US2069929A - Composition of matter - Google Patents

Description

Patented Feb. 9, 1937 v I v I UNITED STATES PATENT OFFICE G(.'iMIPOSI'.I.ION OF MATTER John H. Swanberg, Minneapolis, Minn. assignon,

by mesne assignments, to Koppers Company; a a A corporation of Delaware No Drawing; Application January 1?; 1935 Serial No. 2,267

9 Claims. (Cl. 196152) This invention relates to a composition 01' matthis combination of substances as the flux for ten More particularly it relates to a new type the tar. 1 of fluxed or cut-back tar product that involves The hydrocarbons of the lighter fractions of the use 01 a petroleum distillate or other relapetroleum s 8 generally known, aliphatic 5 tively low-boiling aliphatic hydrocarbons and in nat 11 th h r h h mp unds 6 mixtures of hydrocarbons as the major fluxing compris ng e mm n l weriling fractions agents for the tar. I or the petroleum distillate such as gasoline, naph- It has long been the practice to flux coal tars t and k r se whi h are used in commerce and other tars with lower boiling oils of the same end y. Ve y n Chemical constitution 10 chemical nature so that the tars could be applied which to a large extent d pen s p n h o rce 10 at atmospheric temperature in certain types of t Petroleum, the refining Process and y v road construction and for other purposes. Th additional treatments which they may have been use of the fluxed tar greatly facilitates theapgiven- If e Petroleum distillate has not n plication and spreading of the tar especially subleeted o y Cracking Process in t cases where theris no source of heat available at the it will Consist p p y of Derefflnlc y e 15 site of construction or application. After ape w h varying m nts 1 naphthenes and plication or the fluxed tar the flux is intended unsaturatcs s as flns- O a ly a petro to evaporate rapidly, leaving the original tar to leum distillate of this nature will contain only act as a binding material or protective coating. relatively small qua ti of o c ydro- Sometimes the usual types of tar distillate oils eerbons- In addition, large q es o asoavailable for fluxing actually do not evaporate 1ihe,nephtha8 and lielesehes a being P d at sufliciently rapid rates and at such times the y cracking de pe r um and the i her use of mo rapid evaporating fluxes would boiling petroleum distillates. The percentage of advantageous. Lower-boiling aromatic oils such Da flin p nl Uri-saturate d aroma ic 5 as benzene,'toluene, the xylenes or solvent naphcompounds in Such cracked P ts difier thas, are not used generally because of their high. d y, depending p the p 0! material cost. The usual type of tar flux is often limited ac t t e of cr p ce s, the temin quantity. perature employed in the cracking process and Petroleum distillates are available in large other c a y. th se p ducts from so quantities and at small cost. By taking'various c c prohesscs differ om petroleum distilfractions of a petroleum distillate, fluxes of varylates p d d ou cracking n t y ing evaporation rates are obtained; ,Thus, by uscontain Smaller amounts of p c p unds ing petroleum distillates as fluxes some of the d lar e ut vary g a un s i an n s diillculties encountered at times in the 'use 01' and unsaturates. Th aromatic content of such fluxed t are 1 t Manytypes of Detmcracked products is also variable but usually is 35 leum distillates, however, are not compatible with greater than that of on oncrockcd distillate a tar. Some petroleum distillates, when added to at times isvconsidereble in extent w for tar, cause sludging to take place immediately in the Purpose of the Present invention the Demo the tar. Other petroleum distillates, while they leum distillates that are Particularly efen'ed to 40 do mt'smdgetar immediately, do not form are those which contain principally the parafflnic o ble solutions with the tar and separation takes hydrpcarbme William other combinatilms place in the mixtures on standing. It is an obz prevent them from being compatible wit Ject of the present invention to make sible v the preparation of fluxed tar products whi l l will The boflmg range of the petroleum distillate remain stable and homogeneous for a long or other hydrocarbon oils aliphatic in nature to 4-5 riqd of time containing petroleum distillates or i usled m thehtar of a depeladent other relatively low-boiling aliphatic hydrocar arge y upon; 6 rate 0 evapom on desire A fiuxed tar having very quick setting-up properties b0 oils, having the characteristics mentioned a] fi as the major fl mg agent- This is can be obtained by using the type of petroleum distillate known to industr and'commerce as complished by mixing with petroleum distillate gasoline This material wguld have an mmal material a. material of relatively low boiling point boiling point of substantially 20 c, F.) to which predominates in compounds aromatic in substantially 60 C. F.) and amend point nature or having tar solvent characteristics simiof substantially 0. (350 F.) to substantiallar to those .01 aromatic compounds and using 1y 230 C. (450 F.). The specific gravity may 55 V Y i F.) to substantially 115 C. (240' F.) and an end point in a similar range as that of the usual gasoline.

The range of the hydrocarbons may be increased if desired by using kerosene which ordinarily includes the range of parafllnic hydrocarbons from nonane to octadecane. A kerosene fraction of petroleum may overlap a gasoline fraction and vice versa. Kerosene generally dis.-

' tills from substantially 150 C. (302 F.) to sub-.

vent naphtha. either stantially 300 C. (570 F.) and its specific gravity may be from substantially 31 Be. to substantially 48 Be. The combined fractions of gasoline and kerosene give satisfactory results and in fact any one of the lighter petroleum distillates or special fractions therefrom may be used as conditions demand. Stoddard's solvent, a petroleum fraction, has been found to give improved results when used as described in this invention. The initial boiling point of this latter material is substantially 150 C. (300 F.) and its end point is substantially 205 C. (400' F.) to 210 C. (410' IL).

v A wide variety of tar distillates and other'aromatic ofls may be mixed with the petroleum distillate in order to make it compatible with tar. The desired result can be accomplished by the use of benzene, toluene or the xylenes or a combination of these three. The product called solcrude or refined, and boiling from substantially 100 C. to substantially 300 C. can be used. The distillates from coke oven tar, horizontal retort tar, vertical retort tar, oil tars such as water gas tar, or a combination of any of these distillates may be used to advantage. The boiling range of these distiliate's varies considerably at times, and such variations must be considered. Ordinarily these distillates have initial boiling pointsof substantially 150 C. to substantially 235 C. and in most cases at least 80 percent of the distillates will have been removed at a vapor temperature of 355 C. The predominating characteristics of all these oils in the light of the present invention is their .high'content of aromatic compounds and in fact, any aromatic oil boiling over a considerable range between 80 C. and 400 C. with the major portion of the distillate boiling below 300 C. can be used to bring about the desired result. In addition, close cut fractions or individual compounds taken from these .oils may be used to advantage. pounds should not have boiling points substantlally greater than 300 C.

However, the material petroleum distillate is not limited to tar distillates or aromatic oils and compounds. The petroleum industry is, by the use of new refinin processes and chemical treatments, developing new solvents and fluxes which have solvent characteristics very similar to those of the aromatic oils. Certain of these oils, such as the hydrogenated naphthas, or special fractions thereof, may be used to advantage to accomplish theobjects of the present invention. Up to. the present time, however, no specially treated 9 11mm In such cases the fractions or comtobeusedwiththeproduct has been developed that has the same efilciency as the better aromatic oils for modify ing the characteristics of the untreated petroleum distillate.

Various tars and types of tars may be fiuxed by means of the new fiux set forth above. The invention may be used to advantage with both high temperature coke oven tars and low temperature tars. Other coal tars that may be used include blast furnace tar, horizontal retort tar. and vertical retort tar. Other types of tars such as water--gas tars and oil gas tars including residual tars, residuum tar, Bunker C tar and 'Pintsch gas tar or mixtures ofanyoi these tars and other tars may be used. By residuum tars -or residual tars is meant the condensates resulting from pyrogenous treatment of residual oils, for example, cracker residues, in gas manufacturing processes. Each of these tars, on thescribed herein can be used to advantage with these tar-asphalt combinations also.

A number of procedures-have been developed to change some of the characteristics of tar in order to meet certain economic exigencies and construction problems. It is the custom, at times. to add certain materials. designated in the industry as "fillers" such as. powdered coal, lampblack, limestone dust. or similar materials, to

the tar, thereby modifying its characteristics to some extent by increasing the solids content. Other procedures involve the partial oxidation of the tar by air blowing or by treatment with oxidizing chemicals at various temperatures in order to obtain a bituminous material having certain special characteristics. Such oxidations involve not only the oxidation of the tar itself but also the partial oxidation of a tar oil by such means as Just described, the partially oxidized oil then being combined with a tar pitch to produce a bituminous material having special characteristics. Special tars are prepared at other times by adding tar oils of certain boiling'ranges such 1 as creosote oils or its fractions to the tar, either crude or refined, so as to bring about changes in the characteristics of the tars. Other special tars are prepared by distilling the tar to a pitch and thendissolving the pitch in'tar ofls having certain boiling ranges such as creosote oils or its fractions. The tar oils mentioned in the last three cases are not to .be considered as fluxes because ordinarily their boiling ranges are above those of fluxing oils. In other cases, tars of higher consistency are sometimes obtained by adding pitch to the tar, either crude or refined. .At times, the tar residuals obtained from the hydrogenation of tar or its derivatives or products of similar chemical nature may be used for construction pared from any of the above mentioned tars or combination of tars or tar-asphalt mixtures intended for use in manufacturing fluxed mate rials varies considerably depending upon the purpose for which the fluxed material is intended. In the case of a road primer, a light tar or somewhat viscous tar may be used as the base, enough flux being added to obtain a material having a predetermined viscosity. For the sur-- there may be included either hard or soft pitches.

The new flux described herein can be used to advantage in any of these cases.

It is obvious, from the many factors involved, that no exact figures can be given for the proportions of petroleumdistillate or similar oils to aromatic or similar oils, but that the proportions will vary with the problems to be solved and conditions at hand. The proportion will depend, flrst, upon the type and nature of the petroleum .distillateused. A petroleum distillate containing a high percentage of paramnic compounds and a small'percentage .of aromatic compounds will require a larger amount of aromatic oilsv than a petroleum distillate containing a somewhat smaller percentage of paraflinic compounds and a fair percentage of aromatic compounds. The type of tar will have some influence. In addition to the 'type of tar, the consistency of the tar has influence on the proportion; this is so because the lower boiling aromatic compounds in the tar base itself have an effect on the stability and homogeneity of the petroleum distillate-fluxed tar. For instance, the flux for a light tar base intended for road priming will not require as high a percentage of aromatic oils to be added to the petroleum distillate as a flux to of the cases studied it was found that a larger proportion of a certain type of solvent naphtha was required with a certain petroleum distillate than of a certain type of coal tar neutral oil with that same petroleum distillate in order to obtain comparable results. However, the source and characteristics of the difierent usable types of oils are so variable that it is not possihle to state definitely that any one type is superior to the rest, but in general an aromatic oil with an appreciable percentage distilling to substantially 300 C. may be expected to be slightly better than a lower boiling aromatic oil. 4

Aside from the variables introduced by the chemical and physical characteristics of the materials involved there are other factors that may be of influence in determining the ratio of petroleum distillate to aromatic oils. In some cases satisfactory mixtures could be obtained using 5 parts of tar oil and 95 parts of petroleum distillate as flux, butat the same time it was somewhat difficult to eflect mixing, a continued mixing action and relatively high temperature being necessary. In some cases it may be more practical to increase the proportion of aromatic oils to some extent over the minimum point and thereby make the blendingoperation less diilicult. 'In other cases where economics and avail-- ability of tar oil distillates are of more importance than the rate of set-up of the fluxed tar the proportions of aromatic oil may be varied above the minimum point to suit the conditions. In such cases a commercial gasoline may be used and the proportion of higher boiling aromatic oils can be adjusted above the minimum point so that the fluxed tar can meet certain specifications as to flash point.

In case of petroleum distillates which, by

themselves, cause formation of sludge in tar, the

following blending procedure may be advanta-' geous. The petroleum distillate is mixed with the aromatic oil such as described above and then the resulting product is mixed with the tar to be fluxed. In cases where the petroleum distillate does not sludge the tar immediately but is not capable offorming stable and homogeneous mixtures with the tar it may be more expedient to add the aromatic oil to the tar first thereby allowing it to be more thoroughly liquid at a lower temperature, thus reducing the fire hazard incident to the blending operation. In this second case, no particular procedure is deemed to causedimmediate sludging when added by itself to a tar. However, by mixing as low as 10 parts by volume of water gas tar light oil with 90- parts by volume of this gasoline, a flux was obtained which formed a stable and homogeneous mix ture with the tar. In this case 16 parts by volume of the special flux were used with 84 parts by volume of the tar. The tar used was a refined coke oven tar having a consistency by float test at 32 C. of approximately 180 seconds.

Example II.'-The gasoline used in thiscase did not sludge tar when added by itself, but the resulting mixture was not stable and homogeneous. The gasoline was mixed. with water gas-tar light oil in the proportion of 90 parts by weight of the gasoline to 10 parts by weight of the light oil.

This special flux was added to a tar having a float test of seconds at 32 C. in the proportion of 10 parts by weight of flux to parts by weight of tar, producing a mixture which was quite fluid at atmospheric temperature. The mixture was still homogeneous at the end of the eight months storage.

Example IlI.-The petroleum distillate used in this case was a naphtha having an initial boiling point of 218 F. The tar used was a coke oven tar having a float test of. 16'! seconds at 32 C. Upon the addition of the-straight naphtha to this tar the mixture became non-homogeneous in a short time. A fiux was prepared containing 17.5 parts by weight of crude solvent naphtha and 82.5 parts by weight of petroleum naphtha and added to thetar in the same proportions as in Example I (16 to 84). The resulting fluxed tar was still homogeneous after months of storage. Slightly better results were obtained by using the same proportion of a coal tar neutral oil in place of the crude solvent naphtha, although the flux composed of 10 parts by weight of the neutral oil and 90 parts by weight of the petroleum naphtha was not quite good enough to producea stable I the tar added by themselves. Thespecialfiuxes in mixed tar. 'ihenuxedtarcontainingthelarger,

of the iluxed tars were composedofzlo of the individual parts by .weight of the flux-were used partsbyweight ofthetarineachcase.

was a reilned coke oven having a by weight of tar oil distillate and 90 arts by non-homogeneous while theother tar containing the second naphtha gstillfsatisfactory. The naphtha employed in the iiuxed tar showed a lower aniline pointthan the other naphtha, the lower pointindicating a higher proportion of compounds.

Example ,V.-A viscous distilled coke oven tar was usedas the base'in Aflux composed of 80parts by weight of naphtha and20partsbyweightofneutralcoaltaroil ,pheric temperature and proved to be stable on was added to the tar. in the of 20 parts by weight of flux and parts by weight of tar. The iiuxed tar was quite liquid at atmosstanding for a long period of time.

Example VI.A medium consistency tar base prepared from residuum tar was used in this case. The flux consisted of parts by weight of the same gasoline referred to-in Example II, and 10 parts by weight of water gas tar light oil and l0 parts by weight of the resulting flux were used with 90 parts by weight of the tar. A stable and fluid fluxed tar was produced by. this combination.

ExampleVlL-Ihis example is given to show that by using a nu: consisting principally of petroleum distillates it is actually possible to effect a saving in the amount of flux used for any one purpose over that which would be required if the usual tar flux had been used. The same tar base was used in each case given below but the fluxes were different as indicated. The tar base was a crude coke oven tar having an Engler specific viscosity of 77.8 at' 50 C. and a specific gravity at 25' c. of 1.171. The fluxes were added to the four tar batches in amounts suiiicient to produce viscosities' of the same order.

aoeaoso Itisimpracticaltostaterangesofproportions oftheconstituentsofaiiusortheratiosofvari ous combinations of such constituents suitable forthe various'tars. Inanyins'tance,ifagiven combination-oi gasoline with aromatic hydrocab typeofthisnewflux. Coldpatchroadtarswhich.

consistofaheavydistilledtarandalightflux and also other fluxed, heavy tars will prove to give more satisfactoryresultswhenprepsredusing this new flux. 'lheinvention willilnd application in the manufacture of coal tar paints. slthoughinthiscaseamuohsmallerpercentage ofpetroleumdistillatewillhavetobeusedintheflux than wastbecaseinthespecinc for road, tar fluxes cited above. It should be noted thahthis new flux is actually a universal flux for bituminous materials and as such will eliminate the necessity or keeping large stocks of diilerent types of has where diil'erent types oi iiuxed bitumens are manufactured or used. Its universal iiuxing propertiu lead .to applications "in other fields than those mentioned afive. By

employing the proper proportions and ingredients inthisnewflux,itsusecanbeext'endedbyineluding it in a universal primer for underground pipes, in roof coatings. roof cements and other such materials.

Inviewoftheaboveitcanbeseenthatitis entirely feasible to modify the characteristics of petroleum distillates and similar aliphatic hydrocarbon oils in the manner described herein so that they may be used for the iluxing of tars and tar products and that many advantages arise from the use of the petroleum distillates for these purposes.

Thetars or pyrogenous distillates referred to in the description of the present invention may be defined as blackto dark-brown bituminous condensates which yield substantial quantities of pitch when partially evaporated or fractionally distilled. The pitches referred to are black or dark-brown solid cementitious residues which gradually liquefy when heated and which are produced by the partial evaporation or fractional distillation of the above tars.

What I claim is:-,

1. A composition of matter comprising a substantially homogeneous, stable. flowable, pyrogenous distillate tar product consisting of pyrogenous distillate tar or tars selected from a group consisting of coke oven tar, gas-works retort tar. low temperature tar, blast furnace tar. water gas tar, and oil gas tar; and a mixing liq d containing aromatic hydrocarbon oil originating from coal tar and a preponderant proportion of aliphatic hydrocarbon oil originating from petroleum oil.

p faoeacso condition by the said aromatic hydrocarbon oil.

2. A composition of matter-comprising a substantially homogeneous, stable, flowable, pyrogenous distillate tar product consisting of pyrog-' enous distillate tar or tars selected from a group consisting of coke oven tar, gas-works retort tar, low temperature tar, blast furnace tar, water gas tar, and oil gas tar; and a fluxing liquid containing aromatic hydrocarbon oil originating from coal' tar and a proportion of gasoline greater than that of the said aromatic hydrocarbon oil, the said tar product being substantially free from sludge that forms when aliphatic hydrocarbon oil alone is added to the said pyrogenous distillate tar, and the said aromatic hydrocarbon oil being present in sufficient amount to maintain the said tar product substantially permanently homogeneous and stable. I 1

3. A composition of matter comprising a substantially homogeneous; stable, flowable, pyrogenous distillate tar productconsisting of pyrogenous distillate tar or tars selected from a group consisting of coke oven tar, gas-works retort tar, 7

tion of aliphatic hydrocarbon ofl, of the boiling .rogenous distillate tar or tars selected from a range of kerosene, greater than that of the said aromatic hydrocarbon oil,'the said aromatic hydrocarbon oil originating from coal tar, the said aliphatic hydrocarbon oil originating from petro-. leum oil, the said tar product being substantially free from sludge that forms when aliphatic hydro carbon oil alone is' added to the said pyr genous distillate tar, and the said aromatic hydrocarbon oil being present in sufiicient amount to maintain the said tar product substantially permanently homogeneous and stable.

4. A composition of matter comprising a substantially homogeneous, stable, flowable, pyrogenous distillate tar' product consisting of p'ygroup consisting'of coke oven tar, gasworlrs retort tar, low"-temperature tar,'blast furnace tar,

water gas ta'r,"and oil gastar; and a n n liquid containing a relatively low-boili distillate of pyrogenousdistillate tar and a p rtion of a relatively low-boiling aliphatic pe roleum product greater than that of the said low-boiling distillate of pyrogenous distillate tar, the said tar product being substantially free from sludge that forms when aliphatic hydrocarbon oil alone I .is added to the said pyrogenous distillate tar,

tially 80 C. to substantially 400 C. the major portion thereof boiling below 300 C.,'the said I '1- aliphatic hydrocarbon oil being present in greater proportions thanthe said aromatic hydrocarbon oil; and pyrogenous distillate tar or tars selected from a group consisting of coke oven tar, gasworks retort tar, low temperature tar, blast fur nace tar, water gas tar, and oil gas tar; the said aromatic hydrocarbon oil beingnpresent in an amount suilicient to inhibit precipitation of constituents of tar and suflicient to maintain the said product stable over a longer period than is possible in theabsence oi' the said aromatic hydrocarbon oil.

6. A composition of matter comprising a stable homogeneous pyrogenous distillate-tar product having as a flux a combination of aliphatic hydrocarbon oil originating from petroleum oil and aromatic hydrocarbon oil originating from,

coal'tar, the combined oils having solvent characteristics approaching those of aromatic oil compounds. alone, and containing a preponderant proportion of aliphatic hydrocarbon material which when added without the aromatic hydrocarbon material forms an unstable; non-homogeneous product with pyrogenous distillate tar or tars of the group consisting of coke oven tar, gas-works retort tar, low temperature tar, blast furnace tar, water gas tar and oil gas tar, but

which when added to such tar with the aro-. matic hydrocarbon materialforms a substantially permanently stable fluxed tar product substantially free from sludge. v 7. A composition of matter. comprising a fluxed bituminous product containing constituents of v pitch of pyrogenous distillate tar or tars selected from a group consisting of coke oven tar. gasworks retort tar, low temperature tar, blast furnace tar, water gas tar, and oil gas tar; and a 1 mixture containing aliphatichydrocarbon oil of petroleum oil, and an'aromatic hydrocarbon oil or relatively low boiling point'and originating p from coal tar, the said mixture containing a major proportion of the said aliphatic oil, and

the said bituminous product being substantially s free from precipitate that forms when aliphatic hydrocarbon oil alone is added to the said pitch. 8. A composition of matter comprising a fluxed bituminous product containing modified pyrogenous distillate tar or tars, the said taror tars selected from a group consisting of coke oven tar,

gas-works retort tar, low temperature tar, blast furnace tar, water gas tar; andoil gas tar; and a mixture containing aliphatic hydrocarbon oil of' relatively low boiling point and originating from petroleum oil, and an aromatic hydrocarbon oil oi relatively low boiling point and originating from coal tar, the said mixture containing a major proportion of the said aliphatic oil,

, and the said bituminous product being, substan-' tially free from precipitate that forms when aliphatic hydrocarbon oil alone-is added to the said modified tar.

9. A composition of matter comprising a fluxed bituminous product containing pyrogenous distillate tar or tars selectedfrom a group consist ing of coke oven tar, gas-works retort-tar, vlow temperature tar, blast furnace tar, Water gas tar,

and oil gas tar; and containing asphalt, a rela-