Патент USA US2135458код для вставки
Patented Nov. 1,‘ 1-938 ' 2,135,458 * UNITED STATES PATENT- oFncE sarm'rron or cons'rrruan'rs mom oacmc comaxns Raymond F. Schultz, Wilmington, Del., assignor to E. I. du Pont de Nemours a Company, Wil mington, Del., a corporation of Delaware t No Drawing.‘ - Application December 13, 1935, Serial No. 54,851 . 12 Claims. (Cl. 260-478) the resulting mixture by distillation, extraction, This invention relates to a process for the sep aration 'of complexes into their constituents and absorption; or other means. ‘After the removal of the organic compound there remains the metal more particularly to arprocess for the recovery halide-inorganic compound complex. If, the from complexes, formed between organic com metal halide employed is an alkaline earth metal Ol halide or calcium oxide and the inorganic com ponent of the complex originally treated is vola tile, as is boron ?uoride, such complexes can be broken up‘by heating thereby driving off the pounds and boron halogen containing compounds, the boron-halogen-containing? and organic con stituents. - 'An object of the present invention is to provide a process for the separation of constituents from 10 complexes containing the same. ‘volatile inorganic component. ' Another object of the invention is to provide a process whereby complexes containing an organic constituent and a‘ boron-halogen-containing constituent can'be separated into the organic constituent and the‘ boron-halogen-containing constituent. A fur ther object of the invention is to provide a proc ess whereby a .complex containing an organic constituent and a boron-halide-constituent can ' be freed ofv the organic compound by the addition 20 of a metal halide. A more speci?c object of the ~ invention is t'o'provide a process wherein com plexes containing boron ?uoride and an organic acid, ester, or ether may be so treated that the . organic acid, ester, or ether is freed from the com plex and recovered, the ‘boron ?uoride likewise being recovered 101'1'81158. Other objects and ad vantages of the invention will hereinafter appear. I have found that if a complex, such as those containing an organic and an. inorganic constit is, 0 uent, is treated with a metal halide the organic constituent will beset freeand leave a complex formed between the metal halide and the inor ganic constituent, (should the inorganic portion of the'complex be a metal halide the added metal $2 Ll halide should be a different metal ' halide). Moreover, if alkaline earth metal halides are em ployed, to decompose complexes containing a, boron halide, the alkaline earth metal halide boron halide complex formed will, upon heating, 40 give up the boron halide it contains leaving the alkaline earth halide asa residue. Accordingly, when employing alkaline vearth metal halides it is possible to recover, from complexes containing an organic and a boron-halogen-containing con p. U! stituent the organic constituent and the boron halogen-containing constituent. I ' _ ' Generally, the separation is effected, in the 10 The metal halides which have been found par ticularly well adapted for replacing organic com pounds from complexwompounds containing the organic compound‘and a boron-halogen-contain ing compound include, for example, calcium ?uo ride, zinc chloride, aluminum ?uoride, aluminum chloride, cuprous chloride, lead chloride, iron chloride, tin chloride, calcium ch1oride,,barium chloride, and analogous metal'?uorides, chlorides, bromides'and iodides. While metal halides will replace the organic constituent of , a ' complex compound containing an organic constituent and an inorganic constituent, such as boron tri?uo ride, I have further found that the alkaline earth halides and more especially the alkaline earth ?uorides form a complex with the boron ?uoride from which the boron ?uoride or other analogous ‘easily volatilized halogen-containing compounds may be recovered by heating. Together with the alkaline earth halides such, for example, as the ?uorides, chlorides, and bromides of _ calcium, barium or strontium,—-calcium oxide likewise has the ability to not only displace the organic com ponent of a complex containing boron ?uoride giving a second complex containing boron ?uo 35 ridev and-'caiciumoxide but to permit the recov ery of the-boron ?uoride from complex.“ -‘ The advantages resulting from my process arev readily appreciated when it is realized that when using, for example, boron ?uoride in condensa tion reactions, generally, it has been necessary heretofore to destroy the boron ?uoride complex _ by passing it into water or a water-ice mixture’ .prior to recovery of the reaction products. Nat urally the vboron ?uoride is hydrated by such 45 treatment and must be again dehydrated prior to reuse and the ‘product is greatly diluted.~ In‘ accord with my‘ process, on the other hand, boron ?uoride and the product are recovered in a sub following manner; ametal halide is added to they complex containing both an organic and inor 50 ganic constituent and apparently due to the fact that the inorganic portion thereof reacts more readily with the metal halide than does the or ‘stantially anhydrous condition and the expensive ganic portionpthe former forms preferentially a metal halide-inorganic complex freeing the or 85 ganic constituent which may be removedtfrom methods of separating various organic complexes into their constituents but it will be distinctly 55 dehydration and concentration steps heretofore required are entirely eliminated. ‘ I shall now illustrate by way of examples 2 , . 9,185,458 - , understood that the invention shall not be lim -cium ?uoride. It will be appreciated that when ited speci?cally thereto. ‘ _ employing boron ?uoride as a condensing agent Example 1-188 grams of (CHsCOOHhBFs (1 in organic acid reactions the use of’calcium ‘ mol) ‘was treated with 45 grams Call‘: (.58 mol) ?uoride is particularlyuseful for the reason that in a ?ask attached to a shortx‘fractionation col the condensing agent can be entirely recovered 5’ umn. The mixture was heated in an oil bath to and used over and over- again the sole loss in . not more than 250°-C., during which the acetic acid distilled out. Y About 117 grams glacial acetic catalyst occurring from operating causes rather than from loss due to by-pro'ductv acid was obtained, which is 97.5% of that‘ the formation. _ . ~ I‘ This distillation can be ei-' - Whilemy, invention has been described with 1o fected at atmospheric or reduced pressures. - particular reference to complex compounds which , Subsequent heating of the solid residue, which contain a boron halide it may likewise be em 10 oretically possible. consists mainly of ' Ca(BI"4)s, to temperatures ployed to free the organic constituent from its between 300° 0., and 500° 6.,‘ resulted in-the evo complex with other halides such, for example, as lution of boron ?uoride according to the equa the valuminum halides, tin . halides, titanium 15 . halides, silicon halides, sulfur halides and analogous halides which form complexes. For Approximately 58.5 grams boron ?uoride “was re '20 covered, which is 86.5% of theoretical. ‘Temper; use'in the second step of my process via, the Empte 2.—94 grams of (CHsOOOHlsBl'E (.5 absorption methods are used for recovering one 7 mol) was treated with 25 mm! (.6 mol)’ in a or ' From the other a consideration constituent. ofI the above specifics? separation into its constituents of the wholly in- " ' atures below and above those given may be usedv organic complex,-one of the halide‘ should be 20 more volatile than the other, unless extraction or_ . but the range‘ given is preferred. _ ?ask attached to ashort fractionation column. tlon it will be appreciated that many changes may bemade in the process herein described with out. departing from the scope of the invention or sacri?cing any of the ‘advantages that may be 'I'hemixturewasheatedinanoilbathtonot more than 250° 0., during which time glacial acetic acid distilled over. About 43 grams of» acetic acid was recovered, which is 78% of that 30 theoretically possible. The distillation can be done at atmospheric or reduced pressures. The gBlls can be recovered by heating the solid, which derived therefrom. I claim: ‘ ‘ v - v . ' 1 ., 1. In a process of separating an organic com pound from its complex with a boron halide the consists mainly of NaBFs, to higher temperatures. trample 3.—About 94 grams (CHsCOOH)s.B1"s steps which comprise adding an alkaline’ earth metal halide thereto whereupon the organic con- ' as in la ?ask attached to a short fractionating . stituent is freed from the boron halide andlan column. The mixture was heated in an oil bath alkaline earth metal halide-boron halide "is _ to not more than 250° 0., and about 40 grams of formed, separating the organic constituent,.and ‘essentially glacial acetic acid distilled over. ‘1111s subsequently separating the boron halide from the alkaline earth halide-boron halide complex. 40 was about 67% of theoretical. The distillation 2. In a process of.separating methyl acetate can be carried out at atmospheric or reduced (.5 mol) was treated with 60 grams NaCl (1 mol) Pressures. from its complex with boron ?uoride the steps which comprise adding calcium ?uoride to the complex, separating methyl acetate from the re sulting mixture by distillation, heating the residue containing the ‘calcium ?uoride-boron ‘?uoride ‘ The boron ?uoride can be separated from the solid residue (Nam-B15) lay-further heating to 45 from 300-500’ C. . ,' My process is particularly well adapted for use in the separation of addition compounds contain-' complex and collecting the boron- ?uoride driven in; an organic constituent and an inorganic con stituentv and pore. particularly such addition 50 compounds in which the inorganic constituent is o?. ' , 1 v 3. In a process of separating acetic acid from its complex with boron ?uoride the steps which comprise adding calcium ?uoride to. the complex, , a-relatively highly volatile halide such, for ex-v separating acetic acid from the resulting mixture ample, as the ?uorides,‘ chlorides, bromides, and .by distillation,- heating‘the residue containing the calcium ?uoride-boron/?uori'de complex and col iodides of.boron, but it is likewise particularly useful in the separation of organic containing 55 complexes generally, in which the metal halides preferentially replace the organic compound from its complex with the inorganic halide, among lecting the boron ?uoride driven off. . 4. In a process of "separating propionic acid from its complex withv boron ?uoride the steps comprise adding calcium ?uoride ‘to the .suchcompounds are-included. for example, the, 'which complex, separating propionic acid friompthe re aliphatic acid-boron ?uoride complexes, e, g.. ‘sulting ,mixture by, distillation, heating the ‘resi ~ (encompass. (cmcmcoomim. - omwrmscoomnrs _ due containing the calcium ?uoride-boron ?uo-. ride complex and collecting the boron ?uoride driven off. aliphatic ether-boron ?uoride complexes, e. g.. Y ' (CHDIOsBFJ, <czmlsosnrs -etc., (.1: indicates ‘any integer or,fra_ction), aliphatic ester-boron ' ' _ I ~' 5. A process for the-separation of acetic acid from its'association with boron ?uoride which comprises treating approximately 1 mol of a com- I ?uoride complexes, aliphatic alcohol-boron ?uo-r plex, containing approximately two male of ride complexes'and more speci?cally the com-a ' Y acetic acid and one moi of boron ?uoride, with approximately .58‘mol of calcium ?uoride, dis - plexes formed between boron ?uoride and metha nol, ‘ethanol, propanol, butanol,'l.-isobutanol and higher alcohols. Calcium ?uoride is particularly ‘ tilling the vresulting mixture to drive oi! the acetic ' acid, and subsequen’tLv heating ‘the residue be well adapted to separate not only the organic ' tween a temperature of@300° 0., .to 500°_ c., to _acid-boron ?uoride complex into the organic acid . and a complex containing calcium ?uoride and boron tri?/uoride, but ‘to separate alsov the latter I“. ' complex upon heating into boron ?uoride andcal i evolve the boron ?uoride. . ' I 6. In'a process of separating an aliphatic-or ganic acid from its complexv with; aboron-?uo- ~ the compound the steps which'comprise adding?" ' 3 _ . - arouse calcium ?uoride to the complex. heating the mixture to separate the aliphatic organic acid, and heating ‘the resulting residue more strongly to separate the boron ?uorine compound. ' 7.111 a process of separating an aliphatic or ganic acid from its complex with a boron halide the steps which comprise adding calcium ?uoride to the complex, heating the mixture to separate the aliphatic organic acid, and heating the re 10 suiting residue more strongly to separate the boron halide. ' ' 8. In a process of separating an aliphatic or ganic ester from its complex with a boron halide 10. In a process of separating an organic com pound ,irom its complex with a boron ‘halide the steps which comprise adding ‘an alkaline earth metal halide which preferentially. with respect to the organic compound, forms a complex with the boron halide, separating the organic com; pound from the resulting solution by distillation, and subsequently separating the boron halide by distillation at a higher temperature. . 1.1. In a process oi separating an'organic com 10 pound irom its complex with a boron halide, the steps which comprise adding thereto a metal halide which forms a complex with the boron the steps which comprise addingcalcium ?uoride ‘halide, and subsequently separating the organic compound fromvthe metal halide-boron halide 15 16 to the complex, heating the mixture to separate“ the aliphatic organic ester, and heating the re suiting residue more strongly to separate the complex. _ ' 12. In a process oi'separating'an ‘organic comq 9. In a process of separating acetic acid from itscassociatlon with boron ?uoride by means of pound from its complex with boron ?uoride, the steps which comprise adding thereto a metal halide which forms a complex with the boron calcium ?uoride the steps which comprise pre paring a mixture of the acetic acid and boron ?uoride. and subsequently separating the organic compound from the vmetal halide-boron ?uoride ?uoride with the callcium ?uoride, heating the mixture to separate the acetic acid, and heating the residue to separate the boron ?uoride. complex. boron halide. ' ' . F. SCHULTZ.