2) United States Patent Gilbeau (54) METHOD FOR CONVERTING POLYHYDROXYLATED ALIPHATIC HYDROCARBONS INTO CHLOROHYDRINS (75) Inventor: Patrick beau, Braine-te-Comte (BE) (93) Assignee: Solvay Societe Anonyme), Brussels, (BE) Notice: Subject to any disclaimer, the term ofthis pateat is extended of adjusted under 35 USC. 154(b) by O days an Appl.No: 11915,056 (22) PCTFiled: May 19,2006 (86) PCT Nos PCTIBP2006062462 $371 (o\l), (2),(4) Date: Nov. 20, 2007 (87) PCT Pub. Nos W02006/100320 PCT Pui Date: Sep. 28, 2006 os) Prior P US 200810194848 AI ication Duta Aug. 14, 2008 Related US. Apy Provisional splication No. 6(V734,635, filed on No 8, 2008, provisional application No. 60/734,657, fled fon Now. 8, 2005, provisional application No, 60/734 636, fled on Nox. 8, 2005, provisional application No. 6607734,627, fled on Nov. , 2008, provisional appli= cation No. 60/734 634, filed on Nov. 8, 2005, provi sonal application No, 60°734,688, filed on Now. 8 2005, provisional application No, 60/734,637, filed on Nov. 8, 2005, provisional application No, 60°734,659, fied on Nov. 8, 2008. ication Data (6) G0) Forcign Application Priority Data May 20,2008 (EP) 05103321 May 20,200 (FR) 0505120 (1) neck cure 3134 corp 30127 us. Field of Classification Search (200601) (200601) (2) 68) Sones; S49/SI8 S881 49/518 ‘Se pplication file for complete search history. 650) References Cited US. PATENT DOCUMENTS 2,060,715 A /I936 Arvin 263801 A 12/1936 Dreyfus 248612 A 1/1939. Britonet a 2.198.600 A 7/1940. Pato et a 2248635 A T/941 Marple et a ‘US007S57253B2 (10) Patent No. 4s) Date of Patent: US 7,557,253 B2 Jul. 7, 2009 289,128 A 41958 Napravmikt 2945004 A 71960. Greenlee 290447 A LLI9G0 Anderson al. ROGLSIS A 10/1962. Vrot al 3291227 A 411966 White BA5SS11 A LU/1967 Schwarzer X385908 A S1968. Schwarer SusT28 A 71969 Polaket a BSOSERS A _DUITS Schindler ea 386766 A 21975. Salvan 3968178 A TH9T6 Obrochtet 4200529 491980 Davde-Lagrave AAISAG S — LVI9SS Suciv etal ABUTS A VIOST” Nagao eta 4960.953 41011990 Jakobson tal 497376) A 1/1990 dakobson a SO41.688 A N1991 Jakobson etal S344945 A 911908 Granchard 539.00 A 101994 Teleset a SS7R740 A LU/I996 Auetal 5710350 A 1998 Jeromin et a STMATS A M1908 Shawl sta (Continved) FOREIGN PATENT DOCUMENTS ca. tuism0 82003 (Continsed) (OTHER PUBLICATIONS Anand Novell,“The Pecaration of Moni-and Dichlovoky ding of ‘Geer Anal Far. Biogium Ol. 1, 1930 pp. 8-19 (ith English bare (Continsed) Primary Examiner—Sikael A Witherspoon (74) dutorney, gen, or Firm-Obloa, Spivak, MeClellanc, Maier & Neustadt, BC on ABSTRACT Process for preparing a chlorohydrin, wherein: (a) polyhy: tion mixture obtained in step (a), is subjected to one oF ‘mote teatments in steps subsequent step (2), (6) basic compound is added ta at least one ofthe steps stbsequent 0 step (a) in oder wo reaet at least partly with the chlorohydrin, the chlorohydrin esters, te chloinating agent and the organic acid so as to form the epoxide and sails, ‘The process for preparing the ehlorohydrin acconting to the invention may be inteprated within an overall plan for preparation of an epoxide, as described in the application ‘called “Process for preparing an epoxide starting fom 3 chlorohydrin" ledin henameof SOLVAY S. A-on thesame day as the present application, and the content of which is ‘inconporate hereby reference, Particular mention is made of a process for preparing an ‘epoxide that comprises atleast one step of purifiation ofthe ‘epoxide formed, the epoxide being at east partly prepared by a process of deiydrochlorinating a chlorohydrin, the later being at least parlly prepared by a process of chlorinating @ polyhydroxylated aliphatic hydrocarbon, an ester of 3 poly- hydroxylated aliphatic hydrocarbon or a mixture thereof ‘When the epoxide is epichlorahydin, the preparation of the epoxide may be integrated into a process for preparing ‘epoxy resins. Inthe process secording to the invention, the polyhydroxy te aliphatic hydrocarhon is preferably glycerol and the chlorohydrin is preferably dichloropeopaiol 0 o 18 ‘When the chlorohydrin is dichloropropano, the process according the invention may be followed by the preparation of epichlorohycin by dehy drochlorination of dichloropro- ‘panol, and the epichlorohydrin may beused in the preparation ‘of epoxy resins, ‘Steps (5) and () af the process according to the invention also apply fo mixture contsining the chlorohydrin, chloro lnydrin esters and water that i obtained by reactions other than the reaction of « polyhydroxylated aliphatic hydrocar- ‘bon with achlorinating agen: for example, by hypochlorina- ‘ion of an olefin such as ethylene, propylene orally chloride or by chlorination of an alcohol, such as allyl alcohol, for example FIG. 1 shows a particular scheme of plant which eas be sed to implement the preparation process according to the invention ‘A-reactor (4) is supplied in continuous mode or in batch smede with a polyhydroxylated aliphatic hydrocarbon, an ster ofa polyhydroxylate aliphatic hydrocarbon or mix- ture thereof va line (1) and with catalyst via Tine 2) dhe chlorinatng agents supplied in continous made on batch ‘mode va line (3; distillation colnma (6) x supplied va line (6) with vapors prodiced in reactor (4); a stream is taken off {rom column (6) via line (7) and is intrxtuced into a eon- denser (8); the stream obtained from the condenser is inteo- ‘duced va line (9) into a phase separator (10), in which aque- ‘ous and onganie phases are separated. An additive may be inteoduead into the stream from Kine (7) via line (31) andor into the stream from line (9) via line (32). fraction of the separated aqueous phase is optionally recycled valine (H)t0 {the tap of the column in oder to maintain the refi. Water is introduced into Fine (11) via fine (12). The production of chlorobyirin is distributed herween the organi phase taken ‘fT va line (4) an the aqueous phase taken off va Fine (13). Te residue from column (6) may be recycled to reactor (4) vialine 1). feactionof the heavy preduetsistakenof rom reactor (4) vin the purge (16) and is introduced vi line (17) {nto an evaporator (18), ia which a paial evaporation opera tion is earied out, fr example hy Beating or by gas scaveng- ‘ng with nitrogen oe with wate Vapor; the gas phase contain- ing the majority of the chlorinaing agent of stream (17) is recycled via line (19) to column (6) oF via fine (20) to reactor (4):a distillation or stripping column (22) is supplied withthe Tiquid phase coming from the stripping apparatus (18) via line (21); and the major partof the chlorohydrin is recoveredatthe ‘op of column (22) va ine (23). ‘Optionally, the heavy by-products obtained from eoluma (22) are passed via line (24) int the itering column (25), in Which liguid and sold phases are separated, anda fraction of te liquid phase is recycled via line (26) t0 reactor (4). The solid may be taken off fom the filtering unit (28) via line (27) inthe form of a solid ora solution. Solvents may be added t0 ‘tering unit (25) via lines (28) and (29) for the washing andor dissolving ofthe solid, and may be taken of via line (27). Optionally, a stream is taken off from purge (16) and introduced via line (30) ino filtering column (28). The stip- ping apparatus (18) and distillation column (22) are in that fase short-circuited The examples below are intended to illustrate the invention ‘without, however, imposing any limitation thereon. EXAMPLES 1 TO 18 In Accondance with the Invention In. separating funnel whose base consists of a graduated cevlindrieal tube, water, 13lichloropropanol and aqueousUS 7,557,253 B2 |. perchloric id (Examples 61o 10) sodium chloride (Examples 11 to 16) ‘and calcium chloride (Examples 17 and 18), the eoncenta- tions of which are given respectively in Tables 1 to 4, are mixed vigorously for TS minutes at 25°C, Stering ws halted and then the mixture was allowed to separate into phases. ‘measurement ws made of the heigh ofthe interface berseen the phases over time, Time ze corresponds tothe halt ia stirring. The time ater which the height ofthe interface is ‘constant to +/=1 mm constitutes the duration ofthe phase separating operation, nthe omanic pase, the amounts of hydrogen chlorideand ‘of perchloric acid are measured by acid-based titration, the ‘amount of sodium chloride and of calcium ehloride by argen- timetri titration orby atomic emission specttometty coupled with plasma induction (ICP-AES), depending, respectively, ‘on whether the salt concentrations high orl, anl the water ‘content by the Karl-Fiseher method. The dichloropropanol ‘content is calculated by difference, Inthe aquecis phase, the 20 amounts of hydrogen chloride and of perchloric acid! are ‘measured by acid-based titration, tbe amount of sodium chlo- ride and ofealcium chloride by argentimetre titration, and the dichloropropanol content by vapor phase chromarogr- phy. The water content iscaleulated by difference, The phase separating times and the compositions of the aqueous and ‘onganie pases are reported in Tables 1 to 4 EXAMPLES 1910 22 In Accontance with the Invention ‘The procedure of the preceding examples was repeated 15 using 23-ichloropropan-1-ol and aqueous solutions of per- chloricacidand sodium chloride, the concentrations of which fare given in Tables Sand 6, The phase separating times andthe ‘compositions ofthe aqueous and organic phases are reports in Tables Sand 6, TABLE 1 ‘Agung Oasis pawe Trample (nal) CHP) CHE) CHE) Cop) CHEE) CepiE) Pha muntingtine 3 OM 628 KATZ ORT AHA 1338 0.904 levees mine so1 1893 RAZ 3282 879% LAS 0.167 Jest minute TABLE 2 Aassuiase ‘nasi Addtee 1 13 THEO! Deol Wier CIO’ DI Wer HEIOK Example ines) (eve) Chew) eee Cope) Crew Choe) Phacsruingting ono) 829 sa) waa0 1370 es i ok pan 7 ool 8236s MIS S080 ‘Sani pan hud, pation ‘penis 3h TABLE 3 neal ‘onus Addie 13 13. Exwople (mole _(Coea)_Cowa) CoWA) (owe) Cowie) (oad Pe sant tine 7 omer tas e520 vem 1330 gical cas pain noe 12 amma 8806 keso 120 ‘tection reUS 7,557,253 B2 2 coc 2 ‘onuie cies Aste 134 1. Cec De Pol War CaCO PaL Wie ample _malke) Oop) Cop) Oops) Oops) Cope) TS DCR 1dstionpmpn a ABLE aur sae Sx hs unple inthe) Coes) Copel Coes) Copel Cob) Come! Mase searing tine TBA Mo ABE ARITA 139 Osis pion May sass 137515611979 Srp cds epaton IABLE 6 Nowe las ‘Oni ee ample talks) Gans) Cop) Cons) Oops) Caps) Gon Pate cmpariag tine HOLA A876 0S O38 OUSS tawtimnaminne So #303 ros 992A “The invention claimed is: 1A process for preparing dichloropropanol, comprising: (@) reacting glycera, an ester of glyserol oF a mixture ‘thereof with chlorinating agent in the presence of an ‘organic acid so as to give mixture comprising dichlo- propanol, at lest one dichlonopropanol ester, and water (@) subjecting at least fraction of the mixture obtained in (6) to distillation and/or stripping treatment so 38 to sive a part concentrated with wate, with dichloropro- ‘anol and with at last one dichloropropanol ester, and () subjecting atleast fraction ofthe part obtained in (b) {1a separating operation inthe presence of at least one additives as to givea portion caneentated with dichlo- ‘opropanol and at least one dichloropropanol ester and comprising less than 40% by weight of water, ‘wherein the additive present in (c) comprises an inorganic acid, an inorganic salt or 2 mixture of the two and ‘wherein said separating operation isa decantation hav= ing a decantation time of les than or equal t 120 mine ts. 2, The process according to claim 1, wherein the portion ‘concentrated with dichlofopropanl and a last one dichlo- ropropanol ester in (¢) comprises less than 15% by weight of '3. The process aocordng to claim 1, wherein the decaata tion is performed under the action oF gravity 4. The process acconling o claim 1, wherein the additive present in (6) isan inonganic acid selected fom the group ‘consisting of hydrogen halide, sulphuric, sulphurous, sul o phytic, nitric, nitrous, phosphoric, phosphorous, perchloric chloric,chlorous, hypochlorous, carbonic and beri ace and snxturesthereot '8. The process according to claim 4, wherein the inorganic acid hydrogen chloride and the amount of inoreanie aed in ‘the concentrated part obtained in (b) is greater than or equal to (0.01 grky and less than oF equal 10 170 gk. 6. The provess aeconling to claim 1, wherein the additive ‘comprises an inorganic salt selected fom the group consi ingof meta halides, sulphates, hydrogen sulphates, sulphites, hydrogen sulphites, sulphides, hydrogen sulphides, nitrates, nitrites, phosphates, hydrogen phosphutes, phosphites, hydrogen phosphites, perchlorates, chlorate, hypochloites, carbonates, hydrogen carbonates, pecarbonates, brates ad perborates and mixtures thereof 7. The process according o claim 6, wherein the inorganic salt is sodium chloride and the amount of salt in the eoncen- {rated part obtained in (b) i greater than or equal to 0.4 wg ‘ad les than or equal to 280 gika, 8. The process according to claim 1, wherein the decanta- sion scat out at temperature greater than or equal 0 10° CC and Hess than or qual fo 100° C. 9. The process according to claim I, wherein the amount of \waterin the concentrated portion obtained (@) sess than or equa to 5% by weight. 10, The process according to claim 1, wherein the glycerl she esterof glycerolor the mixture thereof is obtained stating from renewable rw materials 11. The process according to elim al wherein the chlori- ‘quent comprises hydrogen chlorideUS 7,557,253 B2 23 12, The process according to laim 11, wherein the hydro- gen chloride is a combination of gaseous hydrogen chloride and an aqueous solution of hydrogen chloride, or an aqueous solution of hydrogen chloride. 13, The process according to claim 1, wherein the additive Js present in the mixture obtained in step (a), 14, The process according to claim 1, further comprising preparation of epichlorahydrin hy dehydmochlorination ofthe \ichloropropanl 15, The process according to claim 14, further comprising the preparation of an epoxy resin from the epielorohy di. 16. The process acconding to claim 1, wherein the decan- tation operation is carved out ata temperature greater than oF ‘equal to 4° C. and less than or equal to 100°. 17. The process acconding to claim 1, wherein the decan- tation operation i carried out ata temperature greater than oF ‘equal to 10°C. and less than or equal 0 70°. 24 18, The process acconling to claim 1, wherein the decan- tation is earied out fra time less than oF equal to 90 mia, 19, The process according to claim 1, wherein the decan- tation is earied out fr a time ess than oF equal o 60 min. 20, The process according to claim 1, wherein the amount ‘of acid in the fraction of the concentrated part separated off in (b) and subjected tothe decantation operation is greater than ‘requal 10.01 glkg and less thin or equal to 110 gk. 21. The process according to clam 1, wherein the amount ‘of acid in the fraction of the concentrated part separated olin (band subjected tothe deeanation operation is greater than fr equal 103 gk and less than or egal to $0 pik, 22, The process according to claim 1, wherein the amount ‘of acid i the fraction of the concentrated part separated ofTin (b) and subjected tothe decantation operation is greater than Dorequal 1025 gikg and less than or equal t 65 wk.UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 7,557,253 BO Page! of 1 APPLICATION NO. : 11/915056 DATED July 7, 2009 INVENTOR(S) Patrick Gilbeau Itis certified that error appears in the above-dentfied patent and that sald Letters Patent is hereby corrected as shown below: Column 6, line 52, “decantaion” should read “decantation Signed and Sealed this Eighth Day of December. 2009 [utd 5 Capes David. Kappos Director ofthe United Sates Patent and Trademark Ofce