cu») United States ‘US 202201121508 2) Patent Application Publication co) Pub. No.: US 2022/0112150 Al RA, |AGOPALAN et al. (54)_A PROCESS FOR PRODUCIN HYDROGEN-LEAN SYNGAS FOR ACETIC ACID SYNTHESIS AND DIMETHYL ETHER SYNTHESIS, (1) Applicant: ENE S.p.A., Roma (IT) (72) Inventors: Vijayanand RAJAGOPALAN, ‘Bengaluru (IN): Atul PANT, Bengaluru (IN); Ravichander NARAYANASWAMY, Bengaluru (IN) (73) Assignee: ENT S.P.A, Roma (IT) (21) Appl. Nos 17426,508: (22) PCT Filed: Jan. 2, 2020 (43) Pub. Date: Apr. 14, 2022 (62) US.cL cre Ure 6739 (2013.01); COTE 291518 (2013.01); CO1B 3/386 2013.01): COIB 8/1647 (2013.01); COLB 2203/0261 (2013.01); Co1B 2203/06! (201301); COB 2203/1241 (2013.01); COIB 22030238 (201301) ABSTRACT A process for producing acetic acid includes: (a) reacting, via @ catalytic partial oxidation (CPO) reaetion, a CPO reactant mixture in a CPO reactor to preluce a hyd Jean syngas: wherein the hydrocarbons include equal fo oF 86) PCT No. osoni ye PETB MONS greater than about 3 mol % C2+ alkanes; wherein the § 371 XI) hydogen-ean synga inlaeshyogen, carbon mono (2) Date: "Ju. 28, 2021 carbon dioxide, and unreacted hydrocarbons: and wherein : the hydrogen-lean syngas is characterized by a hydrogen to bata teeta ht carbon monoxide (H2CO) mola ratio of frm about 07 to (60) Provisional application No, 62/797,591, filed on Jan. about 1.3. Also included is (b) feeding at last a portion of 28, 2019. te hydrogen-lean syngzs anc dimethyl ether (OME) 10 a a | DME earbonyltion unit to produee methyl acetate and a Publication Classification hnydrogen-cnriched syngas characterized by a 112/CO molar G1) Inch ratio of from about 1.8 10 about 22: and (6) feeding atleast C07 6739 2006.01) ‘portion ofthe methyl acetate and water to a methyl acetate C07 29151 (2006.01) fhydolysis reaction mane to preduce acetic seid and a metha- corn 438 00601), ol steam, rurpecasf- at a Neder! 1 thant Ome 40] Ses synbeis 50 tn Renn Zane e Hocenenes Be 2 s1~] Sires, = 5 i, comz Petnct 5 oo | 2 Sieam sent | Meare | ' ceyerocaaens 40 400)4 | ero cs Ea 35 [asc | 25m Cz. akares | Reador [Haven LP Tag | nee” Prem acee| Ge | Sins Seam Tae Hct | optima Tae (or c00045) Camper hes (GiycoUS 2022/0112150 AI Apr. 14, 2022 Sheet 1 of 9 Patent Application Publication (HOODEHO) . Piby 220 I Did 5 sossaidiwoy (fHD002%HD) OE tevondo TEER 00:2H weans sse6uhs am BIeROY AUTEN wun ST uea|-2H saueyie +23 yjows= uon2eay SISAOUpAH ayereoy |AMeW uonesAuoqie9 awa (20+ (9H) suoquesoipAy) eum quepeey wean jouezon Tz m09:H oo Ns sud ‘se6uhs ie %9 mua? nee peysuua- 4 ‘Buoz uoNreay SISBUUAS awa joueyia jouenan (ieee) 1 ~]se9 261ngUS 2022/0112150 AI Apr. 14, 2022 Sheet 2 of 9 Patent Application Publication oa 1 jeuondo nrmopty ot 3 (09 HOH. ‘se6uAs, Ss (er08H)_) ‘ontwot| — peg [STI weer? | sopeoy soumye +2 rouse 3a Wom ana eral 080 Tor (on) su0He301ph9) sopeey awa. ' aun A a fe eee Clee frcD 1 \ a eee ae ale Vw z00Patent Application Publication COjH2 in Syngas from CPO without CO2 injection === CH4/02=1.7, P=40 bar + CH4/O2=1.7, P=100 bar Apr. 14, 2022 Sheet 3 of 9 US 2022/0112150 AI 0.20: 700 800 900 1000 1100 1200 1300 1400 Reactor Temperature (°C) FIG. 3 1.10 1.00 0.90 0.80 0.70 0.60 Cort, 0.50 0.40 0.30 0.20 700 800 900 1000 1100 1200 1300 1400 Reactor Temperature (°C) FIG. 4Patent Application Publication Apr. 14,2022 Sheet 4 of 9 US 2022/0112150 Al COMM, €03/CO 700 800 900 1000 1100 1200 1300 1400 0.00 COjH2 in Syngas from CPO with CO injection (CO2/CH, Reactor Temperature (°C) FIG. 5 CO2/CO in Syngas from CPO without CO injection = CH4/02=1.7, P=40 bar -— CH4/02=1.7, P=100 bar 700 800 900 1000 1100 1200 1300 1400 Reactor Temperature (°C) FIG. 6Patent Application Publication Apr. 14,2022 Sheet Sof 9 US 2022/0112150 Al ‘CO2/CO in Syngas from CPO with CO» injection (CO2/CH. 900 1000 1100 1200 1300 1400 Reactor Temperature (°C) FIG. 7 H2/CO in Syngas from CPO as a function of COz/C (in legend) at 30 bar (02/C:0.55) 24 oogd 5 90.75 a 22 2 18 16 14 12 1 88 90 Conversion (%) FIG. 8Patent Application Publication Apr. 14, 2022 Sheet 6 of 9 US 2022/0112150 Al H2/CO in Syngas from CPO as a function of CO2/C (in legend) at 75 bar (02/C:0.55) Required CO2/C to get H2/CO = 1 reduces as pressure increases 24 o °. 224{ 00 Do 2 18 o Q 0 | 16 4 o Hg/CO 14be ay o 12 : co 08 80 82 84 86 38, 90 92 Conversion (%) Ha/CO in Syngas from CPO as a function of C3/C (in legend) at 75 bar (O2/C:0.55) and with CO2/C = 0.25 24: 2.2 Oo D002 A005 O01 7 Oma 6 18 GOA » eo Poa ¢ g 16 Ota e Fa OnAle onal 6 12) 1 08 80 85 90 95 100 Conversion (%) FIG. 10Patent Application Publication Apr. 14,2022 Sheet 7 of 9 US 2022/0112150 Al Hy/CO in Syngas from CPO as a function of C3/C (in legend) at 75 bar (O2/C:0.55) and without CO2 in feed 24 a 4 ca ° 2 22 o oF 4 2 oO 18 ©. Q ° 8 16 = 14 12 1 Oo Dos Ao O01 08 80 85 90 95 100 Conversion (%) FIG, 11 Hz/CO in Syngas from CPO as a function of C2/C (in legend) at 75 bar (O2/C:0.55) and with CO2/C = 0.25 24 2.2 2 oh}, —+ as o| ola | © Dy ola a fo 8 16 oO} = o jp A io oe o| ofa o 12 Oo Oo02 Ao $01 08 eB 8 8 8 87 8 89 90 Conversion (9%) FIG. 12Patent Appl H/CO H/CO in Syngas from CPO as a function of C2/C (in legend) at 75 bar (O2/C:0.55) ication Publication Apr. 14, 2022 Sheet 8 of 9 US 2022/0112150 AI and without CO, in feed 24 o q 22 o a 2 oe ota To 18 Oo) A—te 8 2 16 ee 14 12 1 Oo D002 A005 O01 08 %& 68 BCD Conversion (%) FIG. 13 in Syngas from CPO as a function of Ca/C (in legend) at 75 bar (Op/C:0.55) and with COp/C = 0.25 24 po] Oo Oo02 Ads 901 2 One ueen ° 18 a o 2 On OA S16 o x = ° 14 oj ja 12 1 os 88 90 92 94 96 Conversion (%) FIG. 14Patent Application Publication Apr. 14,2022 Sheet 9 of 9 US 2022/0112150 Al H/CO in Syngas from CPO as a function of C4/C (in legend) at 75 bar (O2/C:0.55) ‘and without CO; in feed 24 oO oa 2.2 Og o 2 o 18 16 14 12 H Oo Oo02 Ao O01 i go 9 92 93 94 «895 96 Conversion (%) FIG. 15US 2022/0112150 Al A PROCESS FOR PRODUCING HYDROGEN-LEAN SYNGAS FOR ACETIC ACID SYNTHESIS AND DIMETHYL ETHER ‘SYNTHESIS, ‘TECHNICAL FIELD. {0001} |The present disclosure relates to systems and meth- ‘ods for producing acetic acid and dimethyl ether (OME): tore spscifically the present disclosure cates to systems ‘and methods of producing acetic acid and DME from 3 hhydrogen-lean synthesis gas. wherein the hydrogen-lean synthesis gas is produced via catalytic partial oxidation (CPO): still more specifically, the present disclosure prelates to systems and methods for producing acetic acid and DME via CPO of a CPO redetant mixtare comprising hydrocar- bons and oxygen, wherein the hydrocarbons comprise greater than oF equal t9 about 3 mole percent (mol %) of higher hydrocarbons (e., alkanes comprising 2 or more carbons, C,,) BACKGROUND 0002} Synthesis ges (synges) iss mixture comprising ‘carbon monoxide (CO) and hydrogen (H), a well as small, amounts of carbon dioxide (CO,), water (HO), and unre- ‘acted methane (CH,). Syngas is generally used as an inter- mediate in a variety of synthesis processes, including, sith- ‘out Imitation, dimethy] ether (DME), alcohols, such as ‘methanol, ethanol, oxoaleohols (eg n-butanol et.) ethyl- ‘ene glycol, aldehydes, and the lke. Syngas is produced ‘conventionally by steam reforming of natural gas (steam methane reforming or SMR), although other hydrocarbon sources can he used for syngas production, such as refinery ‘off-gases, naphtha feedstocks, heavy hydrocarbons, coal, biomass, et. SMR is an endothermic process and requires sanificant energy inpat to dive the reaction forward. Con- ventional endothermic technologies such as SMR produce syngas with a H content greater than the required for @ variety of downstream chemical syntheses. In an autother- ‘mal reforming (ATR) process, portion ofthe natural gas is bumed as fuel io drive the conversion of maura gas to syngas resulting in relatively fow hydrogen and high COs ‘concentrations, Conventional combined reforming (CR) technology pairs SMR with autothermal reforming (ATR) 0 reduce the amount of I, present in syngas. ATR produces @ syngas with a lower hydrogen conteat. CR syngas generally has a 1, content greater than needed for many downstream synthesis processes. Furthermore, SMR is a highly endo- thermic process, and the endothemnicity of the SMR tech- nology requires buming fuel to drive the syngas synthesis. Consequently, SMR technology reduces the enerzy + Apr. 14, 2022 hydrocarbons). For example, in sion of hydrocarbons in the Cl ‘actant mixture § comprising greater than or equal to about 5.4,0r3 mol % Cz, alkanes is greater than the conversion ‘of hydrocarbons in’ CPO reactor in an otherwise similar process that produces a hydrogen-lean syges from a CPO ‘eaetant mixture § comprising less than about 5, 4, or 3 mol % C,, alkanes, respectively. [0089] In embodiments, no further adjustment of the H.ICO molar ratio of the hydrogen-lean syngas 18 38 pro- vided prio to dovsnstream synthesis of DME or acetic ac. That is, the herein disclosed CPO system and method can be utilized 10 produce a hydrogen-lean syngas 18 having & H,JCO molar ratio suitable for downstream production of acetic aid or DME (ean (CO molar ratio on the range of fom about 08 ro 1.6). Thus, in embodiments, a process fs disclosed herein exclndes a step ofa step of introducing at least a portion of the hydrogen-lean syngas 15 to a hydrogen recovery unit to decrease the amount of hydrogen in the hydrogenclean syngas 15. Thus, in embodiment, a process as disclosed herein does not comprise altering the HLJCO molae ratio of the hydrogen-Jean 15 between the CPO reactor 10 and the downstream synthesis apparatus ‘Thus, in embodiments, a chemical synthesis system as disclosed herein does not comprise apparatus (.., a hyeo- ‘gen removal unit, PSA) for altering the H1/CO molar ratio fof the hydrogen-lean syngas 15 between the CPO reactor 10 ‘and the downstream synthesis apparatus (e, either the facetic acid synthesis apparatos described hereinbelow with reference tothe embodiment of FIG, 1 or the DME synthesis appamites of the embodiment of FIG. 2). [0090] In embodiments, a process as disclosed here comprises no adjusting of the H/CO molar ratio of the hhydrogen-lean syngas 1 prior to the utilizing the hydrogen- Jean syngas 1$ in downstream chemical synthesis. Thus, in embodiments, a chemical synthesis system as dislosed herein comprises no apparatus for adjusting the FCO ‘molar ratio of the hydrogen-tean syngas 18 prior 10 the downstream acetic acid of DME synthesis reactor [0091] In emboxtiments, a process as disclosed herein does ‘ot comprise removing 2 hydrogen stan from the hydro- slen-lean syngas 15 prioe to utilizing the hydrogen-lean Syngas 1S in downstream acetic acid or DME synthesis. Thus, in embodiments, a chemical synthesis system as disclosed herein comprises no apparatus configured to remove 2 hydrogen stream from the hydrogen-lean syngas 15 beeen the CPO reactor 10 and the downsiream syn- thesis apparatus (eg, DME carbonylation unit 30 described hereinbelow with eference to the embodiment of FIG. 1 oF DME reactor 70 deseribed hereinbelow with reference tothe embodiment of FIG. 2) [0092] In embodiments, the CPO reactor 10 ean produce the hydrogen lean syngas #5 at high pressures (@., greater ‘than oF equal to about 20,25, 30, 35, 40, 45,50 ba) that are required for downstream chemical (e., acetic acid, DME) syntiesi, thus reducing the size of or eliminating the need Tor one oF more compressors 20 (0 compress the hydrogen- Jean syngas 15 prior to downstream chemical synthesis. Aecontingly, the herein disclosed systems and processes for producing acetic acid or DME via & hydrogen-lean syngas ‘oblained via CPO cin, in embodiments, fther reduce fenergy requirements for production of the acetic acid oF DMEUS 2022/0112150 Al [0093] In embodiments, the hydrogen-lean syngas 18 ca have a CO, content of less than about 10 mol %, ess than ‘bout 9 mol %, less than about 8 mol %, less than about 7 ‘mol %, alternatively less than about 6 mol %, alternatively Jess than about $ mol %, altematively less than about 4 mol 4%, altermatvely less thn about 3 mol %, alternatively less than about 2 mol %,altematively less than about 1 mol °%, altematively greater than about 0.1 mol %, alternatively jreater than about 0.25 mol °%, alternatively greater than bout O.$ mol %, atematively from about 0.1 mol % to about 7 mol % altematively from about 0.25 mol % to about 6 mol %, or alterively from about 0.$ mol % to about $ ‘mal %. For example, sie reactions could lead toa hydrogen Jean syngas 18 tht has a CO, content of less than about 7 ‘mol %, alternatively less than about 6 mol %, alternatively Jess thin about S mol %,allematvely fom about 0.1 mol % 'o about 7 mol %, alternatively from about 0.25 mol % 10 about 6 mol %, or altematively from about 0.5 mol % 10 about mol %. As noted hereinabove, the CO, concentration in the hydrogen-lean syngas 18 can be controlled via CO, injection (¢., via CO; stream 7) andor by changing the ‘operating conditions of CPO reactor 10 10094} The amount of CO, ia Heat syngas 18 can be ‘adjusted depending on the downstream application, Ia such applications, the amount of COs in Ha-lean synthesis gas 18 ‘can be adjusted as provided hereinabove, [0095] In embodiments, the hydrogen-lean syngas 18 can be subjected to processing, such asthe recovery of unreacted hydrocarbons, diluent, water, ete. In embodiments, water ‘ean be condensed and separated from the hydrogen-lean syngas 15, eg. in a condenser. As understood, such pro- ‘essing fo the removal of hydrocarbons dient, water, te will aot alter an Hy'CO molar ratio of the hydrogen-teaa syngas stream 15. In embodiments, a process as disclosed herein ean further comprise: () recovering atleast a portion ‘of the unreacted hydrocarbons from the hydrogen-Iean syn= pas 15 to yield recovered hydrocarbons, and (i) reeyeling at feast @ portion of the recovered hydrocarbons to the CPO reactor 10, As will be appreciated by one of skill in the at fand with the help of this disclosure, although fairly high ‘conversions ean be achieved in CPO processes (e. versions of greater than or equal 1 about 90%), the uncon- verted liydrocarbons could be recovered and recycled back to the CPO reactor 1, [0096] In embodiments, a process as disclosed her Junker comprises producing acetie acid or DME from at Jeast a portion ofthe hydrogen-lean syngas, as selectivity of DME and acetic acid is enhanced by syngas having un HCO molar ratio of about 1:1. The term “unit™ (for ‘example in DME earhonylaton “unit” or methanol synthesis, “uni) refers toa unit that can comprise separation equin= sent in addition to the reactor. For clarity. such separation ‘equipment is not depicted in FIG. 1 or 2. [0097] In embodiments, a process as disclosed herein further comprises producing acetic acid from at least 2 portion of the hydrogea-lean syngas 15. In embodiments, ‘ny system and method! for producing acetic acid from the hydrogen-lean synthesis gas 15 can be utilized downstream ‘of CPO reeetor 10,28 per tis disclosure, to produce acetic ‘acid, In embodiments, a process as disclosed herein com- prises producing acetie aid from at least portion of the hhydrogen-lean syngas 18 via intermediate methanol syathe- sis. When producing hydmgen-lean syngas 18 for down- stream aeetie acid production, the CO, concentration in the Apr. 14, 2022 Ihydrogen-lean syngas can be controlled (eg, by CO. injee- jn and/or changing the operating conditions of CPO reac tor 10) t provide small amount of CO, in the hydrogen- Jean syngas 18, as such CO, will inrease the formation of ‘methanol, which is an intermediate in acetic acid synthesis, thus inereasing the production of aectie acid. For example, small amounts of CO; may be desirable inthe hydrogen-lean syngas 15 when feeding a downstream DME reactor 70 (as described hereinbelow with reference tothe embodiment of FIG. 2), wherein small amounts of CO, inthe hydrogen-lean syngas 15 can be desirable t0 increase the production of methanol (which is an intermediate inthe aeete acid pro- duction) and thus enhance DME synthesis 0098] In embodiments, a process as disclosed herein ‘at least a portion ofthe hydrogen 418 and dimethyl ether (DME) 51 10. DME carbonslation unit 30 to produce methyl acetate 38 and hhydrogen-cnrichod syngas; and feeding at last a portion of methyl acetate 38 and Water 36 10a methyl acetate hydro- lysis reaction zone 36 to produce acetic acid 65 and a ‘methanol stream 45A. In embodiment, the hydrogen-en- riched syngas 31 comprises hydrogen, CO, CO., and unre- acted hydrocarbons, and is characterized by a H,/CO molar ratio of from about 14.1.5, 1.6,1.7, or 1.8 to about 18,19. 20,21, or 22, The DME §1 ean comprise DME SIA from ‘4 DME synthesis reaction aone 80 (described furlerhere- inhelow) and/or DME S1B from another source. 0099] Within DME carbonylation unit 30, DME $1 and CO trom hydrogen-lean syngas 18 are converted to methyl acetate. Any suitable earbonylation catalyst ean be wilized in DME carbonylation unit 30, aad DME earbonylation nuit 30 can be operated under any suitable DME carbonation reaction conditions known to those of sil ia the art. Tn other embodiments, methanol earhonylation to produce acetic acid occurs in a single step. [0100] In embodiments, the CPO reactor 10 is character- ied by a CPO pressure: the DME earbonylation unit 30 is characterized by a DME. earbonylation pressure: and the CPO pressure is about the same as the DME carbonation press. In alternative embodiments, the CPO reactor 10 is characterized by a CPO pressure, the DME earbonylation ‘unit 30 is characterized by a DME carbonylation pressure that js greater than the CPO pressure, and atleast a portion fof the hydrogen-lean syngas 15 is compressed in a com- pressor 20 t0 yield a compressed syngas 15° sueh that the ‘compressed syngas 15's characterized by a pressure that is bout the same as the DME carbonylation pressure prior 10 ‘eeding of least a portion of the compressed syngas 15 to the DME earbonylation unit 30 [0101] In embodiments, the size of compressor 20 is Smaller than the size ofa compressor used for compressing hhydtogen-lean syngas in an otherwise similar process that () employs a hydrogen recovery unit for producing a hydro- sen-lean syngas (i) produces a hydrogen-lean syngas from hydrocarbons comprising less than about 3 mol % C.+ alkanes; andor (ii) doos not produce the hydrogen-lean syngas by CPO. [0102] Methyl acetate hydrolysis reaction zone 36 can be fany reaction zone operable to produce acetic acid 68 and ‘methanol 454 from methyl acetate 98 and water 36, and ean be operated under any operating conditions suilable for hydrolyzing methyl acetate into methanol and acetic acid, [0103] In embodiments, a method of producing acetic acid ‘cording to this disclosure Turther comprises feeding atUS 2022/0112150 Al least a portion of the hydrogen-enriched syngas 31 to a methanol synthesis unit 40 to produce another (i.e. a “See- fond’) methanol stream 48B and a purge gas stream 41, Wherein the purge gus stream comprises hydrogen, CO. (CO,, and unreacted hydrocatbons, and wherein at least 8 portion of the purge gas stream 41 is optionally used as ful. Methanol syathesis unit 40 can comprise any suitable methanol synthesis reactor known in the art, ad can be ‘operated under reaction conditions known t those of skill in the ar. 10104] In embodiments, a process for producing acetic cid scconding to this disclosure further comprises: (1) feeding at least a portion of the (eg, frst) methanol stream 45, andior at least portion of the another (eg. second) ‘methanol stream 458 to 9 DME synthesis reaction zone 50 to produce a DME stream SI; and (2) fecding a last @ portion of the DME stream S1A (o the DME caebonylation tit 30. 10105] In embodiments, DME synthesis reaction zone 50 Js operable to preduce DME via dehydration of methanol. ln ‘embodiments, a common reactor comprises both the methyl acetate hydrolysis reaction zone 60 and the DME synthesis reaction zone 80, In embodinients, at least a portion of the ‘water produced in DME synthesis reaction zone 50 is Utilized as the water feed 36 to methyl acetate hydrolysis zone 60. In embodiments, methanol synthesis fom syngas 1 and dehydration of the methanol (48A andor 488) to produce DME occur in a single process unit. 10106] In embodiments, the amount of acetic acid 68 produced is greater than the amount of acetic aeil produced in an otherwise similar process that (?) employs a hydrogen i) recovery unit for peoddcing a hydrogen-lean syngas: produces a hydrogen-lean syngas from hydrocasbons cr prising les than about 3 mol % C, alkanes; audi (i) does rot produce the hydrogen-lean syagas by CPO. 10107] In embodiments, such as depicted in the emboxt ment of FIG. 2, a process as disclosed herein further ‘comprises producing DME from at least a portion of the hydrogen-lean syngas 18. In embodiments, a process as disclosed herein Iuther comprises feeding at less a portion ‘of the hydrogen-Jean syngas 18 to a dimethyl ether (DME) reactor 70 to prodice & DME reaetor eluent 75 comprising DME, methanol, water, and CO, [0108] The DME reactor 70 is characterized by a DME reactor pressure which can be the same or different from the (CPO reactor pressure, When the DME pressure is greater than the CPO presse, the method of prodcing DMB ean further comprise: (1) compressing at leat a portion of the hiydrogen-lean syngas 15 to yield a compressed syngas 15, wherein the pressure ofthe compressed syngas 18 i about the same asthe pressure of DME reactor 7% and (2) feeding atleast a portion ofthe compressed syngas 18°10 the DME. reactor 70 10109] DME reactor 70 can be any reactor known to be suitable forthe conversion of hydrogen-lean syngas 15 (ez. ‘compressed hydrogen-lean syngas 18) into a DME reaeto ‘eflluent comprising DME, water, methanol, and COs, and ‘ean be operated under any suitable eactor operating condi tions known inthe art. DME reactor 70 ea comprise two ‘catalyst system whereby both methanol synthesis and dehy ‘dation of methanol to produce DME occur therein. The method of producing DME according to embodiments of this disclosure can futher comprise separating at least 2 portion ofthe DME reactor eflluent 75 into a DME stream Apr. 14, 2022 82, « methanol steam 81, a water stream 83, and a CO; stream 7B, and optionally recycling at least a portion ofthe ‘methanol stream 81 10 the DME reactor 70, ado optior ally recycling atleast a portion ofthe CO, stream 7B to the CPO reactor 10, [0110] In embodiments, » process for producing DME according to this disclosure provides forthe production of an fmount of DME 82 tha is greater than the amount of DME produced in an otherwise similar process that (i) employ’ a 1H, recovery unt for producing a H,-lean syngas: (i) pro- dices a H-fean syngas from hydrocarbons comprising Tess than about 3 mol % C,, alkanes: andlor (il) does not produce the F,-lean syngas by CPO. [0111] In embodiments, a process as disclosed herein can advantageously display improvements in one or more pro- cess characteristics when compared to conventional pro- [0112] As will be appreciated by one of skill athe at, and ‘with the help of this disclosure, since the CPO reaction is exothermic, very litle heat supply in the form of fuel combustion is needed (eg, for pre-eating reactants in the reaction mixture § that is supplied to the CPO syngas ‘generation section), whon compared to conventional steam reforming. As such, the process for chemical synthesis liring CPO hydrogen-lean syngas as disclosed herein can advantageously generate Tess CO, through fuel burning, ‘when compared to steam reforming. [113] The use of CPO reactant mixtures comprising higher hydrocarbons andlor CO, as deseribed herein pro- vides a high selectivity and thus inereases the overall earbon cfiieney of acetic acid or DME synthesis relative 19 con- ventional processes, Becanse CPO ean be operated at higher pressures than conventional syngas syntheses (eg. dry reforming) utilized to produce hy drogen-lean syngas, enesyy requirements (eg, energy required for compressing of the hhydrogen-lean syngas prior to downstream acetic acid oF DME synthesis therefrom) can be reduced (or such com- pression eliminated) relative wo the coaventional processes [0114] The herein disclosed process for the synthesis of acetic acid provides for the production of a hydrogen- cntiched synthesis gxs 31 (eg. from DME carbonylation ‘unit 30) that can be utilized digecly forthe production of DME in DME synthesis reaction zone $0 without adjust- ‘meat of the H,/CO molar ratio. [0118] Additional advantages of the processes for the production methanol as disclosed herein can be apparent to fone oF skill in the art viewing this disclosure, Examples [0116] Theembodiments having been penerally described, the following examples are given as particular embodiments ofthe diselosure and to demonstrate the practice and advan- tages thereo. I is understood thatthe exasaples are given by \way'of illustration and are not intended to limit the speci Tication or the claims in any manaer [0117] Example 1A syngas process was simulated as an ‘equilibrium reactor in ASPEN. FIG. 3 is a plot of [0118] the mola ratio of COM, in syngas from CPO as 2 funetion of reaetor temperature without CO. injection in the reactant feed for CHO, molar ratios of 3.2 and 17, and pressures of 40 and 100 bar, which shows the CO/H, molar ratios which can be obtained in CPO subject to thermody- ‘amie constraints at different temperatures of CPO reactor 10, FIG. 4 is a plot of molar ratio of COMI in syngas foUS 2022/0112150 Al (CPO asa fanction of actor temperate with CO. inti fora reactant eed comprising a CO,JCH, solar ratio of OS (CHO, molar ratios of 2.2 and 17- and presses of 40 and 100" F1G. $54 plot ofthe COUH, it syngas from CPO 4 funeton of reactor temperature with CO, injection for ‘8 clan! fod comprising a COJCH, mole ratio of ‘CHO, molar ratio of 2.2 and 17, and presses of 40 and 100" [0119] As seen in FIG. 3, above 900° C. and at a low (C10, molarrato synthesis gas having HCO mole tatios Jes'than 2 cam be progueod. rom FIG, 4 and FIG. 8, itis apparent that injecting CO. in the reactant fed expands the ‘operability window of CPO to lower temperatures and higher CI1/O, molar ratios. As noted herein injection of CO, aso provides for an enhancement in carbon elicien§, bocce carbon inthe CO. is converted Wo additonal C AAs a result more CO will be produced per MMBTU of reactant foo (eq, natural zs) according embodiments of this disclosure. This additional CO can contribute oan increase in chemical product (eg. actic acid or DME) throgghpt atthe same fowrate of eacant feed (eg. natural fais) Av sce in FIGS. 35, the CPO reactor can proce the hydhogenclean syngas at high pressures fe, aeater than ot ‘equal to about 25,30, 38, 40,4, 50 bar) Hat are required fordownsieun chemical (eg, acetic aed, DME) synthesis, this alucing or eliminating the need for compression of the hydrogen-ean syngas 1 prior tothe downsteam synthesis ‘of acetic eid of DME. [0120]. FIG. 6s a plot of dae molar rato of CO, CO (COCO) in syngas from CPO as a Tanetion of reactor temperature witout CO; injection for reaetam feeds com- Prising a molaeraio of methane 0, (CH1y0.) 0f 2.2 oF 1.7 fan presires of 40 ar 100 ar. FIG. 7 isa plot of the molar fio of CO, to carbon (COCO) in syngas from CPO as function of reactor temperature with CO, injection for a reactant fed comprising a moar ratio of CO, to mebane (COsCH) of 05, CHO, molar raios of22 and 17, and pressures of 40 and 100 br [0121] FIG, 8 80 plot showing the molar ratio of CO v0 Iydogen (ILJCO) in syngas fom CPO as function of ‘conversion (2) and molar rato of CO, to carbon (COSC) reactant feed (in legend at pressure of 30 bar and Oto eon molar aio (04/0) of 055. FIG. 9 isa pot showing the molar aio of CO to hydogen (H/C) in sy fom (CPO as. function ofthe conversion (%) andthe mae raio ‘of CO, to carbon (COC in the recta feed (in legend) at ‘a presure of 75 bar and an O31C molar ratio of 0.55.8 ean bescen from FIGS, Wand, the molar tina COsCneeded to provide a H-lean CPO syngas hiving a /CO molar ratio of 1 is redaced as prosure increases 0122] FIG. 10s a plot showing the molar ratio of CO v0 hydrogen (HCO) in syngas fom CPO a fonction ofthe conversion (56) and the molar ratio of hydrocarbons having three carbons (C,) 1o carbon (C,/C) inthe reactant Feed in legend) at pressure of 75 ba, O, to carbon moka ratio (OC) of 055, and CO, wo carbon {CO.IC)asaar aio of (025, FIG. 1 isa plot showing the molar ratio of CO t0 hydrogen (HCO) in syngas fom CPO as a function ofthe conversion (2) and molar ratio of hydrocarbons having thre carbons (C,) to carbon (CC) in reactant fod (i Jegend) ata presture of 75 bar, O; to carbon molar ratio (OAC) of 035, and without CO, in reactant feed {0123} FIG. 12 sa pot showing the molar aio of CO wo hydrogen (HCO) in syngas fom CPO as function ofthe Apr. 14, 2022 conversion (6) and molae rato of hydrocarbons having two carbons (C, 10 carbon (CC) ia reactant fod (a legend) at 4 presse of 75 bar. an Op carbon molar ratio (OC) of (0.55 aad a CO, to carbon (COW) mola ratio of 0.28, FIG 13 isa plot the mola ratio of CO to hydogen (HCO) in syngas ftom CPO 8 faction of the conversion (%) and the molar ratio of hydrocarbons having two carbons (C.) to oct! feed (in legend) at peenure OF 75 bar an O, to carbon molar ratio (O/C) oF 055, and ‘without CO, in the reactant fed {0124} FIG. 14 isa plot showing the molar rato of CO v9 Iydeogen (11CO) in yogas from CPO as a function ofthe conversion (%) and the molar ratio of hydrocarbons having four carbons (C,) o carbon (C/C) in the reactant feed (in legend) at a pressure of 75 ba, an Oto eatbon mol ratio (OC) of 0.35, and a CO, 10 carbo (COC) molar rao of 025, FIG. 18 isa plot showing the molar ratio of CO to Iydogen (11JCO) in gas from CPO aso uneton ofthe conversion (5) and the molar ratio of hyrocartoas having four carbons (C,)o carbon (C/C) in the reactant feed (in legend) ata pressure of 78 bar an Ow carbon molar aio (OuiC) of 055, and without CO, i the reactant food {0125} As scea in FIGS. 19 though 18, using reactant nintures § comprising higher hydrocarbons (¢8% Cay Cy unr C,) allows 2 reduction ia the amount of CO, wiz {0 reach 3 molar rato of hydrogen to CO (H,/CO) of about 1, and enables production of hydroge-leansyagss having an HJCO mole ratio of about ata higher hydrocarbon conversion to syngas. {0126} While varius embodiments have ben shown and deseribed, moda thereof ean be made by one skilled inthe a without departing from the spin and teachings of the diselonure The embodiments described herein see exem- play only aod ane not intended to be lining Macy Yarations and modifications of the subject matter disclosed herein are possible and are within the scope of the disclo- sure. Where numerical ringes or linitations are expressly stated such express ranges oF Fimittions should be unde Stood 0 include iterative ranges or Tinstations of ike ‘agnitude falling within the expressly sated ranges oF Timitatons (eg, fom about 11 about 10 includes, 2,3, 4, te greater than 0.10 inchades 0.11, 0.12, 0.13, et). For example, whenever a numerial range with lower limit fun! an oper limit, Ry, is disclosed, any aumber fling Within the range is specially disclosed. In particular, the Following oumbers within the range are specially di closed: R-R, sk" (R,.R,), wherein kis a variable ranging {rom 1 percent w 100 pereat wih a percent ierement jie, kis 1 percent, 2 prcon, 3 porent, 4 percent, 5 percent, 50 percent, $1 percent, 52 perent, 95 pete, 96 percent, 97 percent, 9 percent 99 perent, o 100 percent Moreover, any nunerial range defined by to R aumbers as defined inte above is also specifically disclosed, Use of the erm “optionally” with expect to any element of csi is intended to mean tat the subject element is required, or tkematively, is not required. Bot altematves ae intend to bo within the scope ofthe claim, Use of broader tems Such os compass, includes, having et. should be under stood 0 provide support for narower tems such as con- Siting of consisting essetaly of comprised substantially ot, ee [0127] Accordingly, the seope of protection is not Himited by the description set ont owe but only limited by the aims which follow, that scope including all equivalents of