US2363237A - Production of useful materials - Google Patents

Description

Nov. 2l, `1944.

J. E. HARVEY, JR

PRODUCTION OF USEFUL MATERIALS Filed oct, 91.1942

.ifea/va cam/mm1 50M-M' armar/wy is theiinduction l Prasad Nov: 21, 1944 raoDUc'rroN or USEFUL MATERIALS t Jacquelin E. Harvey, Jr-.,

signor of one-half to S lng Cinpany, East Po Geor Washington, D. C., asouthern Wood Preservint, Ga., a corporation of Application October 9, 1942, .Serial No. 461,500

4 claims. (c1. 19H9) The instant invention relates to th'e 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 productionV 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 extractiva distillation and azeotrcpic distillation. Also may be mentioned mixtures of petroleum fractions characterized by ring structure content as owing 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/croatalytic treatments of unusual length, as for example, for periods of 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 Voils of thepreservative 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 evaporation rates under given conditions acceptable to the trade.

Another object of the instant invention is the reforming of the above named mixtures of hydrocarbons or others whereby to induce toxicity.

Still another object of the instant invention is the induction of usable toxicity in the p1" enceof a gas or gaseous mixtures.

' Yet another object of the instant invention of toxicity in the above named mixtures of petroleum fractions or others, the while or afterwards providing specific means which guard against diminution in saidVV toxicity.

Another object of the instant invention is the release of latent `toxicity in the above named mixtures of petroleum fractions or others.

Another object of the instant invention'is 'the release of latent toxicity in the above named mixtures of petroleum fractions or others byh in-` creasingl the water solubility of said materials.

Other objects of the instant invention will be apparent as flowing from the following disclosures and examples.

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 taras 'the parent material of wood preservative oils,

it is annually produced in this country under f normal conditions to the extent of live hundred million to six hundred million gallons,` This quantity of coal tar is capable of yielding an amount of highly ellective wood preservative oils which would make this country self suflicient 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 (pitchl which,

at best, is a. lowpriced 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 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 prot. Accordingly, over a period of years severa-l hundred million gallons of creosote oil have beenimported into this country. That such a situation should obtain is apparently a paradox in that we annually produce a quantity of high temperature coal tarl 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, 4U Rector Street, New York city, before the Franklin Institute, Philadelphia, Pennsylvania, in Decemt ber, 1932. 'Ihe 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 vbythe petroleum industry, and the high boiling oils of aromaticv content produced by this industry have for several years been tested for their wood preservative efficiency.

`By the term petroleum aromaticv as used herein and in the appended `claims is meant to include mixtures of petroleum fractions characterized by cyclic content and includes specifically various forms and types of naphthenes found in However, very little work has been done on thesev materials. Such `a fact is borne outon page 667 v fReactions of pure hydrocarbons Gustav Egloif,

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

Despite the fact that naphthenes or cycloparaines 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 cycloolens.

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

Gravity 10.8 Flash, P. M. C. C I F 295 Flash, C. O. C. ...l F 290 Fixed carbon L per cent-- 4.9 Pour point F -10 B. S. & W per cent by volume- 0.1 S. U. vis. v100" F 151 S. U..vis. (d) 210 F 41 S. F. vis. 77 F 34.5 Carbon residue 6.8 y Per cent aromatics and unsaturates 82.4 Sol. in CS2 99.8 Loss. 50 grams, 5 hours, 325 F 8.9 Residue of 100 pene per cent 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 50% rec. F 660 60% rec. F 1 675 1Maximum.

In the foregoing tabular data P. M. C. C. means Pensky- Martin Closed Cup; C. 0. 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 inhibit the growth of the fungi 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. modi'ed and/or converted to oils of a more toxic nature having charcal and chemical characteristics which to a great degree indicate that the new product would have good life service after its impregnation into the material tolbe preserved.

The following examples will illustrate several modes of practicing the process of the present invention. The single g`ure of thedrawing repproduced by well known extraction methods isv (1) subjected to a thermal and/0r catalytic treat# ment at a relatively high pressure and thereafter 2) subjected to further thermal and/or catalytic treatment at a relatively low pressure whereby to provide a newly formed oil having less than 30% but more than 5%, and preferably more than 10% saturates in the materials boiling between 270 C. and 355 C., the finally converted material is adapted to yield an oil of the wood preservative type characterized by induced toxic properties,v substantial residual matter above 315 C. or 355 C. and a specific gravity falling between the limits of 0.85 and 1.10, preferably between 0.95 and 1.05.

Example 1.A mixture of petroleum fractions characterlzed by cyclic content selected from the group consisting of aromatic extracts, extractive distillates, azeotropic distillates and fractions having induced cyclic structures as flowing from thermal and/or catalytic action. repeated or otherwise, as for example an aromatic extract of a mixture of high boiling petroleum Ifractions. said extract boiling entirely above 240 C., characterized by more than 30% saturates in` the materials boiling between 270 C. and 355 C. and relatively little toxicity is reformed, modified and/or converted by the present process and toxicity induced therein.

According to the process of the present invention the feed stock is-reformed. modified and/or converted in the liquid phase at a temperature selected between the limits of 400-600" C., as for example at a temperature of 450 C. whilst under a pressure of 1.000 pounds for a period of 30 minutes. The partially beneflciated material is passed to a-second treating zone where without substantial reduction in temperautre it is maintained at a pressureof 500 pounds for a period of 30 minutes.

The beneiiciated material is cooled and inspected. and found to have less than 30% but more than 5% saturates in the 270-355 C. fraction anda substantial percentage of newly formed Vfractions boiling below 210 C. The oil is also bilized to provide a residual as an oil of the wood preservative type having induced toxic properties, about 5% boiling at 210 C. and in excess of 5% boiling above 355 C.

Other things being equal, the toxicity of a preservative oil is proportional to its percentage of unsaturates, that is to say, as the Percentage of unsaturates increases, the toxicity of the preservative becomes more pronounced. It is well understood in the art that the materials in a preservative impregnant boiling between 270 C. and 355 C. are among the least toxic. However, it is discovered that if an attempt is made to convert the entiretyof the materials boiling between 270 C. and 355 C. into unsaturates, reactions take place that' are prejudicial to the conversion of 'aseaaav the oil `to toxic substances, as for example there occurs inordinate gasification and/or reformed high boilingmaterials that approach fixed car:

bon as anupper limit.

It is, therefore, an important part of the present process to so control and coordinate the reforming, modifying and/or converting action in both of the process steps as to provide a treated 4,

material having less than 30% but more than 5%, andpreferably more than 10% saturates in the fraction boiling between 27.0 C. and 355 C. Such acontrol of saturates in the named fraction has the eiect of making toxicity more pronounced while at the same Atime obviationg the operating ills above mentioned.

Example 2,-A mixture of petroleum fractions boiling prependerantly above 210 c. having substantial residual matter above 355 C. charactel-ized by cyclic structures and relatively little toxicity is charged to a pressure vessel and maintained at a'temperature of 440 C. whilst under a pressure of 2,000 pounds for a period of 25 minutes. At the end of the named period thefraction less than 25% but more than 5% saturation. Further inspection discloses that the material has induced toxicity. The overall beneciated material is fractionally distilled to provide a distillate as an oil of the wood preservative type characterized by induced toxic properties boilingL 11/2% at 235 C.and with 15% boiling above 355 C.

'I'he wood preservative wimpregnant of the presi ent process which is recovered from the overall processed oil is not circumscribed by any single boiling limitation, but is rather circumscribed by published wood preservative specifications and/or the preference and acceptance of wood preservative consumers. g

Accordingly, after the stated. oilshave been processed to provide materials of induced toxic properties in the manner stated herein, the preservative impregnant may be segregated from the benefited material to provide a residual, distillate or extract which conforms to any of the following published woodpreservative specifications:

Woon Passsnvmo IMPxrlcNAN'rs i Specifications 1. American Wood 4Preservers Association a. 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% b. Up to 235 C., not more than 10% c. Up to 355 C., not less than 65% 4. American Wood Preservers Association a. Up to 210 C., not more than 8% b. Up to 235 C., not more than 35% 5. American Wood Preservers Association a. Up to 210 C., not more than 10% b. Up to 235 C., not more than 40% 6. American Wood Preservers Association a. Up to 210 C., not more than 5% b.' Up to235 C., not more than 15% 7. Prussian Ry. d. Up to 150 C., not more than 3% b. Up to 200 C., not more than 10% c. Up to 235 C., not more than 25% 8. National Paint lVarnish and Lacquer Association #220 a. 5% at 162 C. b. 97% et 270 c.

9. Southern pine shingle stain oil a. 5% at 137 C.

b. at 257 C.

v1o. Neville shingle stein ell a. I. B. P., C. I b. 5% at 205 C. c. 95% at292 C.

11. orbelmeum -.-270 c., I. B. P.

rapidly brought up to a temperature of 445 C. lwhilst under a-pressure of 1800 pounds. The

thus heated material isdischarged to a vessel4 where it is held under a temperature `of substantially 455 C. whilst in the presence of water gas at a pressure of 1200 pounds for a period of one hour. At the end ofy the hour period` the treated material is cooled and ,inspected and found to have induced toxic properties. It is also found that a substantial percentage of fractions boiling below 210 C. has been inducedand that the materials boiling between 27o-355 C. have less than 25% but more than 5% saturates.

The material of induced toxic properties is then stabilized to provide a residual as an oil of the wood preservative type characterized by induced toxic properties, boiling 1% below 210 C. and having in excess of 10% materials boiling above 315 C.

Instead ofemploying water Vgas as the extraneous gas, hydrogen may be employed and the partial pressure of the gases may be 5-50% or more. Also employable as extraneous gases are methane and its homologues, various reiinery gases, inert gases such as nitrogen and 4those containing carbon. Various purposes are accomplished by the employment of the gas of 'traneous source in both tioned, the thermal protection of the material undergoing reformation, conversion, transformation and/or modification in order'to avoid excess carbonaceous deposits and/or conversion of fractional parts of the material to forms that are substantially non-toxic. If a gas reactive under the process conditions is employed, this gas may also` assist in 'the accomplishing of the stated purpose orothers. The employment of the extraneous gas yor gases noted. separately or in admixture, are to be in one mode of operation, specifically read into all examples in either or both of the process steps. now from the employment of the gas of exof the process steps, but gas in only one step has toxicity induction, as for the employment ofthe a partial benefit toward example by employing Particular benefits the gas .of extraneous` source in the final step above noted which is characterized by a reduction in pressure.

Example 4.-A furfural extract of high boiling petroleum fractions, said extract boiling entirely above 250 C. having substantial residual matter above 355 C. and relatively little toxicity is passed through a series of tubes set in a furnace and rapidly brought up to a temperature of 470 C. whilst under a pressure of 2500 pounds. The thus seated material is discharged to an enlarged vessel and held at a temperature of substantially {15G-460 C. whilst under a pressure of 1500 pounds for a period of one hour.

The overall beneflciated material is fractionally distilled to recover a distillate as arr'oil of the wood preservative type characterized by induced toxic properties boiling 90% between 210 C. and 355 C. l

Inspection of the preservative distillate dis-` closes that the 27o-355 C. fraction has more than 5% but less than 30% saturates.

Example 5.-A flashed petroleum residuum boiling entirely above 270 C. and With/ substantial residual matter above 355 C; characterized by cyclic structures and. relatively little toxicity is passed through a' series of tubes set in a furnace andrapidly brought up to a temperature of 430 C. whilst under'a pressure of 750 pounds. Thereafter, the heated material is discharged into an enlarged zone and maintained at a pressure of 300 pounds where without substantial reduction of temperature it is held forxsuch a period as to' provide more than 5% but less than 25% .saturation in the 270-355 C. fraction.

The heat treated material is fractionally distilled `to recovera distillate having substantially no ends boiling below 200 C. and with 75% boiling up to 315 C. Upon inspection of the dis- Itillate it is found to have toxic properties in excess `of the parent feed stock.

Instead of recovering the oil of the instant process as a distillate or stabilized residual, the overall beneciated oil may be extracted with a suitable solvent, as for' example with phenol, furfural, liquid lsulfur dioxide, cresol, xylol, cresylic acid, aniline, nitrobenzene, chloroaniline. nitrotoluene or the like. After thebeneciated material has been extracted the raflinate is then discarded. The solvent isxremoved from the ,extract and the preservative oil of the instant process recovered from the extract as a stabilized I residual or al distillate. However, if the extract has a boiling range in accordance with published wood preservative specifications tabulated in the foregoing, the overall extract may be used as the oil of the instant process.

Example 6.--A petroleum oil of induced cyclic structures boiling preponderantly above 210 C.,

having' in excess of 20% residual matter boiling above 355 C. and relatively little toxicity is brought up to a temperature of 450 C. whilst under a pressure of 3,000 pounds and held at that temperature for a period of 30 minutes.

atively low toxicity as compared to materials boiling below that temperature. The beneficiated material is cut at a temperature of 270 C. and the high boiling materials heat treated at a temperature of 440 C. whilst under a pressure of 3,000 pounds for a period of 20 minutes. After the 20 minute period the material is discharged into an enlarged zone Where it is held without a substantial reduction of temperature under a pressure of 2,000 pounds for a period of 20 minutes. o

The thus heat treated residual is commingled with the once beneficiated fractions boiling below 270 C. whereby to provide an overall comminglement having a toxicity in excess of the.

overall once beneficiated oil. The commingledmaterials are fractionally distilled to recover a distillatey as an oil of the wood preservative" type characterized by induced toxic properties having` about 3% distilling below 150 C., substantial residual matter boiling above 355 C. and less than but more than 5% saturates in the materials boiling between 270 C. and 355 C.

- Instead of retreating the entirety of the materials boiling above 270 C. only a portion thereof may be retreated and 'certain toxicity benefits'will flow therefrom.

Instead of commingling the entirety of the retreated residual and the entirety of the temporarily discarded and once treated low boiling fractions, only a portion of these two materials may be commingled, lprovided that the conimingled fractional parts provide the desired preservative oil or furnish an oil capable of yielding the desired preservative impregnant.

The temperatures employable in the process steps are lselected between the limits of 350- 600 C., and preferably between 40o-500 6. 4 The pressures in the first step of the process are in excess of atmospheric and are` preferably inexcess of 20 atmospheres, say pressures selected between the-limits of 50-200 atmospheres. However, pressures as rhigh as practicable may be employed. In the second step of the process, pressures in excess of atmospheric l `are generally preferred. However, in the event,

it is elected to operate the lfirst and relatively high pressure step at, say a pressure of from 5 to 50 atmospheres, the relatively low pressure in the second step may be at atmospheric pressure, or below if desired.

The time element of the instant process is so coordinated with the overall pressures in both steps, the relative reduction of pressure in the second step and thev temperatures in both steps as to provide in the 270-355" C. fraction of the overall finally beneflciated material a saturation less than 30% but more than 5%. A few trials withany selected starting material will enable those skilled in the art to provide the correct coordination.

Various catalysts assist in the heat treating of the starting petroleumv oils whereby to provide induced toxic properties. These catalysts are employable in either the vapor phase or the liquid phase, or both, and this provision may in one mode of operation be specifically read into either or both of the steps of all examples.

Among such catalysts may be mentioned the various metals, their oxides, sulfides and carbonates, cellulosic materials and carbon, acti- Vated or otherwise. Various silicious materials including the various clays shaped or prepared Y in appropriate form may also be employed. Various synthetic gels, as for instance the well y A :,aoaaav known hydrogels may be employed as catalytic" materials including speciiically cipitates properly prepared.

gelatinous pre- Also employable are halogens, halids and derivatives thereof, in- Y cluding speciilcally substitution and addition products thereof, as for example and speciilcally substitution and addition products of said derivatives, say a hydrogen halid or the like.

These catalytic materials above mentioned are eiective in promoting the provision of the oils of the wood preservative type having induced toxic properties and these catalytic materials separately, in admixture or two or more employed simultaneously, are to be in one mode of operation. speciiically read into all examples in either or both of the process steps.

Carrying on the process in either or both oi the steps in the presence of catalytic materials has the eiect of smoothing out the operation,

shortening the time necessary for toxicity induction and/or making operations permissible at lowered temperatures. The most eiective catalysts are silicious materials, activated carbon, halogens and derivatives thereof cellulosic materials, syntheticgels and the oxides, suldes and-carbonates of metals.

I claim:

1. In the production of a preservative wood impregnant from the mixture of petroleum frac.- tions boiling preponderantly above 270 C. characterized by a substantial percentage of i materials of cyclic structure content andinherent but inhibited toxicity, comprises: heat treating tions at a temperature limits oi' about 370600C. while under a relatively high pressure ior'a period not in excess of about `30 minutes; thereafter heat treating said material in entirety at a temperature selected between the limits above namedat a relatively low pressure for a period not in excess o! about onev hour; inducing toxicity into the materials under treatment by coordinating the time oi treatment in both periods of heating as to provide in the converted material less than about 30%.but more than about 5% saturation in the 270-355" C. fraction; and segregating from the beneciated material an oil of the wood preservative type boiling preponderantly between 210 C. and 355 C., having an. end point at least as high as about 355 C. and substantial residual materials boiling above 315 C., and in the fraction 27o-355 C. less than about 30% but more than about 5% saturates.

2. 'I'he process of claim 1 with inclusion of carrying on at least one of the operational steps in the presence of an extraneous gas. Y

3. 'I'he process of claim 1 with inclusion oi carrying on the process in the presence of catalytic material.

4. The process of claim 1 in which the segregated wood preservative is a distillate.

JACQUELIN E. HARVEY, JR.

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