1000966343782 2) United States Patent (10) Patent No: US 9,663,437 B2 Torrence et al. (45) Date of Patent: *May 30, 2017 (4) PRODUCTION oF ACETIC ACID Wert gama Bt 5201 wae HIGH CONVERSION RATE, {6462231 BL 102002 Yanagawa etal. (25) ovens: G. Pull Terrence, Leng Ci, TX Soltdn 62 90m Zeta (Gs) Brian W. Hokkanen,Hosson, Sesto7e BE 122008 See a TX (US), Ronald David Shaver, Sharam ba ‘Zou fitece loston TX (08 StooeSat Be 2000 Chewy tal ee Jais772 BE 102006 Prada SLANESE INTERNAL Toate be ‘Cor Mine (73). Assigage: CELANESE INTERNATIONAL Jae BE 42007 Mosk CORPORATION, Ining. TX (US) Taosses 82 $2007 Seucect al Jaa BE 1200) How (*) Notice: Subject io any disclaimer theterm ofthis Tarkou0 BE $2010 Mie Patent exended or aused under 35940219 BD 12010 Kojinn ta US. 154th by 108 de Serve) BD 102014 Hoklanen ea 2oomrovnit AL, 102008 Brose eal ‘This patent is subjee toa terminal diss ggoteszst At* "92008 Saka core sue chaimer sezsi9 (Coutiaved) (21) Appl. No: 1368.80 FOREIGN PATENT DOCUMENIS (22) Filed: Feb, 82012 x ts7sio 102004 6) Prior Publication Data & wiesse “S30 " Sorsa00 a 82009 US 201510066107 AL Mac 14, 2015, i “oss AL i999 * Stitiy * Tope , > aed A S98 Related US. Application Data te ae (6) Continuaton-in-par of application No. 13231.208, a a fled on Sep. 13-2011, now Pat. No. 8877963, yyy DESH A LRDL WO Wodngomsie at 303 G1) men care si72 (200601) COC 51d (2006.01), (OTHER PUBLICATIONS (32) US.CL Intationl Seach Repo and Ween Opinion mast Fe. 6, cre Care S112 201301}, CO7C SV44 913m comeqoading Inston Aptton No PCTUSDOI2 (2013.01) gs2899. (58) el of Cision Sate (ere) See application file for complete search history. 0) a Primary Examiner — Mesthew Conghin USS, PATENT DOCUMENTS. 3760229 A 101979. Paulik ot 4904608 821991 Torrence etal Shnoios> AV 1991 Sma a ‘A G91 Sith Sa A Sir § 334755 A B/L004 ssang29 A Los A 2005 A diver A S:907 Kagotant et a Eggo A 111907 Hesse ea Sieoe2e A 121997 Baker et al SU81252 A 31908 Warmer ta 84096 A 11/1998 onsen SNrTMT A 31999. Dita eta S877 A 31999 Dita eta S8e205 A 31909 Sunley ea ExMs761 A 311909 Piast 5017089 A * 611909 Howard coresui2 ‘60'129 Sp32761 A 811999 Mois. ab Sp42460 A $1909 Guan tal 6140.35 102000 Willams 644930 A 112000 Singh eta 6158792 112000 Leet et a Assistant Examiner —Po-Chih Chen (74) Atornes, Agent, or Firm — Kilpatrick Townsend & Stockton [LP on ABSTRACT A process for producing acetic acid comprising the steps of ‘acting carbon monoxide and at least one of methanol and ‘4 methanol derivative in a first reactor under conditions Clloctve to produce a crude acetic acid product; separating the crude scot acid prodoet into at least one derivative steam, at least one of the at least one derivative stream ‘comprising residual carbon monoxide; and reacting atleast ‘ portion ofthe residual carbon monoxide with atleast one ‘of methanol and a methanol derivative over a metal catalyst a second reactor fo produce acklitional acetic acid. Pref cemably the second reacor is homogeneous reactor and @ reactor carbon monoxide partial pressure i less than LOS MPa 22 Claims, 3 Drawing SheetsUS 9,663,437 B2 Page 2 66) References Cited USS. PATENT DOCUMENTS. 20080287706 AL 11/2008 Powell a. doowon9%a66 AL 11/2008 Seats cal aoooo1o7Ks3 AL 4/2000 Wamer 2ono.0rT06s0 AL 102000 Patt d00o/0rTOSSL AL 102009 Zinobile ota 20100069514 AL_ 32010. Gracey a. 20120078011 AL* 32012 Zinome seoisis 20120078012 AL* 32012 ‘Torrence ea 582519, dorsorTa6ia AL* 72013 Torrence ea. Sa 519 (OTHER PUBLICATIONS Intemational Seach Report and Writen Opinion male Jan. 2 2012 in comesponding International Aplication No, PCTUS2O11 os3539, Inermaional Search Report and Written Opinion mailed Jan. 2s 2013 n corresponding Imernationl Application No. PCT US20U sie 1H, Jones (2002). “The Catva™ Process forthe Manufacture of ‘actic Act Matin Matas Review, 44(), 4108 Miciac! GnuB, ct al, Applied Homogencous Caaysis with Onganometallc Compounds A. Comprehensive Handbook in Tw Nolume, Chaper 21s pp. 27-200, (sta. 1996). ‘Norvaki Yoneda and Yasve Hosono (200); "Acetic Acid Process Catala by ToncallyImmobilrat Rhodium Complex 10 Sid Resin Super’, urnal of Chemical Engineering of Japan, vl. 4, Nout, 536-518. Inenational Search Report and Writen Opinion mae on an 25, 2012 in corresponding Inerational Application No, PCUUSIL S389. International Search Report an Write Opinion mailed on an 25, 2012 in comesponing Internationa Application No, PCT US201I ass, * cited by examinerUS 9,663,437 B2 Sheet 1 of 3 May 30, 2017 U.S. Patent hor |__-lah vel So. 01 HOeW [OMUS 9,663,437 B2 Sheet 2 of 3 May 30, 2017 U.S. Patent os sre ez—} ez —_| 09 Se een cent — | |-s02 How il je Temes me ad we jf se—] | ase HOA Ma, a LI vez 982 tne az f } - ve i ag 882 os ise am. Wz al oz a T Hh : 7 i /* ve = i Lge i po 2 sz won i Cc OI cd zee. 7 / Ny mJ eX ee cee’ } 82 ‘e02 00gUS 9,663,437 B2 Sheet 3 of 3 May 30, 2017 U.S. PatentUS 9,663,437 B2 1 PRODUCTION OF ACETIC ACID WITH HIGH CONVERSION RATE, (CROSS-REFERENCE TO RELATED [APPLICATIONS ‘This application is» continuation-in-part of and claims priority 1 U'S. patent application Ser. No, 13/231,205, filed ‘on Sep. 13, 2011, the disclosure of which i hereby incor Porated by reference FIELD OF THE INVENTION This invention relates to processes for producing acetic ‘eid from carbon monoxide and, in particular, to improved processes, which react residual carbon monoxide 10 form ‘ditional acetic aed, thus improving the overall conversion ‘of the earbon monoxide feed BACKGROUND OF THE INVENTION A widely used and successful commercial process for symthesizing acetic acid involves the catalyzed. carbo- ylation of methanol with carbon monoxide. The eatalysis ‘contains rhodium andor iridium and a halogen promoter ‘ypically methyl iodide. The reaction is conducted by eon tinuously bubbling carbon monoxide through a liquid reac- ‘ion medium in which the catalysis dissolved. The reaction ‘diam also comprises meth acetate water, methyl iodide ‘and the catalyst, Conventional commercial processes for ‘carbonation of methanol include those described in U.S. Pat. Nos. 3,769,329, 5,001,259, 5,026,908, and 5,144,068, the entire contents and disclosures of which are hereby incomporated by reference, Another conventional methanol ‘carbonylation process includes the Cativa™ process, whieh js discussed in Jones, J. H, (2002), “The Cativa™ Process for the Manufacture of Acotic Acid” Platinum Metals Review, 44 3) 94-105, the entre content and disclosure of sich i hereby incorporated by reference During the methanol carbonylation reaction, by-product gases buildup inthe reactor as the erie acetic ncidprocct {s withdrawn into flasher. The build-up ofthese gases i the reactor is offen controlled by venting an off-gas from the reactor to Keep the carbon monoxide partial pressure in the Feacior al an oceplable level to muximize catalyst aetvity and stability. The vented off-gas may comprise carbon monoxide, inert and by-product gases, volatile halogen promoters, acetic acid, water, unreacted methanol, andor methyl acetate. In most methanol earbonylation processes the offgss is processed in one or more recovery units t0 recover volatile halogen promoters, acetic acid, water, unne- acted methanol, andor methyl acetate and return those Fecavered compounds io the reactor. The gases That pass out ‘of the recovery units may be purged andlor diected to 3 flasher vessel to enhance catalyst stability. An example of a recovery tnt is described in US, Pub. Nos. 2008/0293996 ‘and 200910270651, the entire contents and disclosure of ‘which are hereby incorporated by reference USS. Pat. No, 5,917,089 discloses that aa “off-ga8" from the reactor may be fed directly to a second reactor, slong with fresh methanol, 10 produce axkltional carbonylation product, i. acetic acd. The off-gas, as known in the art, however, isnot a derivative steam, 'A pitification section processes the enide acetic acid product fom the reactor fo remove impurities thus providing high quality acetic aed product. These impurities, which ‘may’ be present in trace atonal, alfet the quality of acetic o 2 acid, especially asthe impurities ae circulated through the rwaetion process, whieh, among other things, can result in the build up over time of these impurities, Conventional purification techniques to remove these impurities include lrwating the acetic acid product streams with oxidizers such fs orone, reducers such as hydiogen, water, methanl actvated-earbon, amines, and the like. The twatments may ‘or may not be combined with the distillation of the enude acetic acid product. Typically, during the purification, there ‘are several vents, which purge non-condensable gases ormed inthe reactor. The vented gases may be processed in 1 recovery unit to recover light boiling point components such as the halogen promoter, as described in US. Pub. No. 200810293966, the entire content and disclosure of which is hereby incorporated by reference. The vented gases, which also contain carbon monoxide, that passthrough the reov~ ery unit are typically purged or Msred. The loss of the earbon monoxide represents a loss of the reactants An alternative to the liquid-phase methanol carbonylation process is described in US. Pat. No. 6,617,471, the entre ‘contents and disclosures of which are hereby incorporated by reference. US. Pat. No. 6.617.491 discloses a vapor phase carbonylation method for producing esters and car boxylic acids from reactants comprising lower alkyl aleo- bls, lower alkyl aleofol generating compounds, and ‘mixtures thereof. The method ineludes contacting the reae- tans and carbon monoxide in a carbonylation zone of & carbonylation reactor under vapor-phase conditions with a catalyst having a catalytically effective amount of iridium ‘and tin associated with a solid carier material In view of these references, the need exists for improved pracesses fr processing vented gases during the purification fd separation of the erude acetic acid product to recover reactants and improve the eliiency of the acctic acid production, SUMMARY OF THE INVENTION ‘The present invention is to provesses for producing acetic acid. Ina first embodiment, the process comprises the step fof reating a frst reaction mixture in a first reactor under conditions effective to prosice a cre acctic acid proc. The firs reaction mixture comprises carbon monoxide and at least one of methanol and a methanol derivative, The process futher comprises the steps of separating the enue ‘acetic acid produet into at least one derivative stew ‘comprising residual carbon monoxide. The process may aso comprise the step of reaeting a second reaction mixture in a second reactor to produce additonal acetic acid. The second reaction mixture comprises 1) at least a portion of the residval carbon monoxide in the at least one derivative stwam and 2) at least one of methanol and methanol Gerivative, Preferably, the second reactor is a homogeneous reactor and the second reactor operates at a low carbon monoxide partial pressure, eg. a reactor earbon monoxide partial pressure leis than 1.05 MPa. In another embodiment, the process comprises the step of reacting in a eactor a carbon monoxide feed, eg. a lower carbon monoxide content feed, and at least one of methanol fand 1 methanol derivative under conditions effective to produce a reaction product and a vent stream. The reaction product comprises a crude acetic acid product and the vent stream comprising less than 60 mol % carbon monoxide Preferably, the reaetion in the reactor is homogeneousUS 9,663,437 B2 3 reaction and the reaction is couuhcted a a carbon monoxide partial pressure less than 10S MPa. BRIEF DESCRIPTION OF DRAWINGS ‘The invention is desribed in detail below with reference to the appended drawings, wherein like numerals designate similar pars. TIG, 1 is-a schematic diagram of an exemplary process ‘comprising a homogeneous, high pressure, liquid. phase ‘earbonylation secondary reactor for processing a purged ‘derivative stream fom an acetic aid purification section in ‘aeconlance with an embodiment of the present invention, FIG, 2a is detailed schematic diagram of an exemplary ‘etic acid production process, which includes reveton and separation, and comprises # homogeneous, high pressure, Tiguid phase carbonylation secondary reactor ia aevordance ith an embodiment of the present invention, FIG. 2b is a detailed sehematie diagram of an exemplary soctic acid production process, which inclades resection and Separation, and comprises # homogeneous, high pressure, liquid phase carbonylation secondary reactor in accordance with an embodiment of the present invention DETAILED DESCRIPTION OF THE INVENTION Introdvetion “The present invention generally relates to the production ‘of acetic acid from unreacted, e., residual, carbon mon- ‘oxide that may be present in one or more derivative steams ‘ofa rude acetic acid product. The derivative streams) are ‘obtained during the purification and separation of the cade ‘acetic avid product. For purposes ofthe present application, the separation zone refers to the portion ofthe process that puriies oF separates the erude acetic seid product, In a preferred embodiment, the derivative streams) are vented as streams ofthe separation zone. In one embodiment, the processes of the present invention advantageously increase the overall carbon monoxide elficieney by utilizing. the residual carbon monoxide in the derivative strcims to fon ditional acetic acid. In another embodiment, the processes ‘of the present invention advantageously reduce the amount ‘of carbon monoxide that is purged or Mared from the Purification and separation section “The present invention, ia one embodiment, relates to 9 process for producing acetic acid. The process comprises the sep of reacting a first reetion mixture in a first reactor and under conditions effective to produce a enude acetic acid product. The fist reaction mixture may comprise 1) earbon ‘monoxide; and 2) methanol and/or a methanol derivative The erode acetic acid produet comprises, inter alia, acetic ‘cid and residual carbon monoxide, The residual carbo. ‘monoxide may be dissolved andlor entrained in the erade ‘acetic acid prot, The inventive processes further com= prise the steps of separating the enide acetic acid product flo at least one derivative stream comprising residual ‘earbon monoxide; and reacting a second reaction mixture in ‘a second reactor and under conditions effective to produce addtional acetic acid. The second reaction mixture com prises 1) at least a portion of the residual earbon monoxide ‘in the a least one derivative steamy and 2) methanol andor ‘a methanol derivative, eg, methyl acetate, dimethyl ether, meth! formate and/or dimethyl carbonate. Preferably, the second reictor is a homogeneous reactor. In_preiered ‘embodiments, «reactor carbon monoxide partial pressure in the second reactor) is less than L05 MPa, ex, less than 1 o 4 (MPa, less than 0.9 MP, less than 0.75 MPa, of less than 0.5 (MPa. In terms of ranges, the reator carbon monoxide partial pressure may range from 0.005 MPa to 1.05 MPs, eg. from 0.01 MPa to 1 MPa, from 0.1 MPa to 0.9 MPa from 0.008 MPa 10 0.15 MPa, or from 0.0510 0.15, n one embodiment, the reactor carbon monoxide partial pressure isthe carbon ‘monoxide partial pressure in'a headspace of the second reactor. Unlike the primary reactor of the invention and inlike conventional carbonylation reactors, the inventive secondary carbonylation reactor operates with a low reactor carbon monoxide partial pressure. The low reactor earbon ‘monoxide paral pressure of the pressure invention is sig- nificantly different from conventional reaetors that may carbonylate conventional off-zas streams. These. conven- sional reactors utilize feed streams having much. higher carbon monoxide patil pressures. Tt has now been discovered, surprisingly and unexpect- cdly, that suitable carbon monoxide conversions, acetic acid selectivities and overal product yields ean be achieved even ‘when the second reactor is operated at thelow reactor earboa ‘monoxide partial pressures discussed above. In one embodi- sient the carbon monoxide conversion in the second reactor is.at least 30%, e.g. at least 60%, atleast 90%, or at least 95%. In one embodiment, the selectivity to carbonylated products), eg, acetic acid, methyl acetate, and mixtures thereo, is at least 20%, eg, at least 60%, or at least 90%, Inone embodiment. the aetic acid selectivity inthe second reaetor is a least 20%, ex, at Teast 60% oF at Teast 90%, ‘These conversions and selectivities are achieved by employ. ‘ng a homogeneous reactor as the secand reactor. Conven- tional reaction schemes, eg. heter>geneots reactors, 1 cally require significantly higher reactor carbon monoxide partial pressures to achieve similar carbon monoxide com- Versions, acetic aid selectivities, and produet yields, With- fot being bound by dheory, iti believed that the use of & homogeneous reactor allows for reduction or elimination of ‘reactor vent stream, The reactor vent stream vents from the reactor hy-prodiet gasses, which typically contain amounts fof earhon monoxide. These vent streams are roquied in conventional heterogeneous reaction schemes. By reducing the siz ofthe reacoe vent stream (or eliminating the reactor vent stream entirely), less earbon monoxide is Vented from the process, eg, wasted, and conversions are improved, In the processes of the prevent invention, Tess carbon monoxide is wasted through venting and the overall earbon ‘monoxide conversion is advantageously improved. In one embodiment, the overall carbon monoxide conversion relates tothe conversion ofthe inital earbon monoxide food steam in a first reaction and the conversion of residual carbon monoxide in a second reaction. Overall carbon monoxide conversions, are preferably greater than 90%, eg, greater than 95%, greater than 99%, oF greater than 99.5% ‘As nother benoit, the low reactor carbon monoxide partial pressures ofthe present invention allow the second reactor 4 be operated at lower overall pressure without risk of significant catalyst precipitation. In some embodiments fever if some catalyst may precipitate, the precipitated eata- Ist may be collected and recycled, eg. used inthe primary reactor. Because this catalyst ean be more easily collected and rveyeled, the need for a flasher downstream of the second reactor is reduced or eliminated. Tn a profeered embodiment, catalyst that has prociptated from the reaction mixture of the sscandary reactor may be recovered andlor reeycled to the primary reactor. In one embodiment, the process further comprises the step of separating the enude acetie acid product to form a catalystUS 9,663,437 B2 5 reeyele stream, As such, the catalyst that is present in the ‘rude product may be separated, eg, vita flasher or a Tight ‘ends column, may be removed from the crude stream, Preferably, at least a portion ofthe catalyst recycle stream may be directed to the secondary reactor where it may’ be twsed in the secondary catbonylation reaction. In one ‘embodiment, a slipstream is taken from a light ends column, andr from a flasher and direted t the secondary reactor. Tn another embodiment, the invention relates toa process {or producing acetic acid comprising the step of contacting With af east one of methanol and # methaaol derivative @ ‘carbon monoxide feed stream, ea low earbon monoxide ‘content feed stream, comprising # low concentration of ‘carbon monoxide (a5 compared to conventional carbon monoxide feed streams). eg. from 10 mal % to 9§ mol %, from 25 mol % to 75 mol % of from 40 mot % 0 60 mol % ‘earbon monoxide. Preferably, the low carbon monoxide ‘content fee stream comprises from 60 mol % to about 70, ‘mol % carbon monoxide, In terms of partial pressures, the 2 Jow carbon monoxide content feed streams optionally have ‘carbon monoxide partial pressure of from 10% to 95% of the total pressure of the derivative streams), e.. from 25% 10 75% or from 40% to 60%. In terms of limits, the low tion system. Allematively, the iodide salt may be generated Jnsit sinee under the operating conditions of the reaction system, a wide range of non-iodide salt precursors will react with methyl iodide or hydoiodic acid in the reaction medium to generate the comesponding eo-promoter iodide salt stabilizer. For additional detail regarding. ehodiom catalysis and iodide salt generation, sce U.S. Pat. Nos. 5,001,259; 5,026,908; and 5,144,068, the entireties of which are hereby incorporated by reference ‘When an iridium catalyst is utilized, the iridium catalyst ‘may comprise any iridium-containing compound which is soluble in the liquid reaction composition. ‘The iridium ‘catalyst may be added tothe liquid reaction composition for the earbonylation reaction in any suitable form which dis- solves inthe liquid reaction composition or is convertible to 1 soluble forma. Examples of suitable iridiam-containing ‘componds which may be added to the liguid reaction ‘composition include: IrCB, 3, 1eB3, [1H{CO)2I2, [1(CO) 2CI2, [I{CO}2BE, [I(CO}212]-H, [i(CO)2B!2|-11+ [le (CORHJ-He, — [InCH3)IS(CO2}-H+,— Irg{CO}I2, InC13 3120, InB13 3120, le(CO)12, iridium metal, 17203, IacacyCO}2, I(aeae)3, iridium acetate, [1r3O(OAC)6 (F20)3]10Ac}, and hexachloroiridie seid [F12IC15). Cho- Fide-trce complexes af iridium soch as acetates, oxalates and acetoacetates are usually employed a8 starting. materials ‘The iridium catalyst concentmation in the liquid reaction ‘composition may be in the range of 100 to 6000 ppm. The ‘carbonylation of methanol wilizng iridium catalyst i well, Known and is generally described in U.S. Pat. Nos, 5.942, 460; 5,932,764; 5.883.205; 5.877 348; 5,877,347 and 5.696, 284, the entireties of which are hereby incorporated. hy reference, An alkyl halide eo-eaalyst/promoter is generally wsed in ‘combination with the Group VIII metal catalyst component Methyl iodide is preferred as the alkyl halide promoter Preferably, the concentration of alky! halide in the liquid reaction composition is in the rmge of 1 10 50% by weight, preferably 5 t0 20%. ‘The halogen promoter may be combined with a salt stabilizesieo-promoter compound, which may include salt ‘ofa metal of Group TA oF Group TIA, 2 quaternary ammo= niu, phosphonium salt or mixtures thereof. Particularly prefered are iodide or acetate salts, e., lithium iodide or Tithium acetate, ‘Other promoters and co-promoters may be used as pat of the catalytie system of the present invention as destibed ia US. Pat. No. 5.877.348, the entirory of which is hereby ‘incomporated by reference. Suitable promoters are selected from ruthenium, osmium, tungsten, rienium, zine, cad- rium, indium, gallium, mercury, nickel, platinum, vana- «dium, titanium, copper, aluminum, tin, antimony, and are more preferably selected fron rtheaiuin and ossiium, Spe- Cilie co-promoters ace described in US. Pat. No. 6,627,770, the entirety of whichis incorporated herein by relerence. "A promoter may be present in an effective anoint up to the limit ofits solbilty in the liquid reaction composition andor any Tiguid process streams recyeled to the carbo- ylation mactor Irom the acetic acid recovery stage, Whea tsed, the promoter is suitably present in the liquid reaction ‘composition at molar rato of promoter to metal catalyst of 0 o 8 05:1 181, preferably 21 to 10:1, more preferably 2:1 10 75:1 Asitable promoter ccentation is 400 to S000 ppm. none embodiment, the temperature ofthe earbonsation reaction inthe fis reactors preferably from 150°C. 1 250° Gee, from 150°C. to 225° C, or from 150° C.t0 200° (Cth pressure of the carbonation reaction is preferably fiom 110 20 MPa, preferably Ito 10 MPa, most preferably 15 to 5 MPs In ane embodiment, the fist reaction mixture comprises a reaction solvent or mixture of solvent. The solvent is pecforably compatible with the catalyst system and may Include pure sleohols, mixtures of am alcool feistock anor the desired carboxylic aid andor esters of these two empounds. In one embodiment. the solvent and lighid reaction medium for the (low water) carbonylation process 3s preferably acetic acid The methanol fed steam fed to the fist reactor com- prises methanol andor reactive derivatives thers, Suitable reactive derivatives of methanol include methyl acetate, Gimethy! elcr and meilyl formate In one enbodiment, ‘mixtre of methanol and restive derivatives threo! may be Used as reactants in the process ofthe preset invention Preferably. methanol andlor methyl aceite are se as reactants. Atleast some of the mithanol andor reactive derivative threo wil be conver oan hence present 3, ‘methyl acetate in the guid eaeion composition by reaction ‘ith acetic seid proctor solvent. The concentration inthe Tiquid eaesion mixture of methyl acetate is suitably in the range of from 0:5 wt. % t0 70 wt. 9, ea rom 0.5 wt. % {0 80 8%, fom Tet, 810 38 Wt 9 oF from Ht 96 t0 20 wt %, The carton monoxide fed steam fe to the fis rector nay be escnilly pure oF may contain small armonnts of ‘net impurities sic 28 carbon dioxide, methane, hydrogen, ivogen, noble gases, water and Cl to C4 paralic hyo carbons. The carbon monoxide fod stream preferably com: rises a high content of carbon monoxide, e.g. at least 9S ‘ol, at east 98 mol %, oF at east 99 mol 6. The earbon ‘monoxide feed stcam preferably has higher carbon mon- oxide content reatve to the derivative steams fed to Sccondary rvction zone The earbon monoxide feed steam may also be charac: terized in tems of partial pressure. The carbon monoxide feed stream may have a carbon monoxide pail peestre of atleast 98% ofthe total pressure of carbon monoide feed stream 108, eg. at least 98% or at least 99%, In one ebodimen, the prial pressure of eurbon monoxide inthe carbon monoxide feed anges fom 0.1 MPa to 7 MPa, 2 fiom 0.1 MPa to 35 MPa, or from 0.1 MPa w 1.5 MPa Hiydrogen may be generat inthe earbon monoxide feed sutcam by the water gas sift action. Preferably the partial pressure of hydrogen is maintained at a low level, for ample, less than 0.1 MPa or less tn 005 MPa, che presonee of hydmgen may result nthe formation of various hydrogenation prac “Ther materials used in connection with he proves of this invention may be derived from any suitale source Including natal gas, petoleum, cos, biomsss, and 30 forth ‘As petroleum and natural gas prises facta becoming liber more or ls expensive, methods Tor producing aeetic fc intermediates such as methanol and carbon monoxide from alternate carbon sources have drawn inereasing iter cst In particlan, wn petolum is rolatvey expensive, it fay become advantageous to predice aoatic acid Tam "yes gs (syn) that derive rom more available Carbon source. Aevordinl i some embodiments, someorUS 9,663,437 B2 9 ll of the raw materials for the above-described carbo= ylation may be derived partially or entirely from syngas. For example, both the methanol and earbon monoxide may be derived from syngas. The syngas may be formed by partial oxidation reforming or steam reforming, and the ‘carbon monoxide may be separated from syngas. The syn= as, in turn, may be derived from variety of earbon sources. ‘The carbon source, for example, may be selected from the group consisting of natural gas, oil, petroleum, coal, bio- ‘mass, and combinations thereof. Syngas or hydrogen may ‘ako be obiained from bio-derived methane gas, such as bio-derived methane gas produced by landfills or agricul- tural waste Examples of biomass include, but are not limited to agricultural wastes, forest products, erases, and other cel- Iulosic material, timber harvesting residues, softwood chips hardwood chips, tee branches, tree stumps, leaves, bark, sawdust, ol-spec puper pulp, com, corn stover, wheat sta. rice sta, sugarcane bagasse, switchgrass, miscanthus, an ‘mal manure, municipal garbage, municipal sewage, com- 2 mercial waste, grape pumice, almond shells, pecan shell, ‘coconut shells, coffer grounds, grass pellets, ay pellets, ‘wood pellets, cardboard, paper plastic, and cloth. Soe, e 2. US. Pat. No. 7,884,253, the eatiety of which is ineorpo- rated herein by reference. Another biomass source is black Tiguor, a thick, dark iguid that is @ byproduet of the Kraft process for transforming wood into pulp, which is then dried ‘o make paper, Block liquor isan aqueous solution of lignin residues, hemicellulose, and inorganic chemicels. "Also, US. Pat, No. RE 35,377, incorporated hein by reference, discloses a method forthe prodiction of methanol by conversion of carbonaceous materials such as ol, coal natural gas and biomass materials. The process includes hhydrogasifcaton of solid andior liquid carbonaceous mate- rials t obtain a procest gas which is steam pyrolized with ‘additional natural gas to form synitesis gas. The syngas is ‘converted to methanol which may be earbonylated to acetic seid “The acetic acid, in tur, may be bydnogenated to form ‘ethanol and/or ethanol derivatives, Processes Tor hydroge= rating acetic acid to form ethanol are. described, tor ‘example, in US. Pat. Nos. 7,608,744: 7,863,489; US Pubs lication Nos. US2010/0197985: US2011/0190547; US2OL1/ ‘0190548; U$2011/0275862; US2011/0282110; and in U.S, patent application Ser. Nos. 13/197.743; 13/197.738; 13/299,816, each of whieh is incorporated herein by refer~ ‘ence ia its eatery. Returning to the carbonylation reaction, water may be formed in situ in the Iiguid reaction composition, for ‘example, by the esterification reaction between methanol reactant aod acetic acid product. Water may be intrduced to the carbonylation reactor together with or separately from ‘ther components of the liquid reaction composition, Water may be separated from other components of reaction eom- positon withdrawn from the reactor and may’ be rocyeled ia ‘controlled amounts to maintain the required concentration of water in the liguid reaction componition, Preferably, the ‘concentration of water maintained in the Figuid reaction ‘composition isin the range of from 0.1 wr. % to 16 wt eg. from 1 wt. % to 14 wt %, oF from 1 wt. % to 10 wt 6. ‘none embodiment, the desired reaction rates are obtained ‘even at low water concentrations by maintaining in the reaction medium an ester ofthe desire! carboxylic aid and ‘an alcohol, desirably the aleohol used in the carbonylation, tnd an ational odie im that is over and above the iodide jon that is present as hydrogen iodide. An example of a 0 o 10 prefered esters methyl acetate The additonal fide fon is Sesirably an iodide salt, with lithium iodide (Lil) being preferred. It has been found, as described in U.S. Pat. No. 5,001,259, that under low water concentrations, methyl acetate and lithium fodide-act as rate prometees only when ‘relatively high concentrations of cach of these components fare present and that the promotion is higher when both of these components are present simultaneously. The eoncen- tration of fodide ion maintained in the resetion medium of the preferred carboaylation reaction system is believed to be guile high as compared with what lite prior art there is ‘Sealing with the use of halide sls in reuction systems ofthis sort. The absolute concentration of die ian content isnot 4 imitation on the usefulness of the present invention, ‘As noted above, the earbonylation reaction of methanol to acetic acid product may be carried out by contacting the ‘methanol feed with gasoous carbon monoxide bubbled through an acetic acid solvent reaction medium containing the catalyst ¢.. chodium or iridium, methyl iodide pro- ‘moter, methy] acetate, and/or additional soluble iodide sal at conditions of temperature and pressure suitable to form the carbonylation produet. Without being bound by theory, it is-generally recognized that itis the concentration of iodide ion inthe catalyst system thats important and not the cation associated with the iodide, and that at a given molar ‘concentration of iodide the nature of the cation is not as significant as the effect of the iodide concentration. Any ‘metal ide salt, or any iodide salt oF any onganie cation, or ‘other cations such as those based on aimine or phosphine ‘compounds (optionally, temary or quatemary cations), an be misintsined in the reaction median provided that the salt is sulcieatly soluble in the reaction medium to provide the desired level of the iodide. When the ide is a metal sl preferably it is an iodide salt of a member of the eroup ‘consisting of the metals of Group LA and Group ILA of the periodic table as set fort inthe “Handbook of Chemistry and Physics” published by CRC Press, Cleveland, Ohio, 2002-03 (83rd edition), In particular, alkali metal iodides are ‘efi, with lithium iodide being particularly suitable. Ta low water carbony ation, the atonal iodide over and above the organic iodide promoter may be present in the eatalyst solution in amounts ranging rom 2 wr. °% to 20 wt. 6, eg, from 2 wt. % t0 1S wi %,oF from 3 wi % to 10 wt he methy! aeetate may be present in amounts ranging rom 0.5 wt % to 30 WL %, eg. fom 1 WL % 10 25 WL. %, ‘or from 2 wt, % to 20 wt. 96; and the Tim foide may be present in amounts ranging from 5 wt. % t0 20 W1%, ex rom 5 wt, % 1015 wt, 86,0 from $ Wr. % 10 10.1. %. The catalyst may be present in the catalyst solution in amounts ranging from 200 wppm © 2000 wpm, e., from 200 ‘wpm to 1500 wppm, or from S00 wpm to 1500 wpm, The primary carbonylation reaction yields a erude sootic acid product, which comprises major portion of acetic ‘cid. For example, the erude acetic aed product may com Prise atleast $0 mol % aeetic acid, eg, atleast 60 mol %, atleast 75 mol %,at least 90 mol %, atleast 95 mol %, oF atleast 98 mol %. In terms of upper limits, the erude acetic acid prodiact may comprise less than 99.9 mol % acetic acid, eg, less than 99 mol % or les than 95 mot %, In temns of ranges, the erude acetic acid product optionally comprises ‘rom 50 mol % to 99.9 mol % aceti acid, e.2feom 60 mol % t0 99 mol %, oF from 75 mol % to 9S mol %. In other embodiments, the eride aeaic acid product may have an acetic acid pariah pressure of a lest 50% of the total prossure ofthe erude acetie eid product, atleast 75% atleast 0%, atleast 9$%, or atleast 98% In tems of ‘upper limits, the crude acetic acid product may have aaUS 9,663,437 B2 un ‘acetic acid partial pressure of ess than 99.9% of the total pressure ofthe crude acetic acid product, eg, less than 99% ‘or less than 95%, In terms of ranges, the aetic acid partial pressure may rage from 50% to 99.9% ofthe total pressure ‘of the erude acetic acid product, eg. from 60% t© 99% oF fm 75% 19 95%, Optionally, the ene acetic acid product further comprises methyl iodide (liquid andor vapor). methyl acetate, propionic acid, water, residual catalyst, and acetaldeyde, In one embodiment, the enude acetic acid product may comprise acetic acid, residual catalyst, dis- solved andor entrained carbon monoxide, methyl iodide, methyl acetate, water, permanganate redueing compounds (CPRCS"), and/or other dissolved gases such as carbon oxide, hydrogen, and methane. “The enude acetic acid product may further comprise residual carbon monoxide. In one embodiment, the crude ascetic aed produet comprises residual carbon monoxide in ‘an amount less than 20 mol % els than 10 mol less than $ mol %, of Less than 3 mol %, OF couse, for residual ‘earbon monoxide 0 be reacted with methanol andor 2 methanol derivative to form additional acetic acid, some mount of carbon monoxide should be present, Por example, the crude acetic acid product may comprise residual earbon ‘monoxide in an amount greater than 0.1 mot %, greater than (0.5 mol % or greater than | mol %. In terms of ranges, the ‘enue acetic acid product may comprise from 0.1 mot % 10 20mol % carbon monoxide, e.g, residual carbon monoxide, ‘eg. fom 0.5 mol % to 10 mol % oF from 1 mol % 10 $ mol %, In another embodiment, a flashed vapor phase emde ‘acetic acid product has a earbon monoxide partial presture that is less dhan 20% ofthe total pressure ofthe flashed crude scot acid product, eg, less than 10% less than 5%, or less than 3%. In terms of partial pressures, the Mashed crude cate acid product may have a earboa monoxide partial pressure of at least 0.1% of the total pressure of the lashed ‘ede acetic acid prodvet, eat least 0.5% or at least 1%. The crude acetic acid produet optionally us a carbon monoxide partial pressure of from 0.1% to 20% of te total pressure of the crude acetic acid product, e., from 0.5% t0 10% of from 19% to 5%. In another embodiment, the Mashed crude acetic acid product is ata total pressure of 0.3 MPa and hus a carbon ‘monoxide partial pressure of less than 0.06 MPa, e., less than 0.03 MPa; Jess than 0.015 MPa; or less than 0.009 MPa. Inne embodiment, the lashed crude seetic acid product is ‘at 03 MPa total pressure and the carbon monoxide partial pressure may be of at least 0.0003 MPa, atleast 0.0015 MDa or at least 0.003 MP Separation ‘As noted above, the inventive processes comprise the step ‘of separating the erude acetic aid proc nto one or more derivative streams, At least one of the derivative streams, ‘eg. atleast mo or at least three, comprises at least a portion ‘othe residual carbon monoxide, Preferably, the atleast one of the derivative steams is a vapor. Resa earbon mon= ‘oxide, ex. unreacted carbon monoxide, includes carbon monoxide that has not reacted in the earbonylation reaction ‘and, a such, remsins inthe crude aeetie acid product, In one ‘embodiment, the residual carbon monoxide in the derivative streams) is entrained in the respective stream. Without being hound by thoory itis believed thatthe entrainment of the earbon monoxide is de to the carhon monoxide being ‘conveyed through the guid reaction mixture. In comtms, 3 ‘ypical off gas stream is simply a stream that is removed 0 o 12 {rom the vapor built up in the reactor. Thus, the carbon monoxide in conventions olla streams isnot entrained in the stream, ‘In one embodiment, the derivative streams) comprise less carbon manoxide than the carbon monoxide fed 10 the primary reactor, eg. the fist reactor. In one embodiment, the derivative streams) comprise less than 95 mot % earboo monoxide, eg, less than 80 mel % less than 75 mol %, ess ‘than 60 mol, less than 50 mol %, of les than 40 mol %. In nother embodiment, the vapor phase derivative stream(s) Ihave carbon monoxide partial pressure of les than 95% of the total pressure of the vapor phase derivative stream), eg, less than 75%, less than 608%, less than 50%, or Tess than 40%. In tems of ranges, the derivative stream(s) ‘optionally comprise from 10 mol % t0 95 mol % residual carbon monoxide, eg. from 25 mol % to 75 mol %, oF fro 40 mol % to 60 mol %. Preferably, the derivative sream(s) ‘comprise from 60 mol % to 70 mol % carbon monoxide la ‘one embodiment, the concentration of earbon monoxide in the derivative stream(s) may be atleast $% lower than the concentration of the carbon monoxide fed to the reaction zone 101, eg, a least 10% lowe, atleast 25% lower, oF at least S0% lower. In other embodiments, the carbon monox- ‘de concentration of derivative stream 108 (either in mol % for earbon monoxide partial pressure) may be at least 5% lower than the concentration in a conventional off-gas stiwam, eg, at least 10% lower, at least 25% lower, or at Teast 50% lower. Ione embodiment, because of the re tively low amount of carbon monoxide in the fee, the molar ratio of other reactants, eg., methanol andior’ methanol erivatves, 1o carbon monoxide in the second reactor is greater than 0.02:1, eg, greater than O.L:1, greater than (0.25:1 or greater than 05:1 In terms of partial presses, the erivative stream(s) optionally have a. carbon monoxide partial pressure of front 10% to 95% ofthe total pressure of the derivative steam(), eg. Irom 25% 10 75% or from 40% to 60% In preferred embodiments, at leat a portion of the residual eathon monoxide in the derivative steam(s) is reacted in the second reactor to form additional acetic cil Ta one embodiment, the inventive process fther com: prises the step of compressing the derivative steams) to orm a compressed derivative streams), Any suitable com pression units may be employed to compress the derivative stran(9)- In prefered embodiments, the compressed Gerivative streams) have a feed carbon monoxide partial pressure of at least 003 MPa, eat leat 0.1 MPa, at least (5 MPa, or at least 1 MPa. In terms of ranges, the com- pressed derivative stream(s) may have a feed earbon mon- ‘oxide partial pressure ranging from 0.08 MPa to 1.75 MPa, 2g, from 0.1 MPa o 1.5 MPa or from 0.1 MPa to 0.5 MPa. Te feed carbon monoxide partial pressure is diferent fom the reactor earbon monoxide partial pressure, et, the car bon monoxide partial pressure of the vent gas Irom the headspace of the secondary reactor. In preferred embodi- ‘meals, at lest a portion ofthe residual carbon monoxide in the compressed derivative streams) is reacted inthe second reactor 10 form additional aeetie acid. Some exemplary separation schemes are discussed below in desl Secondary Carbonyl "As discussed above, the inventive process comprises the step of reacting, in a second reactor, a sevond reaction mixture to prodice adlional acetic seid. The second rene- ‘ion mixture comprises at east a portion of the residual carbon monoxide from the derivative stream) and metha- ‘ol and/or a methanol derivative. The rector, preferably, is ‘ homogencous reactor and the secondary (supplemental) carbonslaton that takes place in the second reactor may beUS 9,663,437 B2 13 ‘a homoyeneous revetion, ep. a homogeneous liquid phase reaction. In one embodiment the second reaction mixture is 4 homogeneous liquid phase reaction mixture, In one ‘embodiment, the reaction is conducted over a homogeneous catalyst, eg, liquid phase catalyst. In a prefered embod ‘ment, the methanol and/or methanol derivative and the metal catalyst are liquids andor are soluble in the reaction medium, By conducting the second earbonylation homoge- neously, e@., in a homogeneous reactor, suitable carbon monoxide conversions, acetic acid selectivities, and overall product yields ean be achieved while using # low reactor ‘carbon monoxide parial pressure. ‘In one embodiment, the frst reation mixture comprises ‘first amount of rhodium as a catalyst and the second reaction mixture comprises second amount of rhodium as catalyst. Preferably, the frst amount of rhodium is less tha the seconc amount of thodum, ea least 10% less than, least 25% less than, or at least SO% less than. In one ‘embodiment, the frst reaction mixture comprises from 300 \wppm to $000 wpm shodium, e. from 900 wppm to 1500 2 ‘eppm or fom 1100 wppm to 1300 wppm. In terms of lower Timits, the frst eaetion mixture comprises at least 300 ‘wppm, ea least 700 wpm, at least 900 wpa or atleast 1100 sppm. In tems of upper limits, the fist reaction rixtuee comprises less than 1700 wppm thodi than 1500 wppm of less than 1300 ppm, In one embodi- ment, the second reaction mixture comprises from 500 ‘ppm to 6000 wppm ehodive, eg. from 1500 wppm 53500 wppm or from 2000 wpm to 3000 wpm. In terms of Tower limits, the second reaction mixture comprises a least 500 wppm rhodium, eat least 1000 wppm. a least 1500 ‘ppm or at least 2000 wppm. In terms of upper limits, the second reaction mixture comprises less than 400 wppt rhodiuan, eg, less than 3800 wppan oF less thaa 3000 wp In one embodiment the pressure in the second reactor is Jess than the pressure in the frst reactor, ea Teast 10% Jess, at loast 25% less, or atleast $0% less. Beneficially, hy ‘employing a homogeneous reactor in aecordanee with the present invention, the need to compress the derivative ‘ream() is significantly reduced, which results in increases in overall process eficency. In one embodiment, the pres- stein the second reactor ranges from 0.1 MPa to 10 MP3, ‘eg. ffom 1 MPa to 5 MPa or ffom 2 MPa wo 3 MPa. In another embodiment, the temperature inthe second reactor ranges from 100" C.t0 300° C., eg, 150° C. to 300° C. or 175° C. 10 280° C. In one embodiment, the reaction tem= perature in the second resetor is similar to the reaction Temperature in the first reactor. In other embodiments, however, these two temperatures differ from one another. ‘Alb, the reaction in the second reactor (andl optionally that in the first reactor, as well) may be conducted in 2 ‘counter-curent or eo-current manner. Although the catalyst Torte reaction in the second reactor may be the same a the ‘eatalyst inthe firs reactor, itis preferred thatthe catalyst in the second reaetor is different From the catalyst ia the first reactor. Preferably, the catalyst in the second reactor is tailored to account for ® carbon monoxide stream that ‘comprises lower amounts of carbon monoxide. Preferably, the catalyst in the second resetor is a rhodium diiodide «icarbony| anion that is ionically bound to a suitable resi, ‘eg. polyvinylpyridine or earboa, “The second reactor generally may be any homogeneous reactor suitable for earbonylation of methanol with a rela- tively low carbon monoxide feed stream, Preferably, the second reactors continous sired tank reactor ("CSTR") Inone embodiment, a uibble column reactor may be ullized asthe second reactor to perform the carbonylation. When, eg. less o 14 these reactors are employed as the secondary reactor, the parameters of these reaciors are similar to the parameters Aiscussed above with regard to the first reactor. Tn one embodiment, the second reactor comprises lyst section anda head space. Ina prefered embodiment, the reactor carbon monoxide partial pressure is measired in the head space of the second reactor. ‘Anexemplary earbonylation reaction/separation system is shown in FIG. 1. Carbonylation system 100 comprises carbonylation reaction zone 101, separation zone 102, and secondary reaction zone 103, Other exemplary carbo- ylation systems, including reaction zone and separation zones, that may be used with embodiments of the preseat invention include those deseribed in U.S. Pat. Nos. 7.223 886, 7,008,541, 6,687,078, 630,171, 5.731.252, 5,144,068. 5,026,908, 5,001,259, 4,994,608, and US. Pub. No. 2008) (0287706, 200810293966, 2009/0107833, 200910270651, the entie contents and disclosures of whieh are hereby incor porated by reference. Exemplary reaction zone 101 and separation one 102 are shown in the detiled schematic iagrams discussed below with respect to FIGS. 2a and 26, ‘As shown in FIG. 1, methanol feed steam 104 and carbon monoxide feed stream 108 are fe, preferably continuously fed, to reaction zone 101 to produce crude acetic acid product stream 106, Cride acetic acid prodvt steam 106 ‘may be fod separation zone 102, which produces purified ‘cetie acid prodiet stream 107 and derivative steams 108, 109, and optional derivative stream 110, Derivative stream 108 may be fed to secondary reaction zone 108, Although erivatve steam 108 is shown as a single stream, multiple erivative streams may be yielded by separation zone 102. Derivative stream 109, which may comprise recycled com: pounds. may be fed, e'. reeyced, to rection zone 101 Optional embodiments, optional derivative stream 110 may aso be fed 0 secondary reaction zone 108, In one embod ‘ment, the derivative stream(s) are streams that are derived from'he enide acetic aeid product. For example, the deriva- tive stream() may be streams that result from the separation of the crude acetic acid product, As another example, the Serivative streams may be stress) yielded by flasher, as shown in FIGS. 2a and 2b. In one embodiment, the deriva- tive stream(s) do not inelude conventional off-gas streams. Conventional off-gas streams are merely streams of by- pradhct gases tht build up in the reactor as the erde ocetie acid product is withdrawn, eg, withdrawn into a flasher ‘These oll-gas streams essentially comprise reaction by: products, and do not result from the separation of the ene ‘acetic acid proclut. Thus, conventional off-gas streams are ‘ot considered to be derivative streams. ‘cause the present invention provides for more ellcient utilization of residual carbon monoxide, the inventive pro- cesses and systems may allow larger quantities of off-gas 10 be withdrawn fom the resetor and/or the fasher. These anger quantities may beneficially be used to supplement other streams in the system, e., recycle streams or purip- ‘round streams. In conventional systems, increased off-gas ‘withdrawal would result in increased waste of carbon mon- oxide Derivative stream 108 may be in the figuid-phase or vapor-phase and preferably comprises dissolve andlor eniraned carbon monoxide and optionally methanol and/or its reactive derivatives, preferably methyl acetate, In pre- fered embodiments, derwvative stream 108 js in the vapor- phase. In PIG. 1, derivative stream 108 is fed to socondary eactor IIL, which preferably sa high pressure liquid pase carbonylation secondary reactor,