«» United States ‘US 20050176973A1 <2) Patent Application Publication (1 Pub. No.: US 2005/0176973 Al Friese et al. (Pub, Date: Aug. 11, 2005 (58) METHOD FOR PRODUCING PURE 0) meee eee a TRIOXANE May 17,2002 (DED. 10222 163 (76) Inventors: Katrin Frese, Mannheim (DE); Matthias Rauls, Limburgerbot (DE); Reinhard Freyhof, Frankenthal (DE); Thorsten Friese, Mannheim (DE); Harald Armbruster, Limburgerhot (DE); Hartmut Zelner, Ludwigshafen (DE); Gitta Eghers, Osasbeuck (DE), Bekhard Strofer, Mannheim ( Ludwig E. Heek, Euingen-Neckarhausen (DE); Peter Hildenbrand, Ksrisrube ( Correspondence Address: NOVAK DRUCE DELUCA & QUIGG, LLP. 1300 EYE STREET NW SUITE 400 EAST WASHINGTON, DC 20005 (US) C21) Appl. Nos 10/514 490 (22) PCT Filed: May 13, 2003 (86) PCT'No: — PCTVEPHS/04968 Publication Classification Gl) Ine? com 323/06 G2 US. 549/368 6 ABSTRACT A process for preparing tioxane by'tsimerizaton of Form: aldehyde in aqueous acidic solution and. subsequently removing tioxane from 4 mixture substantially comprising twioxane, ater and formaldehyde (enue trioxane pre’), which comprises 2) distilling the erude trioxane proiet from the trim= ©) crystallizing the wioxane out and ‘© removing it fom the mother liquor snd «subsequently melting it and ©) distilling off futher by-productsUS 2005/0176973 A1 METHOD FOR PRODUCING PURE TRIOXANE [0001] The iavention relates to an improved process for preparing pure trioxane, [0002] | Wren ioxane is prepared (se, for example, DEA 1543300), mixture is obtained which essentially comprises trioxane, Water and formaldehyde. Troxane i extractively removed from this mixture wit the aid of an azcotroping agent, for example a chlorinated azcatroping agent sich as methylene chloride, or benzene. Further eemponeats of the mixtire in subordinate quantities are generally formic acid, methylal and dimethoxydimethy! ether and also methanol snd methyl formate Ina subsequent distillation, the azeotro- ping agent i eecovered and fed back tothe extaetion. In this process (ees for example, EP-A 583 907), lage amounts of Aazeoieoping agent have to be used and recovered at bih energy cost. Emissions which inevitably oovur have to be disposed of in a costly and inconvenient manner, since methylene chloride and benzene are classified as dangerous pollutants [0003] The exteact is neutralized the resting salts ace ‘washed out, Since they influence the polymerization of Trioxane even in small concentrations. In a. subsequent purification ofthe extract by disillaton, the extractant and interfering secondary components ae removed in onler to provide polymerizable tioxane. Further distillation steps ace necessary forthe workup of the aqueous formaldehyde tallinate, of the extractant and aso of the salt-contaiaing waste liquor [0005] Io this process, the extraction is a particularly ccosily and inconvenient step in purifying tioxane and is additionally associated with the use of chlorine compounds, for example methylene chloride, which are undesired from anevologicalpoiat of view. These ae associated with tit ‘environmental conditions. Depending on the extractant, sometimes considerable amounts of trioxane remain in the ‘aqueous phase in the extraction, This resus in lange cc lation stteams. ‘The orgenic solvent intraduces 4 further material into the process. This results ina further workup of the organic phase being required which is associated with losses of trioxane. The washing stops included inthe extrac- tion stage alone furthermore require 25% of the fotal amount ‘of demineralized water used inthe proces, so that omission fof the extraction would also allow the waste water sireams to be worked up to be reduced. [0005] _DE-A 350 86 68 (Hoechst A G., Frankfurt) dis. closes the preparation of highly pure troxane from an ‘aqueous formaldehyde trioxane misture by mullistage erys- tallzation which is at least partially casied out a6 a melt ceqsallization (ayer crystallization). This is carried out ‘sing either directly the aqueous mixture resulting from a trioxane synthesis or an already prepuriied, substantially swalerfree mixture, According to the teaching of the dock ment, useful tioxane yields are only obtained at trioxane concentrations in the starting mixture of at last SO% by ‘weight, preferably at least 95% by weight, owing to the location of the eutectic point. When the water content of the ‘arting mixture is hil (Crom 30 to 50% by weight, the rst, stage of the crystallization is carried out as solution ‘egyialization. Ip order to generate a teioxane concentration in the starting mixture of atleast 50% by weight, fusther ‘workup steps are necessary afler the synthesis. Layer cry tallzation processes are frequently used when the starting Aug. 11, 2005 concentrations of the product of value are relatively high (695% by weigh). Inordero attain irioxane concentration fof 954 by weight inthe starting mistue, the tioxane water szeotrope has 1a be passed over. This passing over of the aveotrope results in an important objective ofthe crystal zation, Le. the saving of process steps by direct erystaliza- tion after the syntess sep, nt being achieved. Inadition, further subsequent treatments ofthe trioxane are necessary even when the purity is higher inorder to attain the neces sary low water contents (50 ppm) for the subsequent polymerization. [0006] ‘The separation of tioxane from gaseous mixtures ‘comprising formaldebyce by absorption in aleohole liquids and subsequent crystallization is described, for example, in DE-A 19833620 and EP-A 976743, Gaseous formaldehyde and trioxane are preferably dissolved in 4 mono- oF poly- hydric alcohol. Trioxane is crystallized out of the solution either ia a layer eeystlization or in contiauous suspension process and then removed, [0007] In a layer exystallization process, crystals ae fro- zen out on cooked surfaces inthe form of coberent, strongly adhering layers. The soliiiguid separation is effected by Simply allowing the residual melt to run off; the purified enpstals are melted. High purities and yields are generally only obtained by repeated, cyclical erystallization, In every stage, the heat of crystallization in the freezing out has tobe removed and then reintroduced in the subsequent melting. In Aiton, the apparatus itself also has tobe hested snd cooled again in cach case. The trioxane yield inthe abovementioned processes is only about 51.4%. [0008] An alternative to layer crystallization described in EP-A 976 743 is a process for suspension crystallization of teioxane [0009] In te crystallization process described inthe prior fc, giseous (rionane is processed, The exystalization is necessarily preceded by the absorption of tioxane in suitable solution. However, as already illustrated, ational process steps and solvents are uneconomical forthe process fad therefore disudvantagcous in the process described, [0010] EP-A S73 850 discloses the preparation of poly Ierizable troxane of high purty by multistage erystaliza- tion with additives. The adltion of additives (alkaline ‘organic compounds, for example tertiaty amines) effectively prevents the formation of “flocks” which, after several operating hours and exystallization cycles af high trioxane contents (295% by weight), are suspected to result from paraformaldehyde formation. The atives are removed in ‘sweating andor washing to such an extent that they are 00 longer analytically detectable and do aot impair the poly merization of the pure toxane. The mixture used for the crystallization inthis case already has a ioxane cootent of 54% by weight. A two-stage layer erystllization delivers irioxane having & purity of 99.9% by weight. The layer cxyslalization desribed has the abovementioned disadvan- tages of high energy demands and the necessity of a high starting concentration of trioxane. [0011] Acconting 19 EP-A 248 487, polyoxymethylene ‘may'be prepared from trioxane which has heen concentrated by rectlication afer the synthesis and then removed from the aquoous synthesis mixture by extaction sing aliphatic hydrocarbons. The extract (trioxane in organic extractionUS 2005/0176973 A1 solvent) is subsequently crystallized. The trioxane puriied by crysillizaton is resuspended and polymerized from the suspension. The disadvantages of extractive removal have already been described above. [0012] DE 19 842 579 describes « process for removing Irioxane from liquid mixtures by highly selectively trans- ferring the tioxane into the gas phase by evaporation and subsequenty recovering it in solid or Iiquid form by cooling And condensation of desublimation. A peoblem with ‘evaporation of trioane at atmospheric presse isthe thermal stress. I is therefoce sensible although unecanomi= cal o use aeaerier gas with which te Irioxane i stripped out ‘of the liu mixture, ‘The process described thus has 10 recognizable advantages for the workup of an aqueous trioxane solution, particularly because the wioxane concen- tration is beyond the azcotrope of troxane and water even before the to purifieation steps of evaporation and desub> Timation, and additional further process steps ae required 10 ‘eenerate pure trioxane [0013] US. Pat. No. 2,465,489 discloses a prooess for recovering trokane from aqucous solutions by enpstaliza- tion, Residues of formaldehyde are removed by Washing ‘with methanol thandl. However, this results in about 30% ff the trioxane likewise going into solution which corre= spondingly reduces the wioxane yield, A futher disadvan- lage is the high starting concentration af a least about 50% by weight of troxane in the mixture which may only be allined by additional preceding prowess steps, [0014] isan object of the present invention to provide a process for preparing and subsequenlly removing iioxane ‘whieh allows very substantial recovery ofthe Irioxane and requires very litle additional solvent and few process steps and also produces fewer by-products, The trioxane obtained stall be highly pure and obtainable in high yields, and the ‘water content in particular shall be very low (below 50 ppm), since there is otherwise no polymerizabiiy [0015] We have found that this object is achieved by a process for preparing trioxanc by trimerizing of formalde hyde in aqueous acidic solution and subsequently removing Iwioxane from a mixture substantially comprising iioxane, water and formaldehyde (crude trioxane product), which ‘comprises [0016] 2) distling the erude teioxane product from the timerization, {o017) [oo1s) (0019) [0020] 6) distilling of further by-produes [0021] The preparation of trioxane from formaldehyde (rimerization) in the presence of aqueous acide solutions is known to those skilled inthe art, for which reason further information on this subject is superfluous. The crude triox- ave produet (mixture alter the trimerization) comprises, in Accordance with the iaveation, trioxane conten of from 30 ‘0 70% by weight, preferably from 40 to 60% by weight at a formaldehyde level of from 3 to 18% by weight, prefer ably from 5 to 12% by weight, and a water level of from 25 {0 39% by weight, preferably fom 25 10.39% by weight. >) crystallizing the trioxane out and ©) removing it fom the mother liquor and 4) subsequently meting it and Aug. 11, 2005 [0022] Trimerization by-products in the crude trioxane product are generally methanol («3% by weight), methyl. formate (<9 by weight), methylal (<4% by weight) formic acid (<3 by weigh), telroxane (92% by weieht of tioxane, from L10 5% by weight of formaldehyde, from 1 o'7% by weight of water and also <03% by weight of high boilers, for example Teteoxane, TOEstrimethoxydimethy] ether, [0034] ‘The exystals may optionally be washed after the removal c) Useful washing mela are water andor aleobols such a5 methanol, ethanol, I- or 2-propanal. Preference is tgven fo carrying out the washing ofthe erystals at washing medium temperatures of 337" C., preferably 35° C. The volumetric ratio of erysals to washing liquid is generally from 1:05 to 1:3, preferably 1:k [0035] Washing with water causes the proportion of water to increase. slightly, while the formaldehyde proportion ‘generally falls elow 0.5% by weight. The tioxane conteat remains very substantially constant al >92% by wight [0086] Ina particulary preferred procedure of washing of the crystals, washing is ellected first with water and then ‘with aleobols, preferably methanol [0037] The crystals obtained in this manner comprise at Teast 98% by weight of trioxane, less than 0.1% by weight of formaldebyde and also =1% by weight of water. [0038] The crystals are melted in the subsequeat stage d) ‘of the process according to the invention [0039] Useful apparatus for stage d) includes insulated lanks with melting circuits (het exchangers using steam or condensate), the liguid phase cireuit of & washing column land sublimers [0040] According tothe invention, the melted crystals are introduced into one or more columns and redistlled (tage ©. [0041] In stage c), TOE, DOE, tetoxane and water in particular ace removed [0042] The disillation stage c) i operited at a pressure of from 0.3 to 2 bar, preferably at atmosphere pressure. The temperature of the liquid feed at atmospheric pressure is from 62 t0 120° C. However, itis also possible to operate the column using an entirely o¢ partially gascous feed (feed temperature 4 120° C, al almospherie pressure), [0043] Io a tow pressure column, the pressure is generally ‘p10 0.3 bar. AL emperatures of from 62 10 80° C., the feed is liquid, and at temperatures of >S0P C. at lesst partially sexseaus. [0044] In the process according to the invention, the aqueous phase (op product) from the purifying distillation (Gtage e) may be recycled upsiream of stage a) andthe bigh boilers from stage e) may advantageously be recycled into the trimerization, Aug. 11, 2005 [0045] After the purifying distillation e) the tioxane is discharged from stage e) aod is transferred to the polymer ination process. In the process according to the invention, ‘no additional components are required. The removal is cllected in few steps and very substantially without the formation of further by-products, Furthermore, a peehict of high purity obtained which, according to the me of the invention, consists of at least 99.5% by weight of trioxane The proportion of water, which is decisive forthe polymer ization, is <50 pp © acid content <5 ppm, the DOE content <100 ppm, aad the TOE content from 100 to 200 ppm. EXAMPLES Example 1 [0046] Trimerization of Formaldehyde, Low Boiler Removal, Batchwise Crystallization of Trioxane Without Washing Step (End Temperature: 21° C), Purifying Disi- lation [0047] Aqueous formaklehyde solution (49% by weight of Tormaldebyde) was concenirated ina falling-tlm evaporator at 68" C. and 0.25 bar. The concentrated formaldehyde Solution (63% by weight of formaldehyde, 34% by weight of ‘water, remaindee: mainly methanol) was fed into the bottom of the synthesis column at almospherie pressure and top temperature of 98° C. The catalyst used was sulfuric acid Trioxane sas concentrated toward the top of the column about 35% by weight. In a downstream distillation column, low boilers were removed, The low boiler seam removed consisted of 36% by weight of methyl formate, 26% by weight of methylal, 9% by weight of methanel, 6% by Weight of DOE, and also small amounts of water and formaldehyde. The resulting mixture of trioxane, formalde- hyde and Water (35.5% by weight of trioxane, 26.7% by ‘weight of formakiehyde, 36% by weight of water, remain der: secondary components, mainly methanol) was erystal lized batchwise in a tubular crysallizer equipped with helieal ster (aboratory version of a enoling disk exystal- lize, capacity: 5 1) starting t 38° C, (cooling rat: 3 K/h, nd temperature: 21° C.). The erysals were removed from the mother liquor on a Screen bow centrifuge at 2000 spa within 3 min, The unwashed erystals had the following composition: 97.3% by weight of trioxane, 1.2% by weight of formaldehyde, 1.4% by weight of water, 01% by weight of high boilers. ‘The crystallized trioxane was melted at stmospherie pressute in an isolated tank under 2 aittogen Atmosphere and transferred at a temperature of 95° C. to 4 distillation eoluma which was operated at almospheriepres- site, Trioxane was recovered 36 a vaporous sidestrean and then condensed, The purity ofthe trioxane after distillation ‘was >90.5% by weight and there was also <50 ppm of ws <5 ppm of formic-acid, 100 ppm of DOE and 160 ppm of TOE. Example 2 [0048] Batehwise Crystallization, Washing. with Water (end Temperature: 10° C.) [0049] A mixture of trioxane, formaldehyde and water (5.5 by weight of trioxane, 26.7% by weight of formal dehyde, 36% by weight of water) was crystallized in Similar manner tothe procedure in Example 1. The crystalUS 2005/0176973 AL lization end temperature was. 10° C. The erysals were ‘washed with Water in a ratio of I (Wolumetri) and, after ‘washing, had a purity of 95.36 by weight (0.2% by weight of formaldehyde, 4.45 by weight of water, 0.1% by weight (of high boilers). The yield of tioxane was 73%, Example 3 [0080] Continuous Crystallization at 10° C., Without Washing Step [0081] A mixture of wioxane, formaldehyde and water (66.1% by weight of tioxane, 26.4% by weight of formal- dehyde, 35.4% by weight of water) wus continuously exys- tallized in a tubular crystalizer equipped with a belical sirer at 10° C. with a residence time of 1 b. The erystals ‘were removed from the mother liquor on sereen bow centrifuge at 2000 rpm within 30. The unwashed erystals, had the following composition: 94,59 by weight of triox- ane, 2.7% by weight of formaldehyde, 5% by weight of water Example 4 [0082] Continuous Crystallization at 10° C., Washing with Water [0083] A mixture of tioxane, formaldehyde and water (6.1% by weight of tioxane, 26.4% by weight of Formal Aehyde, 35.4% by weight of water) was exytallized in a Similae manner to Example 3, excep that a residence time of 2hwvasemployed. After the mother liquor was removed, the fests were washed with Water ina ratio (volumettic) of 1:1 (washing step: 30's, centrifugal drying: 180 s, each at 2000 rpm). The washed crystals have a purity of 92.9% by ‘weight (0.1% by weight of formaldehyde, 7% by weight of water). The formaldehyde content in te crystals was mark edly reduced by the expulsive washing with wate. The higher water content was atibuted to adhering, washing ‘water. The tioxane yield was 79% Example 5 [0084] Continuous Crystallization at 10° C., Washing with ‘Water and Methanol [0085] A mixture of trioxane, formaldehyde and water (36.7% by weight of tioxane, 24% by weight of Formal- slehyde, 35.4% by weight of water) was crystallized in & similar manner to Example 4. After the removal of the mother liquor, the erystals were washed rice with water ‘Aug, 11, 2005 and once with methanol in ratio of 1:1 (volumetic) (each washing step: 30 s, centrifugal drying: 180 s, each at 2000 rpm). 'The erystals were then virually formaldehyde- and ‘iaterffee and had the following compesition: 99% by \weight of wioxane, 0.02% by weight of formaldehyde, 0.3% by weight of water. Owing tothe more extensive dissolving ‘of crystals on repeated washing, the trioxane yield Fell © 536. 1. process for preparing trioxane by trimerizing form- aldehyde in aqueous acidic solution” and. subsequently removing trioxane from a mixture substantially comprising trioxane, water and formaldehyde (crude trioxane product), Which comprises 4) distilling the erude tioxane product from the trimer crystallizing the tioxane out and ‘9 removing it from the mother liguor and 6) subsequently melting it and ©) disilling off further by-products 2. A process as claimed in claim 1, wherein the trioxane is discharged from stage e) and is rasferred to a polymer= ination stage. 3..A process as claimed in claim 1, wherein the mother liquor of stage c) is distilled to recover formaldehyde and teioxane, 44. process as claimed i claim 3, wherein the predomi nantly formaldebydie stream from the distillation of the mother liquor is recycled into the timerization and the predominantly troxanie stcam is recycled into stage a) 5. A process 3s claimed in claim 1 to 4, wherein stage 6) is cartied out as a suspension exystalization 6, A process as claimed in claim 1, wherein stage b) ofthe process i earied ott in one slag 7. A process as claimed in claim 1, wherein an end temperature of <20° C. is set in tage b) of the proces. '8.A process as claimed in claim 1, wherein the erytal- lized trioxane after the removal of the mother liquor (stage ‘is washed and subsequently melted (stage 9. A process as claimed in claim 1, wherein the erystal- lized teoxane is washed with water andor alcobols. 10_A process as claimed in claim 7, wherein the cryt lized teioxane is washed at temperatures of $20" C.