July 6, 1954 R. K. BER PROCESS FOR THE FRODUCTION OF WERNER TYPE CROMTUNE COMPLEXES 2,653,156 Filed June 8, 195l.

SULURPC Act C. H. A. R. G. E.

“CHROWLUM TROXI.OE C.H. A. R. G. E.

f

AWHYDROUS s Croz Cl2 HYDAOCHQEG. AGlo VENTED

ISOAPROPA MOE, CHARGEA, COHOt. AND MIFARGOGEN PUR. G. E.

R. E. F. X. SO, PROPA. N. O.

SEP A R A TE

WASFE H2SO4. 7O of SAPOSAL

NIFROGEN

AAEAR ADD, WATER

SSAAC Atolo, C. A. R. G. E. STEARIC ACE D. REFU X INVENTOR SOPROPANOl. Ado soPROPANot A. A. P. H. A. ft. E. R.

PRO t, CT Czudéa.a GE M7 Patented July 6, 1954 2,683,156 UNITED STATES PATENT of FICE 2,683,156 PROCESS FOR THE PRODUCTION oF WERNER. TYPE CHROMUM COM PLEXES Ralph K. Iler, Wilmington, Del, assignor to E. I. du Pont de Nemours and Company, Wilming ton, Del, a corporation of Delaware Application June 18, 1951, Serial No. 232,142 6 Claims. (Cl. 260-438) 2 This invention relates to the manufacture of chloride, and particularly, stable complex com chromium compounds. More particularly, it is pounds of the Werner type in which trivalent directed to processes comprising the steps of nuclear chromium atoms are coordinated with mixing chromium trioxide, hydrogen chloride and carboxylic acido groups, are provided in which sulfuric acid, the Sulfuric acid having a strength chromium trioxide, hydrogen chloride and sul Of at least 68 per cent and being present in an furic acid of at least 68 per cent (by weight) amount sufficient to maintain the System in an strength are mixed to produce anhydrous chromyl anhydrous state, whereby anhydrous chromyl chloride, the resulting chromyl chloride is sepa chloride is produced, separating the resulting rated from sulfuric acid, and the anhydrous chromyl chloride from the sulfuric acid, com 0 chromyl chloride is reacted with a -lower mono mingling the anhydrous chromyl chloride with hydric aliphatic alcohol to produce a basic a lower monohydric alcohol, whereby reaction chronic chloride. Optionally, contact is effected occurs to produce a basic chromic chloride, and between the basic chromic chloride so produced optionally reacting the basic chromic chloride and a carboxylic acido group, whereby a complex with a monocarboxylic acid, whereby a water 5 compound of the acido group and the basic soluble complex compound of the Werner type chronic chloride is produced. in which a trivalent nuclear chronium atom is In the drawing there is a flow sheet illustrating coordinated with the carboxylic acido group is a preferred process of my invention. The dis produced. cussion of the invention which follows may be U. S. Patents 2,524,803, 2,273,040 and 2,356,161. 20 describe processes for producing a basic chromic moredrawing. readily understood by reference to the chloride and in turn for producing complex chro According to a process of the invention, I first mium compounds of the Werner type. charge Sulfuric acid to a reactor at room tem Iller Patent 2,524,803 teaches a process in which perature. If desired, water may be charged to an aqueous solution containing, by Weight, from the reactor prior to introducing a charge of con 12 to 35 per cent of chromium trioxide and more centrated Sulfuric acid. Chromium trioxide is than 16 per cent of hydrogen chloride is mixed then added to the sulfuric acid solution with with a solution of a monohydric aliphatic alcohol agitation. Hydrogen chloride, either anhydrous containing not more than 4 carbon atoms. Or aqueous, is added below the surface of the Thereafter, the resulting solution can be mixed 30 agitated mixture of chromium trioxide and sul with a carboxylic acid to produce complex com furic acid. The temperature of the reaction mix pounds of the Werner type. The compounds So ture is maintained below 55° C. by means of ex prepared contain water in an amount which ternal cooling. Reaction between the chromium causes gelling upon storage and which is in excess trioxide and hydrogen chloride is thereby effected of that needed to stabilize the complex con to yield anhydrous chromyl chloride. The chro pounds. Consequently, the products are Subjected nyl chloride is separated from the sulfuric acid. - to at least partial dehydration, preferably by The majority of the sulfuric acid is recycled for azeotropic distillation, prior to use. use in the initial step of the processes of my The processes described in U. S. 2,273,040 and invention. U. S. 2.356,161 effect the reaction between a car 40 The anhydrous chromyl chloride, freed of sul boxylic acido group and a basic trivalent chro furic acid, is added to a reactor containing a re mium salt in a nonaqueous solvent such as carbon fluxing lower monohydric aliphatic alcohol where tetrachloride. The ultimate products obtained by a basic chronic chloride is produced. A coor from these processes have to be freed of solvent dinated complex can then be prepared by effect preparatory for use in aqueous dispersion of ing contact between the alcoholic solution con Solution. taining the basic chromic chloride and a carbox While the processes of the above-mentioned ylic acido group. patents are good and give products ultimately In a preferred method for bringing together the having satisfactory quality, it would be advan chromium trioxide, hydrogen chloride and sul tageous to achieve a more economic process 50 furic acid to produce anhydrous chromyl chloride, through increased equipment capacity and shorter fresh concentrated sulfuric acid (99% strength) cycle time and also enhance the stability and is added to the recycle acid heel in a jacketed, shelf life of the product. glass-lined steel reactor. Then, while agitating Now, according to the present invention, im the mixture consisting of chromium trioxide and proved processes for producing a basic chromic 55 sulfuric acid and cooling the mixture to main 2,683,156 3 4. tain the temperature of the system below 55° C., anhydrous or aqueous. Any of a wide variety anhydrous hydrogen chloride is slowly added be of aqueous hydrogen chloride solutions may be low the Surface of the agitated and cooled mix used. There may be used, for instance, 20° ture at a rate controlled to help keep the tem Baumé muriatic acid or 22 Baumé muriatic perature of the reactants below 55 C. acid. Other technical grades of strong a queous While the above method of mixing the chro hydrogen chloride may be used. Anhydrous hy mium trioxide, hydrogen chloride and Sulfuric drogen chloride is preferred. acid is a preferred one, it will be understood that The sulfuric acid used in the processes of the the sequence of mixing the components is not present invention may be any of the commercially 0. available technical grades of Sulfuric acid hav critical. For instance, sulfuric acid may be ing at least 68 per cent (by weight) strength. added to a slurry of chromium trioxide in aqueous If desired, a more refined sulfuric acid of at least hydrogen chloride to produce anhydrous chromyl 68 per cent strength can be used. In those in chloride. In such a method, however, large Stances where aqueous hydrogen chloride and amounts of aqueous hydrogen chloride are prefer 5 Sulfuric acid as dilute as, say, 69 per cent are ably avoided since additional sulfuric acid will used, Sufficient excess of Sulfuric acid should be be required to maintain the reaction system in employed to keep the strength of the resultant an anhydrous state. Still other methods of bring diluted sulfuric acid (after the completion of ing the components together, such as, for in reaction) at or above 68 per cent. Stance, a concurrent mixing of chromium triox 20 On a virgin charge, 98 per cent sulfuric acid ide, hydrogen chloride and Sulfuric acid may is preferably diluted with water to about 72 per be employed. cent strength. The reason for dilution is that The proportions in which the chromium triox when the starting acid is of high Strength, say, ide, hydrogen chloride, and sulfuric acid are 98 to 99 per cent, the resulting mixture is of mixed may be varied, the principal limiting re 25 Such high Viscosity that the gaseous hydrogen quirement being that sulfuric acid be present chloride paSSes through the viscous maSS with in Sufficient amount and strength to maintain little reaction. When anhydrous hydrogen chlor the System in the anhydrous state despite the ide is used, it is preferred to use sulfuric acid hav Water produced as shown in Equation 1. Y ing an initial strength not exceeding 85 per cent. 30 Use of sulfuric acid having an initial strength The proportion of hydrogen chloride to chro above 85 per cent, say, 93 per cent, renders the mium trioxide in the reaction mixture is not separation of the chromyl chloride more diffi Critical. It will be understood that sufficient cult, since the resultant diluted Sulfuric acid hydrogen chloride should be present to react with differs but slightly in density from the chromyl all of the chromium trioxide. If insufficient hy 35 Chloride. drogen chloride is present, some chromium triox As shown in the flowsheet, the sulfuric acid ide may not react and may dissolve in the chromyl used may be a mixture of fresh 98-99% sulfuric chloride. acid and acid recovered in a Subsequent step in The advantages of the processes of the inven the process, which will be more fully set out tion are most fully realized when hydrogen chlor 40 hereinafter. The use of this recovered or re ide and chromium trioxide are used in the pro cycled Sulfuric acid is particularly preferred and portions of at least 2 but not more than 2.5 moles various benefits and economies result from its of hydrogen chloride for each mole of chromi use. The strength of the “recycle' acid following urn trioxide. It will be understood that in Order the removal of the chromyl chloride from the to assure complete reaction of the chronium 45 reaction system is usually about 70 per cent trioxide with the hydrogen chloride and to pre strength. The 70 per cent acid is preferably vent "by-passing' by the hydrogen chloride, the fortified with 98 per cent Sulfuric acid to bring chromium trioxide should be completely sus the strength of the recycle acid to, say, 72 per pended in the reaction mixture. Cent. It is preferred to avoid high local concentra 50 The amount of 98 per cent sulfuric acid added tion of hydrochloric acid and temperatures above to the recycle acid must be such that the re 55° C. These conditions decrease the yield of Sulting quantity of acid is sufficient to remove chromyl chloride by an oxidation-reduction reac all of the water of reaction and to maintain the tion shown by Equation 2. Excess hydrogen 68 per cent critical minimum acid strength. In 55 the event the acid strength should fall below this chloride in contact With chromyl chloride Solu critical value, the yields of chromyl chloride are tion should also be avoided as a consequence of Substantially decreased. An explanation of this the reaction represented by Equation 2. phenomenon is the increased solubility of chromyl chloride in Sulfuric acid of weaker strength than For purposes of this invention, a short reac 60 68 per cent. The dehydration power of the sul tion and holding time is preferred. Yield losses furic acid is also substantially reduced as the due to Equation 2 are thereby decreased. Reac strength of the acid drops below 68 per cent. tion times of from 45 minutes to about two hours After the chromium trioxide, hydrogen chloride are particularly preferred. and Sulfuric acid are mixed to fornin chronyl It will be understood that during the reaction 65 chloride, the temperature of the System being the reactor is preferably kept under a slight maintained below 55° C. as above set out, there Vacuum. At the completion of the reaction, an is obtained a reaction maSS composed of an acid increased pressure can be observed. This indi phase consisting substantially of Sulfuric acid Cates that hydrogen chloride is no longer being and water and a heavier anhydrous phase con consumed. The completion of the reaction may 70 taining chromyl chloride. These two phases are also be indicated by an increased gas flow which Separated. may be detected by means of a suitable flow he separation of the phases preparatory to meter in the “off gas' line. reacting the anhydrous chromyl chloride with a AS has been Set out above, the hydrogen chlor lower alkanol is preferably one utilizing gravity. ide used in the processes of my invention may be 75 Thus, according to a preferred embodiment of 2,688,156 5 6 the invention, the reaction mass is separated into with the processes of my invention should con its phases by decantation. The chromyl chloride tain not more than 4 carbon atoms. There may layer is the heavier. - be used for instance, methanol, ethanol, n-pro It will be understood that the waste sulfuric panol, isopropanol, normal, secondary, tertiary acid, which may contain some dissolved hydro or isobutyl alcohol. Of these, I prefer iso chloric acid, should not be permitted to remain propanol. in contact with the chromyl chloride any longer The amount of lower alcohol required to react than is necessary since chromyl chloride and with anhydrous chromyl chloride is as shown in hydrogen chloride react to decrease the yield in Equation 4, wherein the lower alcohol is, for accordance with Equation 2. Additionally, the 0. recycle contaminated sulfuric acid may react purposes of illustration, isopropanol: with chromyl chloride according to Equation 3 with a resulting decrease in yield. As a practical matter, an excess of alcohol is 5 usually employed, since the alcohol acts as a Solvent for the reactants and products formed Precipitates analyzing, on a dry basis, therefrom. 93.4% Cr2(SO4)3 It will be understood that when the stoichio metric proportion of ethanol is used as a re and 20 ducing agent acetic acid (not acetone as shown 6.6% CrCl3 in Equation 4) is formed. If an excess of eth have been observed to settle out of recycle con anol, say, twice or three times the stoichiometric taminated acid in periods of about one day. quantity is used, acetaldehyde is produced. The The temperature and pressure requirements acetic acid formed coordinates with the chro are not critical in the decantation operation. 25 mium of the basic chromic chloride to form For optimum results, the anhydrous chromyl acetato chromic chloride. By subsequently add chloride should upon completion of this step be ing a longer chain monocarboxylic acid, for in completely free of sulfuric acid contamination. stance, Stearic acid or substances capable of The acid phase obtained after separation from giving stearato groups, the acetato groups may the product phase consists of diluted sulfuric 30 be replaced with stearato groups on the complex. There often remains a residue of the acetato acid of about 70 per cent concentration. This groups which are undesirable if the complex is sulfuric acid phase is suitable for reuse in the to be used for imparting water repellency to hy initial reaction. Preferably, the used acid is drophilic substances. fortified with stronger sulfuric acid to increase 35 the acid strength to about 72 per cent as pre It is particularly preferred for the above reason viously mentioned. In carrying out Such a re to use a secondary alcohol such as, for instance, cycle operation, a substantial proportion of the isopropanol. The product of the oxidation of a recovered sulfuric acid is recycled, although not Secondary alcohol is a ketone, for instance, ace all of the acid is so used. To recycle all the acid tone in the case of isopropyl alcohol, which does continually would effect a constant increase in 40 not coordinate with the chromium. If desired, the amount of acid employed in the initial re the acetone may be readily removed from the action between hydrochloric acid and chromium product by conventional methods. trioxide. Accordingly, a portion of the recovered As already mentioned, a substantial excess of sulfuric acid is withdrawn from the operation a lower alcohol is used to serve as a solvent for following gravity Separation. the reactants and the products of the reaction. The anhydrous chromyl chloride prepared a,c- Another Solvent may, of course, be used but this cording to the processes of my invention is re necessitates a solvent removal step and thereby duced with a lower monohydric aliphatic alcohol conplicates the process. to basic chromic chloride. The chromyl chloride AS previously indicated, the chromyl chloride is preferably fed into a reactor at a controlled rate 50 should be well dispersed when added to the alco under nitrogen pressure and dispersed below the hol. This prevents local high concentrations and surface of the agitated refluxing alcohol. Prior consequently lessens high temperature degrada to bringing the alcohol to reflux the reactor is tion. In the event a large quantity of chromyl purged with nitrogen and a nitrogen blanket chloride contacts the lower alcohol the heat evo established. The reaction between the chronyl 55 lution may be so rapid and the dissipation so slow chloride and an alcohol is highly exothermic. that the alcohol ignition temperature is quickly The heat of reaction is removed preferably by reached and an explosion may occur. During the cooling water in the reactor jacket and reflux chromyl chloride addition the lower monohydric Condense. alcohol should be kept at reflux temperature to 60 aSSure rapid reaction with the chromyl chloride. To insure immediate dilution with excess alco This prevents any build-up of the unreacted chro hol the chromyl chloride should be injected into myl chloride which may later react within the alcohol in a fine stream in a zone of very high creased velocity and eventually cause an explo turbulence. Otherwise, local high temperatures, SIO. - even amounting to a Submerged flame, are 65 When a basic chromic chloride produced by a reached and insoluble chromic oxide is produced. process of the invention is to be converted to Very rapid mixing of the chromyl chloride with the coordination complex With an organic acido the excess alcohol is essential and is preferably group the proportion of chlorine ions united with achieved by injecting the chromyl chloride as a the trivalent chromium by primary valence bonds high velocity stream. The chromyl chloride must 70 must be in the range from about 1.5 to about 3.0, be injected below the level of the liquid alcohol with a corresponding proportion of hydroxyl since mixture with alcohol vapors is likely to groups to satisfy the three primary valences of result in an explosion. the chromium. Thus, a basic chromic chloride The monohydric aliphatic alcohol which is used having two chlorine atoms per chromium will to reduce the chromyl chloride in accordance 75 contain one hydroxyl per chromium. It is par 2,688,156 7 8 ticularly preferred that the proportion of chlo The long chain acido groups, such as Stearato rine per chronium be from about 1.85 to 2.5. groups, make the complexes extremely useful for Especially excellent results have been obtained providing a high degree of Water repellency to using two chlorine atoms. per chromium. hydrophilic Substances. On the other hand, the To convert the basic chromium chloride to a short chain groups may have special character coordination complex With an acido group, there istics in parting special usefulness. For instance, is added to the basic chronic chloride a suitable unsaturated chains in coordinated acido groups, Source of Such acido group. The basic chromic such as occur in beta, furyl acrylic acido groups, chloride is preferably dissolved in an excess of the retain their ability to interpolymerize with ethyl alcohol which was used for the reduction of 0. enic-type polymers and hence to form a chemical chromyl chloride. Of course, another suitable sol bond between the chronium and the polymer. vent for the basic chromic chloride may be used It is often desirable to stabilize a chronium at this point. The free acid or any acid compound coordination complex compound of the Werner capable of yielding the free acid under the reac type produced by the processes of my invention, tion conditions may be used as the source of acido say, for instance, stearato chromic chloride, by grOulpS. adding water in an amount which is less than 7 Thus, One may add stearic acid, for instance, to per cent by weight of the marketed product. a basic chromic chloride in isopropanol solution Stearato chromic chloride having a high Water prepared as above described. It is advantageous content, that is above 15%, gels on Standing. to effect such addition and the formation of the 20 With stearato chromic chloride compositions hav complex at a somewhat elevated temperature. ing a water content of from about 7 to 15 per cent, Decided heat economies can be achieved by adding sludging occurS. the Stearic acid shortly following the formation For satisfactory shelf life an acido chronic of the basic chromic chloride, whereby a portion chloride may have a water concentiation as low of the heat of reaction of the oxidation-reduction 25 as 3 per cent by weight or even lower. However, reaction is recovered. In some instances, it may even at the low value of 3 per cent Small crys be necessary to keep the alcohol-basic chromic tals may deposit upon long storage. Optimum chloride solution at reflux temperature for a period product quality is obtained with Stearato chro of at least 15 minutes in order to dissolve the spar mic chloride having a Water concentration. With ingly soluble carboxylic acid. This heating opera in the range of about 5 to about 6 per cent by tion is, however, preferably avoided since with Weight. Some monocarboxylic acids, for instance, Stearic For ease of operation, the adjustment of the acid, heating promotes sludging. Incomplete com water concentration is generally made just prior plexing at this point generally results in a prod to basic chronic chloride-carboxylic acid reac uct with poor water repellency characteristics. tion step. This is in conformity with the flow The proportion of carboxylic acid to add is gov sheet shown in the drawing. The exact amount erned by the number of acido groups which it is of Water to be added within the Specified limits desired to have coordinated with the chronium can best be determined by a few simple tests atom. For practical purposes it has been found under the Specific conditions of the process that a proportion of acido groups to chromium 4) selected and with the specific carboxylic acid atoms of about 0.5:1 is as high as it is necessary employed. It Will be understood that after a to go in producing the complex. - few simple tests have been run, calculations can The processes of this invention are applicable to be made whereby the amount of water can be the preparation of chronium coordination con computed based upon weight of the chronyl plex, compounds of the Werner type With any 4. 5 chloride. monocarboxylic acid. The acid may be aliphatic, The invention may be more fully understood as in the case of acetic, or it may be aromatic by reference to the following example: Such as benzoic. It may be a short chain acid Eacample such as butyric or a long chain acid such as A slurry of chronium trioxide in sulfuric acid stearic. It may be saturated as in the case of Was made up by adding 280 parts of technical propionic or unsaturated as in the case of oleic. chromium trioxide (99.5%) to an agitated inix ... Representative of other monocarboxylic acids ture consisting of 122 parts of 99% (by weight) which may be used are lauric, palmitic, capric, technical sulfuric acid and 1720 parts of recycled undecoic, tridecoic, myristic, penadecanoic, mar Sulfuric acid contained in a water-jacketed re garic, nondecoic, arachidic, undecydenic, myris 5 5 actor. Cooling water was circulated through telenic, palmitolenic, linoleic, linolenic and elaeo the jacket to maintain the temperature of the stearic, abietic, naphthenic, naphthoic and simi CrO3-ft2SO4 mixture within the temperature lar monocarboxylic acids. A compound of the i’ainge of fron about 35° to 35° C. There was acid, such as an ester or salt, which can liberate the added to the Inixture, below its surface, 2i 6 the free acid under the conditions of the coordi Gi) parts of anhydrous hydrogen chloride. The nation reaction is, of course, equivalent to the free teimperature of the reaction mixture was kept acid. The nature of the Werner type complex chro below 55° C. by external cooling throughout the mium compounds and the nomenclature applied 45-minute period required for completion of the to them is described fully in the above-mentioned eXOtherinic reaction. Chlorine gas produced as U. S. Patents 2,273,040 and 2,356,161. By de a by-product was vented. leting the suffix "-ic' from the name of the car The reaction mass at this point consisted of boxylic acid and adding the suffix *-ato' a system two phases. A heavier layer contained the an of naming the acido groups coordinated With the hydrous chromyl chloride. The lighter phase chromium and hence for naming the chromium 70 Was composed of sulfuric acid of 70 per cent complexes is provided. Thus, stearic acid gives Strength and was contaminated with chromium Stearato groups and the complex is called stearato and chlorine-containing compounds. The two chromic chloride. phases were separated by decantation. 412 parts The properties of the complexes formed vary of chronyl chloride was obtained. The chromyl. With the character of the coordinated acido group. 5 chloride is a limpid blood-red (when viewed by 2,688,156 10 transmitted light) liquid and has the following chiometric excess and in a turbulent state, and physical properties: Said anhydrous chromyl chloride being injected Specific gravity------. 19034 (25° C.) below the liquid level of the isopropanoi. Wiscosity------0.726 centipoises (25°C.) 4. In a process for producing a lower mono Freezing point.------. -96.5° C. 5 hydric aliphatic alcohol solution of a water Boiling point.------17.6° C. Soluble complex compound of the Werner type About; SO pe' cent (1720 parts) of the total in Which a trivalent nuclear chromiurn atom is amount of used Sulfuric acid was recycled and coordinated With a carboxylic acido group, the fortified with 99% sulfuric acid for use in the Steps comprising rapid mixing of anhydrous initial step of the process. 10 chromyl chloride with a monohydric aliphatic 412 parts of anhydrous chroinyl chloride pre alcohol containing not more than 4 carbon atoms pared as above described was slowly added below in the absence of an inert diluent to produce a the Surface of a refluxing liquid consisting of basic chromic chloride, and reacting the basic 1370 parts of isopropanol. Prior to bringing the chronic chloride in an aqueous solution of said isopropanol to reflux, the reactor containing the 5 alcohol. With a nonocarboxylic acid to produce alcohol was purged with nitrogen and a blanket an alcohol solution of carboxylato chronic chlo ing nitrogen flow initiated. The reduction of ride having a water content of no greater than the chronyl chloride to basic chronic chlorifie, 7% by Weight of said solution. Cr(OH) Cl2, by the isotropanol was completed 20 5. in a process for producing an isopropanol in a period of about One hour. Solution of a water-soluble complex compound in order to prevent crystal formation, and Of the Werner type in which a trivalent nuclear thus niinimize the sludge deposition upon pro chromiuri atoia is coordinated with a stearato longed storage, 69 parts of water was added to group, the steps comprising rapid mixing of an the isopropanol solution containing the basic 25 hydrcus chronyl chloride with isopropanol in chromic chloride. he blanketing nitrogen fioW the absence of an inert diluent to produce a basic was stopped and the mixture cooled to 50° C. chronic chloride, and reacting the basic chronic 381 parts of stealtic acid. Was then added and the chloride in aqueous isopropanol with Stearic resulting mixture heated for a period of 70 min acid to produce an isopropanoi solution of ste utes at a temperature of about 40° C. for com arato chronic chloride having a water content plexing. 30 of no greater than 7% by weight of said solu An additional 168 parts of isopropanol was tion, the added. The resulting clear green Solution 6. In a process for producing an isopropanol of Stearato chronic chloride in aqueous isoprop Solution of Stearato chronic chloride stabilized anol Was Stable upon Standing and imparted against gelation and sludging, the steps con reinarkable water repellency to paper treated prising injecting anhydrous chromyl chloride With it. into a Stoichiometric excess of boiling isopropanol cairn: in the absence of an inert, diluent to produce a 1. In a process for producing a basic chronic basic chronic chloride, said anhydrous chronyi chloride, the step which comprises injecting 40 chloride being injected below the liquid level of anhydrcus chromyl chloride in a fine stream into the isopropanol, and effecting contact, between a monohydric aliphatic alcohol containing not Stearic acid and the basic chironic chloride in more than 4 carbon atoms, the alcohol being in the presence of aqueois isopropanol to produce a turbulent state and the chromyl chloride being an isopropanoi Solution of Stearato chronic cho injected below the liquid level of said alcohol. ride having a Water content of from 3 to 6% by 2. In a process for producing a basic chronic Weight of said solution. chloride, the step which comprises injecting an hydros chronyl chloride in a fine stream into References Cited in the file of this patent a monohydric aliphatic alcohol containing not UNITED STATES PAENTS more than 4 carbon atoms, said alcohol being Number maintained at its boiling point and in a turbulent Nare Date state and said chronyl chloride being injected 2,273,040 Eller ------Feb. 17, 1942 below the liquid level of the boiling alcohol, 2,356,16 Iler ------Aug. 22, 1944 whereby rapid reaction is effected between the OTHER REFERENCES anhydrous chromyl chloride and the alcohol. Mellor Comprehensive Treatise on inorganic 3. In a process for producing a basic chronic 5 5 and Theoretical Chemistry, volune ii, page 392 chloride, the step which comprises injecting an (193). hydrous chromyl chioride in a fine stream into Fernelius Inorganic Synthesis, volune 2, page boiling isopropanol in the absence of an inert ... 205-207. diluent, said isopropanol being present in a stoi 60