DOCTORAL DISSERTATION SERIES Chlorination o Petroleum Tractions TITLE %m* AUTHOR %lerf ce/er d at ua.ma UNIVERSITY ••-?>• DEGREE PUBLICATION NO. 111!111 i[11111 'l y 1j111j1111[11 'I'l'l' 1111 '2 UNIVERSITY MICROFILMS ANN ARBOR MICHIGAN $HE PENNSYLVANT A STATE COLLEGE The Graduate School School of Chemistry and Physics ^ORIMTION OF PETROLEUM FRACTIONS A Thesis by Robert Winston Keefer hbmtted in partial fulfillment of the requirements for the degree of Doctor of■■Philosophy December f 194-2 ACKNOWLEDGMENT Thei author wishes to express his deepest appreciation to Dr. M. R. Cannon., without whose aid and direction this investigation could not have been accomplished. INDEX Page Statement of Problem -- .----------------------------- 3 Summary Apparatus------------------------- --------------- 4 Scope of Investigation --------------------------- 5 R e s u l t s ---------------------------- -------- ------ 5 Introduction---------------------------- ------------ 7 Experimental Work Apparatus and-Procedure-------------------------- 29 0 Derating Characteristics of Vacuum Engler, Table I ------------- --------------------- .46 ..Operating Characteristics of Extraction C o l u m n -----------Table I I - 46 --- ------------- 51 Discussion - *--- ---- ------------- ------ -------- ___ _--- 56 Physical Properties of Original and Clay-Treated Original O i l s ------Table I I I -- 57 Ten imn. Distillation of Original Oil-Table IV — — 60 One -mm. Distillation of Original 011-Table V 61 Physical Property Determination -- Solvent Extraction of Original'Oil — Table VI — 62 Physical Properties of Kerosene, Paraffin Wax and Isopentane-----------Table VII - — 63 Summary of Chlorinations'of Gulfpride Oils■Table VIII-- 65 ■Summary of Chlorinations of Original Oils‘ Table IX --- 72 Pro >ert Los of Chlorinated Original Oils-Table X -- 73 2 Vacuum Distillation of Chlorinated Oil - Table XI 74 Summary of Chlorinations of Kerosene Table XII-- 85 Properties of Chlorinated Kerosene Table XIII- 85 Viscometer Efflux Time vs. HC1 Recovered-----Fig. 9- 86 Summary of Chlorinations of Paraffin Wax— Table XIV- 94 Properties of Liquid Chlorinated 94 Chlorination of Isopentane Table XV Table XVI- 95 Distillation of Chlorinated Isopentane---- Table XVII- 95 ^cryloid Blends of Residue from Distillation of Chlorine.ted Isopentane Table Conclusion-------------------- XVIII 96 97 Appendix Sample Calculations -------- _---- _____ loo Calibration of Flowmeter----------- ------- ---------101 Calibration of McCleod G a g e ---- --- --------------- 102 Calibration of' Vacuum Engler Thermocouple---------- 103 Calibration of Siphon C o u n t e r ------ --------------- 104 Calibration of Extraction ColumnThermocouple ------ 104 Bibliography----- : ---- 105 STATEMENT OF PROBLEM > This investigation was of the nature of an exploration into the possibilities available through the reaction of chlorine with various petroleum fractions. A SUMMARY Apparatus Two pieces of apparatus were constructed in connection with the major object of the investigation. These were a self-contained vacuum Engler distillation apparatus and a batch countercurrent solvent extraction column for solvents lighter than the material to be treated. The distillation apparatus is capable of operating at any controlled pres sure between one millimeter of mercury absolute and atmos pheric pressure-. The maximum deviation of the controlled pressure is 2% when operating, at one millimeter and less than 1% at pressures of ten millimeters or higher. The solvent extraction column consists of an 18-foot unpacked length of one-inch inside diameter pyrex pipe with a con tacting and a stripping section and necessary controls. It is capable of operating from very low solvent rates up to five liters of acetone an hour. The chlorination proper was carried out in a large "test tube" provided with means for introducing chlorine, stirring, temperature measurement and control, and gas exit. The necessary auxiliary equipment such as flowmeter, purifying and absorbing trains were attached as required. 5 Scope' of Investigation This investigation centered about the chlorination of a 160 viscosity medium neutral lubricating oil, obtain ed from the Kendall Refining Company, which was used for the more fundamental portion of the experimental work. The research also included study of commercial oils, kerosene, paraffin wax, and isopentane. 1 Results Chlorination of the above materials under varying con ditions led to the following results: 1. Chlorination in the presence of "actinic” light leads to a rapid reaction at relatively low temperatures without the formation of discolored products. 2. Chlorination of lubricating oils in the presence of iron leads to decomposition and tar formation. 3. The density and refractive index increase with an in crease in chlorine content. 4-. . With increasing chlorine content, the viscosity of the material at first increases very s l o w l y and then more rapidly and finally very rapidly. 6 5. The viscosity index of the chlorinated material de creases with increasing chlorine content. 6 . Fire resistance of the chlorinated products, tested by heating them in an iron cup over a bunsen flame, in creases with increasing chlorine content and they finally become entirely non-inflammable. 7. An increase in temperature greatly increases the rate of chlorination but may produce side effects. 8. Chlorination apparently occurs to a greater or less extent on all of the molecules present. 9. Clay treatment of chlorinated products increases their stability markedly. 1 0 . Highly chlorinated lubricating oils, kerosene and paraffin waxes can be produced which are stable to prolonged heating at 120-14-0° C. 7 INTRODUCTION The very large resources of hydrocarbons, especially of a saturated nature, found in petroleum and natural gas makes them the cheapest source of pure organic raw materials. Likewise, chlorine is one of the most abundant chemicals produced and is available at the very low price of one and. three-fourths cents a pound, in tank car lots. These two facts alone make it inevitable that attempts should be mad.e to produce products of i no.us trial importance from the chlorination of petroleum hydrocarbons. Another important fact not to be overlooked, is that halogens are among the few substances which will react readily and directly with paraffin hydrocarbons. Much research has been done on chlorination of hydro carbons and, especially with the lower members of the series, gratifying results nave been obtained. today There are large markets for a considerable number of chlorinat ed solvents such as carbon tetrachloride, methyl chloride, di- and. tri-chloromethane, ethyl chloride, etc. When chlorination is used "in conjunction with other reactions which utilize a chlorinated intermediate, the number of marketed products is very greatly increased. Most of the work on the chlorination of hydrocarbons has been done in the past fifty.'years and the number of 8 publications is staggering. Fortunately, within the past ten years Hass and Co-workers (25-29, 4^0 have succeeded in clearing up the general picture of chlorination con siderably. By assembling, analyzing and checking published data, they have formulated eleven rules (20, 28, 29) which fit the known facts very well and with only a very few exceptions. Before examining these rules, a few generalizations of the chlorination reaction will be reviewed. The reac tion can be carried out by the use of (l) pure chlorine, (-2) chlorine compounds which give up some of their chlorine, as antimony pentachloride and sulfuryl chloride,- salt baths. By far the most important method chlorination by pure chlorine and this method widely used at present. and (3) is the direct is most The initial reaction of chlorine with hydrocarbons can proceed in two ways; i.e., either by substitution of a hydrogen yielding HC1, or by addition to an unsaturated linkage. Subsequent addition of chlorine can either be by further substitution or by the loss of HG1 from the monochlorinated derivative followed by addi tion of chlorine at the double bond thus formed. There is apparently no reason for choosing one or another of the above methods as being the correct one. Both probably are occurring at the same time although with the proper choice of conditions it is thought possible to make the one or 9 the other predominant. Another property of chlorination which very often leads to difficulty is the highly exothermic nature of the reaction. This may lead to very violent and dangerous explosions unless conditions are very eai*efully controlled. Another property which is troublesome is that partially chlorinated derivatives are capable of being chlorinated further so that it is impossible to stop the reaction at any given point. Thus, numerous by-products are always produced in greater or less quantity. Further complica tions arise from the fact that all the hydrogens present in paraffin hydrocarbons will be substituted, although generally at different rates, so that mixtures of isomers will be obtained unless, of course, all the hydrogens are equivalent. . Furthermore, the very corrosive nature of chlorine, especially when moist, and hydrochloric acid makes the handling of these materials difficult. Recently, however, these difficulties have been largely overcome. The following generalizations are the rules derived by Hass and co-workers mentioned above and apply to the chlorination of the homologs of methane. Rule 1. Carbon skeleton rearrangements do not occur during the chlorination of the simpler paraffins if pyroly sis temperatures are avoided.. All the isomers derivable without such rearrangement are always formed. This rule 10 has had more reported contradictions than any other but by careful repetition of the contradictory work with modern rectifying equipment Hass found that the error was not in the rule but mainly in the published experimental work. Rule 1, while based on the formation of monochlorides, has been found to hold for the polychlorides as far as studied. This, however, includes only the polychlorides of ethane, propane, n- and iso-butane. Rule 2. The hydrogen atoms are always substituted at rates which are in the order tertiary> secondary> primary. Rule 3. At increasing temperatures there is an in creasingly close approach to relative rates of the tertiary:., secondary:primary to 1 :1:1 in both liquid and vapor phase. Rule 4-. Liquid phase chlorination gives relative rates of tertiary secondary and primary substitution which are obta.inable only at much higher temperatures in the vapor phase. This also means that a given temperature change pro duces a much greater effect upon the relative rates and therefore ratios in liquid phase than in vapor — phase reac tion. Rule 5. The presence or absence of the following fac tors does not affect appreciably the relative rates of tertiary, secondary and primary substitution: (l) moisture, (2) carbon surfaces, (3) light. These results seem to indicate that the reaction 11 mechanism is the same whether initiated by the catalytic effect of carbon surfaces or by light. Rule 6 . Excessive temperatures' and/or reaction times result in appreciable pyrolysis of the chlorides in the order tertiary/* secondary^ primary. From this it will be seen that from the standpoint of stability to heat the primary chlorides are the most desirable. Rule 7. If a molar excess of hydrocarbon is used and chlorination conditions are maintained constant, the yield of monochlorides versus polychlorides may be obtained from the equation X = KY, where X is the weight ratio of mono chlorides over polychlorides, Y is the ratio of mols of hydrocarbon over mols of chlorine in inlet gases and K is a constant peculiar to conditions. Therefore, in order tq ob tain a larger amount of monochlorides the ratio of hydro carbon to chlorine must be large. Rule 8 . Dichlorination proceeds by two mechanisms, (l) loss of hydrogen chloridie followed, by addition of chlor ine to the resulting olefin and (2) progressive substitution. Rule 9. The presence of a chlorine atom upon a carbon atom exerts, what has been called a ’'vicinal effect” hinder ing substitution on the chlorinated carbon atom and on the adjacent atoms. This would seem to indicate that once a chlorine atom is attached, to a molecule, that molecule woild be more stable and not react as readily as unchlor- 12 inated molecules. Rule 10. Herzf elder *s Rule (stated in 1&93) ,fWhen into a monohalogen compound a second halogen is introduced it always attaches to that carbon atom which is situated next to the carbon atom already united with halogen*' does not apply to chlorinations and in this field must be—re placed by Rules 1 to 9. Rule 11. Increased pressure in vapor-phase chlorina tion of hydrocarbons gives results approaching those ob tained in the liquid phase. The above rules have been generally accepted as representing the known data on chlorination of hydrocarbons. They have been substantiated unfortunately only for the lower members of the methane series and mainly for mono chlorides but they certainly are an indication of-what to expect. As in all organic reactions, the chlorination of hydro carbons is greatly affected by the conditions under which the reaction is carried out. The classic example of this is the chlorination of toluene. Here the use of elevated temperatures and sunlight results in practically all of the reaction occurring on the side chain with the formation of benzyl chloride. Reaction at lower temperatures and in the presence of halogen carriers such as iron results in chlor ination in the ring giving the chlorotoluenes. Here the choice of conditions completely changes the course of the 13 reaction. Various investigators have studied the effect on chlorination of the following factors (19), (1) "actinic” light, (2) halogen carrying catalysts as iron and iodine, (3) metallic oxides, (4) water, (5) sulfur, (6) sulfur dioxide, (7) porous materials, (8) carbon, (9) heat, alone or in conjunction with others, and (10) a silent electrical discharge. Of these, "actinic” light and heat have re ceived the most attention and are the most important. The exact wave length of light which produces the catalytic effect is somewhat of a question. Sunlight, diffused daylight, carbon arc lamp, light from a metallic filament and mercury vapor lamps have been used as sources of "actinic” light (10). In one study (4) on the chlori nation of natural gas an interesting comparison of the in fluence of light of different wave lengths was made. A chlorination was started using a carbon arc lamp as catalyst. After ..a.-.,while, a blue screen'was placed over the arc lamp. There was no noticeable change in the rate of the reaction. The blue screen was removed and in order, green, red, and yellow screens 'were placed between the arc lamp and the reaction vessel and the reaction rate meas ured in each case. After each of these screens had been interposed the rate of reaction decreased almost immediate ly. By replacing the red., green, or .yellow screen with the blue screen, the reaction rate immediately resumed its original magnitude. The screening out of the other colors was of no assistance as the inactive colors caused no meas urable interfering influence. They also studied the effect of ultra-violet light and found that it had very little in fluence on the rate of reaction. These results seem to indicate that blue light is the wave length of light which has the greatest accelerating effect. Quite a few workers have recommended "ultra-violet lamps,T as a source of activa ting light in chlorinations but it is quite possible that light from these lamps of wave lengths other than ultra violet is the effective agent aiding reaction Increased temperature also increases the reaction rate and thus it. is usually used.to a greater or less extent along with the catalysts. However, the complete thermal chlorina tion of an aliphatic hydrocarbon always encounters two dif ficulties: (l) chloroole-fins are formed which may .rapidly polymerize and. form a carbonaceous deposit in the reactor and (S) reaction becomes sluggish as the screening effect of a chlorine atom is multiplied by an increased number. In creasing temperature increases the reaction rate but exces* sive temperatures also greatly increase pyrolysis and must be avoided.. Work with halogen carriers has also been rather ex tensive. Their action is based on the fact that the higher halides are unstable and under proper conditions yield some of their halogen. Subsequent action results from the repeated addi- 15 tion and loss of the halogen. Metals like iron and anti mony and materials like phosphorus,, iodine and bromine which form loose compounds with chlorine are generally used for this purpose. Some work has been done using sulfuryl chloride and phosgene as chlorinating agents. These compounds decom pose at the prevailing conditions, yielding chlorine in a very reactive state. Porous substances and carbonaceous material have been found effective and their action is probably due to the increase in surface area which they present. The mechanism of the substitutive chlorination of saturated hydrocarbons has been under discussion for quite some time. The most generally accepted theory is that the chlorine molecules are broken down into chlorine atoms. This is brought about by the catalysts heat and light by furnishing energy which the molecule absorbs, as follows, Cl2 + Cl2 + A = Cl* + Cl* hv = Cl* + Cl* The reaction then- can proceed in one of two ways with in sufficient evidence at present to determine which is the correct way. (1) Cl* + CH^ =CH3CI + H* ; H* + Cl2 (2) Cl* + CH^ = HC1 + CH3* ; CH3* + Cl2 = HC1 +Cl* -CH3CI + Cl* 16 The bulk of the present evidence points to mechanism No. 2 as being correct. The recent discovery (12) that very small amounts of tetraethyl lead, which is generally thought to yield ethyl radicals when heated, accelerate gas and liquid pha.se chlorinations enormously, tends to support chain mechanism No. 2. Also, hexaphenylmethane which yields triphenylmethyl readily, catalyzes liquidphase chlorination, and. azomethane acts as a catalyst in l the vapor phase. The chain reaction, once started, regenerates the activated chlorine atom and no further catalytic action should be necessary. However, the loose atoms of chlorine can recombine or trie chain may be terminated in several different ways. The collision of a radical or atom with a solid surface such as a wall, collision with oxygen and the collision and combination of radicals will all termi nate the chain. Oxygen has been known for quite a while as a strong inhibitor of chlorination (16, 9) and.this fact is sometimes given as support to the chain mechanism. The stability of chlorinated hydrocarbons to the in fluence of heat is an.important property and has been' summarized quite well by Hurd (30). With the exception of methyl chloride, the lower members of the series and especially the monochlorides, are quite stable to heat up to 400° C. However, the decomposition of the polychlorides 17 of the higher members of the methane series occurs at much lower temperatures. Gardner and Bielouss (19) state that the dissociation point of the polychlorides lies between 120 and 250° C. and that by heating these chlorinated hydro carbons up to 250° C. a practically complete dechlorination can be effected without the aid of any other agent. They also state that this dissociation does not necessarily lead to olefins. This is because the olefins primarily formed undergo a further change in their nascent state; namely, transformation into cyclic compounds by a mutual saturation of their double linkages Aromatic compounds with chlorinated side, chains behave in much the same way a s .aliphatic hydrocarbons. However, wliqn chlorination has taken place on the ring, the aromatic compound is found to be very stable. In. fact, ethyl tetra- chlorobsnzene and ethyl pentachloro benzene mixtures have been proposed (22) as heat transfer fluids. Naphthenic chlorides, on the other hand, appear to be exceptionally unstable. A large number of proposals (see 19) have been made for inhibiting the decomposition of chlorinated hydrocar bons . Most of them involve the addition of basic or un stable materials such as amines, guns,. dyes, and hydro carbons but they generally involve the neutralization or addition of the liberated HC1 rather than a true inhibition.' 13 Carlisle and Levine (7) state that trichloroethylene will not decompose in the light unless oxygen is present and recommend the addition of antioxidants. There has been considerable work done on the chlorina tion of the higher members of the aliphatic and aromatic series, chiefly in the form of complex, inseparable mix tures. Such mixtures have consisted of petroleum fractions such as kerosene (12, 45), vacuum flashed residues (53), paraffin wax, (18, 23, 24, 35) light oil fractions (34, 58, 60) and creosote oil (51). That much work has been done which is unpublished is evident from the huge number of patents granted for the use of chlorinated oils,, waxes, etc. as intermediates in the preparation of other materials. In the chlorination of liquid, paraffins (11), the fol lowing generalizations were found. The chlorinations showed an induction period, a gradual increase in the velocity, a maximum reaction velocity, and a sharp de crease in speed to a constant velocity. This indicates a chain mechanism consisting of a period of activation and one of chain reaction, with a maximum velocity at the trans ition point of the two. The chlorination of kerosene by Padgett and Degering (45) had for its purpose the preparation of detergents using the chlorinated hydrocarbon as an intermediate. They used a narrow cut (95-100° G.) from the kerosene and were 19 interested only in obtaining monochlorides. For this pur pose their chlorinations followed, in general, the rules set forth by Hass and co-workers (25-29)j i.e., liquid phase at about 100° C. and the use of a high hydrocarbon to chlorine ratio. They stopped the chlorination when the chlorine equivalent to one-fourth or one-third of that necessary to form monochlorides had been used. They then fractionated the product in order to separate the mono chlorides formed. alcohols, alkyl These monochlorides were converted to sulfates, etc. for use as detergents. The commercial chi .urination of kerosene fractions has become of interest in recent years because by condensation of the mo no chlorides w i t h .aromatic hydrocarbons and subsequent sulforation, surface-active agents have been produced (25). Another chlorination of Pennsylvania kerosene is re ported in Ellis (11). This was carried out by means of antimony pentachloride in the presence of iodine at 350360° C. However, at such elevated temperatures, pyrolysis as well as chlorination takes place with the result that the products were principally hexachloroethane and. hexa- . chlorobenzene. The chlorination of paraffin wax by bubbling dry chlorine thru the melted wax held at about 70° C. was carried out by Gardner (13). He prepared a series of chlorinated paraffins of varying chlorine content and 20 determined the relationships between chlorine content and density, congealing point, viscosity, and surface tension. The viscosity increased gradually until about k0 per cent chlorine has combined and then increases very rapidly. Density gradually rises at first also and then more rapid ly after 40 per cent chlorine has combined. The congeal ing point (similar to pour point in petroleum) drops rapidly with increase in chlorine content until at about 37 per cent chlorine it reaches a minimum. It then in creases very rapidly again. Hardie (23) chlorinated paraffin simply by passing chlorine into a dispersion of the paraffin in water or aqueous sodium hydroxid.e. Wirth (60) chlorinated hard, paraffin;and petrolatum by the use of chlorine in the presence of manganese dioxide preferably in the form of Welden mud. The chlorination of cracked residue has been studied somewhat by Tropsch and co-workers (53). They diluted their starting material with carbon 'tetrachloride and carried out the chlorination in an ice bath. mention made of a catalyst. There was no The chlorinated product, a dark brown oil, was stripped of carbon tetrachloride by heating to 125° C. under reduced pressure. This product was then treated with benzene and anhydrous aluminum chlor ide. In conclusion, they state that the treatment raises 21 the viscosity and viscosity index and lowers the pour point. However, the final product was "black and the color was not improved by sulfuric acid and / or clay treatment. In chlor inating some vacuum flashed oils they always obtained dark colored products except when only a small amount of chlorine had been introduced. Even in this case, the product turned dark upon standing overnight. The chlorination of various petroleum fractions (nar row boil-ing cuts) corresponding to.. C13 - Cqg have been carried out but no conclusions can be drawn from the meagre data except that the chlorination proceeds very readily, even without catalysts. The chlorination of one fraction try Barth (3) , assumed to be mainly tetracosane, was carried out by bubbling a mixture of chlorine and. sul fur dioxide thru it at a temperature of 90-95°C. The product was a moderately viscous oil, light yellow in color and liquid at 20° C. The presence of sulfur dioxide was said to promote substitution on adjacent carbon atoms so that the resulting halide could be hydrolyzed to a polyhydric alcohol. The chlorination of light oil fractions has been carried out by Koch and Ibring (34-) • They passed the chlorine into the liquid hydrocarbon under unspecified con ditions. Carbon dioxide was admitted simultaneously in order.to cool the material and remove the HC1 which was 22 formed. The stabilization of the chlorinated products is a matter of prime importance and has been the object of much study and many patents (5, 42, 44* 49, 56, 59, 61). They range from materials which combine with the liberated hydrogen chloride,, the removal or conversion of the most active or unstable constituents, and the removal of all of the chlorine and formation of hydrocarbons or hydrocarbons pins other elements. Bishop (5) uses a wash of aqueous sodium hydroxide followed by an extraction with ether or toluene. Montgomery (42) advocates the addition of 0.5 - 1.0% of a hydrocarbon of the pinene or terpene groiip, such as turpentine, pinene, etc. Muskat (44) gives the chlori nated material a concentrated sulfuric acid treatment at 40-100° C. for from 2-5 hours. One of the standard methods seems to be the use of the condensing action of aluminum chloride with the subsequent removal of the sludge formed. The addition o f 'calcium phenyl stearate to remove HC1 formed by decomposition is said (56) to be effective in the case of chlorinated naphthalene. Wirth (59) de scribes the stabilization of chlorinated oils-by heating them with a basic reagent and causing them to absorb sul fur at a temperature below 100° C. In another patent (61) he uses a current of steam after the addition of a small amount of caustic alkali. 23 The uses made of chlorinated products are very numer ous.' The use of large quantities of chlorinated solvents was mentioned in the earlier paragraphs. They consist wholely of the lower members of the methane series and are used as the chlorinated material itself. The chlorinated kerosenes, waxes, etc. are generally not used as the chlor inated material but only as intermediate. An exception to this statement is in the preparation of fire- and water proofing materials. the desired products. Here the chlorinated molecules are One method, of flame-proofing con sists (13) of chlorinating solvent naphtha until AO to 50 per cent of chlorine has been absorbed, and a crystalline product"separates from the mother liquor. This crystal- ' line chlorinated.product is then incorporated with wax, asphalt, or similar combustible organic insulating material and gives them flame-proof qualities. Another substance used in a similar manner is s. chlorinated heavy petroleum such as.. "asphaltic oil". A.recent development (2) for imrjarting fire resistance to fabrics has been advocated in England. Preparations of a chlorinated organic material such as petroleum oil on a relatively inert material preventing premature dechlorina tion - manganese and zinc borate - with a volatile solvent, filler, sand pigment are recommended for imparting resist ance to fire, -water.and mildew. The degree of chlorination 24 is 40 to 80%. When the textile fabric is exposed to fire or the temperature at which it undergoes combustion, chlor ine is released in the form of hydrogen chloride which tends to exclude oxygen and stop the flame. The borates added to the composition not only prevent premature de chlorination hut cover the fibers where they are highly heated, preventing glowing and creeping of the fire. The pigment .protects the chlorinated material from decomposi tion by light. The preparation of lubricating oils by chlorination usually involves the condensation of the chlorinated material with an aromatic compound in the presence of anhydrous aluminum chloride. TTew Jersey Paraflow (8), Standard.Oil of pour point lowerer, is prepared by slowly adding paraffin wax, chlorinated to approximately 10-12 per cent, to a mixture of equal weights of an aromatic hydrocarbon (e.g., benzene, naphthalene or anthracene) and aluminum chloride. Kerosene is used as a solvent. After the reac tion, the aluminum chloride sludge is withdrawn and the Kerosene and unreacted wax removed by distillation. The extreme complexity of the mixtures so obtained can be estimated if we recall that there are over three and one third million possible eicosaries (C20H46)> ea°fr these gives all the theoretically possible mono- and poly-chlor ides and a single naohthalene nucleus may condense with 25 from one to eight of the various chlorides. It seems possible that a sample of pour point depressant might be made up to a considerable extent of molecules of which no duplicate is present. Fisher and Koch (16) studied the production of lubri cating oils from the lighter hydrocarbons obtained from carbon monoxide-hydrogen synthesis. This material was chlorinated up to the equivalent of six chlorine atoms per molecule and was then treated with xylene, benzene-, na phtha1ene, etc., and ab o ut 5 per cent a1umlnum chi orId e . The final products, lubricating oils, are said to contain less than 0 .IS of chlorine and to have an average molecu lar weight of 450. As mentioned previously, Tropsch and co-workers (53) obtained a more viscous oil with a higher viscosity index by a similar procedure. opaque black. Their product, however, was an Anderson (l) recommends a small portion of synthetic oil, obtained by condensing chlorinated paraffin wax and benzene in the presence of aluminum chloride, bee added to heavy transmission gear lubricants to increase their effectiveness. ricating oil. Lowes (39) similarly obtains a lub Sanders (51) recommends a chlorinated creosote oil be blended with lubricating oil to form a good cutting oil. A process for producing resins by chlorinating the 2.6 polymeric constituents of cracked petroleum distillate has been developed by Morrell and Egloff (4.3) . Such consti tuents,. after being separated from the distillates, were mixed with phenols, cresols, tar acids, or other 'compounds, then heated, to 300° F. and chlorine introduced until the mixture became relatively viscous. Fulton (17) also ob tained resins by chlorinating a cracked petroleum fraction up to 10-15% and then distilling the product. Distilla tion removes chlorine, hydrogen chloride and any volatile oily constituents. The preparation of pour point depressors are made in general by the same method as outlined above for Paraflow. Lieber (35) catalytically condenses paraffin, chlorinated to approximately eleven per cent, and. then distilled up to 600° F. The residue is used. He later (36) also used 1;% of "a condensation product of a halogenated "tall oil" and benzene, naphthalene or xylene. Pier et al (46) have patented a similar process as has Rieff and Badertscher (50). High or "extreme" pressure lubricants are also pre pared, by the use of chlorinated materials. One process comprises mineral lubricating oil, free sulfur, and chlor inated paraffin wax. Chlorinated hexane is also said to improve the lubricating properties of mineral oil. Lincoln and Byrkit (37) have patented an extreme pressure lubricant 27 consisting of a paraffin base oil mixed with 20$ or less of halogenated foots oil containing 10$ chlorine. McNulty and Simmer (71) describe a lubricant prepared by adding an active chlorine compound, such as chlorinated wax, plus a small amount, 0.01-1.0%, of an old. soluble cycloaliphatic amine such as dicyclohexylamine serving to avoid corrosion. Whittier (5 7) advocates a mineral lubricating oil plus five per cent of a phosphorized fatty oil plus 1 to 6 per i cent of a highly chlorinated hydrocarbon such as heptachloro Propane as an extreme pressure lubricant. Wetting and emulsifying agents are in general obtained by converting the chlorinated hydrocarbon into an alkyl sulfate. Keller and Gofferye (33) obtained■wetting agents by treating polychlorinated hyclrocsirbons with alkalies and sulfonates giving products containing sulphonic and. bisul phate groups. Kowakani and Maruyama (31) treated chlori nated hydrocarbons with caustic alkali or carbonates to cause salt formation and dechlorination. The use of chlorinated paraffin wax in the preparation of antioxidants has been described by Loane (38). The method consists of a condensation with naphthols or polyhydroxy benzenes in the presence of aluminum chloride. Pier and. Christmanu (77) recommend a product obtained by condensation of a high molecular weight halogenated hydro carbon and elementary sulfur for prevention of oxidation of lubricating oils. Gardner and Bielouss (19) produced drying oils in an interesting manner. They chlorinated liquid paraffin and then dechlorinated it by heating to 250° C., in the absence of catalysts, driving off the chlorine as hydrogen chloride. The products consist of olefins mixed with cyclic hydro carbons produced by ring closure during the dechlorination. Ellis states (12) that chlorinated hydrocarbons containing more than nine carbon atoms and at least two halogen atoms may be reacted with alkalies to obtain a drying oil. Monohalogenated paraffin wax may be reacted with a mixture of potassium acetate and acetic acid or potassium stearate, butanol, sodium Iodide or dibutylarnine and xylene to yield a plasticising or impregnating agent. 29 EXPERIMENTAL WORK Apparatus and Procedure In order to properly carry out this investigation it was necessary to construct certain pieces of apparatus. For separation'of chlorinated products as well as for analytical Insights of the starting materials, a self-con tained vacuum Engler distillation apparatus was built. This apparatus, complete with pumps and control features Is mounted on a laboratory table and needs only water, gas and electrical connections to.make it operatable anywhere. The general arrangement of the distillation apparatus is shown in Fig. 1. The Hy-vac oil pump, being rather old and. inefficient, was used to back up a three-stage mercury vapor pump. The capillary leak was placed in the line between the pumps and the surge tank so that the pulsations caus.ed by the intermittent operation of the leak would be smoothed out as much as possible and not be felt at the distillation flask. The regulator, shown In Fig. 2 is con nected directly opposite the leak so that It will react instantly to any pressure surges and thus give closer pres sure control than would otherwise be possible. From the surge tank are the necessary leads to the IvlcCleod Gage and to the distillation flask and receiver. The vapor lines i Gages Surge Tank Flask Receiver v/afor Fig. / Flow Diagram o f Vacuum Enaler o F ig . 2 P re ssu re R e g u la to r 32 all constructed of standard nine millimeter glass tub- Thc temperature was controlled by the capillary leak method; that is, the pumps were capable of pulling a greater vacuum than required and the leak left in enough air, inter mittently, to keep the pressure at the proper value. The leak was controlled by the regulator shown in Fig. 2, act- licaids. 33 tain requirements: (l) Their vapor pressures must be low enough at ordinary temperatures so that they do not evap orate uncler operating conditions; i.e., one rum. pressure; (2) The upper liquid ”D !t must not be capable of conducting even a small electric current while (3) the lower liquid ”Gn must carry this current readily. The most trouble was encountered in obtaining the liquid (ft) since most liquids with suitable vapor pressure characteristics can not be made to conduct electricity. This difficulty-was overcome by dissolving sodium chloride in glycerin. Although the solubility of the salt is low, it is sufficient to conduct the current providing the two contacts are placed close enough to one another. The upper liquid (D) wa.s dibutyl phthalate and is entirely nonconducting. The density of pure glycerine is 1.260 gr,/. ml. and that of ■dibutyl phthalate is 1.04-5' gr./ml. effective density of 0.215 gr./ml. This gives an When operating at one millimeter of mercury absolute pressure, a change in pres sure of 1.6/ would theoretically move the interface by one millimeter and a change of 3.2% would move this interface two millimeters. Much less than a two millimeter movement is required to operate the relay; in fact, by observation, it moved about one millimeter. The maximum deviation of pressure would therefore be about two per cent. Glycerine has quite a high viscosity and it was 34 thought that tliis might make the action of the relay slug gish and lead to a greater deviation of pressure. In order to help overcome this the U-bend tubing connecting the two lower bulbs of the regulator was constructed of quite large (13 mm.) glass tubing. This., along with the very slight movement necessary for operating the relay, was very successful since In actual practice the pressure at the MeCleod gage did not vary by more than 2.0%. . This excel lent control is probably aided by the large (ten gallon) surge tank and the location of the capillary leak directly opposite the regulator. The purpose of the upper bulbs was to provide as nearly as possible a constant liquid level which increases the accuracy of the regulator. The lower bulbs were designed to prevent momentary strong pulsations from pushing the upper liquid from one side down around the U-bend and over into the other side, thus ruining the pressure control. The determination of the pressure of the system next to the distillation flask was made by means of a MeCleod gage and a closed-end U-tube manometer. The MeCleod gage was calibrated using two scales, one which gave a compres sion ratio of 30:1 and the other 90:1 when the pressure was in the vicinity of one millimeter of mercury absolute. During all distillations at one millimeter, readings were taken using both, scales. If condensable gases were present In the MeCleod gage, the compression of it to different 35 ratios would condense a diffei’ent amount of this gas and hence give different readings for the apparent pressure of the system. Therefore, if the pressures shown hy hoth scales are Identical then the readings are accurate and no condensable gas was present to cause Inaccuracy. When operating at ten millimeters of mercury pressure the MeCleod gage was used as a primary standard but the closed-end U-tube gave accurate enough, readings for a continuous check on the pressure. The distillation flask shown in Fig. 3 is similar to the Vacuum Engler flask in use in the Petroleum Refining Laboratory. A one liter flask was used so that large samples could, be 'accommodated although usually the charge amounted to 300 ml.-and each cut was thirty ml. or ten per cent. The vapor temperatures were obt'ained at the top of the columnar extension of the flask neck by means of a eopper-constantan thermocouple constructed of No. 22 Leeds and Northrup wire. This couple was -standardized against another thermocouple which had been calibrated by means of a Bureau of Standards thermocouple. The e.m.f. developed was read by a Leeds and Northrup Portable Precision Poten tiometer which is capable of readings to 0.001 millivolts or approximately 0.1° C. The flask was heated by means, of a Glass-Col hemispherical mantle and controlled by the use of a Variac. The fla.sk and neck up to the lip were well / 0.5c cm 37 lagged while the upper area acted as a condenser. material Any condensing above the lagged section was prevented from flowing back down the column by the lip which directed the condensate down the side arm to the product receiver. The product receiver and fraction cutter are shown in Fig. A- It consists of a flat base plate constructed of half inch boiler plate upon which rests the sample bottles and the distribution device. It is covered by means of a g glass bell jar through the top of wdiich are the product receiver line and the vacuum line. This bell jar is sealed to the base plate by means of melted paraffin, applied while the receiver is under a slight vacuum. A perfectly air-tight seal is obtained in this manner although care must be taken not to form too thick a coating of paraffin as a thick coat tends to crack, thus breaking the seal. The distillate flowing down from the flask, drops into the funnel (A) and is distributed to the proper bottle by the copper tubing spout (B). The funnel is supported by the cylinder (C) which rotates upon the stationary vertical shaft (D). On the lower end of the rotating cylinder (C) is fastened-a: wheel (E) containing ten spokes. The two rods (F) extending up through the spokes of the wheel, shown at the lower right in the figure, prevent the wheel and hence the funnel and spout from rotating. These two rods are so placed that when -a spoke of the wheel (E) is 38 v//n n j /irrm F ig . 4 P ro d u c t R e c e iv e r & F r a c tio n C u tte r 39 resting against one, the other is midway between two spokes. When it is desired to change from one bottle to another one of these rods is pulled down and a spring, not shown, rotates the wheel against the other rod, pulling the spout of the funnel about half way to the next bottle. This first rod. is then pushed back up into place and the other one pulled down allowing the spoke of the wheel to come against the first rod by rotation of the wheelT- This sequence of operations moves the spout of the funnel com pletely to the next bottle. The rods (F) which are used for these operations are merely one-quarter inch steel rods covered by pressure tubing. This pressure tubing is fastened at the lower end to the rod and at the upper end to a short section of pipe soldered to the base plate. One source of difficulty in the pressure regulation arose from the fac.t that the. dibutyl phthalate absorbed air or moisture when not in use and these gases 'would slow ly come out of the liquid during operation at one milli meter of mercury pressure. Since control is based on main taining the system at a pressure equal to that of the closed side of the regulator, this gas coming up in the closed-off side would naturally ruin any pressure control. This dif ficulty was overcome by wrapping some resistance ribbon around that side of the regulator and heating the liquids while the vacuum was being obtained on the system. This 40 procedure effectively drove out the gases and no trouble was then experienced with the pressure control. After a distillation, it is advisable to open stopcock (A) and close stopcock (B), thus keeping the regulator under vacuum. The other major piece of apparatus built was the 23foot solvent extraction column. Essentially, it consists of 18 feet of 1 inch inside diameter pyrex pipe with a contact ing section, stripping section and. auxiliary equipment. It was designed to operate with solvents lighter than the material to be treated. In operation the heated solvent enters the bottom of the column, forced in by virtue of its greater pressure head, and comes in contact with the material to be treated, which remains mainly down in the contacting section where' it is thoroughly agitated. The solvent oil solution rises through the column t o :the stripping section on top where the solvent is vaporized, precipitating the oil which-drops back down the column as reflux. This reflux consists of numerous bubbles of oil, fairly uniform in size, which drop slowly down through the rising acetone. The vaporized solvent is carried as a vapor up to a condenser where it is condensed and run into a solvent -supply tank. This supply is higher tha.n the stripping section of the column so that sufficient head is available to force the solvent in at the bottom of the column. The main section of the column, consisting of the 1 inch 4-1 pyrex pipe, is jacketed by 45 mm. glass tubing provided with inlet and outlet lines so that cooling water may be passed through the jacket. In Fig. 5, the contacting section of the solvent ex traction column is shown. It Is a 10 inch length of 2 Inch inside diameter pyrex pipe joined to a 4 inch length of 1 inch pyrex pipe. Passing through the brass plate on the bottom are, reading left to right, (l) drain pipe, (2) stirx’er, (3) solvent entrance line, and (4) a small copper tubing carrying thermocouple wires. The liquid in the con tacting section is very vigorously stirred by the motordriven stirrer. The solvent entering the contacting sec tion is hot, having been heated by a lo-lag immersion heater placed Inside the solvent line. The entire contact ing section Is well' lagged to prevent the loss of heat. This method of operation; i.e., mixing hot oil and solvent, enables us to approach equilibrium much more rapidly than would be possible if the solvent and oil were contacted in the cold. As the hot solution starts up the column it is cooled by the jacket water and the excess oil will precipi tate out . In actual operation the entire lower 3 or 4 foot of the column looks like a cloud due to this precipitation. The copper tubing carrying the thermocouple wires is sealed at the top along with the junction of the wires. Thus, the temperatures recorded for the contacting section are for F ig . 5 C o n ta c tfn g . S e c tio n 43 t hi s ther mo c o up 1 e . The stripping section located at the top of the column is shown in Fig. 6. Vaporization of the solvent is accom plished by means of the steam heated steel cylinder (S) in the center. The condensate line from this cylinder extends to near the bottom so that the steam entering at the top forces the condensate out and keeps the cylinder practically clear of condensate. The solvent vapors formed pass out through the 3/4 inch opening on the plate and hence to the steam heated heat exchanger (li) which carries them up to the condenser. From the condenser the solvent flows through a siphon counter into a supply tank. A constant head is maintained on 'this supply tank .by the apparatus shown in Fig. 7. A 300 cc. supply of acetone was stored in auxiliary tank (T). When the level in the main supply tank falls below the en%gs£j$^ the glass tubing (V) ? air will pass up through i t s p l a c e some of the solvent in (T) . This solvent flows down the tube (L) into the reservoir bring ing the level back up_, sealing tube (V) and stopping any further flow o f t h e tank. This extraSKHMSEuiiil is very easy to operate and once conditions an occasional 'check. it - requires no attention other than When the desired equilibrium is reached the extract sample is withdrawn from the stripping section through the small copper tubing (P) by means of 44 O /-~;q .O Sfr/pp/ng- :- -h ec n o n % ■44& Fa. 7 C o n s ta n t H ead A p p a ra tu s 45 vacuu.ru and a raffinate sample, if desired, can be drained from the bottom of the column. Table II, page 46, gives a summary of the operating characteristics of the column. A flow diagram of the actual chlorination apparatus is shown in Fig. S. The chlorine coming from the cylinder passes through a flowmeter, containing concentrated sulfuric acid, and hence through chromous sulfate solutions which re move any oxygen present in the chlorine stream. Leaving these bubblers, the chlorine enters a drying tube contain ing anhydrous calcium chlorid_e which dries the chlorine before it passes into the hydrocarbon in the reactor. The exit gases from the reactor pass into a 25% solution of potassium iodide where they are absorbed, as explained later. The reactor consists of a 16 inch length of 3 Inch inside diameter pyrex pipe with one end sealed shut, form ing a large tTtest tube” . The hydrocarbon, to be chlorinat ed, is placed In this reactor and the chlorine introduced under the surface by means of a tube. 4 m m * glass tubing delivery An air-driven stirrer, acting through a mercury seal, is used to agitate the mixture. A long-stern thermometer is also placed In the liquid and, on some runs, a rough viscometer is present. Surrounding the reactor there is an outer js.cket consisting of a 12 inch length of 4 in.cn in side diameter pyrex pipe covered on the lower end by a brass plate. Connections are made to this jacket, enabling the 46 TABLE I Operating Characteristics of Vacuum Distillation Apparatus 1. Controlled Operating Pressure - 1 ram. Hg to .atmospheric 2. Pressure Deviation - 2% at 1 mm.- Hg, much less at higher pressures. 3. Charge 4. Number of Fractions - 10 5. Operation of Fraction Cutter - Manual 6. Maximum Temperature ---------- 100 to 500 cc. 4O0°Cin still. TABLE II Operating Characteristics of Solvent Extraction Column 1. 2. Solvent ------------------- Lower density than treated material. S o l v e n t ------------ ------ Boiling Point under 100° C. 3. Solvent B a t e 4 . Operating Temperature ---- 0—5 liters per hour. 10° to Boiling Point of solvent 5 . Maximum C h a r g e ------------ 600 cc. 6. Maximum Total Extract - - - - 1 0 0 7. Amount of Solvent Needed— 8. Batch Operation cc. at 4 liters. one time. 0o 0o oa On Removal Reacf or Chlorine XJ Absorber an M Fig. 8 Chlorination Flow Diagram -n <2 48 reactor to be heated by steam or hot water or cooled by cold water. This jacket covers the lower 12 inches of the 16 inch reaction "test at its top by tube" and is sealed to the reactor a rubber gasket. Sometimes during chlorinations the chlorine delivery tube would become clogged by solid chlorinated materials building up a dangerous pressure in the chlorine purifica tion train. This danger also occurred when the inlet tube to the exit gas absorber became plugged, as very< frequent ly occurred. To avoid the danger of flooding the room with chlorine when the pressure increased,a safety trap was inserted in the chlorine line just before the drying tube. This consisted of a 17-tube of sufficient length filled with concentrated sulfuric acid. When the pressure built up to a certain value, the chlorine would bubble out through the U-tube, whence it was carried by tubing to the outdoors. For purposes of safety all connections of rubber to glass between the chlorine tank and the reactor w e r e 'se cured by copper wire. The rubber stoppers on the chronpus sulfate bubblers were also fastened with copper wire. Care must be used during chlorinations to prevent any. i rapid decrease in temperature of the reactor. When the temperature drors there is a decrease of pressure within the reactor from the twin reasons of contraction of the 49 gases above the liquid and the greater. .solubility of gases in trie liquid. If the temperature drops too rapidly the potassium iodide solution will be drawn back into the re actor ruining the run. For the removal of any oxygen present in the chlorine, chromous sulfate solutions were chosen according to the recommendations of Stone and Beeson (52). The preparation of the chromous sulfate solution is brought about by reducing a freshly prepared 0.1 molar sulfuric acid chrome alum solution by means of a Jones redactor. Detailed procedure follows: The amalgamated zinc was prepared by stirring approximately 250 grams of C.P. zinc in 100 ml. of 3 N hydrochloric acid for thirty seconds. Then 100 ml. of 0.013 M mercuric chloride solu tion (5 ml. of a saturated solution at 25° C. diluted to 100 ml.) were added to the zinc acid mixture. The stirring was continued for three minutes, after which the amalga mated. zinc was washed thoroughly with water by decantation. The amalgamated zinc was then put into a piece of glass tubing approximately 30 cm. long and 22 ram. in diameter. The chrome'alum solution (0.4 molar) was passed up through the amalgamated zinc, after the. set-up had been thoroughly flushed with 00^. The light blue chromous solu tion emerging from the top "was run directly into the flasks which were to be used. These flasks must also be flushed 50 with CO2 before the chromous sulfate solution is run into them. \vhen tne ame.1 g s.ma t ed zinc solution is not in use it must be stored, under water after washing all the acid from it. The absorption and subsequent analysis of the exit gases was carried out by a 25% solution of potassium iodide (21) in distilled water. The use of this solution enables the determination and differentiation of absorbed chlorine and the hydrogen chloride from the same sample. The hydrogen chloride in the gases is absorbed by the potassium iodide forming potassium chloride and hydrogen iodide. The chlor ine absorbed, again forms potassium chloride and liberates free iodine. For analysis, an aliquot portion is'with drawn from the absorber and titrated directly with sodium thiosulfate. The amount of this solution used represents the amount of free chlorine' which was present in the gases.Then, to the same sample, a small quantity of potassium iodate crystals are added. These react, with the hydrogen iodide present in the solution, liberating free iodine which is again titrated by sodium thiosulphate. The amount used this time is representative .of.the hydrogen chloride in the absorbed gases. ■The chlorine cylinder was weighed on tne heavy—duty fulcrum balance in the Chemical Engineering Laboratory. Teighings on this balance are accurate to one gram. By 51 making weighings before and after the chlorinations and byabsorbing and analyzing all of the exit gases, a chlorine balance can be made. This chlorine balance can be checked, when no volatile material is present in the reactor, be cause any excess chlorine entering over that leaving has to be equal to the increase in weight of the reactor after the loss of hydrogen as hydrogen chloride is accounted for. Physteal Proyerty Petermlnation Buring the course of the investigation it was neces sary to obtain and interpret certain physical properties of the materials encountered.. The densities of the materials were determined by pvcnometers. Viscosities were, determined by the use t»f the modified Ostvald viscometers as described by -Cannon and Fenske (6) and A.S.T.M. viscos ity index calculated. The Indices of refraction were ob tained by use of the Abbe type refractometer situated in the Chemical Engineering Laboratory. Melting points were obtained in the standard -manner and softening points by a modification of -■the proposed A.S.T.L. ring and ball method. It was necessary to know the approximate composition of the original oil used. For this purpose use was made of the methods advanced by Waterman (5 5) and further developed by the Petroleum Refining Laboratory. In order to run a 52 Waterman analysis on an oil it is necessary first, to liave certain physical properties of the oil and second, to have certain charts relating these properties. The 'physical properties necessary are (l) index of refraction (n§3), (2) density (dpo)* (3) viscosities in centistokes at 100° F. and. 210° F ., and. (4 ) aniline point. The charts used were obtained from the Petroleum Refining Laboratory of The Pennsylvania. State College. The aniline point of an oil is the temperature at which a 50-50 volume mixture of the oil and water-white, double-distilled aniline become com pletely miscible. In order to illustrate the calculations necessary, the Waterman analysis, of the original oil will be made. ‘The necessary data are: n|° = ■d2o 1. 1.4778 ~ 0.8620 gr./ml. Visln0O F = 36.33 Centistokes ViSp1Q = 5.67 Centistokes Aniline Point = 105.0° 0. First it Is necessary to calculate the specific refrac tion from density and index of refraction. (ng0)2 - 1 Speoific Refraction = ( m u s k = _ - °-3283 1 d _ = fi.A778’)2-I x (1.a 7 7 8 ) W 53 2. Next the molecular weight is determined from the chart of Keith and Roess (32) or calculated by the equation of Fenske, McCluer and Cannon (15)* using the viscosi ties at 100 and 210° F. The value determined is in creased by ten per cent. Mol Wt. = (360)(1.10) = 396 3. Using the chart (ref. 55,"p. 667) relating molecular, weight, specific refraction, and aniline point, we get an aniline point known as ”chart aniline point”; theoretically, the aniline point of the completely sat urated oil. Chart aniline point = 111.6 4. The per cent aroma tics present can now be calculated by using the experimental and ”chart” aniline point. T>er cent Aromatics = (0.6S)(chart A.P. - experi mental A. P.) Per cent Aromatics = (0.68)(111.6 Per cent Aromatics 5. = 105.0) 4 The aniline point of the hydrogenated 011 is tnen detenu ined (theoretically) by use of same values. Aniline Point Hydrogenated '= Exptl. A.P. (Chart A.P. + (0.8) - Exptl. A.P =.105.0 + (0.8)(111.6-105. = 110.3 54 6. The specific refraction of the theoretically hydrogenat ed oil is then determined using the molecular weight and the aniline point hydrogenated from same chart as in 3. Specific Refraction, Hydrogenated = 0.3274 7. From the chart (ref. 55, p. 663), using the molecular weight and hydrogenated specific refraction we calcu late the total per cent cyclics. This is the ratio: l Specific refraction of all paraffins - specific refrac tion, hydrogenated and divided by specific refraction paraffins - specific refraction of six membered con densed naphthalenes, all values read using the molecular weight found in 2 . fa Cyclics = ( 8. p ^ — ) (100) - ('0 *333^ - '0;3074) (10Q) ~ 23 The percentage of naphthenes is therefore the total per cent total cyclics minus the per cent aromatics. Per cent Haphthenes = 19 9. The percentage of paraffins is 100 minus the per cent cyclics. Per cent Paraffins = 7 7 10. Using the same chart as in 7, the number of rings per molecule is determined, using the specific refraction, hvdroeenated and the molecular weight. The horizontal 55 curved lines on this chart are labeled from one to six rings per molecule and the value read by interpola tion. Rings per Molecule = 1.5+ 11. Calculation of the value of nx Tt in the empirical for mula CnHp +x is as follows: x \% Aromatics 7 C „. 1 r-, ^ , fe l ^ hthenes '% Total Cyclics] LRo * R±nSsJ (I-6) + [%. Total Cyclic . Rings * 1)(-2) x - ('23) (1*5) (-6) t 12. (1.5 - l) (-2) - -2.5 The value of n is then obtained by a weight balance: (12) (n) + (2)(n) + (l) (x) = -M.W. 14n +. (-2.5) = 396 n 13. = 28 .5 Our oil has the formula c2 8 .5 H54-5 56 DISCUSSION Since this investigation was of the nature of an exploration, various fractions of petroleum were chlori nated. The fractions used included kerosene, lubricating oil, paraffin wax, and isopentane. The preliminary runs were made on lubricating oils which Included Gulfpride S.A.E. 10 and S.A.S. AO commercial oils and a. 160 viscosity medium neutral oil obtained from the Kendall Refining Company. This neutral had been treated In the following manner. It had. been dewaxed to zero pour point and had a flash point of /i.25/A30° F. Prior' to solvent treating, its viscosity was approximately 195 S.S.U.- (A2 Centistokes) at 100° F. Ten per cent of the dewaxed, stock was removed by phenol treating and the raffinate-filtered to a yield of 100 barrels of oil per ton of clay, based on new earth. A summary-of the properties of this Kendall oil, here after known as "original oil”, are shown in Table III. The runs on the Gulf pride oils ’were mainly qua.llta.tive in nature and thus no physical property data were determined. Included in Table III are the .pro.pert.ies of the claytreated original oil. -This clay-treated oil was obtained by treating the original oil in a. A2 mm. inside diameter tower, filled with activated clay, until the oil was waterwhite . The yield of water-white.material was about 33h of the amount charged. The properties listed in Taole III TABLE III Physical Properties of Lubricating Oils Used in this Investigation Oil Untreated Original Clay Treated Original ■ Density (doo) 0.8620 0.8586 R.I. 1.4778 1.1752 (ng°) Viscosity-Cent!stokes 100° F. 36.33 35.23 '210° F. 5.67 5 .63 V .I . (A.S.T.M.) Color (A.S.T.M.) 104 2y Aniline Point °C. 105-0 Molecular' Weight 396 % Aromatics ^ 7o Naphthenes % Paraffins Formula 4 .19 77 C28.5H54-5 108 0 107.3 5a were determined by the procedures outlined in the preced ing section. Prior to the actual chlor inations of the original oil, it was subjected to vacuum distillations at one and ten millimeters of mercury pressure and to solvent extraction in the extraction column, using acetone as the solvent. These distillations and extractions were carried out with the dual purpose of testing the equipment and of obtaining additional data on the original oil. The results of the two vacuum distillations are given in Tables IV and V. As can be seen, reducing the pressure from ten to one milli meter of mercury'lowers the vapor temperatures recorded -L or the fractions by about 5Q° C. (90° F.). The other propertie s are approxrina tely the same, at both pressures. The six solvent extractions on the original were carried out under as nearly identical conditions as pos sible. In each case the charge was 500 ml. and the tem peratures and solvent rate ad-justed to the same values. Table VI summarizes the results of these runs. Runs E-l and E-2 .were apparently contaminated by material such as p i p e 'compound present in -the system due to construction. These two were therefore not used although data on Run E-l are included in the table. The raffinates from tne last four runs were combined and clay treated In order to im prove their color. This clay treated raffinate was then 59 used for some of the chlorinations and its properties are listed in Table VII. The kerosene used in this investigation is a commer cial grade which was obtained from the stock room. This material was used as obtained but it had a slight yellow tinge and therefore, for one of the runs, it was subjected to clay treatment which readily gave a water-white product. The properties of the untreated and the clay treated kero senes are also given in Table VII. The isopentane was ob tained. from the Petroleum Refining Laboratory and its properties are listed in Table VII. sity data are for pure Isopentane. The viscosity and den These values are un doubtedly close enough to the actual properties. .of the Iso pentane used for the purposes of this investigation. The , - paraffin wax, likewise, was obtained from, the stock room. It was a hard white wax with a melting point of 51-53° C. A survey of the literature on chlorination indicates that, in order to obtain the most stable materials, primary chlorides should, be the main chloride present in the product. Also, a review' of H a s s T rules of chlorinations shows that liquid phase chlorinations at elevated temperatures favors high yields of nrimary chlorides over the secondary and. tertiary chlorides. For thus reason, all ch3-orinations in this I lives tigation were carried out In the liquid phase. In fact only, the chlorination of isopentane and pernaps kerosene would have been feasible in the vapor phase. 60 TABLE IV Distillation No. D-3-10 10 mm. Distillation of Original Pressure = 10.00 ± 0.05 mm. H g . Material Vapor Temp. OF. °C. n20 D 20 1.4778 0.8620 Viscosity--Centistokes V.I, 100® F. 210° F. ; Original - - 36.33 5 .67 104 Cut* 1 245 473 1.4760 0.8588 22.94 4.24 96 Cut 2 2.53 487 1.4763 0.8595 26.14 4-83 101 Cut 3 256 493 1.4766 0.8599 28.38 4*85 101 Cut L 260 500 1.4769 0.8606 30.75 5.10 102 Cut 5 265 509 1.4771 0.8611 33-15 5.35 104 Cut 6 2.70 518 1.4773 0.8617 35.75 15.65 106 Cut 7 274 52.6 1.4778 0.8622 38. 71 ■5.90 104 Cut 8 278 533 1.4781 0.8627 42.05 6.23 104 Cut 9 283 542 1.4782 0.8631 4 6 .24- 6.66 105 1.4822 0.8691 77.06 9.27 104 Residue _ — * Each cut represents 10% of the charge. 61 TABLE V Distillation No. D-5-1 10 mm. Distillation of Original Pressure = 1.00 ± 0.02 mm. H g . Vaoor Temp OF'. Mate rial °C. Orig inal - — ngO d 20 Vi scosity--Centistokes 100° F . 210°F. V.I 1.4776 0.8620 36.33 5.67 104 Cut* 1 195 363 1.4771 0 .8617 22.86 4.19 91 Cut 2 201 394- 1.4771 0.8613 26.52 4.61 97 Gut 3 206 403 1.4771 0.8616 29.10 4.91 100 Cut 4 210 411 1.4772 0.8612 31.47 5 .18 103 Cut 5 21A 419 1.4772 0.8615 34-10 5.41 102 Cut 6 217 423 1.4776 0.8615 36.41 5.70 105 Cut 7 222 431 1.4776 0.8616 39.11 5.94- 104 Cut 8 226 439 1.4776 0.8615 42.27 6.29 106 Cut 9 232. 449 1.4778 0.8612 46.03 6 .65 106 — _ 1.4313 0.8673 78.30 '9.56. 108 Residue Each cut reoresents 10% of the charge. 62 TABLE VI Extraction of Original Oil Column Temp. = 22° C. Contacting Section Temp. = 40° C. Solvent Rate = 3*8 liters Acetone per Hour Run No. E-l ' jjj Fraction % of Charge 20 nD Viscosity-Centistokes 100°F. 210°F. V.I Extract 1 7.3 1.4922 Extract 2 4.6 1.4890 Raffinate 88.1 1.4700 Extract 1 9.0 1.4982 11.8 1.4950 8.2 1.4998 11- 0 1.4949 7.0 1.5025 11.0 1.4947 6.8 1.5.020 55.64 6.38 57 10.8 1.4960 48.60 6.11 70 — 1.4728 34»02 5 .57 112 — 1.4778 36.33 5.67 104 4? Comb . Ext. 2 & 3 Extract 1 Comb . E xt. 2 & 3 Extract 1 E-5‘ Comb. Ext. 2 & 3 Extract 1 E-6 Comb. Ext. 2 Sc 3 * Combined Raffinates from E-3, E-4, E —5X E-6 Clay-Treat ted Charge TABLE VII Physical Properties of Combined Raffinate, Kerosene and Isopentane Material on p, Clay-Treated Combined Raffinate 1.4728 from Untreated Kerosene 1.4461 Vi sco sity-Centistoke s 100° g. 2X0° F. V.I. 34-02 5.57 112 1.60 - - n a20 Color 0.8545 1 (A.S.T.M.) 0.7980 Yellowish Tinge Clay-Treated Kerosene 1.4457 1.62 '; - - 0.7980 Water-White Isopentane 0.363* - - 0.620 1.3570 * At 20° C. Water-White 64 As mentioned previously, the;preliminary work was per formed on commercial oils of light (S.A.E. 10) and heavy’ (S.A.E. 40) grades. A compilation of the general results of the five chlorinations is show, in Table VIII. These runs were made mainly in order to test the general proced ure of the chlorination and to iron out any difficulties or awkward operations in the chlorination apparatus. These first runs were made without much control over the conditions which are known to be catalytic; i.e., light and heat. The chlorinations were run during the day and at night so that at times the sunlight catalyzed the reaction and the rest of the time the chlorination was run in the dark. Since iron was present in the reactor conditions varied so as to produce directly opposite types of chlorina tion; cf., chlorination of toluene. ho attempt was made to hold the temperature constant and so it varied as the heat of reaction varied; i.e., the faster the chlorine was passed in, the' greater heat of reaction developed and the higher the temperature of the reaction mixture. Run C-l-10, chlorination of the light S.A.E. 10 oil, was started, using a small electric motor to operate the stirrer but it was soon found that the continuous operation, especially when the chlorinated material became vrscous, .was too severe for it. The brushes wore out very Q u i c k l y and the armature became -badly scored, so that an air—driven TABLE VIII amrnsry of the Preliminary Buns on Gulfpride Oils Iron Tacks Served as Catalysts in all of the Following Runs Approx.' * Increase Hydrogens Temp. °E’. in height Run Ho. Oil C-1-4-0 Gulfpride S.A.E. 10 40 C-2-99 10 99 Gulfpride S.A.E. 40 C-3-35 0-4-102 C-5-100 '' JD cl 3.0. Gulfpride C fi'•1 ?• it ’• 10 ■ U>’ • - 80 124 . Replaced 17 Fluid Very tacky 26 Black 1ax xy Deep Barely reddish flows brown Asphaltic ^ appearance free carbon Fluid Very tacky 35 51 102 92 19 105 Remarks Barely Deep Reddish flows Brown 11 100 Color Fluidity 100°C. 20°E. 22 Solid Very deep red Solid Black Solid Heavy Brittlesyruuy friable appearance of rosin O L O Heavy syrupy Very brittle sed on assumed formula CnH2n where n = 28 ^ Mey be due somewhat to water which.entered or to local overheating during stripping operations. O' 66 stirrer was substituted clnd used very successfully. The air-driven stirrer even operated very well on viscous materials although the air pressure had. to be quite high. In this first run sodium hydroxide solutions of about 2.5% strength were used in the gas absorbers. Much trouble was encountered due to the plugging, by precipitated sodium chloride, of the constricted gas delivery tube in the abj sorber. This tube had been constricted in order to de crease the size of the escaping- gas bubbles and thus aid their absorption. As the chlorination continued, the oil gradually be came more viscous and darker colored. As it became, vis cous, it foamed considerably and towards the end. there aoneared to be nothing -— i *—3 but foam in the reactor. This foam had a rather light orange color but when the oil had set tled. its- very dark color was apparent. The removal of the chlorine and hydrogen chloride gases dissolved in tie■reaction mixture was attempted by the use of heat and vacuum. .The reactor was heated to 100° C. by means of steam condensing in the jacket and vacuum was applied by a water-jet aspirator. This method, of gas removal apparently is not successful since the product still smelled strongly of hydrogen chloride after several hours treatment. Run C-2-99 'was a chlorination of the same type oil 67 (S •A •a » AD) ®-t an average temperature of 99^ C. using iron as a catalyst. During this run steam condensing in the jacket held the temperature of the reactor mixture at 99°C. The oil darkened very rapidly and at the conclusion of the run considerable black solid material lined the inside of the reactor. Although the oil definitely darkened more rapidly than it had when chlorinated at room temperature, the final very asphaltic appearance is probably due, in part, to other causes. These include (l) the add.ition of a small amount of water which was drawn back into the re actor from a manometer when the temper a ture dropped, sudd.enly, and (2). the decomposition of the product during, subse quent gas removal attempts. Since the gas removal from the chlorinated lubricating oil in the first run (C-l-40) had been unsuccessful, a higher temperature, obtained by electrical' heating, was tried,. No better results were ob tained and due to difficulties in stirring some local over heating with its accompanying decomposition undoubtedly occurred. The sodium hydroxide solution absorbers plugged frequently even when the gas delivery tube was flared. The next two chlorinations were carried out on the more viscous S.A.E. AO commercial' -oi l . : One of .tne- runs (C-3-35) was made at room temperature and the other (C-A-102) at 102° C. witil steam in the jacket. cases was iron. The catalyst in both At room temperature tne oil became too 68 viscous before very much, chlorine had. "been introduced.. Like the previous runs on the less viscous oil, the color gradually changed from its original yellow through.- orange and. finally to deep red or brown. At the higher tempera ture, however, this darkening was much more ra~pid and the oil was darker for any comparative chlorine content. The removal of dissolved gas was brought about by bubbling car bon dioxide through the heated (100° G.) chlorinated pro ducts while maintaining a. high vacuum on the system. This method: proved satisfactory except that the time necessary was long - ten hours in the case of the more highly chlori nated oil (0-1-102). Considerable success was had in keeping the sodium hydroxide absorbers open. This was' brought about by the simple'expedient of using a more dilute solution. A 10% solution was used for these runs and, although requiring more frequent changing, it eliminated the constant checking feviously required.. During the early part of the chlorina tion of the S.A.E. 4,0 oil at 102° C . with an iron catalyst (Run C-4-102), a dry ice-acetone trap, maintained at tem peratures lower than -35° C., was placed between the reac tor ail the absorption flasks. This trap was maintained at the low -temperature.for a period of several hours but aosolute'ly nothing was condensed. This indicates tnat all of the chlorine during the early stages of cnlorina oion- reacts 69 completely since tne boiling point of liquid chlorine i s ' -34*6° C. The liquifying point of hydrogen chloride (-84°C.) cannot be reached using acetone and dry ice. Chlorination C-5-100 was made on the light S. A. Eh 10 commercial oil at 100° C. using an iron catalyst. In the belief that the darkening of the oil may be due to oxida tion, an antioxidant,, urea, was added to the oil. amount of urea represented .1.0% by weight. The There was no noticeable slackening in the rate of discoloration of the oil- in fact,, it appeared to have been hastened. The rate of reaction of the chlorine was considerably slower and much ..more chlorine passed through the oil unreacted than in the parallel run w i t h o u t :urea; i.e., Run C-2-99• Aside from these differences and the fact that the product con tained no asphaltic material, the results of. this run are' similar to those of the parallel run on this oil. An attempt to use pyrogallol for removing oxygen from the chlorine steam instead of chromus sulfate solutions, which are time-consuming in preparation, proved to be a failure’ since the chlorine reacted directly with tne pyro gallol. Unfortunately* the samples of the absorbers were lost and thus no material balance check could b e o d t a m e d of the run on the S.A.E. 10 oil using urea (C-5-100). From, these first five runs there were certain obser vations and conclusions to be drawn as to the conauc o of 70 subsequent chlorinations- The major ones were: (l) hie'her temperatures favor the more rapid darkening of the oil under the conditions studied; i.e., iron catalyst; (2) the apparatus needs the safety trap, explained under the apparatus and procedure section, with an exit outdoors to prevent accidents which would release chlorine into the room; (3) chlorinations should be carried out under more controlled conditions of catalyst and temperature .and^ (l) a less time-consuming method of gas removal was desired. It was desirable to know how much of the absorbed exit gas was chlorine and how much was hydrogen chloride. A knowledge'of this enables one to determine how much of the entering chlorine reacts by addition and how much by substitution. The hydrogen chloride absorbed represents an. equivalent amount of. chlorine which reacted substitutively. A t o t a l .chlorine balance shows how much more chlorine entered than was accounted for in the absorbers and this Is therefore the amount of chlorine which reacted by addi tion. In order to distinguish between the chlorine and hydr-ogen chloride' the solution in the absorbers was changed to potassium i o d i d e . A 25% solution appeared to be the strongest concentration which could be used witnout causing excessive plugging of the delivery tube: during aosorption. The chlorination of the lubricating oil fraction of petroleum was accomplished in runs 0—6 to C—13 and C—19 • 71 A summary of these chlorinations is given in Table IX and the physical properties of a few of the products is given in Table X. Four of the runs (C-6 to C-9) were made on the clay treated combined raffinates from extractions E-3 to E-6 described above. Run C-6-S2 was performed in a carbon tetrachloride solution and with enough steam in the jacket to maintain this solution at its boiling point. No iron or other catalyst was used except the action of daylight during the day. The reaction proceeded more rapidly than any of the proceeding chlorinations, which may have been due to the decreased viscosity caused by the addition of the solvent. ficulties. The solvent, however, caused operational dif Since the reactor w a s 'maintained at the boiling point of the solution, CCl^ was condensing on the cover plate and the w a l l s . This condensate attacked the neoprene rubber gasket sealing the top of the reactor and also rubber stoppers causing black solutions of the rubber to drop into the oil. This probably hastened the blackening of the oil although It was definitely darkening before any dissolved rubber entered it. The final product was very black, although no solid, matter was present. This product was stripped of gases by flushing with C.Og under vacuum for some time. It still smelled faintly of hydrogen chloride and so'was placed in a TABLE IX ■Summary of Chlorinations of Original Oils See Tables III and VII for properties of charging material No. Tenro. °C. Catalyst Charge C-6-82 :Combined Raf- 82 : finat.es from E-3 to E-6(S) 103 C-7-103 ” Per cent Increase in Weight Due"to Due to Audi- Substition tution Total None Approx. Per cent Hydrogen Replaced Remarks 36 36 8 Black, very fluid Black, asphaltic deposits Black, fluid, some deposit Actinipv light’™' Fe in dark - 43 43 9 - 48 43 10 C-3-100 ■" C-9-30 »»■ . 30 I! 0 37 37 8 Original 100 I! 0 38 38 3 Black, much asphaltic deposits (Table X) Jj ack, fluid(Table X) 0 48 43 10 Black, asphaltic dep. 21* 36 57 10 97 115 20 144 167 31 ikv Deep orange, (Table X) Light orange, very viscous Light orange, solid C-10-100 C-ll-30 C-12-36 100 it 30 36 It 18 it ■ 18- t 20 Original (S$ t! *J>A (s) C-13-18 — / tr Actinic light** W - - W W W - n ** Carbon Arc Lamp. ■>* ice of solvent (ccip. should be 22/o to satisfy all unsaturati< ro Properties of Chlorinated Original Oils Studied in this Investigation (See Table IX) Run 20 Treatment__________ ^20______ nD C-9-30 (Chlorinated Product ( neutralized by < Aaimonia and Filtered ( C-10-100 C-12-36 Clay Treated Chlorinated .Product • Viscosity-Centistokes 100° F. 210° F. 7.1. 1.019 1*499 2044 H .21 64 1.019 1.510 357.4 18.61 4.9 1.5175 297.7 49.17 -5 1.128 74 TABLE XI Distillation No. D- 6-1 Vacuum Distillation of Original Oil Chlorinated at 100° C., with iron, to a 30 Weight Per Cent Increase Pressure = 1.5 - 0.1 mm. Hg Each cut represents 10% of charge Material Vapor Temp. 20 a nD_______ 20 Viscosity-Centistohes 100°F. 210°F. V.I. Cut 1 * 1.4790 0.8803 19.63 3.99 114 Cut 2 * 1.4790 0.8816 27.64 4 .81 104 1.4802 0.8832 30.02 5.20 115 1.518 0.9470 1126 74-05 U7 Cut 3 Residue - * hot reliable (See tent p. 79 ) Petroleum Ether soluble portion. 75 condensing vapor bath stripper employing (b.p. 25 3 C.) as tne neating medium. Dowtherm A However, the mater ial when removed from the stripper smelled -much more strong ly of HC1 than it had previously. When cold, it was solid and had an asphaltic appearance. Undoubtedly, almost decom position took place and therefore a lower temperature should be used for stripping. "Actinic” light, obtained through the use of a carbonarc lamp, and elevated temperature were used as catalysts for the next run (C-7-103) . All equipment coming in con tact with the oil was made of glass. The oil turned gradually but the reaction rate was very good. dark In fact, so far as the chlorination was continued, no slackening of the rate as had always been noticed previously was observed. The final oil was jet black, however, and contained quite, a bit of asphaltic material. It -was. stripped of dissolved gases by flushing with CGg at 100° C. There was a distinct odor of HC1 in the stripped'product. A similar run was then made, again with the combined r affiliate at 100° C . , but an iron stirring rod was'used as a catalyst arid, the reactor was completely enclosed. This prevented daylight from entering and catalyzing the reaction. The oil darkened almost at once and. soon was jet black. The reaction was also slower . than the previous run and there'was more tendency for the chlorine to pass through unreacteu. 76 The final product was found t o .contain some asphaltic material indica.ting decomposition. Carbon dioxide and vacuum were used to remove the dissolved gases but were not entirely successful. In the above runs a rough scale, weighing to 1/2 oz. (14 g r .) , was still being used so that no attempt to check material balances or determine chlorine by difference was made. This procedure is upheld by noting that in the usual run which would involve approximately 100-120 grams of chlorine from the cylinder, the difference between the chlorine entering and that accounted for by the absorbers was never more than 15 grams. That is just about what the accuracy in weighings was and therefore the error in addi tion reaction calculations would, be about ±100/. In order to avoid this large error, a heavy duty fulcrum balance in the Plant Testing Laboratory was tested and found satisfactory f or- -1he weighing of the 30- 0 ound chlorine cylinder to ±1 gram. 'This, balance was used in all subsequent runs. In the next run (C-9-30) , again using the -combined raffiliate and an iron catalyst, conditions were maintained the same except for the temperature which was controlled at about 30° C. by proper adjustment of cooling water to: the jacket. Once again the oil turned -black soon after chlorination was started and a considerable amount of asphaltic material was formed. .The reaction was very slow 77 compared to the chlorination of this oil using actinic lignt (Hun C— 7—103) anct also quite a hit slower than the similar chlorination at 100° C . A material balance indi cated that more PiCl had been evolved than should have been even if all of the chlorine reacted by substitution. This indicates that decomposition has occurred, giving rise to unsaturation or ring coupling and loss of an extra amount of hydrogen chloride. The chlorinated material this time was first given the same treatment for gas removal as had the preceding runs; i.e., heat, vacuum and CO2 flushing. Then gaseous ammonia was passed through the oil, under vacuum, for an hour or so. This use of ammonia was recommended by several factors. " First, ammonia being basic would readily neutral ize any acidic gases like HC1 and the resulting ammonium chloride could be filtered, or water washed out of the oil. Second, from consideration of Hass1 rules of chlorination it is evident -that tertiary chlorides are the most unstable Also, the reaction of ammonia and tertiary -chloride's occurs ■easily and the net result would be the substitution of an unstable chloride with a more stable amine. Third, amines have been advocated as stabilizers for chlorinated hydro carbons and this fact along with the second one would lead to a much more stable product. The last' two runs on the combined raffinate oil were 78 repeeted. using iris original oil in order 'bo check and see whether or not natural stabilizing compounds of the original oil had b e e n removed by solvent extraction. The run on the original at 100° C. with an iron catalyst (C-10-100) dif fered from the similar run on the combined raffinate (C-8-100) only in the fact that no asphaltic material was formed. However, this chlorination of the original was not continued as far and it is possible that the same result would have b e e n obtained had the same amount of chlorination been attained. temperatures The chlorination of the original at room (C-ll-30) gave the same final product as its counterpart on the combined raffinate (C-9-30) the oil did not darken nearly so rapidly. although Both chlorina tion products of the 100° C. and the room temperature runs on the original were treated with COp, vacuum and then ammonia for removal of gases. The ammonium chloride was filtered off in coarse fritted glass funnels. The physical properties of the products obtained by ■ the above chlorination of the original at 100° C. and 30° C . with iron -catalyst (Table a ), tend to bear out the general izations found in the literature; i.e., the density, refrac tive index, and viscosity, all increase witn increasing chlorine content. The. viscosity incisx nas dropped from ius original 104- to 64 and 49* It is interesting to note un«.t, although both products contain almost identical amounts of 79 chlorine, the one obtained by chlorination at the higher temperature (C-10-100) has had a greater increase in these properties. The product from the chlorination of the original (100° C., iron catalyst, 3&fo weight increase) was subjected to a vacuum distillation (D-6-l) in an attempt to separate the non-chlorinated material from the chlorinated products. The pressure was meant to be one millimeter of mercury and when that pressure had been reached the still heat was turned on. However, before any product had been obtained, the pressure increased and got out of control. It was soon discovered that, instead of d.is tilling, the chlorinated oil was cracking and giving off gases so rapidly, that the pumps could not maintain a pressure of 1 mm. . A Thermo couple was'therefore inserted between the heating mantle and the distillation flask, the heat was -..regulated' to such a value that the pumps could hold a pressure of approximate ly. 1.5 mm." of Eg and the distillation continued. Three 1C$ cuts v/ere obtained before the temperature of tne neating mantle reached, its safe limit. The distillation, proceeded. so slowlv that no reliable vapor temperatures were obtained. The lack of any light boiling.material in the chlori nated uroduct is an indication that all of tne moj.ecu.xes. in the oil have been chlorinated to a greater or .Less degree. This is in agreement with the general chlorination rule so which states tnat once a chlorine atom, lias entered a molecule, that molecule becomes more stable to further chlorination. The first two cuts were third one was Quite dark. jet black and the Some of this color was probably due to impurities from the bumping of the liquid in the flask. The residue was a semi-solid asphaltic mass. This, mass was treated with petroleum ether at a temperature of about 70° C. and the soluble material removed. -.When stripped of solvent this was the residue sample. The properties of these cuts and the residue are given in Table XI. A comparison of these cuts obtained from the above distillation brings out some interesting details. The refractive index and the density indicate that a con siderable portion, i f -not all, of the chlorine had been lost-. . These properties are almost as low as the original oil was before chlorination. The viscosities, compared to the original oil, have been lowered and the viscosity index increased appreciably in the case of two of the cuts. ' Tne most surprising material is the residue which has tne highest viscosity index although it is a much more viscous material. This material is jet black and its viscosity had to be obtained-by use of a special viscometer for opaque liquids -developed by Cannon and llenske (6a) . A review of the preceding runs showed'that, of the 81 possibilities available by use of iron, "actinic” light and neat, only one nad not Deen tried. — low temperature and "actinic” light. These accordingly were made the con ditions for the next run (C-12-36). The temperature during this run was maintained at approximately 36° C. and the carbon arc lamp used as a light source. The oil quickly turned orange and then gradually became deeper orange as the chlorination progressed. But, for the first time, the chlorination gave a relatively light colored product. On standing overnight, however, the chlorinated oil gradually darkened. To test the effect of heat, a sample of this material was heated, to 100° C. for a short while. Ib immediately became black, gave off considerable hydrogen chloride, and practically solidified into an asphaltic mass. It looked very much like some of the preceding products. The oroduct obtained above by the chlorination of tlieoriginal at 36° C. with "actinic” light was;tested for solubility.in various solvents. By comparison with the original oil, the only difference was that, whereas the original was. soluble to a h extent of only about 6 ml. in 100 ml. of acetone at room temperature, the chlorinated Product was completely soluble. This is another indica tion that chlorination occurs on all of the molecules present in the original oil. The chlorinated product did not tend to darken when it na<x been uilxuced. v/±th a solvent 82 as It had v/hen no solvent was present. Also, that small portion of chlorinated product which, as soon as the chlorination vi/as completed, was removed and. roured Into a beater did not darken at all. Since the material left in the reactor turned dark, it would appear that the darken ing may not be due to oxidation as had been thought, but to condensation or polymerization. Fortunately, the dark col ored product, when passed through activated clay regained Its color and was now stable to prolonged heating at 100° C. Clay treatment, therefore, seems to be a good method for stabilising chlorinated products. The properties listed in Table X for Run 0-12-36 are for this clay treated material, host noticeable is the fact that the viscosity at 100°- F . is about ten times as great as that of the product from the chlorination of this original at. 100° C. with iron (C-10-100) while it 'actually contains little more chlorine. The viscosity' index likewise dropped more -than would be ex pected. These changes may be due •to either a change in type of product, obtained or to -the more rapid change In property oer Increase in chlorine content In tins region. The former reason is indicated by tne fact t.nat a consider able araount of chlorine reacted by addition while none .wad . ' k ' I apparently done so previously. Run C-13-1S on the original was then made at as low a temperature as could be obtained py tne cooling uc. uer in S3 -jacket -18° C. ca mu h- s f . the T>le caroon arc lanap ias- used as Tne reaction proceeded somewhat slower tlian in wecs u i n g run which. must have been due to the decreased tftiii arature since CCl^, had been added to decrease the vis cosity- The oil hardly changed color during the chlorina tion but once the run was completed it gradually darkened upon standing. Clay treatment was used to remove the dark color and stabilize the product since heat again caused de composition of the untreated product. The final product was- a very viscous orange red. liquid which was very tacky. The water -7/hi t e clay treated original oil was chlori nated (C-19-20) i n an attempt to get.a water-white chlori nated product. The conditions were practically identical to B u n C-13-18 - low temperature and actinic light. •,The oil slowly turned.yellow and at the end was as yellow as .the product of more chlorine. C-13-lo .although it contained considerably This material was clay treated and stripped; h o w e v e r t h e high temperature necessary for complete strip ping caused discoloration.- The final stripped -product was solid. It is -very Interesting to note that the per _cent in crease in weight due to addition (Table IX) is just about the same In the three runs (C-12-36, C— i3-lcJ and C--l9-20) on the original oil even though the total increo.se in of the oil varies from 5 7 to 167. Tne value s.j.so is very " 84 close to toe theoretical amount necessary to sat.urate the original oil. The important observations and conclusions which can be drawn from this series of runs are: (l) chlorination at low tenner at ures in the presence of actinic light as opposed to other conditions studied produces desirable light colored products, (2 ) clay treatment is a very satisfactory method of stabilizing chlorinated materials, (3) all of the molecules present in an. oil are apparently chlorinated, (4) viscosity, density and refractive index increase greatly while the viscosity index drops rapidly with, an increase i n chiorine content. The next series of runs was carried out on kerosene both untreated a m clay treated. The properties of these kerosenes have been given in Table VII. A summary of chlorinations of kerosene is given in Table X I I . in accord ance with the results of the shove runs on lubricating oil, these chlor Inations were made with nact ini c,T light as cr O catalyst. The first run (C-14-19) on kerosene at 19“ C ’honed that reaction was much more rapio. unan nati oeen une case for the oil fraction. 11 The chlorinated product was a t vel low, non—viscous fluid • it was stripped of as previously and then clay treated in a tower. It caiue through the clay yellow but gradually turned to a purple color . ;A second clay treatment gave a light yellow proauct TABLE XII Summary of Chlorinat-ions of Kerosene Actinic 1ight wa s activator in all cases. % Increase Run Mo. Material C-14-19 Kerosene Tenro. r. in Weight % hydrogens* Total By Addition Replaced Product 19 69 19 14 Light jellow fluidburns C-15-21 H 21 95: 19 19 Light yellow fluidburns C-16-19 I! 19 187 9 38 Light yellow plaster does not burn 70 200- 9 41 Light orange plaster does not bin’ll Clay Treated Kerosene TABLE XIII d20 = 1.138 ii Properties of Kerosene Chlorinated to a. 69% Weight Increase at 19° C. Using nActinic,!.Light o C-22-70 1.5020 Vis*100 = 15.33 Vis‘210 7.1. = 2.76 = -36 03 Ul Viscomjeffr. E ffluxJIim t R un ... cove C.-i Chlon'natim^. of.. Kermm 0 80 160 HC! R ecovered 240 ~ 9 r• 300 87 which was stable to prolonged heating at 100° C. The product thus obtained burned slowly with a very sooty flame The properties of this product are given in Table XIII. R un C-15-21 was made under Identical conditions but the chlor ination was carried further» A rough viscometer was put in the reactor so that its lower end was in the chlorinated material' and its upper part extended through the plate covering the reactor. By this arrangement a rough measure of the viscosity of the kerosene could be ob tained without removing any from the reactor. Figure 9 is a. plot of the efflux time of the kerosene against the amount of hydrogen chloride recovered in the absorbers. This .graph is very similar' to one which would be obtained by plotting viscosity against chlorine content. This graph bears out the observation that the viscosity increase grad ually with chlorine content initially but soon starts to increase very rapidly. The final --product of this run showed the same tendency to become purple as had the pre vious one but repeated clay treatment stabilized It. This product also burned with a sooty flame. The extensive chlorination of kerosene was next car ried out (Run c-16-19) under the same conditions as before. Although chlorinated to the- high degree of 187^ increase in weight which is equivalent to a compound containing about 63f> chlorine by weight, there was practically no dis coloring of the kerosene . The chlorxuca. ueu- o..>ene v.as 88 was lied with water and dilute soda ash solutions, clay treated and finally stripped under vacuum at 100° C. The product is a light yellow, almost plastic substance at room temperature which is very stable to prolonged heating she 100° C. It will ignite- in direct -flame but immediately goes out when the flame is removed. Run C-22-70 was a similar chlorination using, however, the clay treated kerosene -and chlorinated at a higher tem perature. The increased temperature was used to speed up the reaction which had been very slow towards the end of the previous chlorination. An attempt was made during this run to use a mercury vapor ultraviolet light as a catalyst in place of the carbon arc lamp. The results were dis appointing. -.Although supplying a little catalytic effect it was by- no means adequate and therefore the carbon arc lamp was again used. This result tends to bear out the work of Baskerville and Riederer (4 ), who found tnat blue light and not ultraviolet catalyzed the chlorination of methane. The final product was treated as in Run C-16-19 but, due -probably to the fact that dark colored material had entered the kerosene as a result of tne action of GCl^ on the wire insulation, tne final product was somewhat ciamer. It was like a plastic, very tacky semi-solid, which would not burn except in an open flame. The increase in tem per at ure very effectively speeded up tne reuccion r/ithout 89 causing any harmful discoloration. It is interesting to note, in Table X I I , the amount ox the increase in weip:ht which is due to addition. The two chlorinations yielding low chlorine content products (C-14-19 and C-15-21) had 199a of their total per cent increase in weight caused by addition. The run . giving highly chlorinated products (C-16-19 and. C-22-70) had only 9% of their total per cent increase in weight caused, by addition. Here there is an agreement between runs of similar chlorine contents but wide dissimilarity between the runs of different chlorine content. Decomposition in the more highly chlorinated products is indicated since decomposition of chlorinated molecules yields hydrogen chloride which, when absorbed in the absorbers, indicates a greater amount'of reaction by substitution than actually occurs. This reduces the apparent reaction by. addition which is determined by dif ference . The assumed formula of the kerosene (CnPl2n ) re- auires a 39^ increase in weight for complete satisfaction of unsaturation. Three runs were made on the 51—53° C . melting point paraffin wax mentioned previously. marized in Table XIV. The results are sum The first two runs (C-17-21 and C-2I-4.O) were carried out atHlow temperatures with "actinic” light as catalyst and to a very hign ■.cnlorine content. The third, run ^C—23 — 50) was mau.e at a slightly higher tern Denature in order to speed up reaction wxiich was 90 very rapid at first bat which, after a while, slowed up consider ably. Both were washed and clay treated before being stripped. The stripping was attempted at I400 C. with high vacuum and. a stream of C02 to remove solvent but the products were too viscous at this temperature. They were finally stripped at 160° C. but turned slightly yellow during the process, having been water-white previously. This product -was a very brittle and friable, clear solid with a softening point of about 65° C. A n attempt to pla.sticize it with 20% castor oil yielded a very tenacious non brittle plaster solid with a softening point of just about room temperature. The other run (C-23-70) was made to obtain a liquid clilorinated wax since Gardner (18) had shown that the con gealing point of paraffin wax decreases to a minimum, -18° C. in his case, and then rises sharply again with increase in chlorine content. The product obtained in this investiga tion, after washing and clay treatment, was a water-white slightly viscous liquid with a congealing point (similar to Pour Point) of -17° C. This congealing point was in almost Perfect agreement .with Gardner!s work. perties are listed in Table XV. Tne physical pro It has a high viscosity index and a density greater than that of water. There is very little unsaturation in the paraffin wax s m c e o.ll of the chlorine appeared.to react by substitution as shown in Table XIV. 91 Next a chlorination was run on isopentane (Run C-1&-20) maintaining the conditions of low temperature, 20° C ., and "actinic” light. The reaction was very rapid and very little chlorine passed through unreacted. Quite a bit of the isopentane was lost by evaporation even though an ice trap was put in the exit line. When approximately one- fourth of the hydrogens had been replaced with chlorine, the water-white material was flushed with ammonia, washed, and dried with CaCl2 • sharp odor. The finished product had a very A summary of this run and the properties of the product are presented in Table XVI. The density and refractive index are quite high compared to the original material. This product will burn. In anattempt to separate the chlorinated compounds, a distillation (D-7-735) at atmospheric pressure was per formed on the chlorinated isopentane. ...When the still heat was turned on, the first product obtained was a white crystalline solid which condensed on the delivery line. and. above the flask lagging. The distillation was discontinued and this white' material collected.. The still temperature had risen to about 220° C. and this solid may have been due to decomposition or condensation. The aistilia oio.h was continued and five liquid cuts .obtained. xhe residue las quite discolored which usually is evidence of decomposition. To improve the color, this residue was c h y treated. The 92 properties of tlie several cuts and the clay treated residue are given in Table X V I I . The cuts all had a. very sharp characteristic odor while the white•crystalline solid had a strong odor of camphor. This white material did not have a definite melting point but melted over a range from 130 to 145° C. One form of artificial camphor, bornyl chloride, has 3- melting point of about 130° C. and another, isoborryl chloride, a melting point of 1A5-1500 C. The camphors sub lime at low temperatures and most of the material obtained above was lost by sublimation. Blends of the clay treated residue and acryloid KF, 55.7 weight per cent active, were made and viscosities and viscosity indices calculated. In Table X V I I I . These values are tabulated They show remarkably high viscosity indices approaching very close to maximum values at the higher weight per cent b lends. • A n attempt was made to chlorinate purified cotton in the solid state. The cotton was held, at a temperature of 100° C. by steam and exposed to the rays of the carbon arc lamp while In an atmosphere of chlorine. After several hours it was evident tnat tnere was no reaction and tne run discontinued. Commercial rosin, mainly abietic acid., Wets o.lso chlor inated . Trouble was encountered, however, In obtaining a- good solvent for it. o The solvent finally used was benzene. 93 Of course benzene will react with chlorine also but under the conditions of the chlorination, elevated temperature and ’’actinic” light, the chlorination was supposed to be quite difficult. Quite a large amount of the chlorine did react with benzene however. The final chlorinated rosin was a light, pink colored solution. When ammonia was passed through this solution it turned to a dark muddy brown which clay treatment did not clear at all. necessary temperature When stripped at (160° C.) the product decomposed and gave a black carbonaceous mass. % Increase in Weight Run No. C-17-21** Temp. °F. 21 Due to Due to Addition Substitution .0 C-21-10 40 0 C-23-50 50 0 175 % Hydrogen Total 175 173 49 Replaced 34 173 34 49 10 Product Light yellow fri able solid Softening Point= 65° C. Softenfing Point= 65° n Water white viscous liquid Burn Ho Ho. Yes * Based on CnH2n+2 where n = 28. *** All runs made in presence of CCly TABLE XV Properties of Paraffin Wax Chlorinated to 49$ Weight Increase at 50°C. with Actinic Light Catalyst•(C-23-50) rip0 = 1.4.918 & 2 Q = 1.087 Viscosity (210° F.)= 12.60 - Viscosity (100° F.) = 138.8 Viscosity Index = 89 Congealing Point = -17° C. 95 TABLE XVI Chlorination of Isopentane (C-lo-20) Conditions: Carton arc lamp and 20° C. Increase in Weight: Product: -1. 137fo corresponding to tricliloride. c5h9ci3 2. Clear,- colorless liquid with character istic odor. ngO = 1.5042 3. dpQ = 1.421 4. Viscosity (100° F.) = 3.64 TABLE XVII Distillation No. D - 7-735 DistIlla.tion of- Chlorinated Isopentane Pressure - Atmospheric (735 mm. Hg.) Each cut represents 1.0% of charge Material Cut F .Temp. ° E . ^ n^ ^20 ? 1.4928 - Viscosity-Centlstokes 100° F . 210 F. - Cut 2 175 1.4972 1.360- 3.05 Cut 3 180 1.5022 1.408 3.24 Cut 4 208 ’ 1.5031 1.415 3.32 Cut 5 200 1.5051 1.423 3•48 1.5172 1.497 4*91 Residue-'''- - Clay treated. ■if- Solid material present in this cut. I .42 96 TABLE XVIII AcryJ-oid Blends of Residue from Distillation of Ch.lorina.ted Isopentane W t . % Aoryloid in Blend Viscosity-Centistokes 100° F. ~~210° E. Viscosity % of Max. Index______ V.I. 4.4 11.44 3.36 185 51 7.6 18.58 5-43 197 71 11.9 31.92 3.95 175 82 . 15.0 45.52 12.43 167 35 97 CONCLUSIONS As s. result of tnis Investigation trie following con clusions liave been drawn: 1. Chlorination in the presence of "actinic” light leads to a rapid reaction at relatively low temperatures without the formation of discolored product’s. 2. Chlorination of lubricating oils in the presence of iron leads to decomposition and tar formation. 3. The density and refractive index increase with an in crease in chlorine content. A. With increasing chlorine content, the viscosity of the material at first increases very slowly and then more rapidly and final Iv1 " very rapidly. 5. The viscosity index of the chlorinated-, material de creases with increasing chlorine content. 6. Fire resistance of the chlorinated products, tested by heating them in an iron cup over a bunsen flame, in creases with Increasing chlorine content and. they finally become entirely non-inflammable. 7. An increase- in temperature greatly increases tne raoe of chlorination but may product side effects. 8. Chlorination apparently occurs to a greater or less extent on all of the molecules present. 98 9. Clay treatment of chlorinated products increases their stability markedly. 10. Highly chlorinated lubricating oils, kerosene and paraffin waxes can be produced which are stable to prolonged heating at 120-140° C. 11. Gardner1s (18) work on paraffin wax indicating a minimum congealing temperature at Increasing chlorine contents is substantiated. 12. The observation (4) that ultraviolet light is not the active constituent of TTactinic,! light in catalyzing chlorinations is supported. 13* The darkening of some chlorinated products upon stand ing seems not to be caused by oxidation. . 14. The production of high viscosity index materials by chlorination and subsequent treatment is a definite possibility. 99 A P P E N D. I X 1 100 Sample Calculations Run C-16-19 (Kerosene at 20° C. with actinic light) Data for absorber A, Amount of solution = 210 ml. Sample used = 1.0 ml. Normality of sodium thiosulfate = 0.1367 Thio used to titrate nClprr = 0.55 Thio used to titrate r,HClT! = 22.80 Or. Cl2 as Cl2 = (0 .55) (0.1367) ( ^ ) (0.0355) = 0.56 gr >■ Gr. Cl2 as HC1 = (22 .80) (0.1367) (-21Q) (0.0355) - 23.2 gr. "i For total run g r . Clp as Cl2 = 120 . g r . Cl2 as H01 = 2 5 7 g r . Cl2 introduced (from Gl2 cylinder) = 6 5 7 ■gr. Clp accounted for = (2) (257) +■120 = 634 g r . Cl2 unaccounted for =-23 - gr. Cl2reacting by addition. Increase in weight = 257 + 23 - ~ Sr . Original weight of Kerosene = 146 gr. % Increase in weight = (~p^r) (100) = 137 Increase in weight per 'fo i-Iycirogen replaced — 4,.93/ (Based on CnH2n where n = 13) 101 Increase in weight due to substitution = 273 - 23 = 250 gr. % Increase in weight due to substitution = 23o x 100 = 171 116 % of* Hydrogen replaced = 23LL = 35^ 1 A-72 / ■> c? - /'■> o 9 Calibration of Flowmeter The flowmeter was calibrated by the use of chlorine which was absorbed in potassium iodide solution. Readings of time and scale reading were made and titration gave the amount of chlorine used. Scale reading Liters Chlorine oer Hour 12.5 mm. 1.10 23 .0 1.74 42.5 3.25 29.0 2.23 This calibration holds only in the range covered. When the flowmeter was used at. higher rates, it served merely; as a running check on the chlorine flow. 102 McGleod Gage Calibration V-j_ = vo 1 tune or bulb and capillary V2 =.volume of capillary “ pressure on system P2 - pressure on gas when compressed into capillary (Vs) 4 H • = difference in level of mercury in capillary and side arm when gas is compressed into volume V2 its pressure will be: P2 = Pi + but (1) ” ^2^*2 or assuming perfect gas. PlVi h2 (3) — V2 Substituting in (l) Pi V-t -P. - P-i + V2 Solving a / (A) H 1 / \ H(y~l'Y0""v 3— ? Py - — Data on Me C Leoa Gage: Diameter of caxiillary = 0.262 mm. Volume of flask to capillary. ='57.00 ml. Length of capillary = 35.5 cm. 2 = yT D 2 t _ (yf) (0.262)2 (35.51 = 1.92 ml. n r ~ L" 4 -t m m ?! “ ^ II = 1.92 57.00-1.92 . 23.0 ?! t J I 103 Vacuum Engler Thermocouple Calibration The vapor temperature thermocouple was calibrated against a standard thermocouple in constant temperature baths and the e.ui.f. read by a Leeds and Northrup Portable Precision Potentiometer. Unknown T.C. e .m .f . Microvolts T e mp era tur e Standard T.C. e .m .f . Microvolts 100° F. (37.78° C.) 150.2 150.2 210° F. (98.88° C.) 419.0 419.0 Since the thermocouple was in perfect agreement with the standard, the calibration of the latter was used. E = 38.84 T + O.O4532 T2 - 0.00003011 T3 E = microvolts T = 0 C. The sta.ndard thermocouple was standardized by J. M. Geist against the Petroleum Ps.efining Laboratory *s std.no.ard D. P. 1 thermocouple which in turn, had been standardized against a platinum resistance tnermomecer• 104 Siphon Counter Calibration Ace tone was nun from a constant head, reservoir through the siphon counter. The number of* trips, the volume and the time were recorded from which the trips per minute and liters per hour were calculated. N o . of Trips 1 2 3 1 1 1 1 Time (Sec.) Volume (ml.) Trips/Min. Liters/hr. 45.0 38.2 34-2 29.3 45.7 48.9 54-3 13 27 40 14 14 14 14 1.33 3.14 5 .23 2.05 1.31 1.23 1.11 1.04 2.54 4-21 1.72 1.10 1.03 0.93 Extraction Column Thermocouple Calibration A thermocouple made in the same manner as the ones on u the extraction column was standardized against a standard thermocouple in constant temperature baths and tne e.m.f. read by a Leeds and Northrup Portable Precision Potentiom eter. -The .standard thermocouple was the same as the one listed above under Vacuum Engler Thermocouple Calibration. Temperature e.m.f. Microvolts 100° F . (37.78° C.) 150.2 210° F . 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