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us United States cz) Patent Application Publication — co) Pub. No.: US 2014/0148617 A1 oy oy my 3) ey @2) (60) Fries et al. PROCESS FOR PREPARING FORMIC ACID Applicant: BASE SE, Lachwigshafen (DE) Jnveatorst Donat Marka Fries, Mannheim (DE) Klaus-Dieter Mobi, Hockenieim (DF) Martin Sehiifer, Grunstadt (DE); Daniel Schneider, Frankenthal (DE); Peter Bassler, Viembeim (DE); Stefan Rittinger, Mannheim (DE) Joaquim Henrique Teles, Waldsee (DE) Assignee: BASF SE, Ludwigshafen (DE) Appl. Now 14/088,805 Filed: Now. 2013 Related U. Application Data Provisional application No. 61/730.007, filed on Now: 27,2012. 1 US 20140148617. (43) Pub, Date May 29, 2014 ication Classification on (200501) 2 CO7C SUAS (2013.01) 562/609 on ABSTRACT Process for obtaining formic acid by thermal separation of a steam comprising formic acid and a vetary amine (Dia ‘whieh, instep (a), aliquid steam comprising formic acid, ‘methanol, water and tertiary amine (1) is produced by com: bining methyl formate, water and tertiary amine (1, Irom therein sep (6), methanol is separated off and in step (c), Formic acd is removed by distillation fom the liquid stream cblained in 2 distillation apparatus, wherein, whea methy! formate, water and tertiary amine I) are combined, methyl formate, water and optionally tertiary amine () are first intro- duced instep (al) ina molae ratio of Oznfamine wal inimef toa 20.1 ,and from 70t0 100% the hydrolysis equlirinm possible is set and then, in step (@2), tertiary amine (1) is Introduced in a molar ratio of 0.1 sn{amine to a2V/n(mefo to al)x2, andl the mixture i reacted. Patent Application Publication May 29, 2014 Sheet 1 of 5 US 2014/0148617 A FIG. 1 2 > 2 > + 4x 2 4 [1x} 2 144) 4b Al A2 B ic ¥ | Ho 1d 1 1 Patent Application Publication May 29, 2014 Sheet 2 of S FIG. 2 US 2014/0148617 AI 1x A2-i,A2-ii > BoP z ba Patent Application Publication May 29, 2014 Sheet 3 of S US 2014/0148617 AI FIG. 3 Patent Application Publication May 29, 2014 Sheet 4 of 5 US 2014/0148617 AI FIG. 4 ie x AD ie] Ads bel ataii HO [ a2-i by a2 ae t 7 edly [ee 8c} |8a 3x 37 F eb Patent Application Publication May 29, 2014 Sheet 5 of S US 2014/0148617 AI FIG. 5 fa A Ati ffariH™p[azs Mazi] oi ad Be Y US 2014/0148617 Al PROCESS FOR PREPARING FORMIC ACID (CROSS-REPERENCE TO RELATED "APPLICATIONS, [0001] This application claims benefit (under 35 USC 119 {)) of US. Provisional Application Ser. No. 61/7304007, fled Nov. 27,2012, which is incorporated hereinby reference in its entirety. BACKGROUND OF THE INVENTION [0002] |The present invention relates toa process forobtsin- ‘ing formie seid by thermal separation of a steam comprising Tommie acid and & tertiary amine (I), which, a a pressure of 1013 hPaabs, hasa boiling point which sat least $°C. higher than that of formic acid, in which a Tiquid stream comprising formic acid, methanol, water and tertiary amine (I) i produced by combining meth! formate, ‘waterand tertiary amine (1), from 10t0 10Peby weight ofthe ‘mcthanol comprised therein ae separated ff from the liquid stream obtained from step (8) and formic acid is removed by distillation from the liquid stream ‘comprising formic acid, water and tertiary amine (1) obtained from step (b) in adisillation apparatusat a temperature atthe bottom of from 100 0 300° C. and a pressure of from 30 10 3000 hPa abs, [0003] | Formic acid is an important and versatile product. It Js used, for example, for acidification inthe prodvetion of ‘animal feeds, as preservative, as disinfectant, as assistant in the textile and Teater industry, as a mixture with ts salts for dicing aircraft and runways and also as synibeti building block in the chemical industry 0004) The most widespread process at present for prepar- Ing formie acid isthe hydrolysis of meth formate which ean be obtained, forexampl, om methanol and earbon monox- ‘ie. The aqueous formic acid obtained by hydrolysis s sub- sequently concentrated, for example using an extraction sux- iary suchas a dialkyfomamide (DE 25 45 658 Al). 0005} -Inakltion, obtaining formie acd by them disso- ation of compounds of formic acd and a tertiary nitrogen base is alsn known, These compounds are generally acidic nmonium formates of tertiary nitrogen bases, in whieh the formic acid has reacted beyond the stage of classical salt Jormation with the tertiary nitrogen bases form stable add tion compounds bridged by hydrogen bonds. The addition ‘compounds of formie acid and wertiary nitrogen bases can be ormed by combining the tetiary nitrogen base and a formic ‘acid souree, Thus, for example, WO 2006/021,411 discloses the preparation of such addition compounds in general by () ‘tect reaction ofthe tertiary nitrogen base with formic ae, ) by Wansition metal-catalyzed hydrogenation of carbon dioxide to Formic acid in the presence ofthe teniary nitrogen base, (i) by reaction of methyl formate with water and sub- sequent extraction ofthe resulting formic acid by means of the terary nitrogen base an (iv) by reaction of methyl for- mate with water in the presence ofthe tertiary nitrogen base. 10006} ‘The genera) advantages of using addition com pounds of formic acid and tertiary nitrogen bases for obtain- ‘ing formic acid are that the sition compounds firstly bind the formie aeid strongly enough to withdraw the formie acid from the medium, forexample the reaction medium, in which the formic aid has been formed by chemical synthesis or, for ‘example, from a dilute formic acid solution, and thereby allow the formic acid to be separated off more readily inthe May 29, 2014 {orm ofits addition compounds, but are weak enough forthe ormic acid subsequently wo beable to be released again rom the addition compounds by thermal dissociation in order to ‘obtain it in concentrated and purified freeform. [0007] EP 0.001 432 A discloses a process for oblaining Toxmic acid by hydrolysis of methyl formate in the presence of a tertiary amine. in particular an alkylimidazole, to form addition compounds of formic eid and the terary amine ‘The hydrolysis mixture obtained, which comprises unreacted methyl formate, Water, methanol, addition compounds and tertiary amine, is freed of the low boilers methyl formate and ‘methanol ina first distillation columa. In a second column, the remaining bottom product is dewatered. The dewatered bottom prot from the second column, which still com prises addition compounds and tertiary amines then fed toa {hird column and in this the addition eompounds are ther- ally dissociated into formic aeid and tertiary amine. The formic acid liberated is removed as overhead product. The tertiary amine collects in te liquid phase and is recirculated tothe hydrolysis, [0008] DE 34 28 319 discloses process for obtaining Toxmic acid by hydrolysis of methy formate. The hydrolysis rixture obtained, which comprises unreacted methyl for ‘mate, water, methanol and formie acid, i freed ofthe loss boilers methy] formate and methanol in a first distillation column, The aqueons forme aed obtained at the bottom is subsequently extracted with a relatively high-boiing amine, in particular a relatively long-chain, hydrophobic CoCyq- ‘eialkylamine, in the presence of an additonal hydropobi solvent, in particular an aliphatic, eyeloaiphatic or aromatic Ihydrocarbon, and thereby converted into an aqueous addition ‘compound of formic cid and the amine. This is dewatered in ‘second distillation column, The dewatered addition com- pouind obtained atthe bottom is then fed to a third distillation column and thermally dissociated therein. The hydrophobic ‘Solvent is present both in he overnead stream and the toms {rom the column. The gaseous overhead stream comprises ‘mainly the formie acid liberate together wit the hydropho- bie solvent. Ths steam is Fiquelied again inthe condenser Tis results in formation of two phases, namely apolar onic acid phase and a hydrophiobie solvent phase. The formic acid phase is discharged as product and the solvent phase is ‘turned as runback tothe caTumn, Du tothe presence of the hydrophobic solvent, complete dissociation of the adduct, whieh according to the teaching of the DE fist publication ‘secure without decomposition of formic acid, canbe achieved. The (vitally) formic aeid-free bottoms comprise the hydrophobic amine and the hydrophobic solvent. This is recitculated wo the extraetion lage. 0009} Wo 20061021,411 describes a process for obtaining Tormic acid by thermal dissociation of an addition compound ‘of formie acid and a tertiary amine (quaternary ammonim Tormate), in which the tertiary amine has a boiling point of from 108 to 175° C. Alkylpyridines are mentioned as pre- ferred tertiary amines. The specific boiling ange of the ter ‘iary amines inereases the color stability of the formic acid ‘obiained, The addition compound o be used ean in general be ‘obiained from the tertiary amine and a formie acid source. ‘The output from the adduet synthesis is advantageously fintlyfrced of volatile consttwentsanthenfadtothetherml sissocation. The thermal dissociation i carried out as usual ina distillation cokamn, The formic sci liberated is removed asoverhead product. The tetiry amine whieh may sillcom- US 2014/0148617 Al prise residues of formic acid collects i the Hguid phase and ‘can be recirculated wo the formic acid source. [0010] | EP 0563831 A reports an improved process forthe thermal dissociation of an addition compound of formic acid and tertiary amine (quaternary ammonium formate) 10 give qormic acid, The addition compound tbe usedcan in general be obtained from the tertiary amine and a formic acid source ‘The output from the synthesis is advantageously firstly freed ‘of volatile constituents and then fed toa distillation column, ‘or thermal dissociation. The improvement comprises essen- tially carrying out the thermal dissociation of the addition ‘compound inthe presence ofa secondary formamide whieh ‘increases the color stability ofthe formic acid obtained. The Tommie acd liberated is removed as overhead product. The tertiary amine and the secondary formamide collect in the Tiguid phase and can be recirculated to the fonnie wei souree. [0011] WO 2012/000.96¢ teaches a process for obtaining Jormic aeid by thermal separation of a stream comprising Jormic avid anda tertiary amine, in which combining tertiary amine and a formic acid source produces a Tiguid steam ‘comprising formic acidanda teriary amine ina molarratioof from 0:5 to 5, from 10 to 1086 hy weight of the secondary ‘components comprised therein are separated off and fommic acid is removed by distillation from the resulting liguid ‘ream ina distillation apparatus a «temperature at te bot ‘om of fom 100 t0 300? C. anda pressure of from 300 3000 [Pa aad the bottom output Irom the distillation apparatus is separated into 180 Tiguid phases of which the upper liquid phase is enriched in tertiary amine and i recirculated to the ormie aeid souree andthe lower liquid phase is enriched! in Tommie acid and is recirculated to removal of the sscondary ‘components andor tothe distillation apparats. [0012] EP application No. 11 194 619.0 teaches an ‘improved proces: for obtaining formic acid by thermal sepa- ration of a stram comprising formic acid and a tertiary amine, in which a liquid stream comprising formic acid tertiary amine and water is produced by combining tertiary mine anda formie seid souree in the presence of water, water ‘and organic degradation products of the tertiary amine are removed and formic acid is distilled from the resaling liquid stream ina distillation apparatus, where the steam comprise ing water and organic degradation predicts of the tertiary amine which has been separated off i separated into two liquid phases, the upper liquid phase ie removed and the lower, watercomprsing lighid phase is recirculated to the omic acid source. The process described in EP application No. 11 194 6190 allows the relatively simple removal and discharge of various volatile by-products and degradation products ofthe tertiary amine [0013] EP application No. 11 194 607.5 teaches un ‘improved process for obtaining formie acid by thermal sep ration of a stream comprising formic acid and @ tertiary amine, in which a iguid stream comprising formic aid and tectary amine is produced by combining tertiary amine and a ormic acid source, secondary components comprised therein ‘are separated of, formic acids distilled rom the resting liguid siteam in's distilation apparatus, the bottom output Jom the distillation apparatus i separated into 10 Tighid phases al the upper liquid phases recirculated othe formic ‘acid souree and the lower liquid phase is reireulted t the removal of secondary components andor the distillation ‘apparatus, where low boilers ae separated off by distilatin fmm the upper liquid phase an the depleted stream is reci= ‘culated, The process described in EP application No, 11 194 May 29, 2014 607.5 allows the relatively simple removal and dischae of various volatile by-products and degradation products ofthe ‘ervary amine, [0014] Itisanobject of the present invention to discoveran improved process for obtaining formic acid by thermal sepa- ration of a siram comprising formic aeid and a tertiary ‘amine, Which process has advantages over he prior art and is able to give formie aed in high yield and high conceatration In particular, the improved process should also function st bly over long operating times and produce formic acid in ‘const high purity. The process should naturally be able to be carried out very simply and with a very low energy con- sumption BRIEP SUMMARY OP THE INVENTION [0015] We have surprisingly found! a process for obtaining ormie acid by thermal separation of stream comprising ormie acid and a tertiary amine (D) which at pressure of 1013 hPa abs has aboiling point which isat east S°C. higher ‘than that of formie ac, in which a liguid stream comprising formic acid, methanol, water and tertiary amine (2 3 pro- «duced by combining methy formate, watorandtertary amine (and from 10 0 100%4by weight of the methanol comprised therein are separated off from the liquid stream obtained! rom step (a) and {ormie acid is removed by distillation from the liquid stream comprising formic aid, water and tertiary amine (1) obtained rom step (bin distillation apparatus at a temperature at the bottom of from 100 to 300° C. and a pressure of from 30 10 3000 his abs, ‘wherein, whea methyl Formate, water and tertiary amine (1) fare combined in step a), methyl Formate, water and optionally tertiary amine 1) reintroduced in step (a1), where the molar ‘iio ofthe tertiary amine (1) optionally introduced inta step (21) “namine to 21)" to the methyl formate inteduced into step (al) “a{mefo toa) is such that esminet9e1)mimeo 00.1, ‘and from 70 to 100% of the hydrolysis equilibrium possible ‘under the previling conditions is set ata temperature of roma 50 to 200° C. and, in step (a2), tertiary amine (is subse- ‘quently introduced into the stream obtained ia step (01), ‘where the mola ratio of the tertiary amine (1) introduced in step (@2)intathestream obtainedin step (al) "naminet 2)" to the methyl formate introduced into step (a1) “a(meto to al)" is such that and the resulting mixture is reacted at a temperature of from ‘5010 200°C. so asto give the Tiguid stream comprising formic ‘acid, methanol, water and teriary amine (1) mentioned under ©), where the molar ratio the total tertiary amine (Dinteoduced into step (@) “n(amine to a)" t the total methyl formate introduced ito step (@) “nme to-)” isa east O1. BRIEP DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING [0016] FIG. 1 shows a simplified block diagram of a yen- tral embodiment ofthe process of the invention, [0017] FIG. 2 shows a simplified block diagram of a mock- Tied embodiment in whieh the second stage A2 of the apps US 2014/0148617 Al ratus for producing a steam compris amine (2) and water is divided into ADs [0018] _FIG.3 shows furher simplified lock diagram ofa ‘modified embodiment in which the second stage A2 of the ‘apparatus for producing a stream comprising formic avi, tertiary amine (1) and water is divided into theoretically infinite numberof substages A2-i, A2-ti, AZ to. A2-7, [0019] FIG. 4 shows a simplified block disgram ofa pre- {ered embodiment for obtaining formic acid by hydrolysis of meth! formate [0020] FIG. § shows a simplified block diagram of labora- tory plan | formie acid, tertiary o subsages AZ and DETAILED DESCRIPTION OF THE INVENTION 10021] |The tertiary amin () used instep (a) of the process ‘of the invention has, a a pressure of 1013 hPa abs, a boiling point which is at least S® C. higher than that of formic acid. The tertiary amine (1}to be used preferably has. a boiling point which sa east 10°C. higher, particularly preferably atleast 50°C. higher and very particularly preferably at least 100°C. higher, than that of Formic acid. In a prefered altemative ‘emboviiment ofthe process the invention, the tertiary amine (Dc be used fas, a a pressure of 1013 hPa abs, an absolute boiling point of atleast 111°C, of at bost 151° C. in a very prefered altemative embodiment and of atleast 201°C. in a most preferred altemative embodiment, restriction in respect of an upper limit value forthe boiling point is not rocessary since a very low vapor pressure of the tertiary nine (I) is basically advantageous for the process of the Jnvention. Ingeneral, te boiling pointof the tertiary amine (I) js below 500" C. at a pressure optionally extrapolated by known methods from vacuum to 1013 hPa abs [0022] The methyl formate to be used inthe process ofthe Svention is generally introduced in liquid form. The methy formate to be used an come from various sources. The inds- teally most important source forthe syathesis of methy] Formate at present is earbonylation of methanol. In adlition, recirculated methyl formate which has not been reacted in the hydrolysis and has been separated ofT ina subsequent step, for ‘example, can uo be used in the process of the invention, 10023] The water tobe used inthe peocess ofthe invention fs generally ikewise introduced in liquid form, To avoid sradual salting-up of the apparatus, preference is given to using demineralized or deionized water 10028] According tothe invention, it has suprisingly been ound that tertiary amines (I) tend to be methylated in the presence of methyl formate to form thecomrespondingmiethy- Jammonium formate and this effect has a negative influence ‘even tnder the reaction eonditions usual nthe prior at inthe production of formic acid by hydrolysis of methyl formate in the presence ofa tertiary amine, especially during. relatively Jong running time ofa numberof weeks or months. Inthe case ‘ofa tertiary amine (1) having thee identical radicals R, for ‘example C,-Cy-alkyl, the methylation reaction mentioned ‘would be, for example, a flows, where Me is methyl wig ‘ome [MexR [e00y May 29, 2014 [0028] The mertylamm be redissoviated, with the starting amine NR, being obtained back agai in @ reaction which is the reverse of the reaction equation (A) anda tertiary amine having a methy1 group and alkyl formate being formed in another reaction shown in ‘reaction equation (2), w Dest coor ewes = ‘oe (0026) Furthermore ithas been found in the content ofthe invention thatthe teriary amine comprising a methyl wroup is formed according to reaction equation (B) tends ns to reaction equations (A) and (B), sd by methyl formate and dissociate In this way, the tertiary amine originally used ean he succes: sively dissociated through to trimethylamine, [0027] Organic degradation products ofthe tertiary amine (0) are thus obtained via the reactions mentioned. For the purposes ofthe present invention, the tern “organic 15 deg- ‘dation products ofthe tertiary amine (1) refers generally to ‘compounts which reformed by chemical transformation of the tertiary amine (1) with breaking of bonds originally present, reformation of nitrgen-carbon bonds or chemical {ransformation ofthe radicals bound tothe nitrogen and any climinated radicals [0028] Organic degradation products ofthe tertiary amine (Dean ead to contamination ofthe formic acid be obtained ‘according to step (@). In addition, onic degradation prod- vets of the tertiary amine (P) having a boifing point in the range from that of formic acid to that of the tertiary asin (1) tendo accumulatin the distillation apparatus used instep (€) and thereby increase the energy’ constmption in he distill ‘ion apparatus. Organie degradstion products of the tertiary amine (2) which do not accumulate in the fonnic acid 10 be isolated so ast reduce its purity would have to be discharged father places in the process in order to prevent uncontrolled ‘cumulation, [0029] The EP application No. 11.194 619.0 mentioned above does relate to the targeted discharge of particular ‘organic degradation produto the tertiary amine (1) but only those which ean he separated off together with water instep () under the prevailing process conditions. Since the sepa- ‘nition according tothe teching of EP application No. 11 104 619.0is preferably caried out by distillation, this also pref- erably concems only those degradation products which can be separated off fom the remaining stream by disillation by the gis pase and subsequent condensation, [0030] EP application No. 11 194 607.5 also describes the tangeted discharge of particular organic degradation products ofthe tertiary amine 1). Inthe ease otis discharge oo, the ‘degradation products are separated ofTby distillation via the ‘205 phase and subsequent condensation, albeit from a differ ent steam and at a different point than in EP application No. 11194 619.0. [0031] Apart fom the problems of possible contamination ‘ofthe formie acd to be obtsined an the discharge of organic degradation products ofthe tertiary amine 1, the degradation ofthe tertiary amine (I) naturally also leads toa loss tertiary ‘amine (J, withthe consequence that further amounts of this US 2014/0148617 Al ‘continually have to be introduced. I therefore, a smaller loss of tertiary nomiclly advantageous 10032] Inaddition it kslso surprisingly been found inthe ‘context of the invention that quaternary methylammonium Tormates as are formed, for example, by reaction equation A) ‘catalyze the decomposition of fomic aid into carbon dioxs ‘de and hylogen wider the customary process conditions of the hydrolysis of methyl formate and he subsequent work-up ‘of the reaction mixture 10033] Ithss now surprisingly been found, secording to the Jnvention, thatthe degradation of the tertiary amine (2) 10 orm the organic degradation products ofthe tertiary amvine (0) aad in particular the methylation of the tertiary amine (1) by methyl formate to form methylammonium formate (as shown by way of example in eaction equation (A) ean be significantly reduced if, when metiy! formate, water and tertiary amine (Dane combined in step (2), (1) methyl formate, water and optionally tertiary amine (1) are introdueed in step (a1), where the molar ratio of the tertiary amine (I) optionaly introduced into step (a) “n(amine to af)” to the methyl formate introduced into step (a1) “(met to 21)" is such that ean ta1yrifo 990.1, 10034} and from 70 t0 100% of the hydeolysis equilib- ‘ium possible under the prevailing conditions is seat & temperature of fom 50 to 200° C. and, (2) in step (a2), tetiary amine () is subsequently introduced ino the stream obtained in step (a), where the molar ratio oF the tertiary amine (1) introduced in sep (a2) into the stream ‘obtained instep (al) “nfamine to 22)" tothe methyl formate Introduced into step (a1) “n(mefo wo al)” is such that Deane onl a2 [0035] and the resulting mixture is reacted ata tempera tur of fom 50 t9 200° C.so as to giveth liquid stream comprising formie acid, methanol, water and tertiary amine (I) mentioned unde (2) “where the molar ratio of the total tertiary amine (1) introduced, ino step (a) “a(amine t0 2)" to the total methyl formate Introduced into step @)“atmefo to 2)" isa east 01 [0036] |The methylation ofthe tertiary amine (I 10 metby- ammonium formate can be effectively redveed by the above. mentioned measures according othe invention, Which leads not only toa redetion inthe concenteation of methylammo- nium formate in the process but also to a reduction in the subsequent reactions, for example the subsequent reaction represented by reaction equation (B) [0037] As reaction apparstuses forthe reation according to the invention of methy] formate, water and tertiary amine (hy itis possible to use all apparatuses which are suitable in Principle for this typeof reaction. These are generally known to those skilled inthe art. They comprise, for example, inter alia, stirred vessels, cascades of sired vessels, Now reactors, tue reactors, microreactors and residence vessels, in each ‘ease withor without direct cooling and with orwithout further inernals. The two steps (a1) and (a2) ean, depending on the ‘embodiment, be carried out ina single reactor or in Wo oF ‘more reactors connected in sees. If the two steps (al) and (42) are carried out ina single reactor, itis generally avan- ‘agents to counter backmixing, In the ease ofa low reactor, sulicently Tow baekmixing is often present asa result ofthe ratio of the flow to the intemal cross section, so that itis possible for no Taree internals toe required here, In the May 29, 2014 case ofa tube reactor orifice plates ora meandering flow path, Tor example, may effectively prevent bockmixing. [0038]. ‘The rao ofthe volume available forthe reaction in step (a to the volume available for the reaction instep (22) is generally from 0:01 to 10 in the process ofthe invention, For the purposes of the preset invention, the term volume refers to the actual empty volume, The volume of possible internals, for example, is therefore not counted as part of the actual empty volume. The abovementioned volume ratio is preferably from 0.05 to, particularly preferably fom.0.08 to 2, very pareularly preferably fom 0.1 to 1 and in particular rom 0.15 1009. [0039] The methyl formate, water and tertiary amine (1) 10 be introduced in step (a) and (a2) can in each case come from ‘ne oF more sourees, Possible sources are, for example, the introduction of fresh stating material from outside the pro- cessor te introduction of recycle streams from the process itself, The inclvidua food streams to steps (a) and (22) ean, {or example, be introduced separately, previously partially sxe or completely mixed, [0040] Step (a1) will be described in mone detail below. [0041] Intheprocess of theinvention, the molar ratio ofthe Tertiary amine (1) optionally introdoced into step (a!) nam to the methyl formate intradces into step (1) “nme to a)” is such that Oanamine toe eieo toa where the mathematical formulation comresponds to a range orthemolarrati in question of from0to.1. Themolar ratio {amine to al Yameto to al) is preferably from 0 10 0.08, particularly preferably from 0 t9 0.02 aad very particularly preferably Irom Oto 0.01. The smaller the molar ratio ofthe {ertary amine (1 optionally introduced to the methyl Formate intodueed instep (a), the smaller is, generally, the forma tion of undesirable organie degradation products of the ter tiary amine (1) under otherwise identical conditions. The ‘ntrociction ofthe tertiary amine (I) nto step (a) can there- {ore even be omitted, which corresponds to a molar ratio of {amine to al Jn(mefo 1 al) of O and also expressed by the “optionally” inthe wording of the description of step (a). 0042} ‘The amount of water which isto be introduced into ‘sep (a) in the process ofthe invention is advantageously set 50 tha, fist, the reaction mixture is not diluted too grt ‘whieh would otherwise make the futher work-up more dif ficult owing tothe high dilution and large volume streams, ‘and, secondly, a sufficiently high conversion to methyl for ‘mate also takes place. In general, a molar ratio of water t0 vethyl formate, caleulated from the Water introduced into step (al) “n(water to al)" to the methyl formate introduced into step (al) “n{mefo toa!) of from 0.1 to 10 appears to be advantageous. The molar ratio mentioned is preferably 20.2 and particularly preferably 203, and preferably <8 and par- siculerly preferably 26 [0043] In step (a1) of the process ofthe invention, from 70 to 100% of the possible hydrolysis equilibrium under the prevailing condition is set. Parameters which influence the hydrolysis equilibrium are, for example, the prevailing cor centrations of formic acid, methanol, water, methyl format and, ifintrodeed into step (a), also the tertiary amine (P and ‘aturallyalso the temperature and the prevailing pressure. For the purposes ofthe present invention the hydrolysis equilib- ‘um isthe dimensionless K valve according tothe equation US 2014/0148617 Al A fesonnicasi)matanc) oet Fnme) om ©, where e(...)s in each case the prevailing conceatration ia ‘ol per liter Equation (D) applies regardless of whether of not tertiary amine (i preset in step (al) and regardless of whether the four components mentioned are present in free orm, in ion form (for example as formate anion HCOO- instead of formic acid HCOOH) on complexed form, Thus, or example, “ormic acid)” also comprises the concentra tion of any’ formate anion HCOO— present. The percentages ‘ction then corespondto the proportion othe maxima K value whichis theoretically possible under the prevailing ‘conditions [0048] In sp (a1), preference is piven to seting 275%, Particularly preferably 280%, very particularly preferably 285% and in particular 290%, ofthe hydrolysis equilibrium possible under the prevailing conditions [0045] _Thesetting ofthe hydrolysis equilibrium in step (a1) js, at given ratios of amounts ofthe starting materials, advan- tageously effected by setting an appropriate residence time at a paricular temperature. For the abovementioned temipera- ture aig fom 30 10 200°C, anaverage residence time inthe range from 0001 to 5 hours, preferably from 0.02 to 2 hours ‘and particularly preferably from 0.05 to 1 hour, has been found to be advantageous. The higher the temperature, the ‘more quickly can the setting of the hydrolysis equilibrium ‘generally be and the shorter can the avemge residence time therefore also be, [0046] The hydrolysis in step (a is preferably carried out ‘ata temperature of #70? C., particularly preferably 280° C. and very panicuarly preferably 290° C., and preferably 12150? C., particularly preferably 2140 C. and very parieu- larly preferably =130° C. The hydrolysis in step (a) is gen- erally carried out ata temperature of from 70 to 150°C. Ithas ben found that the Formation of undesirable orwanic degra- dation products ofthe tertiary amine (I) generally inereases ‘with increasing temperature and relatively low temperatures ‘are therefore advantageous in this gard. Funbermore, the ‘corrosion rte increases with temperature, so that relatively Tow temperatures are also advantageous from this point of view. On the other hand, the reaction ate also decreases with decreasing temperature, so that at very low temperatures the residence time required for particular conversion increases sgnificantly and unecopomieally large reactors would there- ore berequired. Its advisableto find compromise between thetwo eflects, which i also reflected in the abovementioned temperature ranges. 10047] The liquid stream obtained from step (a i subse- quently introduced ito step (22). Step (a2) will therefore be ‘described in more detail below. [0048] _Instep (a2), tetiary amine (I) isthen introduced into the stream oblained instep (a). In the process of the inven- tion, the molar ratio ofthe tertiary amine (1) introducedin step (42) into the stream obtained instep (al) “n(amine 22)" 10 the methy! formate invoduced into step (al) “a(mefo toa)” is sue that cemaninet 22 nef ali, ‘herein the mathematical fomlation corresponds to range for the abovementioned molae ratio of from 0.1 to 2. The ‘molar ratio n(amine to 22)/n(meo to a1) is preferably 20.13, particularly preferably 20.15 and very particularly peeferahiy 202, and preferably 19, paricularly prelerably 21.8 and very particularly preferably s17, in particulars. May 29, 2014 [0049] "In step (a2) of the process ofthe invention it is Principle possible to introduce Further water and methyl f ‘mate in addition to the water and methyl formate aleeady present inthe steam from sep (a), [050] Ir further water is troduced, the amount thereof is dally set so that, firstly, the reaction mixture isnot diluted too greatly, which would otherwise make the Further Workup ‘more dificult because ofthe high diluion and lange volume steams, and, secondly, an advantageous effect of any type results in the father hydrolysis the methyl formate present ‘or at another point in the further process, Advantageous effects can be, for example, shift in the equilibrium in the rection of formic acid or an advantageous work-up of the ‘action mixture In general, itis advisable to find a balance between the advantages and disadvantages, [0051] The same applies to the ation of further methy! Tormates, [052] The hydrolysis instep (a2) is carried out ata tem- perature of frog $0 to 200°C. Icis preferably easied out ata femperature of 280° C. and particularly preferably 250° C., and preferably =170°C. and particularly preferably =1 50°C ‘The hydrolysis in step (a2) is generally caried out ata tem- perature of fom 70a 150° C- In step (2), too, the formation of undesirable organic degradation products of the tertiary amine (I) and the corrosion generally aso increases with ‘increasing temperature and relatively low temperatures are ‘advantageous in this regard, On the other hand the reaction rate also decreases with decreasing temperatire, 80 that at very low temperatures the residence time roquted fora par ticular conversion increases significantly and uneconomi cally lange reactors woud therefore be required. Itis therefore advisable instep (22), t00,to find a compromise between the two elfets, which is also reflected in the abovementioned femperature ranges. Accordingly, the temperatures in step (al) and step (a2) can therefore differ. Within one step, tem- perature differences as result of heat evolved inthe reaction ‘active invluencing ofthe temperature by heating or cooling fare conecivable and possible [053] In step (22) ofthe process of the invention, prfer- tence is given to setting from 50 10 100% ofthe hydrolysis equilibrium which is possible under the prevailing con tions, particularly preferably =60%, very particularly prefer ably 270% and in particular =80%. As mentioned above, the hydrolysis equilibrium is, for example, influenced by’ the prevailing concentrations of formic seid, methanol, water, ‘methyl formate, and also of tertiary amine (I) since this binds formic acid and naturally also by the temperature and the prevailing pressure. The setting ofthe hydrolysis equilibrium sn step (82) at given ratios ofamounts of stating materials, advantageously effected by setting an appropriate residen time at a particular temperature. For the abovementioned temperature range from 50 to 200° C, an average residence time in the range from 0.01 © 5 hours, preferably fom 0.2% 3 hours, particularly preferably fom 0.3 to 2 hours, has been ound to be advantageous. The hihor the temperature, the Taster does he seting of te hydrolysis equilibrium generally ‘eet and the shorter ean the average residence time aeor ingly also be, [0054] Furthermore, the molar ratio of the total tertiary ‘mine (1) introduced int step (a) inthe process ofthe inven- tion “namin 10 a)" to the total methy! formate introduced into step (a) “n(mefo to a)” is generally at least 0.1. Here, {amine toa) comespondsto the sum oFallamountsofteriary (0) whiek are introduced overall into step (a), ie the US 2014/0148617 Al sum of nfamine to al) and ofamine to 22) in the process sivided into steps (al) and (22). Comrespondingly,n(mefo to ‘8)comesponds fo the sum ofall amounts of meth! formate Which are introduced overall into step (a). Inthe process 30%% and very particularly preferably 50%. Usually, upto 99%, advantageously up t0 59.59%, more advantageously up to 99.9% and, in the utmost best cases even upto 100%, ofthe amount of enzanic depra- dation produetsof the amine are reduced inthe hydrolysis ‘utp, 10070] The Tiquid stream produced on combining methyl ormate, water and tertiary amine (I) in stp (a) generally as ‘amolar ato of formic acid to tertiary amine (1) of from 0.110 10. The molar ratio is preferably 20.5 and particulary pret= ‘erably 21, and also preferably s5 and particularly preferably May 29, 2014 33. The molar ratio mentioned is based on the total liquid ream, regardless of whether is present asa single phase oF plurality of phases, [0071] The liquid stream comprising formie acid and ter- ‘iary amine (1) whieh is produced instep (a) generally has a concentration of formic aid plus tertiary amine (I) of from 1 {0 99% by weight, based on the total amount ofthe stream. ‘The steam mentioned preferably bas a concentration of for mie acid pha tertiary amine (1) of =$% by weight and par ‘icularly preferably 215% hy weight, Even when particularly high concentrations of Formic acid plus teetiary amine (1) in the liquid stream produced in step (a) are desirable for the {unter purification and isolation ofthe formie ac, the outlay in tems of apparatus and process engineering required 10 ensue these high concentrations instep (a) also increases. For this reason, the abovementioned concentrations. are advantageously 290% by weight inthe process of the inven- tion. From 10 to 100% by weight of the methanol present in the liquid stream obtained from step (a) are separated of rom ‘his liquid stream, The concentration of methanol in the ighid stream produced instep (a) will hereinafter be refered 0 as "Cea (Steam fom stp (a). The liquid stream depleted in mellanol corresponds to the strcam which is fed to the istllation apparatus as per step (¢). This concentration will hrersinafter be referred 10 98 “Cyerna (feed steam to stop (©) Theabovementioned removal of methanol is thus based fom the quotient Ca ed se 1 6p A Cok (HF Hp (OGM 10 by wiht [0072] Preferences given w 220% by weight and partieu- Jarl preferably =30% by weight ofthe methanol being sepa- rated off in step (6). Usually up to =99.9% by weight and advantagenusly 9 99% by weight ofthe methanol are sepa- rated of, [0073] The way in which the methanol is separated off is ‘inconsequential forthe process of the invention, Thus, for ‘example, the customary and known methods fr the separa- ‘ion of quid mixtures can be used. Separation by distillation ‘may be mentioned frst and foremost and is preferred. a this, the lguid mixture is separated in a distillation apparatus [0074] Apart from methanol, unreacted methy] formate and also fier secondary components are naturally also present in te stream from step (a) Here, the term secondary compo- ‘ens generally refers to all eamponents which are comprised in he liquid stream obiained in step (a) and are nether formic ‘cid nor ferary amine (1) Examples which may be men- tioned are water, methanol, methyl formate, possible organic degradation products ofthe tertiary amine (1), dissolved inert gases, and also other components [0075] It is generally advantageous, in addition to metha- ‘ol, o also separate off other secondary components, i pat ticular, methyl formate, but also water from the stream fro step (@) For the separation of the other secondary compe ‘ents itis also generally possible to use the customary and ‘known methods forthe separation of liquid mixtres. Partie Jar mention may likewise be made of separation by distill sion, with italso being possible, depending onthe positions oF ‘the baing points, for some of this separation tobe performed together ina distillation apparatus, Thus, forexample, metha- tol and other low-boiling secondary components such as US 2014/0148617 Al methyl formate can be separated off at the top or as a side ‘ofllake steam, However, tis also conceivable to separate of high-boiling secondary components at the bottom and the mixture comprising formic avd and tertiary amine (I) a8 side sreum or even as overhead produc. Apart from separation by lisillation, membrane, absorption, adsorption, crystal tion, precipitation, fitraton, sedimentation or extraction pro- cesses are also possible. A combination of a plurality of separation processes is also possible, 10076) tis naturally also possible to combine a plurality of separation steps which may also be based on different meth- ‘ods, The design ofthe separation step of separation steps can, be undertaken using conventional technicel knowledge. 10077] ‘The main critical factor forthe order ofthe removal ‘ofmethanol and futher secondary components by distillation is the positon of the boiling points. Thus, i is particularly advantageous fistly to separate off methyl formate st the top ‘ofa first distillation apparatus. This ean then preferably Be recirculated to step (a) with the yield of formic sei based on the methy] formate used being able tobe increased signifi ‘cantly thereby. Methanol is advantagoously taken off 35 side ‘ofltake stream from the sume dstilstion apparatus, However, asanaltemative itis also possible to separate off methanol in «a separation distillation apparatus, The methanol which has been separated can, for example, be reused inthe synthesis oF thy! formate, Ina subsequent distillation apparatus, water 1nd any farther secondary components which can be sepa rated off together with water by distillation ean then advan- tageously he removed via the top. The water which has been separated off ean also be recirculated wo step (a), Since stall fmiounts of secondary components are sill comprised in the water which has been separated off, the recirculation avoids specific disposal of the water which has been separated off. “The bottom product obtained afer the removal of water and any further secondary componecas in this particulary advan- tageous variant comprises formic acid residual water and tertiary amine (1) According to the invention this ean then be passed to step (¢). [0078] 1 water is separated off in addition to methanol in step (b) ofthe process ofthe invention, the amount of water separated off is generally from 10 to 100% ofthe amount of ‘water comprised in the stream fom step (a) Preference is _given to 220% and particularly preferably 230% and prefer- ably =97% and particularly preferably 395% of teamountof ‘water comprised in the stretm from step (a) being separated coffin step (6), 10079] Although the formation of omwanie degradation products ofthe tertiary amine (1 significantly reduced by the measures according to the invention for reducing the formation of organic degradation products of the tertiary amine (), it is not completely prevented. It is thorefre also ‘advantageous inthe process of the invention to separate off the organic degradation produets of the tertiary amine (1) removed together withthe water according othe teaching of EP application No. 11 194619-Oand discharge them from the process, For this purpose, the steam comprising water and ‘organic degradation produets ofthe tertiary amine which has ben separated off in stop (b) is separated into two liquid phases, the upper liquid phase comprising the organic depra- dation products ofthe tertiary amine (1) is removed and the lower, water-comprising iguid phase is recirelated to step @. May 29, 2014 {0080} Of oure, fuer process steps apart rom step CO) a be carried out etn steps () and (c) inthe proces of the invention (0081) Finally, formic acid is removed by dsilaton in a stilton apparats ata temperate a he bottoms of fon 10010 300°C slo pressure of fem 3010 3000hPaabs rom the lguid stra obtnine fom step (b,x disillation appa ‘ates for this pups, itis in principle possible to use the pparstuses knows to tone skied in thea for sch separ thn tasks or can be designed by a person skilled inte at ‘sing gener tecnica know edge {0082 The distillation apparatus usually comprises not tly the ata column boy with internals but aso ine, fn overhead condenser and a bottom vaporizer. In adit, these can naturally also comprise further peripheral appari- {uses o intra, for example alah vessel in he oo ine (or example to separate ps and iq in the feed w the column body), an infemodiste vaporizer (for example for improved heat integration af the proces) of intemals for voiding or reducing aroslfnnation forexaniplhestable trays, demistrs,colesersor deep-ed cision iter). The coluna body ean Be equipped, for example, with ordered packing, random packing elements or tay. The nnber of ‘heoretical plates reyuie is dependent in particular, onthe ‘ypeorteriary amine (1), heconcentaion of formic avi and {erry amine (1) in the feed tothe distillation apparatus i, step (6) and the desired concentration or the desired purity of the formic acid, and ean be determined ina conventional Way byaperson skilled inthe at. The mimer of theoretical plates required is generally 28, preferably = and particularly pre. erably 27- There areinprinipleno upper limits. However, or Practical reasons will be usual owe generally 270-opton- Aly 250, theoretical plates or even 330 theoretical plats. {0083}. The steam comprising fomnic acid and teriary mine (from step (b) ean be ed or example as side stra tothe colama body ia the disilon apparatus [0084] 4 fash evaporator forexample, can optionally aso prececetho alton, To ep the themnal streson the stra {ed into the distilation apparatus as smal as posible ts sneraly advantageous to feed this in in a atively low Fegion ofthe distilaon apparatus. Thus, instep (e), the stream comprising formic eid and terry amine ) is pre erably fel inn he region a the lower quarter preferably in the mgion ofthe lower ith and particolry preferably in the region ofthe lower sixth, of tho theoratical plates present, ‘th disc ntodton nto he botom nstarally also being comprised her {0088} As an sltematve, preference isso given, instep (6) to fed sid streams compesing formic aed ad tertiary famine (1) from step (6) into the bottom saporzer of the sili appara [0086] The cistiaton apparatus is operated at a tempera ture athe Botom of fom 100 to 300” Cand a presure of {rom 30 to 3000 hPa abs. The cistlation appara is prefer ably operated at temperate atthe bottom of 3120" C. rartcuany preferably 140°C, and preferably 2220° Cand Palticularly preferably =200° C. The presnir is preferably 50 hPa abs, particularly preferably 200 hPa abs, and pele bly =1500hPs abs and particulary prcrably 2300 hPa abs {0087} Depending onthe composition a the feed compe ing foie and teary amine () othe cstilaton app ris, fom aid can Beabaned as overhead pret aor Se poet fom the distltion apparatus Ifthe fod come prises constituents having boiling point lower tan ta of US 2014/0148617 Al Jormic acid, it may be advantageous to separate these off as ‘overhead procict and separate off the formic acid at side ‘oftiake in the disillaion, Inthe case of possible dissolved. tases in the fed, its generally also possible vo separate ofT the formic acid together with heseas overhead produc. Ifthe ‘eed comprises constituents having boiling pois higher than that of formic ae, forme aed is preferably separated of by dlistilation 2s overhead predict, but optionally instead oF ditionally in the fom ofa scond stream a the side offtake. ‘The constituents which have boiling points higher than that of formic acid are inthis case preferably taken off in an addi tional side stream, The sie stream comprising secondary ‘components ean optionally herecreultel ost (b) in onder to separate off the secondary compontels [0088] Formic acid having a content of up t0 100% by ‘wojght can be obtained inthis way. In general, formie acid contents of from 75 to 99.995% by weight can be achieved ‘without problems. The balance to 100% by weigh is mainly ‘Wate, with other components suchas possible decomposition products naturally also being conceivable as materials apart from formic acid and the tertiary amine (1)introduced into the N- ad two o all thee radicals can also be joined 10 ‘one another to fom chain comprising atleast four atoms 10120] | Examples of suitable amines are: 0121] | Trin-propytamine (bpyo:s g2y~156" C2), treme Dutylamine, — ri-n-pentylamine, "triG-metiyibutyD) amine, ti-n-hexylamine, t-n-heptylamine, tri-n-octy- amine, trin-nonylamine, wisneeylamine, wisn ‘undeeylamine tr-n-lodeeylamine tr-n-tridecylamine, Uwicntetradeeylamine, tr-n-pentadecylamine, iene hnexadecylamine, 1i@-ethylhexy!amine, wi2-propyl- Deptyamine May 29, 2014 {0122] Dimethyldecylamine, Minedylcewkeyanine lied2ppumne (Pros yea 127” C.), di-n-octylmethylamine, tbat, da nag may mony nan ea-hoglniytay amine, ghey iso amin den bogies he nine rorya [0123 Trejlopentyhmins, rey amine, y- loping, Welwyn a devs thre obted by oneor me mete pee Pe 2pm Ligh Doug or Pgh? pesT Eon [0124] Dimethyicyclohexylamine, methyldicyclohexy- Tanne, dyes thet taming, cimetyeychpentyaninc, ety lumine melvin (0125 Triphenylamine, methyldiphenylamine, ethy!- ipkeyline pepyidpeyanioe, bunpaey timing 2ayhesestominimehiphe lamin, j-palamne, dppy pen amin titupiprplmine.” Hs sites pny amine ‘ricaylaning ety cay lamin, sey tininc ua dctoves tee abst by ene or toe meth eiy pops pons BUS 2.5091 cedaughppyl spe [0126] _1,5-Di(1-piperidyl)pentane, N—C,-C, ,-alkyl} Peings, NN, Cally igen No Cibalglymolidoes NCC ytimiantes s cere tarot sition yon or me me fig prop pop ebupl uor Pmt 2-propyl groups. [0127 18-Disabiey[S40}ndse-ene CBU" Iduliabigeloa 3 apetan Nancy arieyc [i ocime Cregane) Nenciyoewabigery 1) hoa Crnaage) eeabieen2 2 hoa mmc TaSevateryet TRO 0) peda Crs) [012] This tral sso posible owe inte of vai Sonera amines () ine poses he enon, Nat fay all tray anne (eden pc have at8 porte of 1013 APs abs ling pols wich a ca The tan hat of foie acs [012] Among the above-described teary ais othe fever! Sul a) pretence in tn geno ein SRE be eas ly Rae eae oder te cosh, inepenemly of one anor, Ubrasied or Eothat, eee: et ips aalpiaseor aaa toda ing nec ease fom 1 Loeb ts pe rbd fen teen sms, heel eon Stoms ny alse. inpedany of oe sot eee A asroprup eleced fou he gop cosa of © tnt No oral he ras on ab ons Saner fom saute a compridaget a our [0130] Preference is given to at least one of the radicals on {healph-carbonaom,t on theafon om und dicey ‘to the amine nitrogen atom, having two hydrogen atoms. [0131] _ Inthe process of the invention, particular preference [Renenwasiyganamincaihe ener omola()inich the radicals R' to R® are selected independently from the troup coming of, ah Corey Ben ‘and phenyl as tertiary amine (I). imethylodecylamine, US 2014/0148617 Al 10132] _Very particular preference is piven to using a satu- Fated amine ofthe general formula (la) as tertiary amine (2) ia the process ofthe invention, 10133] -Inpanicolar an amine ofthe general forma (a) ia shih the radicals R! to R® are selected independently fom the group consisting of C,-Cy-alkyland C,-C,-eyeloalky, in particular trisn-pentylamine”tr-n-hexylamine,trien-epty= Jamin, t-2-0ctylamine, dimethyleyelohexylamine, methy- dicyclohexylamine, dioetylmetbylamine and dimethyldccy~ Jamine, is used as teriary amine (2 in the process of the ‘vention, Most specifically an amine of the general formula (la) in which tho radicals to Rare selocted independently fiom the group consisting of C,-C,-alky, in particular ri-n- pentylamine, tr-n-hexylamine, ten-heptylamine and tri-n- ‘etylamine, is used as tertiary amine (1) inthe process ofthe invention, 10134] In a futher embodiment, amines which have @ branch on the alpba-carbon atom (the carbon stom bound 1). [0137] Tonic liquid, 10138) The type and amount of the individual forms is Jnconsequential for carrying out the process of the invention. 10139] FIG. 1 shows a simplified block diagram of a pen- ‘eral embodiment of theprocess ofthe invention. Inthe figure, the indivivl les have the following meanings [0140] A1-First stage ofthe apparatns for prodeing 2 steam comprising formic ack teary amine (1) and water [0141] 42-Second stoge ofthe apparatus for producing stream comprising formic acid, terary amine (1) and Water 0142] B=Apparatus for separating of methanol and ‘optionally ether secondary components [0143] C-Distilation apparatus [0144] | Mesh formate via stream (La) and water via stream (1b)are fed tothe first stage ofthe apparatus for producing ‘stream comprising formic aid, tertiary amine (I) and water May 29, 2014 Acconting tthe invention, acetin amount of etary amine (Qyean alo be introduced vastream (Le), However, ead ‘ion of tertiary amine (to A1 eanalso be omitted. In FIG. 1 {his is indicated by a broken-ine ar, At least part of the hydrolysis reaetion takes place in Al, The reaction mixture is then fed va stream (1x) fom the first stage AL tothe second stage A2 o the apparatus for producing a stream comprising formic acid teniary amine (1) and water. The addition of tertiary amine (I) takes place via stream (1d). The steam (2) comprising formic aid, tertiary amine (I) and water i sub- sequently taken off from the second stage A2 ofthe above- ‘mentioned apparatus and passed to removal of methanol and ‘optionally further secondary components in apparatus B. This is preferably a distillation apparatus. Methanol and any fur- ‘ther secondary components Whichhave hoen separated offare taken off via stream (3). The steam enriched in formie acid and tertiary amine (1) is fod via steam (4 to the distillation Apparat C. In this, formic acd is separated offas steam (5 by distillation. The bottoms from the distillation apparatus C fare taken off as stream (6). [0145] Ifthe apparates Bis preferred distillation appara- ‘us, this can also have, for example, the configurations di closed in FIG. 120 130f WO 2012/000,964. Thedstillation Apparatus C can, for example, have the configurations di closed in FIG. 210 7 of WO 2012000.064, [0146] FIG. 2 shows a simplified block diagram ofa mod fied embodiment in which the second stage A2 of the appa- ‘tus for producing steam comprising Formie eid tertiary (anal water is divided into two substages A2+i and ‘Tertiary amine (1) isin each case intxluced Viasteams and (Idi) The apparatuses A1, A2, Band C have the ‘meanings indicated in FIG. 1. [0147] FIG. 3 shows further simplified block diagram ofa ‘modified embodiment in which the second stage A2 of the apparatus for producing a stream vomprising formic tertiary amine (2) and water is divided into 8 theo infinite numberof substages A2-i, A2-i A ‘iary amine () isin each case introduced via the streams (1a), (Lda), (14) w (14-7). The apparatuses AL, A2, B fd Cikewise have the meanings indicated in FIG. 1 [0143] 4 preferred embodiment for obtaining formic acid by hydrolysis of methyl formateis shown in FIG. 4 by means ‘of a simplified block diagram. In the igure, the individual Tetters have the following meanings: 10149] Al-first stage of the apparatus for producing a stream comprising formic acid, tertiary amine (1) and water, which comprises the substapes Al-iand AL-it [0180] "A2-seeond stage ofthe apparatus for producing a stream comprising formic acc, tertiary amine (0) and water, which comprises the substapes A2-i and A2+i [0181] "B-disillation apparatus for separating offmetha- nol and optionally further secondary components [182] C-disillaion apparatus for obtaining. formic cid [0153] | D=phase separation vessel [0154] | E-phase separation vessel [0185] F-distlation apparatus for separating off low boilers [0186] | G-disillation apparatus for separating off high boilers and reissociating quatemary methylsmmonium formats [0187]. Y-metering spparatas [0158] Methy! formate (streams (1a) and (3b)) and water (Gtreams (1b) and (3x)) are fed fo the first stage AL of the US 2014/0148617 Al apparatus for producing a stream compris tertiary amine (I) and water and mixed in substrat this, not reaction mixture isthe fed to substage AI foremost has the function of a residence vessel and provides the reaction mixture with time for further reaction in the ‘direction of equilibrium, From the residence vessel, the rae tion mixture then goes via stream (1x) to the second stage A2 ‘of the apparatus for producing a stream comprising fone id, tertiary amine ())and water Thisis likewise divided into two substages. In substage A24, the frst part of the tertiary ‘amine 1) added via the metering apparatus Y and steam, (a), 50 that formic acid ean reat with the tertiary amine (D). In addition, further hydrolysis of methyl formate also takes place, The reaetion mixtuee is then passed on to substage ‘A2 i into which tertiary amine (1s ikewise introduced via the metering apparatus ¥ and stream (8). Further reaction of ormic acid with the aed tertiary amine (1) and also further hydrolysis of methyl formate take place in substage A2-i As ‘apparatus for Al and A2, itis possible 1 use for example, a tubereactor which has orifice plates athe transitions between sages and substages, The temperature in the reactors advan- tagenusly regulated by means of built-in heat exchangers. ‘cooling coils) nd by targeted settingofibe temperature of the tertiary amine (I) tobe added in. AD and AD, 10159] The reaction mixture is then taken off as steam (2) fiom the apparats A2-ii and fed tothe apparatus B. Stream (2) comprises predominantly formic aed, tertiary amine (1), ‘methanol, water and unreacted methyl Format, [0160] In the distillation apparatus B, unreseted methyl ormate (stream (3b)), methanol formed in the hydrolysis (stream (3a)) and water and organie decomposition products ‘ofthe tertiary amine (I) (stream (e)) are separated off fom, stream (2)-Siream (3b) comprising unreacted methyl formate is recirculated wo the apparatus Al, The methanol separated ‘off via stram (3a) can, for example, be reusod for preparing methyl formate. Steam (2¢) comprising water and organic ‘degradation prodacts of the tertiary amine (I) is fed to the phase separation vessel F and separated into two liquid Phases. The lower phase comprising water is recirculated as stream (3x) tthe apparatus A. The upper phase comprising ‘organic degradation products ofthe tertiary amine (is diss ‘charged fom the proces, Formic seid and terary arsine (1) taken off via stroam (4). This additionally comprises residual amounts of water, 10161] Stream (4) is fed to the distillation apparatus C. ln this, the fonmie acid is removed by disillation via stream (5) ‘as everhead product, via stream (5a) as side product andor via steam (Sb) as side product, Depending on the boundary ‘conditions, ic. especially the composition ofthe feed stream (G)to the distillation apparatus Cand the desited purity ofthe ori acid, formic acid ean be obtained as stream (S) atthe top or as stream (Sa) s side product in the present embodi- sent, Water-comprising formic acid is then taken off as side product via stream (Sa) or (Sb). In somecases, tmay'even be ulicient to remove formic aid or water comprising formic id purely via stream (3) as overhead product, Depending on the specific embodiment, the side stream (Sb) or even both side streams (5a) and (5b) can thus be dispensed with [0162] The bottom product from te distillation apparatus ‘Cis fas stream (6) to the phase separation vossol DAs an alternative, the phase separator vessel D can also be ine gated into the distillation apparatus C. Te bottom products Separated into two Tiquid phases inthe phase separation vessel May 29, 2014 D. A heat exchanger for example, can also optionally be installed between the distillation apparatus C andthe phase separation vessel Din onder coo! the bottom stream taken oll Although lower phase separation temperature generally Teads to somewhat better separation in respect of the formic acid content, it results in an additional outlay and energy ‘consumption beeanse of th use of heat exchanger. Advan- tages and disadvantages therefore have ta be weighed against ‘one another in each ease [0163] The lower guid phase ffom the phase separation vessel Dis taken offs stream (7a) and recirculated as seam (7b) to the distilation apparatus C. ln a preferred embodi- ‘ment, pat of stream (7a) ean be taken off and fed as stream (Je) to the distillation apparatus G. In addition or as an alter ‘ative, the distillation apparatus G can sso be supplied with other streams aot shown here. Thus, for example, itis gon ‘sivable to introduce #substteam of the bottom opt from the distillation apparatus C into the distillation apparatus G. There, the stream is distilled under reduced pressure and part, ofthe quatemary methylammonium formate is redissoeiated {nto tetiary amine (1, with the steam comprising formic ack and tertiary amine (1) being taken ofT atthe top and fed as stream (7a) to the distillation apparatus B. The bottom prod- vet is discharged from the process. 0164} ‘The operating conditions ofthe distillation appara~ tus G, eg, pressure, temperature, residence time, amount of ood stream, are generally a compromise between good di sociation conditions for the quaternary methylammoniam ormateat a very low degreeof decomposition of formic acid Ifthe distillation apparatus G is not operated, quaternary zmmonium formates accumulate inthe process, espe- cially i the bottoms from the distillation apparatus C and in the lower phase from the phase separation vessel , with the associated and above-described negative consequences for the process [0165] ‘The upper liquid phase from the phase separation vessel Dis taken off ia stream (8a) and recieulated to the ‘metering apparatus ¥. The metering apparatus ¥ can be, for ‘example, a reservoir provided with a ill level measurement and two regulated metering pumps for dispensing the streams (Gal and (Se). Furthermore, the metering apparatus Y can also ‘comprise heating or cooling elements for controling the tem perature ofthe streams (8d) and (Se). substream (8b) is fed {o the distillation apparatus FI ths, ow boilersare removed by distillation as stream (82) and the steam depleted in low boilers isrecirculatedas stream (8) tothe metering apparatus Y. [0166] In another, prefered embodiment for obtaining for ‘mie eid by hydrolysis of methyl formate, dhe methyl formate stream (Ia) is intrduced not dirty into stage AT-i but into the distillation apparatus B. This embodiment is generally ‘advantageous when the methyl fomate available as stream (1a) is stil contaminated with residual amounts of methanal for example due to a preceding methyl formate synthesis stage With partial conversion of methanol and incomplete ‘work-up of the methyl fommate. As a result of the diect introduction of stream (1a) into the distilagon apparatus B, the methanol comprised ean be separated off as stream (33) and, for example, rcireulated to the methyl Formate synthesis Stage This variant makes it possible to omita meth formate! ‘methanol separation entirely in the methyl formate synthesis sage and thus ta save an entire distillation column an thus also energy in ongoing operat US 2014/0148617 Al 10167] In a further, preferred embodiment for obtaining ormic acid by hydrolysis of methyl formate, both the meth] Jormate strewn (La) and the water stream (1b) are exch intro- ‘duoed not direc into stage AL- but into the distillation apparatus B, As regards the water steam (Tb), this embod mien! is generally advantageous when hot condensate oF steam is available as water source, since in this way the thermal energy stored thercin can be uilizedin thedlstlation apparatus B [0168] For the sake of eompletenes, it may he mentioned that, in a futher emboxtiment, itis naturally aso possible to inteduce the methyl formate stream (Ia) into the apparatus AL but the water stream (1b) into te distillation apparatus BB. This is advantageous when, for example, low-pressure ‘excess steam is available, 10169] In the variants mentioned, specific varias in respoct of the embodiment of the distiltion apparatus 1 having one, two or even three distillation columns are pos- sible as disclosed, for example, in FIG. 12 to 13 of WO 2012/000.964. The variants having one or two distillation ‘columas are prefered for the design of the disillation app ratus B. For the sake of complotenes, it may be mentioned that, particulary inthe embodiments having one or two dis- lation columns, these can also be configured as thermally ‘coupled columns ora dividing wal column, 10170} ‘The process of the invention makes it possible to ‘obtain formic acid starting fom methyl formate in high yield ‘and high concentration by thermal separation of a seam, ‘comprising formic acid and a tetary amine [0171] The formation of undesirable onganic degradatio products ofthe tertiary amine (I) can be ellectively reduced by the gradation according to the invention ofthe combining ‘of methyl formate, water and tertiary amin (I). This enables, ‘even without tangetod removal and discharge ofthe degrada: tion products mentioned, the concentration of these in the system to be kept a alow level over a prolonged period of ime and negative effects a be significantly reduced. Ina tion, significantly less tertiary amine i imeversibly decom posed as «result ofthe measures aeconding tothe imvention, 0 that significantly less fresh amine has 10 be introduced rom the outside, This makes the process not only simpler but ‘also relieves pressure on the environment by lower coasump= 10172] Especially in combination with additional measures Jor removing and discharging the small amount of organic degradation produets of the tertiary amine (1) which ae sl, formed, for example the measures deseribed in BP appl tion No, 11 194 619.0.nd EP application No, 11 194 607.5, gradual accumulation of low boilersena he particularly effec tively countered. Disadanlages suchas slow inerease in the ‘energy consumption in the distillation apparatus for theamal Separation ofthe stream comprising fone acid and tertiary famine and also a slow deterioration in the quality of the Jormie asa result of nereasing contamination with low boil- ‘ers ca thus be avoided particularly ellicienty. The appara tuses forremoving and discharging the abovementioned deg- rodation predicts can also he made much smallerasarcsultof the measires secordng tothe invention, which ives furhee advantages inthe construction the provess apparatus anda ‘ongoing operation 0173] The process of the invention can be operated very ably with, atthe same time, constant high purity of the omic acid produced overlong operating times, The formic ‘seidoblained has low color nomber and high color aumber May 29, 2014 stability. The process can be carried out simply, reliably and ‘with slow energy consumption, [0174] Laboratory Pant 1 [0175] Laboratory plaat 1 was employed for examining the continous process, The simplified block diagram of labor- tory plant 1's shown in FIG. 8. I the figure, the individual Jetiers have the following meaning: 10176] _At-first stage of tho apparatus for producing a stream comprising formic acd, tertiary amine (I) and ‘water, which comprises the substages AT-iand ATi [0177] _At-i-stired vessel (Volume 0.3 1, electrically heated) 0178] AL-i-pipe reactor Gntemal diameter 80 mm, length 1200 mm, filled with 2 mm glass spheres, elo wically heated) [0179] A2-second stage the apparats for producing a stream comprising formic acid, tertiary amine (1) and water, which comprises the sbstages A2-iand A2-it [0180] 2-i-tube reactor (internal diameter 80 mm, length 1200 mm, filled with 2 mm glass spheres, elec: twically heated) [181] A2-j-ube reactor Gntemal diameter 80 mm, length 1200 mm, filled with 2 mm glass spheres, elo wically heated) [0182] - Y=Vessel as a metering reservoir (5 I volume) [0183] | BI-Disilation apparatus comprising column ‘ody Gnteral diameter SS mn, equipped with wo mesh ‘packings each having a packing height of 1.3 m and 2 specific surface area of 750 mlm", withthe inlet for stream (2) being located beeen the two mesh pack: ings), ol-heated falling film evaporator and condenser ‘and also regulable ranback distributor atthe top of the column [0184] B2-Distlation apparatus comprising. columa body intemal diameter 55mm, equipped with 12 bobble cap trays in the stripping section and 10 buble cap trays in the enrichment seeton, with the inlet for stream (34) being located betweea the two sections and the inlet for stream (Sb) being located inthe stripping section}, oil-heated falling film evaporator and con- denser and also regulable runback distributor atthe top of the eolamn [0185] CI=column body Gotemal diameter 43 mm, ‘equipped with a mesh packing above the bottom having ‘a packing height of 0.66 manda specifi surface area of 500 m*/m° and also a further mesh packing having & packing height of 0.91 m and a specific surface area of 750 im, with the side offake for siream (Sb) being, located between the two lower mesh packings and side offiake for stream (Sa) being located between the 160 ‘upper mesh packings) and condenser and also regulable rrunback distributor atthe top of the eolum [0186] | C2-vil-heated falling fim evaporator [0187] _D-separate phase separation vessel (volume 0:3 [.oil-heated) [0188] | F=phase separation vessel [0189] _F-distllation apparatus having a column body Gnteral diameter 30 mm, equipped with | m of Sulzer CY packing (750 mim"), with the inlet fr stream (a) ‘being located beneath the packing) ol-heated bottom ‘vessel andalsoregulablerunbackedivideratthetop ofthe colmn US 2014/0148617 Al [0190] | G-evaporation apparatus for removing high boil- cervand dissociating quaternary melhylammoniam fore mates (glass vessel having a Volume of 2 1 and oil- ‘operated heating coil) [0191] The apparatus and Lines are composed of a nickel- based alloy having the material number 2.4610. The mass flows were measured by means of a coriolis flow meter Laboratory plant 1 was operated continuously 10192] In all experiments in the Taboratory plant 1, the ‘content of formic eid was in each ease determined by poten- tiometee titration with 0.5 N NaOH in water and the content ‘of water was detemained by the Karl Fischer method. Al ‘ther organic components were in each ease determined by ‘2s chromatograply [0193] Laboratory Plant 2 10194} Laboratory plant 2 was employed for examining the “deconposition of formic acid inthe presence of methsl-n- hexylammonivm formate. It comprised heated double- walled glass vessel K having an internal volume of 1 1 for ‘evaporation and a further, cooled vessel L having aninteral volume of I I or condensation ofthe vaporized medium, Aa cil-heated heating coil was located in the lower part of the jnner vessel ofthe double-walled glass vessel K. In addition, the double wall was also oil-heated, To regulate the or into the double-walled glass vessel K, the latter comprised a fill level regulator. Rebween K and [there was # condenser ia which the vapor from K was condensed and introduced as such into L. The vessel L. comprised both an outlet for con- _densed Tiquid produet and for gaseous components. Th level in the vessel was always high enough for the condensed ‘vapor From Kobe introduced under the surface of the Lig. {flow meter was loceted inthe outlet for gaseous compo- rents 10195] Determination of the Content of Methytr-n-Hexy- Jammoaium Formate [0196] The detemnination of the content of methytri-n- hexylammoniam fonmate was carried out by means of ion ‘chromatography. To be able to analyze even low concentra tions, each determination was carried out using 2 sample of ‘bout 1 I. Firstly, the low boilers (in particular methyl for. male, methanol and water) were evaporated under reduced pressure at 3 hPa abs (3 mbar abs) and 30° C. The sample, Which comprised formic acid, wibexylanmine, methyli-n- hexylammonium fomnate and possibly further intermediate and high boilers, was subsequently neutralized by means af 50% NaOH in water. This formed thre phases: aheavy phase ‘comprising an aqueous sodium formate solution, « middle phase comprising methytr-n-hexylammoniui formate and ‘an upper, aoupolar amine phase. The phases were separated from one another andthe eontent of methyltr-n-hexylamimo- niu formate was determined in the middle phase by means ‘of ion chromatography. 10197] Determination of the contents of methylsipemty- ammonium formate and methyl-n-oetylammonivm for 10198] Apart fom the determination by means oF on ehro- ‘matography, the dissociation products of methyhri-n-hexy- ammonium formate were also determined by means of was ‘chromatography. Here, methylaihexylamine, which is not N— nd to oF al three radicals are optionally joined! to. one another to form a chain comprising atleast four atoms. US 2014/0148617 Al May 29, 2014 23 16. The process according o claim 15, wherein the radicals RR to are selected independently from the group consisting FCC, pally], Cy-C,-cyeloalkyl, benzyl, and phenyl 17. The provess aovording to claim 16, wherein the radicals R! to R’areselected independently from the group consisting of Cally