US2798085A - Synthetic hard wax - Google Patents

Description

July 2, 1957 G. D. FRoNMULLl-:R ET Al.. 2,798,085

SYNTHETIC HARD WAX Filed March 14, 1955 @2030405060 705090/oQ//o` United States Patent SYNTHETIC HARD WAX George D. Fronmuller, Mamaroneck, and Michael J. Mirra, Woodside, N. Y., assignors to Commonwealth Color & Chemical Co., New York, N. Y., a corporation of New York Application March 14, 1955, Serial No. 494,214

17 Claims. (Cl. 2150-450) The present invention is directed to the production of synthetic waxes and more particularly to a method of producing such a product which resembles carnauba wax in Various desirable properties.

Attempts have heretofore been made to produce such a wax by various methods. For instance, tank bottom or microcrystalline waxes have been oxidized to' render them emulsiable, but in the process their hardness suffered. To increase the hardness and toughness of the waxes, resins such as polyethylene wereblended in, but then the emulsion forming properties usually suiered.

Also, processes are known whereby high molecular weight hydrocarbons are oxidized in order to form fatty acids for the purpose of preparing soaps and the like. According to one such process, the oxidation was in the presence of a metallic soap having drying properties. However, such a process was unable to produce a wax of a hard type. In another process, normally liquid hydrocarbons were heated in the vapor state in the presence of a catalyst with oxyen-containing gases for the purpose of producing low molecular weight alcohols, aldehydes and acids. It has also been proposed to produce such alcohols having from 8 to 18 carbon atoms by similarly oxidizing the hydrocarbons in the vapor state. However, none of these processes was adapted to produce a wax product.

The presentinvention is intended and adapted to overcome the diiculties and disadvantages inherent in the prior art, it being among the objects of the inventionrto produce a wax which is comparable to carnauba in its hardness, high melting point and its ability to form emulsions.

It is also among the objects of the present invention to provide a process for producing such a product which utilizes a low cost and plentiful raw material and which is economical in operation.

It is further among the objects of the present invention to provide such a process which is easy to controlland which is capable of obtaining the desired characteristics in batch after batch.

In practicing the present invention there is utilized a raw material source which is plentiful, consistent and economical. A raw material which satisfies these conditions are the hydrocarbon waxes produced synthetically by the Fischer-Tropsch process, which is fully described in the literature. In this process carbon monoxide and hydrogen at atmospheric pressure are passed over catalyst such as cobalt, iron or nickel, at about 200 C. `The reaction involved is as follows:

By varying the proportions of carbon monoxide and hydrogen plus the catalyst, reaction time and temperature, high molecular weight aliphatic hydrocarbons can be produced, as described in the article by Craxford, Trans.

2,798,085 Patented July 2, 1957 2 Faraday Soc. v. 35, p. 946 (1939). Thus by controlling the process variables a synthetic hydrocarbon wax having the desired molecular weight, melting point, isomer content and hardness can be assured.

If a Fischer-Tropsch hydrocarbon wax is oxidized under the proper conditions and in the presencey of specific catalysts in accordance with the present invention, a high melting emulsiiable wax will be produced. Furthermore, if this oxidized wax is then treated with certain metal compounds so that the fatty acid salts of this metal are produced, the hardness of the wax s increased without adversely affecting the emulsiable properties of the wax.

In conducting the process the hydrocarbon used is limited and held at a temperature of about C. until the peroxide initiating agent is added. Air is bubbled through the mass continuously during the addition of the peroxide. The temperature is then raised to 150-155 C. The temperature may then be reduced to about C. and a suitable metal added thereto such as the metals of group II-a and II-b of the periodic table. The initia# tors are generally either organic or inorganic peroxid-es, and are capable of acting as agents promoting the oxidation of the hydrocarbon.

In the oxidation of the Fischer-Tropsch hydrocarbons, some of the main products are fatty acids and their esters. Therefore, the oxidation was controlled by following the formation of acids (acid value) and esters (ester value). If the acid value and ester value (acid value plus ester value=saponication value) are plotted as the oxidation proceeds against time, the effectiveness of the peroxide catalyst can be shown. The curves which are presented vare average data from oxidation procedures which will be described later.

The accompanying drawing constituting a part hereof consists of curves illustrating the nature of the invention, and in which Fig. 1 is a series of curves showing the course of oxidation of hydrocarbons with and without catalysts;

Fig. 2 shows curves indicating the hardness of various products; and

Fig. 3 illustrates the solvent retention of various products, including those of the present invention.

Referring to Fig. l, it illustrates the course of the oxidation of the hydrocarbons under various conditions of operation. The oxidation of the Fischer-Tropsch waxes using benzoyl peroxide as the initiating agent, together with metallic zinc is shown in curves A, B and C, indicated in solid lines. Curve A is the acid value; curve B is the ester value and curve C is the saponification value. Curves A', B' and C show the course of the oxidation of said wax, using only benzoyl peroxide as the initiating agent, the amount used in both cases being about .2% based upon the weight of the hydrocarbon being treated. Curves A", B and C show the course of the oxidation of the same hydrocarbons where no catalyst at all is used.

The saponiication curves C, C and C are straight lines passing through the origin. The equation for a straight line passing through the origin can be indicated by Y=mx, where m is the slope of the line. The slope of curves C and C can be viewed as a rate function, e. `g. rate of formation of esters and acids with time. Thus if the slopes of the straight lines are known the effectiveness of catalyst or other factors in the rate of oxidation can be evaluated.

3 4 Thus it is shown that increase in the rate of oxidation with TABLE C the use of benzoyl peroxide is appreciable as indicated in Table A' Wave Length (microns) It was .also found that if a secondary catalyst is used in conjunction with the initiating agent (peroxides) the rate 3.48 5.77 6.86 8.87 13.75 13.95 of oxidation was `further increased. For example, if the oxidation of Fischer-Tropsch hydrocarbons is carried out optical Density using benzoyl peroxide as an initiating agent and zinc as a secondary catalyst, the oxidation rates are increased (1) Unoxidized Eisher-Tropsch further as indicated 1n Fig. 1 at C :and Table B. 10 gtg Ffnaifglef 79 04 26 .04 .23 .24

e (2) oxidized F-T Wax: Acid value oi23, Sap. value of 58. .88 .30 .37 .14 .28 .28 (3) iFfleau' Wavxii TABLE B 798184 .9o .as .3e .29 .293 .291

Curve Slope Rel. It is believed that these peaks represent dilerent types of (m) Rates carbon-hydrogen bonding. At 5.77 microns, peaks were (D Curve 0 (no catalyst) 4.9 1 noted in the oxidized wax .andcarnaub'awax and it was (2) Curve C' (0.2% benzoylpewxide) 8.1 1.5 plainly absent in the unoxidized sample. Absorption at (3) Curve C (0.2%benzoylperoxdep1uSZiI1CmetaD 17-8 3-6 20 this wave length is believed to indicate the existence of carbonyl bonding (e. g. acids, esters, aldehydes, ketones, etc.). Absorption at 8.87 microns also indicates the pres- Y ence of carbonyl bonding, 'a peak was noted in the car- The function of zinc metal as a catalyst is not fully nauba wax run but was :absent in both the oxidized and known, but the indications are that it may not act as a unoxidized Fischer-Triopsch Wax samples. The main intrue catalyst in that the zinc is partially used up during dication which this data presents is that there was no indithe oxidation. It is believed that the zinc is used up in cation of carbonyl bonds in the Fischer-Tropsch unoxithe production of fatty acid salts. This is indicated by dized wax. It is believed that esters and acids which are the fact that the oxidized wax has an ash content of 0.3- the oxidation products cause the peak absorptions, in the 0.4%. It is also possible that the reaction of the zinc with 30 oxidized run. The wax samples were melted as they were the oxidation products of the wax may not be the whole tested with the infra red rays. cause of the catalytic effect noted. The zinc could also This wax was melted at a temperature of 100-105 C., provide the active centers upon which the oxygen and then the benzoyl peroxide was added. The air was then hydrocarbon molecules react. Thus, any reaction between bubbled through the molten wax at a rate of 12-15 liters a the zinc metal and the oxidation products (fatty acids) minute. The temperature was then raised to 120 C. and may be secondary with regard to the catalyti effect Shown at this point the zinc was added to the reaction mixture. The temperature again was raised to 150-155 C. for the duration of the reaction. The oxidation was followed Example l by testing for the acid and saponication values during the course of the reaction. It was found that by stopping The hydrocarbon wax is melted and heated to C. the oxidation when the acid values were between 10-20 in a glass lined or stainless steel vessel. The benzoyl and the SaPODiCaGD Values Were beWeeIl 30-60, a Wax peroxide is added and an oxidizing gas (air) is bubbled With the desired Properties Was ebtallledthrough the molten wax. The system is then heated to The apparatus Wlllell can be usedhlu the Oxldatlon 0f C and 'the Zinc (mossy or Sheet) is added. The 45 the Fischer-Tropsch wax was essentially as follows: In reaction temperature is then maintained at 155 C. laboartory runs a three necked, mun@ bottom glass ask for the duration of the Oxidation :was used as the reactor. The air was inyected by means of The air which is passed through the reaction vessel is a glass tube or a fritted glass gas disperseiatorand the flow p of the air was controlled by means of a Fischer-Porter previously dried and ltred' .Fn was @und thai .satls' 50 owmeter.' The wax was heated by an electric mantle factory -results were obtained i'. the relative humidity of and the temperature was Controlled by a merc to merc the au' 1S zdf-26% or a dew Pomt of 55 F' The alf rate thermoregulator. The exhaust gases were passed through used was 10-15` liters per minute per pound of liydrOCal'- a series of condensors and expansion chambers so that bOIl t0 be OXlCllZed The Oxidation iS SOPPed When the any condensable material may be collected. On larger desired acid and ester values are obtained. 55 scale operations (50 lbs. of wax) steam jacketed stainless A typical run which gives satisfactory results is as steel or aluminum reactors may be used. follows: Among the desirable properties ofthe wax are good emulsifying characteristics so that very ine particle size 500 gra-ms Fischer-Tropsch wax emulsions may be formed and a hard wax of a melting 1 gram benzoyl peroxide 60 point of 85 95 C. with a light color. These properties 60 grams zinc (mossy 01- Sheet) -are obtained if the conditions of oxidation are followed as described, until a wax with an acid value of 10-20 'Ihe Fischer-Tropsch wax used in this run had .a melting aud a siapomcatlfn Value of, 30-60 1S obtamed The point (A S T M.) of 220 F an isomeric content of time (Fig. 1) required to obtain these acid and saponif'iless than 10% and 20% to 60% of the Wax can be dis 65 vcation values is fr orn'three to six hours of oxidation tilled at 670 F. at 2 mm. pressure. To further charunder the. s-taitefi condmons' acterize this wax infra-red abso tion data was com iled other mmatmg agents may be used Wlth Satlsfactory rp p. results. Other peroxides which were used were urea fn the unoxldlzed and oxldlzed, waxes* 'uns data l? gwen peroxide, lauryl peroxide, potassium persulphate. in m Table C (below) along wllll absofpuon data m far' 70 general it is believed that those agents which are capable 'Haube WaX- The Values glVeu u1 Table C are the OPuCal of producing free radicals may act as initiating agents in deUSlY Values at tlle Peaks fOuIld Within the Wave length the oxidation of hydrocarbons. This is thought to be the -range studied. It may be noted that the peaks found at 'case with the peroxide class both organic and inorganic. 3.48, 6.86 and 13.75 and 13.95 were present in all three It is further believed that better results are obtained cases studied. 75

if the peroxides are soluble in the wax to be oxidized and Voxidized waxes were studied.

'slowly to room temperature.

Weense if "the decomposition temperature "of the peroxide 'is higher than the melting point ofthe wax, which is'the case with benzoyl peroxide.

Metal catalysts which were tried other than zinc were copper and iron. Their catalytic veiects were Anot as great as zinc, plus the fact that both copper and iron cause undesirable color formation in the oxidized wax. Therefore, the optimum catalytic effect was found with the use of benzoyl peroxide and zinc.

Temperature also has an effect on the rate of the reaction; generally its rate increases with the temperature. A temperature much 'over 150 C. causes the wax to begin to soften due to some cracking effects. Since a hard wax is desired to compromise reaction temperature of about 150 C. was found to be satisfactory. A prolonged reaction time, especially at high temperatures,

also causes the wax to discolor, (le. fg. Ait becomes yellow). Therefore, in order to obtain a desirable oxidized wax it is best to carry out the oxidation at a fast rate at a vmoderate temperature, e. g. l404l55 C. v

Example 2 In view of the fact that there is a `large demand for a hard, high melting wax which can form a tine particle size emulsion, the emulsion forming properties of the It was found possible to form a tine emulsion by one of the 'standard procedures in the art; the method is as follows:

(l) 40 `parts of oxidized wax VFischer-T'ropsch Wax with an acid value of 10-15 and a saponication value of 35460.

(2) 4 parts 2-amino-2-methyl-1-propanoL (3) 8 parts of oleic acid.

(4) 1 part of borax.

(5) 240 parts of water.

Melt (1) to l00VC. add (2) and (3) to the wax. Heat '(5) to 95-`100 C. and add (4) to the water. Slowly add the wax emulsiiier system to the water-borax system at 95 l00 C. The whole mixture is agitated with 'a high speed, high shear agitator. After all the waxemulsifler is added to the water, the emulsion is mixed The emulsion produced in this fashion is a good base for a dry-bright polish.

In studying the hardness of the Fischer-Tropsch waxes it was found that the higher the distillation `range of the wax (Ie. g. a higher average molecular weight) the harder the initial and oxidized wax would be. Therefore, if hardness in waxes is sought after, the starting raw materia-l should be a wax with a high distillation range. The initial hardness of the unoxidized wax will determine to a large -extent the hardness of the nal oxidized wax; in general the harder the starting raw material is the harder the oxidized wax will be. There is invariably some softening effect in the wax after oxidation as shown in Fig. 2. This softening effect is probably caused by some cracking effects on the hydrocarbons plus the inherent softness of the oxidation products a's compared to the hydrocarbons.

It was found possible to harden the Vox'idized wax co'nsiderably by forming a small percentage of certain metal salts of the fatty acids in the oxidized wax. Upon forming the metal salts of the fatty acids it was found possible to increase the hardness (decrease the penetration values) by 30% to 60% as indicated in Fig. 2. It is `believed that most multivalent metals show this property of increasing the hardness of oxidized waxes upon forming their salts with a small percentage of the fatty acids in the oxidized wax. Those metals which appear to give the best results in decreasing the penetration values of the waxes are those elements in group IIa and group IIb in the periodic table. Of the metals in these groups, strontium and cadmium salts of the fatty acids gave the best results in terms of increasing the hardness of the waxes. Other metals'tried thus far were magnesium, zinc,

considerably.

parent oxidized wax.

'iron a'nd copper. These metals upon forming their salts `also increased the hardness of the wax but not to the same TABLE D Wax Flora carnauba wax. Y Oxidized F-T wax where 40% was distilled at 670 F. at 2mm. Acid value of r12. Sap. value of 47. Strontiurn salt vof oxidized wax E where ash content as SrO was 1% on `weight of the wax.

Cadmium salt of oxidized wax E where ash content was 1% on weight of wax.

Oxidized F-T Wax where 60% distilled over at 670 F. 4at 2 mm. pressure. Acid value- 13. Sap. value-50.

Typical commercial oxidized microcrystalline wax.

` lAcid value 20-25-Sap. value 55-65.

Strontium salt of oxidized wax indicated in B. Ash

content of 1% as SrO.

On forming the metal salts, the hardness is increased VThe penetration values decrease from 30% to 70% depending on the temperature and the Curve C (strontium salt of the higher distilled oxidized wax) compares very favorably with carnauba wax in terms of hardness. All the other waxes used as shown are considerably harder than the typical oxidized microcrystalline wax.

Example 3 There are a number of methods used to form metal salts 'of fatty acids. The methods used thus far in our investigation were as follows:

If the oxidation is carried out in the presence of the metal or one of its salts, some fatty acid salts will be formed. This is the case as described with zinc. Carrying out the oxidation in the presence of zinc metal an ash content of 0.2 to .4% on the weight of the wax is obtained. This ash is in the form of zinc oxide. Thus in the process of oxidation the oxidized waxes will con# tain a small percentage of zinc salts. It is believed feasible to carry out the oxidation in the presence of another metal, e. g. strontium or cadmium so that the desired salt formation will take place.

Example 4 Another method of forming some acid salts of the fatty acids present in the oxidized wax is to react a salt of the metal with the finished oxidized wax. For example, on taking a salt such as strontium acetate or cadmium acetate and mixing it with an oxidized wax at l50170 C. for l to 3 hours, causes the wax to harden.

( 1) 10() gr. ofoxidized F-T wax with an acid value of 23 (2) 5 gr. of cadmium acetate On heating (l) and (2) together for 1 to 3 hours causes the acid value to decrease and the hardness of the wax to also increase. Similar results were obtained with copper acetate, magnesium acetate and strontium acetate. It is probable that there is some exchange reaction going on between the metal salt and the fatty acids in the wax. The salts used tend to decompose on heating, thus facilitating the salt formation with the fatty acids.

Example 5 Still another method used to form a small percentage of the salts is as follows:

(l) 1250 grams `of oxidized F-T wax with an acid value of 16.7 and a zinc ash content of .3%.

(2) 12.5 grams of potassium hydroxide (3) 91.25 grams of strontium chloride (SrClz.6H2O) (4) 2500 grams water .Melt (l) atl C., add (2) to (4) and heat to boil.

Then add the potassium hydroxide solution to the wax with agitation. An emulsion is formed due' to the formation of the potassium soap of the fatty acids present in the oxidized wax. After the emulsion is formed and the temperature is still at 95 to 100 C., the strontium chloride is added. The emulsion is thereby precipitated. After the emulsion is precipitated it is filtered and washed thoroughly with hot water. Then the Wax is dried completely at 110 C. for 4-5 hours. By this method the amount of salt formed can be controlled readily. In the case presented here, the amount of potassium hydroxide used was .223 mole as compared to .342 mole of strontium chloride. The final wax has a total ash content of 1.25% on the weight of the wax.

If all the fatty acids in the Vwaxlwere to be tied up by the potassium hydroxide `in' forming the emulsion, 20.8 gr. of KOH should be used (e. g. 1250x167). In the example Acited only 12.5 ,grams of KOH was used, so

that' 57.2% of the available fatty acids are tied up. In

the exchange reactionV between Vpotassium and strontium there resulted a decrease of in the acid value of the wax. This corresponds to complexing 30% of the 'available fatty acids in the wax'or stating this in another fashion the exchange reaction between potassium and strontium is 52.4% eicient. The indications are that only trace amounts of potassium salt remain in the precipitated and dried Wax.

After forming the metal salts of the wax acids, the physical appearance of the wax changes somewhat. It appears as a brittle hard wax whereas before the salt formation it was more amorphous. The crystalline form of the wax appears to have changed after the metal salts are formed in the wax. In the example cited, strontium chloride was used to form the salt. Other ionic salts of other metals were also tried with similar results, such as cadium iodide, copper chloride, magnesium chloride, zinc chloride, etc. The relative amounts of metal salts to be used can be varied to a great extent and the amounts used in the cited example are not meant to be restrictive but rather to indicate the general order of magnitude to obtain the desired results.

The emulsion forming properties of the wax do not vsuffer upon forming these Various metal salts. Using the procedure previously described to form the emulsions, very line particle size emulsions can be formed. The melting points (90 to 95 C.) of the oxidized and the oxidized-salt wax did not change. The color of the wax changes somewhat depending on what metal salt is being formed. For example, on forming the strontium salt of an oxidized wax the color changes from pale white to light tan. The hardness increases considerably (Fig.

.2) on forming these various salts.

A property which changes considerably is the solvent retention ability of the salt-wax over the oxidized wax.

This property is very important in the manufacture of solvent type polishes such as shoe polish and furniture polish.

To illustrate this point, solvent retention studies were performed on:

(a) The unoxidized Fischer-Tropsch wax (b) Oxidized Fischer-Tropsch wax (c) Oxidized Fischer-Tropsch wax which contained the cadmium salt of the fatty acids in the wax V(d) Flora carnauba wax ,tention of 2O Vparts of unoxidized Fischer-Tropsch wax in solution in 57 parts of Stoddard solvent. Curve B is directed to the solvent retention of 20 parts of oxidized wax in the same amount of solvent, said wax having an acid value of 12 anda saponication value of 44. Curve C represents the solvent retention of a wax oxidized in accordance withthe present invention and containing a cadimum salt. Curve D indicates for comparison purposes, the solvent retention ofFlora carnauba wax.

The solvent retention properties of the product of the present invention are greatly improved when the wax is in the form of the metal salt. In this product the solvent evaporates more slowly than even carnauba wax, which is very desirable in the solvent polish lield.

The acetyl values, which measure the presence of alcoholic hydroxy groups and the OH groups of hydroxy acids, range from about 35 to 53 with an average value of about 43. In the process of treatment of the starting material the peroxide values change, rising to about 18,000 P. P. M. in the second hour and then decreasing to about 11,000 P. P. M. after tive hours; in the last hour there is a rapid decrease in the peroxide value down to about 400 at the end of the operation. The range in the product is Yfrom about 5,000 to about 400, and preferably the value should be not over about 500.

The distillation range of the product at about 7 mm. mercury pressure is as follows:

Above this temperature cracking and decomposition takes place.

Other properties of the product include the lactone value which measures the lactones and some of the acid anhydrides present. The lower the value the harder the Wax, which is desirable for bulling and polishing characteristics, better emulsiiication results. The product has a lactone value by the Leukowitsch method of 3 to 30. The saponiiication value lies between 30 and 60 and it measures, in mg. of KOH per gram of product, the sum of acids and esters present. The melting point ranges from 180 to 210 F. The compounds are substantially straight chain substances containing not over about 10% of isomers, and they are practically completely saturated. the consistometer hardness (Abrams) ranges from 35 to at temperatures of 130 to 80 F.

The products have approximately the following properties:

Acetyl value 35 to 53. Peroxide value 400 to 5000. Distillation at 350 C 60%. Lactone value 3 to 30. Saponication value 30 to 60. Melting range 180 to 210 F. Consistometer hardness 35 to 85. Acid value l0 to 20.

We claim:

1. A method of treating solid waxy Fischer-Tropsch hydrocarbons which comprises melting said hydrocarbons, introducing into the molten mass an initiator of reaction, said initiator being a peroxide soluble in said hydrocarbon and having a decomposition temperature higher than the melting point of said wax, passing an oxygen containing gas therethrough, introducing a metal taken from group IIb of the periodic table of elements while introducing said oxygen containing gas and heating to a substantially higher temperature but below the decomposition temperature of the wax for several hours.

2. A method according to claim 1 wherein, after said heating there is added a compound of a metal having a valence of more than one to form soaps of acids in said product to increase hardness thereof.

3. A method according to claim l wherein, after said heating there is added a compound of a metal having a valence of more than one taken from groups IIa and Hb of the periodic table of elements to form soaps of acids in said product to increase hardness thereof.

4. A method according to claim 1 wherein, after said heating there is added a compound of iron to form soaps of acids in said product to increase hardness thereof.

5. A method according to claim 1 wherein, after said heating there is added a compound of copper to form soaps of acids in said product to increase hardness thereof.

6. A method of treating solid waxy Fischer-Tropsch hydrocarbons which comprises melting said hydrocarbons, introducing into the molten mass an initiator of reaction, said initiator being a peroxide soluble in said hydrocarbon and having a decomposition temperature higher than the melting point of said Wax, passing an oxygen containing gas therethrough, introducing a metal taken from group Hb of the periodic table of elements while introducing said oxygen conaining gas and heating to a substantially higher temperature but below the decomposition temperature of the wax for 6 to 7 hours.

7. A method of treating solid waxy Fischer-Tropsch hydrocarbons which comprises melting said hydrocarbons, introducing into the molten mass an initiator of reaction, said initiator being a peroxide soluble in said hydrocarbon and having a decomposition temperature higher than the melting point of said wax, passing an oxygen containing gas therethrough, introducing a metal taken from the group consisting of zinc, copper and iron while introducing said oxygen containing gas and heating to a substantially higher temperature but below the decomposition temperature of the wax for several hours.

8. A method of treating solid waxy Fischer-Tropsch hydrocarbons which comprises melting said hydrocarbons, introducing into the molten mass an initiator of reaction, said initiator being a peroxide soluble in said hydrocarbon and having a decomposition temperature higher than the melting point of said wax, maintaining a temperature of about 100-125 C. and passing an oxygen containing gas therethrough, introducing a metal taken from group IIb of the periodic table of elements while introducing said oxygen containing gas and heating to a substantially higher temperature but below the decomposition temperature of the wax for several hours.

9. A method according to claim 8 wherein the temperature is raised to about 140-175 C. after the addition of said metal.

10. A method according to claim 9 in which said metal is zinc.

11. An oxidized aliphatic wax melting at temperatures i@ of 180-2l0 F., the infra red absorption at wave length 8.87 microns showing the absence of a peak and showing a peak at 5.7, having a negligible iodine value, an acid value of 10-20, and an acetyl value of about 35-53, the saponification value being about 30-60.

12. An oxidized aliphatic wax melting at temperatures of 180 210 F., the infra red absorption at wave length 8.87 microns showing the absence of a peak and showing a peak at 5.7, having a negligible iodine value, an acid value of 10-20, and an actyl value of about 43, the saponication value being about 30-60.

13. An oxidized aliphatic Wax melting at temperatures of 180-210 F., the infra red absorption at Wave length 8.87 microns showing the absence of a peak and showing a peak of 5.7, having a negligible iodine value, an acid value of 10-20, and an acetyl value of about 35-53, the saponication value being about 30-60, the peroxide value being about 400-500 P. P. M.

14. An oxidized aliphatic wax melting at temperatures of 180210 F., the infra red absorption at wave length 8.87 microns showing the absence of a peak and showing a peak at 5.7, having a negligible iodine Value, an acid value of 10-20, and an acetyl value of about 35-53, the saponication value being about 30-60, said wax containing soaps of metals having a valence of at least 2.

l5. An oxidized aliphatic wax melting at temperatures of 18G210 F., the infra red absorption at wave length 8.87 microns showing the absence of a peak and showing a peak at 5.7, having a negligible iodine value, an acid value of 10-20, and an acetyl value of about 35-53, the saponitication value being about 30-60, said wax containing soaps of metals taken from groups IIa and Hb of the periodic table of elements.

16. An oxidized aliphatic wax melting at temperatures of 180 -210 F., the infra red absorption at wave length 8.87 microns showing the absence of a peak and showing a peak at 5.7 having a negligible iodine value, an acid value of 10-20, and an acetyl value of about 35-53, the saponication value being about 30-60, said wax containing soaps of iron.

17. An oxidized aliphatic wax melting at temperatures of l2l0 F., the infra red absorption at wave length 8.87 microns showing the absence of a peak and showing a peak at 5.7, having a negligible iodine value, an acid value of l0-20, and an acetyl value of about 35-53, the saponiiication value being about 30-60, said wax containing soaps of copper.

References Cited inthe tile of this patent UNITED STATES PATENTS 1,834,865 Pungs et al. Dec. 1, 1931 2,318,669 Carr May 11, 1943 2,391,236 Hirsch Dec. 18, 1945 2,660,601 Dickinson Nov. 24, 1953 OTHER REFERENCES Warth: The Chemistry and Technology of Waxes, Reinhold Pub. Corp., New York (1947), pages 271, 272.

Claims (1)

1. A METHOD OF TREATING SOLID WAXY FISCHER-TROPSCH HYDROCARBONS WHICH COMPRISES MELTING SAID HYDROCARBONS, INTRODUCING INTO THE MOLTEN MASS AN INITIATOR OF REACTION, AND INITIATOR BEING A PEROXIDE SOLUBLE IN SAID HYDROCARBON AND HAVING A DECOMPOSITION TEMPERATURE HIGHER THAN THE MELTING POINT OF SAID WAX, PASSING AN OXYGEN CONTAINING GAS THERETHROUGH, INTRODUCTING A METAL TAKEN FROM GROUP 11B OF THE PERIODIC TABLE OF ELEMENTS WHILE INTRODUCING SAID OXYGEN CONTAINING GAS AND HEATING TO A SUBSTANTIALLY HIGHER TEMPERATURE BUT BELOW THE DECOMPOSITION TEMPERATURE OF THE WAX FOR SEVERAL HOURS.

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