10 0 PATENT SPECIFICATION Application Date: July 28,1927, No, 10,807 far, duly 23, 1927. One Complete Left: May 23, 1928. Complete Aocepted : Oct. 23, 1928. . No. 19,698/27. PROVISIONAL SPECIFICATION. No. 19,597, A.D. 1927, Improvements in or relating to the Manufacture of Aliphatic Acid Anhydrides. We, Buns Cxtaxasn Inez, of 8, Waterloo Place, London, S.W. 1, a com any moorporaie’ in accordance with the lava of Great ritain, Hexey Drexrus, of 8, Waterloo Place, London, S.W. 1, & citizen of the ‘Swiss Republic, “and Waurun Bapzn, of tho Works of fitish Celanese “Limited, “Spondon, near Derby, 4 citizen of the Swiss Republic, do hereby eclare the nature of this invention to. be as follows : ‘This invention relates to the manufso- ture of anhydrides of aliphatic acids and especlaly'40 the manaechure ‘ acetle "Ao Se ere we soe "gate men seat hatte eg cele oe SES EF hoe Sa ae ae aris Sle, Soe ices at Siero 7a Pisccording ‘to one form of execution of a) 2NaPO, +20H,COOH =: 0) 2NaPO,. ‘the frention may ae a acid, ihe Sion emi sl, E seete of ce cloaca sie of ee clres ce See i meer a te preferably” by. boling ‘the mixture.” By Sis rane gh ldo ai snhyitie ay be sacl podind, the tabi boing separated dom We ene tion ‘mixture, for dostanoe by” distation or by filtration with or without subse- ent distillation, “Accord +o the relative proportions of metaphosphate and acetic acid employed ‘cid soditm pyrophosphate or acid. sodium ‘orthophosphate re. produced with the feete andre, Pox inlance when. st stantially » equimoiecular proportions feo. acid’ "and. ofthe ‘mmephoephae (Feckonod ag NaPO,) are employed the esidue consists largely or, mainly of acid fodimm ‘pyrophosphate, whereas if sbout ‘two moleealar equivalents of acetic. acid are employed tho residue consists largoly of mainly’ of acid sodium orthophosphate ; in these cases. the reactions probably pro: ceed according to the equations -— fasHLP.0, + (CH,CO),0 acid sodium pyropho acid sodium ox 1m order to utllte the dehydrating ca sity. of the metaphosphato to. the full wo pelombly. use auffeent. acct acd. to Enno the mnctaphosphato™ to acid Sodium orthophosphate eg, about 2 mole cules of seco seid for soak, molele of metaphomphate (reckoned ay NaPOs) Dy Tsing excent of elie aod Ga exces ver the 2 moleonls) miximres ‘et cet fait ‘and soetio tnhydrde. may" be btained which are ghiy’ uneil for Industrial Westpition prowess such for Instance. asthe manaficte of cellos corte ‘When the residue contains acd sodium Hrosphate i mag, with ‘or without EPriae 1/1 to MH,COOH Natl PO, £2C11500),0 phosphate. separation of the acotio enhydride, be employed for reaction with further acctio acid “to ‘produce further acotic anhydride, For instonco a further mole. ular proportion of acetic acid (or if Aesired! an excess of acetic acid) may be added to the residue and the mixture again heated or Dolled and the anhydride 80. produced recovered at above deseribed. ‘The residues from the reactions (ister "sh rss, const “substan. dally of acid orthophosphate or acid. pyro. phosphato or of mixtures of auch phos- hates) may readily be transformed. into etaphosphate may be made to 299,342, 85 i) 85 90by @ mixture. of disodium hydrogen phos- phate and sodium avetate maybe pro may then be treated with fresh acetic acid or sodium acetate to produce further 2 200,842 verve for Wwoating froch quantities of genction in presence of a nonaqueous 90 cell acid, and thus the precess may be diluent, suelt for example as “aeetio conducted ‘ap ¢ continuous cyclo of opere- anhydride. "For instance, "we may ‘heat, -. Cons "For inotance the resliues may be or preferably boil, « mixtare of soda ‘5 heated, ine manner Known for the pro- metaplogphate and. sodium acclate. with stig op etaporpats "om. Site, cbs ‘ad erate 8 rilophosphates. oF ack Ymphatee, guiydsiie so. produced by distillation o nd "the” metaphosphiate "so" produoed by iltation with or without subsequent routed “with fitsh “acolio ocid”in the distillation, By these means highly’ sxtise 10 manner shove desoubed; or when the factory yields ef acetic auhiydide may bo Felts “Cone “outta of sd oblate eg ® Srthophosphate ‘they maj According to relative proportions of Reatel fo. form.” acid’ pyrophosphate metaphosphate and acetate” employed Hand of napa, sh ex "eons er neutral 15 pyrophiogphate. may ‘inilaiy ‘be treated sodium) “orthophosphate aze prod Bite weaie aca fogether with the ‘anhydride. ‘Thus for 45 Svc pier form of acon tne, "ohn ula equnole tion of the invention we may employ a etlar ong “of the mctaphosphato fetal acetate, for instance an allay or (record aa NaPO,) and sodiom acetate 2 aliali earth “acotate, “instead of acetic are employed the residue consists I Sci, ‘The acctates aro, preferably or mainly of ‘neutral sodium pyrophes- 50 tiple nee aoa fer Plate, whereas, it about two molestlar frguch form of exccution we may for equivalents of sodium ncctate. are example, melt" sodium acoiato with a employed the residue. consists largely 25 sodium salt of a motaphoophosio acid and or mainly of neviral (iisodivm) ortho- soptrate the anhydride. by distilation or phosphats, in these. cases, the reactions 85 Dy fteation with’ or witlont subsequent probably. prooeed according tothe equa: ebillation, ie Proferabiy however we perform the . ) 2NaPO, + 20H,COONa -Ne,P,0, + (CH,C0),0 ‘Deutral sodium pyrophosphate «0 a) 2NaBO, + CH;COONa BNP, + 2(CH,C0),0 outral (iisodlam) ordhophomphte Tn onder to utiliss tho dehydrating duocd. ‘This mixtaro muy bo evaporated capacity of tho motaphosphato to'tho full to dryness, and by further heating. (ore < We prterably uso’ suficient godium ferably’ under reduced pressure) "trans- 95 65 Seta to tsatorn te mesphoepate fo formed sito a, mixta of sod pyro ‘the noutal (sodium) arthopbosplate. phosphate and” sodium. acetate. "This Wien te residue ‘om’ the, rosction fevulting mixture may be heated, ‘or pre- contains noutral sodiun pyrophosphate ib ferably boiled with ‘x. suitable. non: may, with or without, stparition of the aqueots solvent, "such “for instance as 100 "70 aectlo “anhydride, be ‘employed to react acetic anhydride, "to produce futher with forther quantities of sodium acetate acatic anhyatida or with acclip acid, “For. instance va ~ "Or for ‘instance when the resus con--= Ficthor molooular “onuivalent of sodhian ssto Iangely or vainly of nsutral (tre aovinis-may bo added to tho residue and sodium) “orthophosphate ‘or "of neutral 105 76 tho mixtare heated, or proforsbly bofled sodium. pyrophosphate, the residue. may af inion "have snk ane ete fh ay in own mre © acetic. anhydride, so produced ‘re- produce disodium hydrogen phosphate covered as above desorbed QiogHPo,), ‘This may then bo treated sith Whore’ tho residues consist langely of aqueous fetio acid and. aunmonia to pro 110 ©'e0. manly "of “neutral pyrophosphate of of duce a mixture of eld sodium ammonium foie “orthophospiate "they "may" be phogphate (miorocoanio alt) and sodium oovered as tetaphosphste oe as noutral Rodtate. which may be separated by fruo- Pyrophosphate by sutable treatment after tional” crystallisation, for instance by __. Midiicatlon (preferably ‘with acct acd) cooling the solution” at suitable concer 118 85 ani the process thus mado a continuous frtion whereby the seid sodium smmom- cyole of ‘operations, For instance, ven ium phosphate. is lexgely or entirely pre- Ske estto const largely or melaly of siptvied and the eoclun soetato romtins neutral (irodium) orthophosphate,” it in eolotion, ‘The seperated sodium _--. may be mized with about one moleoular - ammonism pospate may then be heated 10 00 equivalent of aqueous aoctic sold. where- to. produce ‘sodium. motephomphate which10 2 65 0 299,242 ‘acetic anhydride. ‘The sodium acetate separated from the acid sodium ammon- ium phosphate may be recovered from the solution and utilised for the production of aoctic anhydride by the process of the invention, ‘Tho ammonia liberated on heating the acid sodium ammonium phos- phato may be used for treating disodium ate (ne camels above) "to produée "further aunties of wetinm ston phe habe for uae in the proces o ‘Tt will thus be seen that the utilisation of thes ad he xenon of ho procera a continuons eyele of operations Though somewliat, more somplosted. when salis of aoctio acid are employed instead Of Ste 2, leat vary. ofiint recovery and ‘itlaation of the reagents. ‘p wil be ‘wlerstood. thatthe. above Torma"of execution of the invention are given only by way of lustation and are Sino way Linitatie. Tatead off sodium acetate we ma employ potasium acetate or other Gr earth alla or other metal nostate Further we may employ mixtures of sodiuin scetato of othet lait or earth Sit or other seta next’ with cots ‘When employing mixtures of acetates and acetic acid we preferably ‘employ exoest acetic acid to aot as diluent for the reaction, For instance. we may heat, or preferably. Qoil, a mixture of sodium Zootate and sodium metaphoephate (or pyrophosphate) after dilution ‘with glacial Zest acid or after dilution, with © ais fire of scetio acid and soctio anhydride, ‘and recover the acetic anhydride so. pro” iced by distillation or by fltrtion with ‘oF without subsequent distillation, Th. performing. the invention with acotates or mixtures ‘thereat and acetic acid, the” acetates should preferably be employed in their anhydrous form, Tid of set, ed oF Sates, we may em ‘other aliphatic acids ot fodium or other alkali or alkali earth oF ottprtand of alten sale af om salts. of ie acids of lower dogreo of hydration tan Sthonbombore Sd wo ray, gaacy otassinm or any other salts” (inelu eid salts) of such acids, Dated this 23rd day of July, 1927 ‘T, I, WHITEHEAD, Chace Patent Agent, ent Department, British Cslanese Limited, 8, Waterloo Place, London, 8:7. 1. PROVISIONAL SPECIFICATION. No. 19,598, A.D. 1927, Improvements in or relating to the Manufacture of Aliphatic Acid Anhydrides. Wo, Bums Onuassr Lmnrap, of 8, Watetloo Place, London, S.W. 1, & com: pany incorporated. in accordance with the Tawa of Great Britain, Huxny Dezvrvs, of 8, Waterloo Place, London, 8.W. 1, and “Waurs Bapun,’ of the ‘Works of British Celanese Limited, Spondon, near Darby, bath emf the | Sui Republic, do doclare the nature ‘his invention to be as follows -— ‘This invention relates to the mannéao- ‘ture of anhydrides of aliphatic acids and especially Yo the man ‘of acetic anhydride. “Aecording to the invention we have now tod hs “alae syd” fon ood tag ld factory’ produood by seating alipheto Node end/or metal SEBhsts ade with ono "or mow poe Hse acl of love dope of Hyaaton on ertaophogphons, a pocielg’ the invention we may for inttance mix ‘acsta sok,” preferably a etl fo a hm ght mes cee ee es Bese ak Baad t, Sane seh ee ae eas aa a sacl ake cpio 3d are produced wih oie Deo eee en ed mora “e es seid atone ly_or entirely to pyrophosphoric acid, whereas if about 2 molecular oes Tae oad steele penton aay 2S 85 95 100 — a,4a 290,342 4) 2HPO, +2CH,COOH = (CH,CO),0+H,P,0, shosphorie acid by 2HPO, +4CH,COOH ~ (CH,CO),0 + 2H,PO, crthophosphorie sett 5 In oder to utiliso the | dehydratin capacity of th metaphosphorio acid to the full wo ‘preferably uso. sufficient acctio seid te tsiorsfmetaphesphoro sc fo Orthophosphorie acid eg. about two mole. 10 oules of avetio acid for each moleoule of ‘metaphosphoric acid (reckoned. as. 11PQ,). By ‘sing excess acctio acid (i.e. excess ‘over the 2 molecules) mixtures ‘of acetio acid and acetic anhydride may be 18 obtained” which are lghly” useful for Industrial aeotylation processes. such for instance asthe manufacture of ‘cellulose seotate. When the residue from the reaction 20 contains pyrophosphoric acid it may, with < @& without separation of the aoctic ~ anhydride, be employed for reaction ‘with further acetio add. to. produce ‘further ag, Sots jabato, "For tance further moleoular Proportion of agetio acid (or i Gesired an excess of acetic acid) may’ be added to" the residue and the mixture ‘gain heated or boiled end the anhydside 50, produced recovered as above described. 20 “dhe: “residues from’ the reactions (whether "such residues consist. ‘subst tially of erthophosphorie acid or of, pyro. phosphorie acid of of mixtures of such Acids) may readily’ be transformed into a 385 metaphosphoric atid, which may be made to serve for treating fresh quantities of aeotio eid, ond thus the provess may be conducted as a continuons eyele of opera Yions.. For instance the residues may be 40 heated, in the manner Imown for the pro- ‘uation of metaphosphorie acids from orthophorphore seid "or prrophophore fcid, and the metaphosphonc acid £0 duced treated "with fresh acetic. acid in 45 the manner above desoribed > or when the residues consist substantially’ of ortho: hosphorio acid they may if desired be Feet fo “Ton pyrophorprie acid instead of metaphosphorie acid, which yrophosphorie acid’ many” similaly be 60 ‘ented with Sresh acetic ac. ‘According’ to another and more prefer- able fom of exeeotin of the fnventin we may employ © metal acetate, for instance Sn allall or earth alka attate, instead 55 of acetic ac. In such form of execution we may for example heat a. mixture of sodium acetate dpa metabo ad and saat the anhydride by distillation. Preferably 60 however we perform the reaction in. pre- sence of 2 non-aqueous diluent, such’ for instance as "gece, anbydsie, For Instance we may heat, or preleraty, bot, 2 mintare of a metopbosphorie acid and 65 inate oth get eds td ty” distiltion or. ‘by" stration "with or without subsequent distillation, By these Ineans highly satisfactory yields ef tcetio 70 anhydride may be obtained. “According to the relative proportions of the mctponors aid ane netic employed acid sodium pyrophosphate or Givoditm hydrogen pharphate are, pro- 75 hued fogtlee sth the atti. Thus, for instance, when substantilly equimole- cular proportions of_ the ‘metaphosphorio facia Geekoned a HPO,) anit sodium ett are emplayed the eidue coasts 8) yor mamly. of acid sodium pyro- phosphate, weress if about’ 2 maléclar Gquivalents " of sodium acetate are employed. the’ residue ‘consists ngely or mainly of disodium hydrogen phosphate, 85 Jn these cases the reactions probably pro: ceed according to the equations €)_BHLRO, +20H,000Na = (CH,00,0 +NePsO, tid got 0 @) SHPO, +40H,000Na~=3(6H,C0),0 + 2NagllPO, phate disodium hydrogen phosphate: In onder to utiliso the dehydrating capa- city of the ‘metaphosphorie aid to the fall sve. preferably so. euficientscetato. t0 5 Ueansform. the ‘metaphosphorio acid to lsodium hydrogen phosphate, ‘When’ the resid fom the reaction contains acid "sodium "pyrophosphate. it may, with or without separation of the 400 aoetio"anhyaride, be ‘employed, to. react with further quantities of sodium wectato oF with acelie seid, ‘For’ instance Farther molecular equivalent of sodinn fostete may bo added and. tho mixture heated, or preferably boiled, after dilu- 105 ‘tion with acetic anhydride, and the acetic anhydride so produced recovered as above deseribed. “Wher the, pees const lenge or mainly of acid sodium ‘prrophoephate oF Aisoditon ydrogen phosphate they may be recovered as metaphosphorie acid or pyrophosphoric acid by @ suitable trent. ment, and thus the process may be con ducted az a continuous eyele of operations, LIS For instance when tho’ residue consists largely or mainly of disodium hydrogen10 15 0 % 200,342, 5 Phosphate it may be acidified in_ known Tanner to. prodico orthophosphotie acid which may be hed Yo produce ¢ meta josphorio. acid. of pyrephosphoric aci ‘ehh ony then bo rea ith eek toctic acid oF sodium aceiate to produce forther acctio” anhydride, Or, for instance, ‘when the residue consists largely or mainly of acid sodium pyro- BBspbate 1 mey be tated with st jown manner to ‘produce an orthophos- phate, ‘This may then be treated with Scids ‘in known manner to produce ortho- Blogpore cid ‘hich may he atl o produce a metaphosphorie oid. of a pyr0- Phosphoric aed which may then be Treated with fresh ‘acetic acid or sodium aootate "to produce further acetic anhydride ‘Or, if desired the residue from the rese- tion nay be Heated in mown mone to ‘produce 4 sodium metaphosphate or P3r0- Bhorghate wai nny be employed for tho Execution of the process of our” eo; ‘Application No, 19,597 27 of even date herewith, Te will bo understood that the above forms of excoution of the invention fre given only by say of illustration and fre Aino way’ linitative ‘Instead ol sodium acctate we may employ potassium acetate or other allalt ‘or earth alkali or other metal acetate. ‘Farther we may employ mixtures of sodium acetate or other alkali or other metal acetate with acetic acid. 35 ‘When employing mixtures’ of acetates and acetic acid wo preferably employ ‘excess acetic acid to act as diluent for the reaction. For instance we may heat, or preferably boil, a mixture of ‘sodium 40 fostate with a metaphosphorio acid after ‘lution ‘with glacial acetic acid or after ilution "with a mixture of _acetio ‘anhydride and acetic acid, and recover ‘the anhydride so ed, ‘by distillation 45 or by filtration with or without subsequent distillation, Tn performing the invention with acetates or mnixtres ith, acetic ca th ace cal py te timployed in their abyydeous form. Tsfead of cee. acid or etates we ray employ any ether algkstic acd ot on br othe alkall or lal cnsth oF ‘ter tatal salts of ch ois 3 Dated his 29rd day of July, 1027. "T, L. WHITEHEAD. Chartered Patent Agent, ‘Patent Department, British Celanese Limited, 8, Waterloo Place, London, 8.WV. 1. COMPLETE SPECIFICATION. ‘Improvements in of relating to the Manufnoture of Aliphatic Acid Anhyérides. We, Bums Onaxass Lneran, of 8, ‘Waterloo Place, London, S.W. 1, a com? piny ‘aenporaiad in aciordanee with the ws of Great Britain, Haney Duevrus, ‘of 8, Waterloo Place, London, S.WW. 1, fa citizen of tho Swiss Republic, ‘and ‘Wauren Bapex, of the Works of British Celanese Limited, Spondon, near Derby, av ctizen of the Swi Republic, do hereby declare the nature of this invention as jp was manne the we is te, ba Be formed, 10 be particularly describe ascertained in and by the following state- ment — "This invention relates to the manufac. ture of anhydrides of aliphatic acids and expecially to the wcture of acetic ih previous Spocifeation No. 280,072 ‘Hemy Dreyfus has described how phos- Phone voids maybe employed as setae By the thenanl dxomponon i thera decomposition ot avetle acid. ecoraag to, the preset faventon wo have now found that alipatie anhydrides (and especially acetio. anhydride) ean be telat pruned hy seating Hoo Gliphatio’ acids. andor metal malts) of alighaiio acids. vith phosphoric ‘acids of 85 fower degree of hydration than. ortho- Dhoephone acid and Jor sate of such phos- Bhorke acids (as for instance with meta- Shospborie acid or hori ackd or {Bhatia or ear ala at thosphorie ot sphoro acid). PhRording toe form of execution of te invention we maya aot sl, Preferably glacial acetic acid (in presence Pritbeente® of acetic. anhydside), with a 95 sodium sat of & mete fe reaction being ceclerated by heating preferably boiling. the. mixture, By. this Freans @ high yield. of avetio. anhydride ay’ be reatily’ produced, the anhydride 100 Ping soparated from the reaction mix. fare’ for” instance, ‘by distillation oF by ‘leration with or “without subsequent. di dilation "Recording to the relative proportions of 108 metaphospiate and acetic. acid employed {oid Sodiom pyrophosphate or seid. sodiumje 299,942 is 30 35 45 105 Ho ‘orthophosphate are produced with the set anlydrde. ‘Potato won eth stantially equimaleeujar proportions 0 teetio acid""and. of the "metaphosphate (reckoned as “NaPO,) aro employed the Fesidue. consiste largely ot mainly of acid sodium pyrophosphate, whereas if about two molecular equivalents of acetio acid are employed the residue consists largely for mainly’ of acid sodium orthophosphate; 10 in these eases the reaotions probably pro ceed according to the equations :— a) 2NaPO, +2CHjCOOH=NeyH,P,0, +(CH,CO},0 scl sodium pyrophosphate 5) 2NaPO, +4CH,COOH = 2NaH,PO, +2(CH,CO),0 ‘acid sodium orthophosphate. In order to utiliso the dehydrating copa- city of the metaphosphate to the full we preferably uso suffigiont acetio acid to ‘transform the metaphosphate to acid sodium orthophosphate, eg. about 2 molo- ine ef ool aid fs Sah melee of tetaphosphate (reckoned ns NaPO,). By tusing’ oxoess of avctic acid (lo. an" excess over the 2 molecules) mixtures of aoctio acid ‘and acetic anhydride may be obtained which are’ highly useful for {industrial acetylation processes such for {instance as the manufacture of cellulose acetate, ‘When the residue conting aid sodima pyrophosphato ib may, with or without Separation of tho. avetio. anhydride, be employed for seaotion ‘with further fcetie’ avid "to ‘produce further acetic anbyabide. “For stfonce « farther mole: cular proportion “of acstio acid (or if Gisired an excess of avctio acid) may’ be added to tho residue and the mixture ‘ynin heated or boiled and the 50, produood recovered as above described. residues from’ the reaotions (Grhether “such residues consist ‘substan tially of acid orthophosphate or acid pyr0- Phosphate or of mixtures of such phos- hates) may readily. be transformed into Inotaphosphate which "may be made to serve for treating frosh’ quantities of Acetic acid, and thus the process may be conducted ‘ag a continuous eyele of operi- tions. For instanco the residues may be heated, imo manner known for the ‘pro- duction “of metephosphates “rom eid orthophosphates of acid pyrophosphates, and the” metsphosphate so produced treated with fresh “acetic ‘acid’ inthe manner hove described ; or when the edie “emit subtatilly "of acd orthophosphate they ‘may if desired be hheated fo” form” acid” pyrophosphate Instead of metaphosphate, which acid Pyrophospbate. may ‘tnileiy "bo treated th fresh soeto acd. ‘Recording to. another form of ‘exeen sion of the invention we ‘may employ «65 fetal acetate, for itstanoo oh lll or SH hacia ie eel fold, ‘The acctaies are preferably enipioyed in there anhydrous for! och form of execution ‘we may for 70 example. mel sodium. eoctato. with & sow of etapa a nd Separate the auhydride by" distiltion. or by Altration with or without subsequent aludlation 8 Preferably however we perform the resotion in presnce. of a "non-aqueous diluent, ee for example as acetic subydride. For instance, "we may ‘heat, or ‘molsphorphate. and. sodium’ acetate with seat ankydide and recover tho acetic syste ao. produced by” istilation or iby Bteation with or without subsequent lsllation, By these means highly tatis. 85 Iastony los ot sce spade ay be obtained, “According to relative proportions of metaphospliate” and” acetate employed vent Pyrophosphate or neutral (eae 90 tedium “orchophoephate "are "produced together ‘ith the anbydide, ‘Bay for inatance, “when substantially equliol: cular proportions “of the metaposphate (reckoned as NaPO,) and sodium acetate 05 are employed the residue consists largely Gr mainly of nevizaleodium ‘pyroplos. phate, whereas about two ‘Taolular quivalente of sodium aoctate. are ermployed. the resdue consists largely 100 oe munly of outal”(4tsodium) onthe Phosphate, fn. ‘these ‘casey the, reactions Probably pnooeed according 40" the equa: Ems ©) 2NaPO, +2CH,COONa —Na,P,0, + (CH,CO),0 neutral sodium pyrophosphate @) 2NaPO, +4CH,COONa =2Na,P0, +2(CH,CO),0 neutral (trisodium) orthophosphate. In onler to utilise the dehydrati capacity of the metaphosphate to the we preferably use suficiont, - sodium acetate to transform the metaphosphate to the neutral (trisodium) orthophosphate. When the residue from the reaction contains neutral sodium pyrophosphato it 115 ag, wath howd eparation of the acetic, anhydride, ‘be emy to react, ‘with further quantities of sodium acetateone ; Sa Sa GE Fo totem Tw Ge bo wg tak ito i seg 008, ane 2 wt dike cetion fe Parmer anc ets ee of ope wii may he al fo She rele aod Uno ra Soup when Meanie, hove pcembiy tote nel eomerta me Gave inest 70 son "hace ng and Ooo et Suey ect the ote ne fet Ss Ma ne gos re a weety ox threes, Mes FE aetod thd th abere ag May meal ronnie a eel te inet eT ext ordnponts heey MS egy ott ad Be fever sp aT, sea ee ne eran by waa peer aes ey natal we Sntn Cray ich seat, at) Inhale ees ial vs Sa Meco Abc tah Sry eee ae % epee ot, nan, whey oe a cong me of he sn cmt Te oo old dna er cut seul (een) Steno SN it tal Sowa wih cet say be mise ik cht oe ge ay MaRS ager, Se ll he 8 uo mice of eats 88 Fg maces of dion hype hs. "When soak ty ‘caper Fab ei ale ay be FS, sa a a du he Bee ats mye obedient, Seen a aes ee ate aaa ae ie ag cy ee reemd em) Sees pbs elphaphate t_ 99 ied no ine Oli TE, ets fe al i gh ephatend oto sett, Ts pre) ie divton yuh oe Fools ace may he Meteo Bet oS AT aS rapa, fay aed a 4 mete on, Tat el ae saad oe ap aims sen, sweh or anes 02 aud sve donor bp iianon wh 95 ae rs duel by tion Se ste hp toy we “ion tl tg we Poe fr taco when hp lag pe Ian oe Sha ls sity net ormniny of gl a ome ye Et crt or gs oe crmeuiaatn etl Se el a a i Seth din Mowat “Hea na i et eel a nO gaa ee eae hyo then FE sieaiam Motte udeied mth oriepomboro ae we “iy employ ERitiog, Pa my homie mth aa a osing ay ee te sk po pmo oe Fa) of ohh ei . ie nie of oes apm Set iets of exton nt recom a) sn soon Ae oe ana Tessa euch ag be pred Uy tae of he uw ysl al ee ee i re cs malig Eectoign' at ale one Bs geaponpno 10 ig rey, te dion geotools seein ley “or sets ee Sata Qe yah mms Sd A a ena aly he per eg ee ee eee ao am pment onl, mey hen tay enc, 118 esi, ee, set elo TBegret wtih ng hn e weta wth Uy A he mlive onrton of fe eat a”, gon we ne dee er eae ane Hho te, matin sinatesa ss maim etl apart he ot 5 eae ER FeS Pataki 10 eon orate may bp Ngoced GRMOQLORIES® or Slade hn Hf helt and ai for gr ro te, A Sale ope chain’ of co “nyie, the fo tll oe Epi al cero ty Harsh ammonia a i ant poe ‘te co meg hanes Se cain tenis Sarat at "apne 1s ae Ce ea ee odben rte pols (oad aaa dit Sndaae eee sey ha ays Phwpte Ae an med ere epee! oc tmaing ar) rns aah canaed ly ig i ect ot icon sl tase SS 08 290,342, ceases the reactions probably proceed according to the equ 6) SHPO, +2CH,COOH =(CH,C0),0 2.0, f) 2HPO, +4CH,coo! (CH,CO),0 +2H,P0, 5 orthophosphorie acid Tn owder to utlise the dehydrating eaptcity’ of the metephosphosie acid te the full wo profrably use buflcent aeetie igo Gullrm mepiosphonic acd to 10 orthophosphorie wed eg. about to mole. Gules of ste ci of en melon of Ietaphosphorio acid (teckoned as TIPO) By ‘ising. excess aoctio ackd (re. exoce over the 2 molecules) mixtures ef cetio 15 cid “and ootie anhydride may be obtained which “are highly uselel for Industrial “etylation procetes. such for instance’ ag the manolsctur of ‘exlalose acetate. 20 Tithen the zevduo from, the reason contains pyrophosphorio acid 8 may, with or cptatin a “he ae anhydride be employed for reaction ‘wit further acetic acid” to produce further 25 acetic anbydside. For indlancn, x fusthey molecular proportion of acetic acid (or, if dred, en excess of octio ac) maybe < aidded"to"the sesdue and “the. misiore Again heated or holed. and. the enlyanile 30 80 prodnced recovered as above descabed residues from the reactions (whethar ~ such residues conalstsubstantlly af ‘orthophioepharo acid ot of pyrophosphosis ‘cid or of mixtures of euthasids} may 85 readily. bo transformed inti a "metaphos, ings sla wh nag be mae to Serve for treating fresh quuntiies of asetio acd, tna tus tho precy may bo sonal 4 continuous” eyele of opseations For 40 instanco'the residues ‘may "he heated, a fhe manner known for the production of Iitaposphosic” acids tron orthephoee Phorit ‘ncid_ or pyrophosphorio aid,” and ‘ho- metaphospioro™ acid so. produced 45 treated" with “fresh acetic stid" nthe manner above ‘ewatbed or sehen, the residues const ‘substantially of ortho: horie acid. they may if desired be ested. to “dorm pyrophorpoti ae instead of metaphosphotic scie, whieh 60 Pyrophosphorio acid “anny” stmallnty "be ated wih fresh scot ald Sota ee Instance, an kai or earth elie sestete, ‘Beem on alo ee camps fae of Sogation mag or bee nena sere the" ameemnmotar sad sd Petia hor ae pa ment, Mme Palomo diluent, such for instance as cet eae Fie ate ye gg Sag eatmem ae BY et Re a mt sme Begs tm am ees wih aimee one te ace by filtration with or without subsequent 70 Beene pace Sie eepent fag iad de ames EY sao? Ci eee ee sonny al Rg cpl ee a an cet in trae adele ha eae agen, hoor re po. dee nes me Se eas. Ths an prop eM a ag toa, Feline a Re thee oat Se ea ne eee, OS mae oe caplet cots ESR Ny, of ag sn py. ae ee Se ao Male ant ty seplred i ie pis a oF Pacer mae pha, ieee earns 90 9) 2HPO, +2CH,COONa = (CH,CO),0 + NasH.P,O, ‘acid sodium pyrophos srophogphats 4h) 2HPO, +4CH,COONa =2(CH,CO),0 + 2Na,HPO, 1h onder to uibe the dahydrsting cap 85. clio the mtaphospost Sed toe Rt Te seri “to Toit acto to Enutom. ile “metaphespore acl fo isodlum hydngen pogplote, ‘When’ the sesdde "Bom the zeaction 100 contains acid “Soom "pyrophophate. fay, with or sitions Doueton of the teat snhytide, bo eaployel to renee ‘ith furthar-quentie of sodium aceite Or (ith scctie oily ‘Rot nsianog’ ¢ 105 Farther moteotias “equivalent of toa, codium hydrogen phosphate. goctate may be added and the misture heated, or preferably boiled, after dil. on wie oate emigre, and the serio anhydride so produced recovered as above described. ‘sth, dns, com, gly 0 rainly of acid aodiom pyrophosphate oF Glsodiam hydrogen phoeplate they may be recovered as metaphosphorie acid or pram. Phosphoric aed. by t suitable tcathont, nd thus the prootis may be conducted ag 115 4 continuous eyele of operations Forccd 60 _vankydride ‘and sceti 299,342. 9 instance, when the residue eonsiste largely or mainly of disodium hydrogen phos ‘phate it) may be scidiGed im. Jehown fnanner to ‘produce axthophosphoric acid which may be heated to prodiice a mota- oephorio acid or pyrophosphoric acid Whit, may ‘hen "be uedied sth teen sectig’ acid or sodium acetate to produce further acetic anhydride. Or, for instance, when the residve consists largely ‘or mainly of acid sodium ‘pyrophosphate 4t maybe ‘treated ‘with acids in imnown mantisr to produce an -orthophosphate, This may then bo treated with acids in mown mianner to. produce orthophosphorio. acid whish may bo heated to produce. a metaphosphorie acid or @ pyrophosphorie feid Arhich may then bo treated with fresh gvetic. acid or sodium ‘acctate to produce further acetic anhydride. Or; if desired, the residue from the reaction may be heated in mown manner to produce a sodium motaphosphate oF pyrophosphate which may be employed. Jae the ‘production of further quantities of anhydride in tho manner hereinbefore ‘indicated. It will be understood that the above forma of execution of the invention fre given only by way of illustration and are in no way limitalive, Tnstead” of sodium acctate we may employ potassium acetate or other alll, overt la rote meal ciate, x we may employ mixtures sodiam acetate or other alkali or other ‘otal acetate with aoetio acid. Woon gnploing misuse of acinae and ‘aootio acid we. preferably “employ txocsr acetic acid to nod as diluent for the reaction. For instance, we may heat or preferably boil, a mixture of sodiom Soetate with a ‘motaphosphorio acid after dilution with glacial aostio acid or after dilution “with” a mixture of acctio ‘eid, and recover ‘he anhydride eo. produced, by distillation ‘of by filtzation with oF without subsequent Stallion i" petiorming the invention with acetates or mixtures thereat with acetic ‘oid; the acotates should preferably be ‘employed in their anhydrous fora. Tinea of acl, tld or ecelate, wo may employ any other aliphatic acide or fodiom er other alla or altali earth or ater metal salts of sok acid in_performing tho invention we may, as hereinbefore indented, heat or boil the Various reaction mixtures to aogelerate the formation of the anhydride. Whilst ssuch renction mixtures may be heated or boiled in any suitable manner, the best results appeat %0 be obtained’ when. the heating ‘or boiling is pesformed” at teme peratures of between about 100° and 250° C, and especially at temperatures of from about, 120" and 180° Gn chess ‘whore seetic or other aliphetie seid Caused to seach with the seid. phosphoric ftcid. (and/or phosphate) and. where. the Tong point. of the said aliphatic acid Is not suiflelentiy zaised by admixture. with the phosphorie acid (end for phosphsts) to cafe he eg tre be aed St the desired temperature, the. bel Tay of course be performed tinder” ine retool. presto, pressures of up to. 3 Stmospheres usually sufling “Tor this ppurpte. ; Th cases where salts (je. either salts of aliphatic acids or salts of said phosphoric ‘cide or salts of both of such" acids) aze employed for producing. the anhydride it i otin adv. ak life em, such for instance aa Kiselg Gr infsorial earth with the reaction mix: tres, such admixing serving ia many cases to provent aking Te -wil of oure be. understood that in casea "where the anhydride ie dstiled from the tesotion mixtures, much distil. tion may ‘be efeoted under any desired prowure, eg. under normal atmospheric Dprsure’ ‘oF ‘under seduoedpresmro, Frrther, if desired, such distilation may be aided by blowing alr, carbon, dioside other Sadifeent gar through the rea don vere ‘The following examples serve to lus- tuate’ one form of execution of the inven. on, St being” understood ‘nt these are given only by way of ilustration and in So way aalimitatve. 100. Ibs, of sok oe ahc , of “sodium mtaphoepbate_ in LLL with "150 °Ibe, of ‘anhydrous powdered fedium acetate “and” 30 ib. "of dry {fusorial earth. ‘The resulting mixture is stived in e pen snd bested to about 150° C._‘Tho pean is closed and connected swith “a condenser and. receiver. Glacial Xeetic “acid is slowly and -continuensly faded to the mixture at such speed. thst the mixture ‘appears just moist, ‘The 115 heating’ and addion’ of acetic acid are faintained so long aa acolo. anhydside in the distillate, ten the “acetio S28 eupply Ja cutoff and the veadue ds filea”“dry” ‘The residve. remaining after distillation is ‘composed substantially of ‘tisodinm orthophotphite ‘whilat the” dis tilato is composed: substantially of 88 to 80 'Ibs, of acetio anhydride snd about 350 The, glacial acetio nc 0 6 5 100 108 uno’ 135 xaos 2 damit of 10 cs of un oe mphato (inthe Jor ol 8 omer), 160 pants of anhydrous powder Sodium” aootdle ond "20" parte of Gry 19010 299,342, 10 1s 85 ee eects fe Seah Crate th onda aires in Lt Say en a a oot aid in liquid form ie added fo the ae ae eae S ate eae Sete oak ee aes oe sos i a ee ae nat era fy Teeuahing Yao gannee of ihe rection yore te ened me Recomposed “substantially entiely to” tie “Ech tay cme wt Lc aay ont sscertained the ature of out maid inven- wena GaeTe Endl is ate 1. Process for the manufacture of aliphatic “anhydrides (and expecially acetic anhydride) characterised in that gui lia sedan or metal sats ofc elds ate cae to fact ith Bon than ‘rthophoophose asd auor ‘ih gale ofeach phonpons st Process according’ #0. Clsim 1 and whoroin the reaction is performed. by heat Jng am all, carth alla or othor metal fs of acotio or other sliphatie ald” with fn allall or earth alzalt sat of motaphos- hore acid or of pyrophosphoxlo acid in Dreenoe or ‘altenes of a non-aqueous Sitent. ee ely Ge Le cot Hise aes ali wa Sle Se esp beac see ean Cam peu eect Zar Pear ofan oe sroponiag Tasha awe oy Bes gone Si 9 from about 150° to 180° C. SO ees alps ta et tions, the ‘residues “from. the reaction, Sea oa fein denied, eng See oe ae manufacture of acetic or other aliphatic anhydrides sub- stantially as hereinbefore described. Dated this 23rd day of May, 192 ‘T. L. WHITEHEAD, Ghartered Patent Agent, Patent ent, British Celanese Limited, 8, Waterloo Place, London, 8.WW. 1. Abingdon: Printed for His Majesty's Stationery Ole, by Bungoss Son {ie 364 a5 tog 50 60 0