petroleum origin by processes analogous to that of the present invention, the feed stock utilized as starting material or the process adopted, or both, were such as to provide an oil boiling about at 270 C. or in another instance with only 0.8% 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 distillation range:

Oil, per Distillation cent The oil above named after its impregnation into cellulosic materials to be preserved is entirely too volatile to provide an acceptable preservative impregnant.

It is, therefore, an object of the instant invention to provide a vapor phase process which yields a reformed petroleum oil characterized by induced toxic properties having at least about iii-20% residual matter above 315 C.

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 change in molecular structure which occurs during the practice of the present process. Thus "a reformed petroleum oil is a modified, converted and/or transformed oil, and includes an oil reformed by substitution, addition and/or subtraction from the moiecular structure of the feed stock.

We have discovered that some of the mixtures of petroleum fractions have very substantial residual matters 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 hiah boiling oils that have substantial residual matters above 315 C. or 355 C., we are able by subjecting them to vapor phase reforming conditions to simplify and stabilize the structure whilst providing in the finally beneficiated oil substantial residual materials above 315 C. or 355 C., at the same time unveiling the toxic qualities. and if the process is carried to an extent to provide specific gravities in fractional parts of the beneficiated material as noted in the following tabular data:

Fractions Low limit High limit 0. 801 l. 0048 0. 850 1. 0315 0. 914 l. 0691 0. 973 l. 1175 and preferably carried to the extent to provide specific gravities in fractional parts of the beneflciated material as noted in the following tabular data:

from the beneflciated material the excess oi fractions boiling below 210 C. as required by commercial specifications (or specifically whatever other low boiling temperature is specified), we are able to use the residue as a commercial wood preservative impregnant with acceptable toxic properties. In the event this material has too great a residue at 355 C. or has too high a coke residue for any particular service the desired preservative oil may be secured as an extract, distillate or residue having no excess of the desired materials at 355 C. or an excess of coke residue.

The following examples will illustrate several modes of practicing the process of the instant invention.

Example 1.-A so-called petroleum aromatic, relatively non-toxic, having substantially no ends boiling below 270 0., materials boiling at about 355 0., specific gravities of 0.9251 and 0.9537 in the fractions 270-315 C. and 315-355 0., respectively, is subjected in the vapor phase to a temperature of 500 C. whilst under a pressure of 1,000 pounds for such a length of time as to provide newly formed materials boiling below 210 C. and in fractional parts of the beneficiated oil a specific gravity falling between the limits noted in the following tabular data:

Fractions Low limit I High limit 2l0-Zi5 C 0.801 1.0048 315-355 C 0. 973 i. 1175 and preferably for such a length of time as to provide in the fractional parts of the beneflciated oil a specific gravity falling between the limits noted in the following tabular data:

Fractions i Low limit High limit 21o-2a5c 5 0.820 0.9m 3l5-355 C 1.001 1.1025

(Madison 51'?) than the parent feed stock to such 55 an extent as to be useful as wood preservative. The induction and/or provision of the specific gravities in the fractional partsof the beneficiated oil mentioned above is a valid test for the induction of toxicity in the fractions referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment.

The overall beneficiated material may be used as a preservative or for any other purpose to which toxic oils are put. If desired. a wood preservative impregnant complying with specifications extant or of consumer preference,-may be segregated from the overall beneflciated oil as a stabilized residual, distillate or extract, and in the event the extract has non-permissible low boiling ends, the extract may be stabilized to the desired extent by removal of low boiling ends.

As illustrative of wood preservative impregnants that are meeting with consumer acceptonce and which may be segregated from the overall beneficiated material of the instant process. the following tabular data show several published specifications:

Woon Pamaava'rrvs Imrnmnm'rs Specifications 1. American Wood Preservers' Association it. Up to 210 0., not more than 5% 1). Up to 235 0., not more than 25% 2. American Wood Preservers' Association a. Up to 210 0., not mor than 1% b. Up to 235 0., not more than 10% 0. Up to 355 0., not less than 65% 3. American Wood Preservers' Association a. Up to 235 0., not more than 0. Up to 300 0., not more than 16%% c. Up to 355 0., not less than 45% 4. American Wood Preservers Association :1. Up to 210 0., not more than 8% b. Up to 235 0., not more than 35% 5. American Wood Preservers Association a. Up to 210 0., not more than 10% 0. Up to 235 0., not more than 40% 6. American Wood Preservers Association 0. Up to 210 0., not more than 5% b. Up to 235 0., not more than 15% 7. Prussian Ry.

(1. Up to 0., not more than 3% b. Up to 200 0., not more than 10% 0. Up to 235 0., not more than 25% 8. National Paint Varnish 8r Lacquer Association #220 a. 5% at 162 0. b. 97% at 270 0. 9. Southern pine shingle stain oil a. 5% at, 137 0. b. 95% at 257 C. Neville shingle stain oil a. I. B. P., 150 C. b. 5% at 205 0. c. 95% at 292 0. 11. Carbolineum 270 0., I. B. P.

By the nature of the process it is obvious that modifications of existing specifications or other and more exacting specifications may be met.

As mentioned in the foregoing the process variables are so coordinated as to jointly provide newly formed fractions boiling below 210 C. and a preferred limit of specific gravities in the fractions 210-235 C. and 315-355 C. of the beneficiated oil.

In lieu of jointly controlling the process as to provide the aforenamed specific gravities in the 210-235 0. and 315-355 0. fractions of the beneficiated oil, the proper control may be evidenced in accordance with the following example:

Example 2.-Select a material comparable in chemical analysis and boiling range to the feed stock mentioned in Example 1. Subject same in vapor phase to a temperature of 505 C. whilst under a pressure of 2,000 pounds. Carry on the process for such a length of time as to jointly provide (l) newly formed oils boiling below 210 0. and (2) in the fractions 235-270 0. and 315-355" 0. specific gravities falling between the limits noted below:

and preferably between the following limits:

Operating under the conditions above named a period of about one and one-half hours will illus.. tratively serve to provide a. percentage of newly induced materials boiling below 210 C. and specific gravities falling between the preferred limits in the fractional parts of the beneficiated 011 above noted.

At the end of the named treatment period the oil is condensed and inspected, and is found to have induced toxic properties. The induction of the specific gravities in the fractional parts of the beneficiation stated in the present example is a valid test for the induction of toxicity in the fractions referred to, and further is an indication that toxicity has been induced in other fractions of the material under treatment.

Example 3.Se1ect a material comparable to the feed stock mentioned in Example 1. Subject same in vapor phase to a temperature of 525 C. whilst under a pressure of 3,000 pounds. Carry on the process for such a length of time as to jointly provide and/or induce (1) newly formed oils boiling below 210 C. and (2) in the fractions 2'70-315 C. and 315-355 C. specific gravities falling between the limits noted below:

and preferably between the following limits:

Fractions Low limit High limit 270-315" C 0. 942 1.0541 3l5-355 C 1. 001 l. 1025 Operating under the conditions above named a period selected between the limits of 30 and 40 minutes will illustratively serve to provide a percentage of newly induced materials boiling below 210 C. and specific gravities falling between the preferred limits in the fractional parts of the beneflciated oil noted above.

When the period of treatment has been completed the oil is cooled, condensed and inspected. It will be found that the overall beneficiation requires a smaller concentration for given growth inhibition of wood destroying fungi than the parent feed stock to such an extent as to be useful as a wood preservative. The induction of the specific gravities in the fractional parts of the beneficiated oil 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 induced in other fractions of the material under treatment.

Example 4.-Select a petroleum aromatic extract boiling preponderantly above 270 C. and materials boiling at least as high as about 355 C. Subject same in vapor phase to a temperature of 510 C. whilst under a pressure of 1500 pounds. Carry on the process for such a length of time as to jointly provide (1) newly formed oils boiling below 210 C. and (2) in the fraction boilin between 315 C. and 355 C. a specific gravity falllng between the limits of 0.973 and 1.1175, and

preferably between the limits of 1.001 and 1.1025.

Carrying on the process under the conditions of the instant example a period of about on hour and 15 minutes will illustratively serve to provide a percentage of newly induced materials boiling below 210 C. and a specific gravity falling between the preferred limits in the 315-355 C. fraction of the beneflciation.

At the end of the processing period the oil is cooled, condensed and inspected, Find in the beneflciation a toxicity in excess of that of the parent feed stock. The induction of the specific gravity between the limits stated in the materials boiling between 315 C. and 355 C. 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.

As noted in the tabular data shown in the foregoin giving boiling range specifications for oil wood preservatives, many preservative oils are possible of segregation from the beneficiated feed stock of induced toxicity. As for example, an oil boiling within the carbolineurn preservative range,

in which instance the segregation would have an initial boiling point of about 270 C., the fractions 270-315" C. and 315355 C. of which, would have specific gravities falling between the limits of 0.914-1.0691 and 0.973-L11'15, respectively,

Example 5.Practice the process of Example 1 with a molybdenum oxide catalyst.

Example 6.Practice the process of Example 2 with a chromium oxide catalyst. Example 7.--Practice the process of Example 3 with a vanadium oxide catalyst.

Example 8.Practice the process of Example 4 with a tin oxide catalyst.

Example 9.Practice the process of Example 1 with a molybdenum sulfide catalyst.

Example 10.Practice the process of Example 2 with a chromium sulfide catalyst.

Example 11.-Practice the process of Example 3 with a vanadium sulfide catalyst.

Example 12.Practice the process of Example 4 with a tin sulfide catalyst.

Example 13.--Practice the process of Example 1 with the coprecipitated oxides of copper and chromium as catalytic materials.

Example 14.Practice the process of Example 2 with tin chloride as catalytic material.

Example 15,-Practice the process of Example 3 with aluminum chloride as catalytic material.

Example fit-Practice the process of Example 4 with iodine as catalytic material.

Example 17.-Practice the process of Example 1 with iodoform as catalytic material.

Example 18.Practice the process of Example 2 with hydriodic acid as catalytic material.

Example 19.Practlce the process of Example 3 with chlorine as catalytic material.

Example 20.--Practice the process of Example 4 with bromine as catalytic material.

Example 21.Practice the process of Example 1 with a hydrogen halid as catalytic material.

Example 22.--Practice the process of Example 2 with ammonium chloride as catalytic material.

Example 23.-Practice the process of Example 3 with pelleted bentonite clay as catalytic materlal.

Example 24.Practice the process of Example 4 with activated Attapulgus clay as catalytic material.

Example 25.Practice the process of Example 1 with a silica hydrogel as catalytic material.

Example 26.Practice the process of Example 2 with a silica hydrogel impregnated with an aluminum salt as catalytic material.

Example 27.--Practice the process of'Example 3 with bentonite and an adsorptive clay as catalytlc materials.

Example 28.-Practice the process of Example 4 with a siliceous material impregnated with a metallic oxide as catalytic material.

Example 29.-Practice the process of Example 1 with a siliceous material impregnated with a metallic sulfide as catalytic material.

Example 30.Practice the process of Example 2 with coprecipitated alumina and chromia hydrogels as catalytic materials.

Example 31 .--Practice the process of Example 3 with a synthetic silica-alumina gel as catalytic material.

In the Examples 1-4, inclusive, instances have been cited wherein the starting feed stocks have very small percentages, if any, of materials boiling below 270 C. The instant process, as illustrated by Examples 1-4 incl sive, or others, is adapted to thermally treat in vapor phase, within the processing limits herein disclosed, a mixture of petroleum fractions characterized by relatively little toxicity, as for example the so-called aromatic extracts, having fractions boiling within the wood preservative range and thereby provide an overall treated oil requiring a smaller concentration for a given growth inhibition of wood destroying fungi than the starting feed stock to such as extent as to be useful as a wood preservative impregnant.

Various catalysts assist in the reforming, transforming, modifying and/r converting of the starting petroleum oils whereby to provide materials of induced toxic properties. Many catalysts other than noted in the foregoing are also employable as effective substances. Viewed broadly, the oxides and sulfides of metals may be used as well as the carbonates and metals themselves. Cellulosic materials and carbon, activated or otherwise may be used with advantage. Especially effective as catalytic materials are oxides and sulfides of metals, siliceous materials, halids, halogens and derivatives thereof, including specifically substitution and addition products thereof, as for example and specifically substitution and addition products of said derivatives, say a hydrogen halid, employed in Well known manner.

The catalysts employed in the instant process are reforming" 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, subtraction or substitution.

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 400-600 0., and preferably between 425500 C.

Various pressures are employable as for instance 10, 50, mo atmospheres or higher, and these pi ssures are so coordinated with the temperatures selected 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 inducing operation in the vapor phase, the parent material may be segregated 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 restriction, subjecting the highest boiling cut to the lowest temperature, etc.

The time element is specifically selected so as to provide in the overall beneficiated material newly formed materials boiling below 210 C. and specific gravities in the fractional parts described falling between the stated limits. Using any given feed stock, a few trials will enable those skilled in the art to determine the correct period of treatment.

It is to be understood that the treatment periods shown in Examples 1-4 are for purposes of illustration only. With some feed stocks the period of treatment necessary to provide the stated specific gravities in fractional parts of the material undergoing treatment may be only a few minutes. Thus the period of treatment in the instant process may be viewed broadly as that time required to induce (a) newly formed materials boiling below 210 C., and (b) specific gravities in fractional parts of the beneficiation falling between the disclosed limits.

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 for other phase or phases in another example where the substitution or addition is obviously workable.

Minor changes may be made within the scope of the appended claims without departing from the spirit of the invention. In the claims aflixed to this specification no selection of any particular modification is intended to the exclusion of other modifications thereof and the right to subsequently make claims to any modification not covered by these claims is expressly reserved.

We claim:

1. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C., characterized by a substantial percentage of "petroleum aromatics, and inherent but in-' hibited toxicity, the process which comprises:

subjecting said material in vapor phase to a temperature selected between the limits of 400-600 C.; unveiling toxicity in the material under treatment by carrying on the process for a period not substantially 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. and specific gravities in the fractions 210-235 C. and 315-4355" C. of the beneficiated material, falling between the limits of about 0.801-l.0048 and 0.9'i'3-l.l175, respectively; and segregating from the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C, and 355 C., said oil characterized by induced toxic properties and at least about 10-20% residual matter above 315 C., the fractions 21!)- 235" C. and 315-355 C. of which have specific gravities falling between the limits above noted.

2. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 0., characterized by a substantial percentage 01' "petroleum aromatics," and inherent but inhibited toxicity, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600" C.; unveiling toxicity in the material under treatment by carrying on the process for a period not substantially 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. and specific gravities in the fractions 235-270 C. and 315-355 C. of the beneilciated material, falling between the limits of about 0.850-l.0315 and 0.973-1.11'75, respectively; and segregating from the beneflciated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxic properties and at least about 10-20% residual matter above 315 C., the fractions 235- 270 C. and 315-355 C. of which have specific gravities falling between the limits above noted.

3. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C. characterized by a substantial percentage of petroleum aromatics, and inherent but inhibited toxicity, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600" C.; unveiling-toxicity in the material under treatment by carrying on the process for a period not substantially in excess of about one hour, the period being so selected with reference to the chosen temperatures and pressure as to jointly provide newly formed materials boiling below 210 C. and specific gravities in the fractions 270-315 C. and 315-355 C. of the beneflciated material, falling between the limits of about 0914-10691 and 0.973-L1175, respectively; and segregating trom the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 365 C., said oil characterized by induced toxic properties and at least about 10-20% residual matter above 315 0., the fractions 270-3l5 C. and 315-355 C. of which have specific gravities falling between the limits above noted.

4. The process of claim 1 with inclusion 0! CERTIFICATE OF CORRECTION.

Patent No. 2, 363 ,2ii5.

carrying on the process in the presence of a reforming catalyst.

5. The process of claim 2 with inclusion of carrying on the process in the presence or a reforming catalyst.

6. The process or claim 3 with inclusion of carrying on the process in the presence of a reforming catalyst.

7. The process 01' claim 1 with inclusion of carrying on the process in the presence oi a catalytic material selected from the group consisting of oxides and sulfides 0! heavy metals.

8. 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 oi heavy metals.

9. The process of claim 3 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.

10. The process of claim 1 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, includin substitution and addition products thereof, as catalytic material.

11. The process of claim 2 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including substitution and addition products thereof, as catalytic material.

12. The process of claim 3 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including substitution and addition products thereof, as catalytic material.

13. The process of claim 1 with inclusion of carrying on the process in the presence of siliceous material as catalytic agent.

14. The process of claim 2 with inclusion 01' carrying on the process in the presence of siliceous material as catalytic agent.

15. The process of claim 3 with inclusion or carrying on the process in the presence of siliceous material as catalytic agent.

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

November 21, 191 1;.

JACQUELIN E. HARVEY, JR., ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 59, for "10% rec. l. 518" read "10% rec. Q F. 565; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th dayof February, A. D. 191,6.

(Seal) Leslie Frazer "A m. Acting Commissioner of Patents.

270 0., characterized by a substantial percentage 01' "petroleum aromatics," and inherent but inhibited toxicity, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600" C.; unveiling toxicity in the material under treatment by carrying on the process for a period not substantially 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. and specific gravities in the fractions 235-270 C. and 315-355 C. of the beneilciated material, falling between the limits of about 0.850-l.0315 and 0.973-1.11'75, respectively; and segregating from the beneflciated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., said oil characterized by induced toxic properties and at least about 10-20% residual matter above 315 C., the fractions 235- 270 C. and 315-355 C. of which have specific gravities falling between the limits above noted.

3. In the induction of toxicity into a mixture of petroleum fractions boiling preponderantly above 270 C. characterized by a substantial percentage of petroleum aromatics, and inherent but inhibited toxicity, the process which comprises: subjecting said material in vapor phase to a temperature selected between the limits of 400-600" C.; unveiling-toxicity in the material under treatment by carrying on the process for a period not substantially in excess of about one hour, the period being so selected with reference to the chosen temperatures and pressure as to jointly provide newly formed materials boiling below 210 C. and specific gravities in the fractions 270-315 C. and 315-355 C. of the beneflciated material, falling between the limits of about 0914-10691 and 0.973-L1175, respectively; and segregating trom the beneficiated material an oil of the wood preservative type boiling preponderantly between 210 C. and 365 C., said oil characterized by induced toxic properties and at least about 10-20% residual matter above 315 0., the fractions 270-3l5 C. and 315-355 C. of which have specific gravities falling between the limits above noted.

4. The process of claim 1 with inclusion 0! CERTIFICATE OF CORRECTION.

Patent No. 2, 363 ,2ii5.

carrying on the process in the presence of a reforming catalyst.

5. The process of claim 2 with inclusion of carrying on the process in the presence or a reforming catalyst.

6. The process or claim 3 with inclusion of carrying on the process in the presence of a reforming catalyst.

7. The process 01' claim 1 with inclusion of carrying on the process in the presence oi a catalytic material selected from the group consisting of oxides and sulfides 0! heavy metals.

8. 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 oi heavy metals.

9. The process of claim 3 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.

10. The process of claim 1 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, includin substitution and addition products thereof, as catalytic material.

11. The process of claim 2 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including substitution and addition products thereof, as catalytic material.

12. The process of claim 3 with inclusion of carrying on the process in the presence of a halogen, halid or derivative thereof, including substitution and addition products thereof, as catalytic material.

13. The process of claim 1 with inclusion of carrying on the process in the presence of siliceous material as catalytic agent.

14. The process of claim 2 with inclusion 01' carrying on the process in the presence of siliceous material as catalytic agent.

15. The process of claim 3 with inclusion or carrying on the process in the presence of siliceous material as catalytic agent.

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

November 21, 191 1;.

JACQUELIN E. HARVEY, JR., ET AL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows: Page 2, first column, line 59, for "10% rec. l. 518" read "10% rec. Q F. 565; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 20th dayof February, A. D. 191,6.

(Seal) Leslie Frazer "A m. Acting Commissioner of Patents.