Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. TbeS) nadto,teccoeaearmxuei fhg xlso ik hc a eutdi n of 93% one of in selectivity resulted high has a which industry. risk, sustain petrochemical explosion to of high history 4.5% of the of is in first conversion mixture accidents namely, The devastating cyclohexane/air low most purpose, the 1). a the addition, (Scheme this by In hydrogenation for restricted phenol S1). processes is (iii) (Table prevailing, industrialized and hydration, though three cyclohexene safe, are process, from (ii) there far oxidation, is Currently, cyclohexane cyclohexanone/cyclohexanol (i) of atom-economic. production the or oleum for efficient, corrosive sulfate. processes industrial of ammonium unwanted existing use the of the However, generation avoiding the thus and tandem, acid in sulfuric and (AlPOs) aluminophosphates and nanoporous cyclohexanone metal-doped between gap the bridge in- greatly automotive and appliances, and goods consumer - electronics, overall the and crease electrical packaging, as such ε INTRODUCTION 1. hydrogenation esterification, acid, acetic cyclohexene, Cyclohexanol, Catalysis and Keywords Kinetics Engineering, Reaction on obtained 5. acetate are cyclohexyl heading: 99.7% Technical of of hydrogenation selectivity the high hand, and other 99.5% the of acid conversion On acetic catalyst. high with hydration. Cu/ZnO/SiO2 and cyclohexene cyclohexene La-promoted limited, of of the thermodynamically esterification higher that not the substantially than is for is lower cyclohexanol which (Ea) also to catalyst, energy 15 mol–1, activation Amberlyst kJ apparent commercial The 60.0 the ratio over is hydration. stoichiometric K cyclohexene 333–373 the of of at cyclohexanol. that range esterification to than temperature hydrogenation cyclohexene the by for in followed cyclohexene ?68% acetate, always of cyclohexyl is conversion to equilibrium acid determined acetic with for experimentally esterified intermediate The key is the benzene cyclohexanol, of hydrogenation of partial production the of for esterification–hydrogenation production cyclohexene the on based process novel A Abstract 2020 7, July 2 1 Baoning Zong cyclohexanol of efficient production and green for esterification–hydrogenation Cyclohexene a efcll ovre otefre ydhdoeain n h rnfraino ylhxnn to cyclohexanone of transformation latter the the and with dehydrogenation, by cyclohexanol, adipamide)). former and/or (poly(hexamethylene the cyclohexanone to to converted ε benzene facilely of be transformation can multiple-step a volves arlca spoetdt reach to projected is caprolactam ua University Fudan available not Affiliation - - caprolactam. arlca stemnmro yo- plcpoatm.Tehg eadars h industries, the across demand huge The (polycaprolactam). nylon-6 of monomer the is Caprolactam ε- 1 1 arlca,wsdvsdadvldtdfrtefis ie nti rcs,ccoeeeotie rmthe from obtained cyclohexene process, this In time. first the for validated and devised was caprolactam, h yunfeng zhu , ylhxnli loakypeusro dpcai,oeo h ooesfrnylon-66 for monomers the of one acid, adipic of precursor key a also is Cyclohexanol ε - arlca osmto ntenln6industry. nylon-6 the in consumption caprolactam 1 4 a liang gao , $ hmsadRj aesilul eeoe re n-tppoesto process one-step green a developed skillfully have Raja and Thomas 86blinb 2019. by billion 18.6 ε - arlca yuigrdxadai ie oeitn nthe on co-existing sites acid and redox using by caprolactam 1 e liangyou wen , 1 3 h nutilmnfcueof manufacture industrial The 1 agHao Wang , 5 6 1,2 h eodpoeswsdeveloped was process second The h siae aktvleof value market estimated The 1 n igu Qiao Minghua and , ε - arlca in- caprolactam 2 ε Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. P6mdu-rsue50m-aaiygasatcae ro oterato,10go mels 5were 15 Amberlyst of an g with 100 reaction, fitted the calorimeter to reaction Prior RC1 autoclave. TOLEDO glass METLER mL-capacity on 500 medium-pressure out MP06 carried were studies Thermodynamic study acid Thermodynamic acetic 2.2.1 with (A.R.), cyclohexene acid of acetic Esterification (A.R.), 2.2 cyclohexene Benzene, Gas. La(NO Haipu grade. Beijing and analytic 15 of Amberlyst Reagent. were chemicals the Cu(NO specified, not green If and efficient, safe, Chemicals a 2.1 in cyclohexanol the additive. of EXPERIMENTAL produce fuel shortcomings to 2. or the fuel promising and of highly solvent, devoid is antiseptic, manner. process processes of as and esterification–hydrogenation that used industrial limited cyclohexene than widely existing thermodynamically novel higher is not substantially the that is is ethanol Therefore, alcohol which yields that selectivity. to K, and simultaneously found ester conversion 333–373 We acetate of high of stoichiometric of hydrogenation cyclohexanol. range the usually the to temperature is at And, hydrogenated the esterification then hydration. in cyclohexene is cyclohexene [?]68% for latter always benzene conversion The is of equilibrium hydrogenation ratio acetate. determined partial the cyclohexyl experimentally from to the obtained acid cyclohexene cyclohexanol acetic process, of viable. with production this not the In for economically process is 2). esterification–hydrogenation (Scheme process cyclohexene novel this a developed, report we be Herein, can com- separation very catalyst and right high. is conditions very particular a reaction is in unless the requirement step between that energy mismatch hydrolysis and the the Furthermore, splitting, process, phase conditions. during latter reactions, multiple the reactions For to side due application. plex common practical from are process formation this olefin cyclohexanol. reactions. and produce limited formation rium to ether investigated process, widely former transesterification. been the esterification– cyclohexene for have including However, esterification–hydrolysis, processes, other 1) and above, demand. mentioned (Process transesterification energy processes 3.7% the industrial of three to order from up Aside the adds in greatly is (Process which and thermodynamics feedstocks, low in unreacted reactants or is the the 3) cyclohexanone/cyclohexanol and of of 1) 2) 1 yield much (Process (Processes (Process pass how selectivity 83.7% per in as of the either defined order 2), bottlenecks literature the is the and in of economy industrial because is atom However, the economy Trost, on atom product. to based overall cyclohexanone the benzene According The (including from in cyclohexanol starting S1. up of processes Table yield end three in pass these per compiled via of and data conversion process) economy first low atom the a overall for the at illustrates kept 1 be risk. Figure explosion must phenol. high oxidation to of hydroperoxide cumene is cumene oxidation, and of 25% cyclohexane cleavage and to hydroperoxide, analogous cumene Furthermore, to oxidation 298 cumene at propylene, ppm of (200 selectivity water selective, with cyclohexanol 12.7%. cyclohexene highly high of about gives miscibility only poor hydration is the hydration cyclohexene to due Albeit efficiency low 1980s. K of is late reaction the the in 99.3%, Chemical Asahi by 7 n 0 p t33Ksmltdb se ls.Mroe,teeulbimcneso fcyclohexene of conversion equilibrium the Moreover, Plus). Aspen by simulated K 393 at ppm 500 and 3 ) 2 [?]3H < 49 Poes3.I nuty h ylhxnlyedi mrvdb asvl circulating massively by improved is yield cyclohexanol the industry, In 3). (Process 14.9% 2 10 ,Zn(NO O, 13–15 h rdcino hnli opiae,wihivle h lyaino ezn with benzene of alkylation the involves which complicated, is phenol of production the 15,16 12 eie,lk seicto ecin,tasseicto ecin r yia,equilib- typical, are reactions transesterification reactions, esterification like Besides, een h ecatrfr obnee n h rdc eest cyclohexanol. to refers product the and benzene, to refers reactant the Herein, 3 ) hs rwak ral nraetecs fpoutsprto,tu inhibiting thus separation, product of cost the increase greatly drawbacks These 2 [?]6H 8,9 o h hr rcs,wiepeo yrgnto occoeao a be can cyclohexanol to hydrogenation phenol while process, third the For 2 3 ,Na O, ) 3 [?]6H 2 SiO 2 21 eeprhsdfo &.Tegsswr ucae from purchased were gases The J&K. from purchased were O 3 h diinlmrti httehdoeaino cyclohexyl of hydrogenation the that is merit additional The · 9H 2 ,adNO eeprhsdfo iohr Chemical Sinopharm from purchased were NaOH and O, 2 17,18 < ec,Fen n owresconcluded co-workers and Freund Hence, 55 Poes3) (Process 95.5% 19 < 93 Poes2). (Process 99.3% 20 sesterified is < 5.1% 11 Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. ,12,15 .5 n )wr rprdb h rcdrsdsrbdaoeecp o h mut fthe of amounts the for except above described procedures Cu the The by prepared used. were salts 2) zinc rate and and heating 1.75, copper a 1.5, with K 1.25, 623 times 1, at 10 calcined washed Cu and and h The the 24 filtrated during for were respectively formed K precipitates Cu 383 were were The as at precipitates silicate denoted dried The min h. was sodium K 12 cake in rpm. of 5 filter for beaker of 500 mol The a aged at into water. 2 were dropwise stirring deionized precipitates and added with mechanical the simultaneously nitrate, typical under were Then, zinc temperature a solutions of addition. The room In at mol water. deionized h 1 method. of 1 co-precipitation nitrate, mL 500 the copper in by of dissolved prepared mol were 1 catalysts synthesis, hydrogenation Cu/ZnO-based The twice. preparation least Catalyst at 2.3.1 repeated acetate were cyclohexyl studies of kinetic Hydrogenation and 2.3 thermodynamic the Both kg. in unit h taysaeatr1 nsra.Te,tepoutwssmldeey1 o tlattretimes, three least least at at for evaluated h were 12 catalysts every The sampled was chromatographically. product reactor gas the times the Then, into three duplicate. analyzed pumped stream. in was was on was sample acetate h catalyst each cyclohexyl 12 The and K, after 483 state sand. mL steady quartz of 12 h the with temperature to packed g size reaction were same 15 5.0 the approximately the bed at to of of catalyst down height sand the a quartz cooled of with with being sides cm diluted 1 catalyst Both H of as-prepared in reactor. the diameter activated the of inner g an in 10 and loaded fixed- testing, m stainless-steel was typical 1.2 a a with of In equipped length unit a cm. high-pressure with flow reactor continuous a tubular on bed conducted was test activity The preparation. the during testing nitrate Catalytic lanthanum 2.3.2 of mol 0.1 of addition the ester. follows: resulting g the as dimensionless. 60 represents calculated is rate C6E is while flow which cyclohexene, rate a represents reaction at C6 The which reactor in the state. into steady the pumped purged continuously reached further was has was was ratio reaction catalyst bed molar catalyst the prescribed the a in ( h reaction, with water the catalyst acid to of the acetic Prior content 316L of and sand. of the g quartz made until 1.0 with was N h Then, filled with cm was 24 10 method. space of for remaining Fischer length mm K The Karl and (0.1 depicted 378 the sand mm is at by quartz 4 set-up with dried determined of experimental diameter as was The inner 1% 15 the below Amberlyst reactor. with fixed-bed reactor steel. tubular plug-flow stainless The a on S1. Figure conducted in were studies kinetic The identical. were ratio. detection analyses gas acid/cyclohexene the successive study analyzed on two acetic and Kinetic based in sampled prescribed 2.2.2 judged liquid was with a was the liquid acid esterification the of with of acetic period, compositions autoclave equilibrium certain Karl and the the the a the that cyclohexene into for of N by and attainment temperature with determined pumped MPa, desired The MPa as were the 0.3 chromatographically. 0.6 1% to g to below to heated 200 pressurized was being pressurized was of catalyst After and autoclave weight the sealed the in total was water Then, catalyst a of the test. content containing tightness the autoclave until air The h 24 method. for Fischer K 378 at dried –1 ahsuywsls o – ,drn hc h ffletwssmldsvrltmst nueta the that ensure to times several sampled was effluent the which during h, 2–3 for last was study Each . 2 x t33Kt eoewtr fe en olddw oblwterato eprtr,cyclohexene temperature, reaction the below to down cooled being After water. remove to K 373 at Zn –1 –1 1 ihteH the with Si o 2h h eutn aaytpeusrwspleie,cuhd ivdt 05 ehs and meshes, 30–50 to sieved crushed, pelletized, was precursor catalyst resulting The h. 12 for 1 2 2 Zn aayt ( catalysts o 20m min mL (200 flow 1 Si 2 . F 2 etrmlrrtoo 0adasse rsueo P.Terato reached reaction The MPa. 5 of pressure system a and 30 of ratio molar /ester stettlmlrflwrt nmlh mol in rate flow molar total the is x < d ,05 .5 ,12,15 n )adCu and 2) and 1.5, 1.25, 1, 0.75, 0.5, 0, = p < –1 . m oaodtmeauernwywslae nterato zone. reaction the in loaded was runaway temperature avoid to mm) 0.8 n P)a 9 o 4ha apn aeo 0Kmin K 10 of rate ramping a at h 24 for K 493 at MPa) 3 and 1 Zn 1 Si 2 La 0.1 aaytwsas rprdi iia anrecp for except manner similar a in prepared also was catalyst 3 –1 And . W y Zn ersnstectls aswith mass catalyst the represents 2– x y ersnstemlrfraction, molar the represents Si 2 aayt ( catalysts d p < . m diluted mm) 0.5 y .,0.75, 0.5, = -1 After . 2 for Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. erae rdal o6.%a 7 .We h ctcai/ylhxn ai seeae o3 h cy- the 3, to elevated is ratio acid/cyclohexene which K, acetic 333 the at When 79.1% K. is At 373 conversion cyclohexene at expected. the as exothermic. 68.0% ratio 1, is to acid/cyclohexene acid of gradually acetic acetic ratio decreases the with acid/cyclohexene esterification increasing cyclohexene acetic cyclohexene when of stoichiometric improved in esterification the is the F-24 conversion ho- that Engelhard cyclohexene reflecting and than The temperature, clay, active the acid-treated more in F-24 was increase 15 Engelhard acid. Amberlyst acetic resin, that with genular found IR-120 Sharma Amberlite and used the frequently than most the active mogeneous of more one was is reactions. which 15 styrene, acid-catalyzed crosslinked in on resins acids. cata- based ion-exchange with acetic acid resin olefins solid polymeric different of Many macroreticular esterification at acidic catalyst. the H cyclohexene the for or to as used of (HSiW) acid 15 HPA been conversion Amberlyst silica-supported acetic as using equilibrium with such temperatures the lysts, cyclohexene and determined ratios of molar experimentally esterification acid/cyclohexene before, we of tackled lacking, reaction been are the not has of acetate parameters cyclohexyl thermodynamic acid the acetic Since with cyclohexene method of 3-window Esterification the and 3.1 Gatan mm, a 0.6 DISCUSSION was which AND aperture to RESULTS The incidence kV, GIF mode. 3. collection. EFTEM the 200 mapping the eV, at elemental under 10 during recorded was operated were slit applied microscope images filter was filter electron energy energy the G2 The of F20 width attached. was TECNAI spectrometer FEI 2001 an GIF on conducted were obiig hn 0m f4%o Fwsaddadsirdvgrul.Teslto a iue o200 to X-ray diluted powder was Pro solution X’Pert Philips The a vigorously. on stirred HNO acquired and wt% 2 was added 25 The pattern mA. was of XRD was K mL HF The catalyst Cu analysis. 20 of using the for to diffractometer 40% of water added of composition distilled was mL with bulk catalyst 20 mL The the Then, h. Elemental of Thermo 8 boiling. mg (ICP–AES; for to 200 spectroscopy K Exactly emission 343 Intrepid). plasma-atomic at coupled IRIS outgassed inductively was the by catalyst determined resin acid the rements, N acetate) techniques cyclohexyl Characterization of cyclohexyl 2.5 cyclohexyl of of moles moles moles reaction)/(initial reaction)/(initial after (initial cyclohexanol after of as (moles acetate) acetate as calculated calculated cyclohexyl was was cyclohexanol of to hydrogenation selectivity moles during reaction)/(initial – acetate after cyclohexyl acetate acetate of cyclohexyl conversion of The (moles as cyclohexene) of calculated moles cyclohexene) was reaction)/(initial of acetate after moles heating cyclohexyl cyclohexene the of to calculated was moles at selectivity esterification – during K The cyclohexene cyclohexene 473 of of conversion moles to the (initial results, raised as chromatographic was the of which basis K, the On x 333 min K at mm 5 set 0.2 of was x min rate column heating m K the 5 (50 of of column temperature chromatograph rate initial capillary gas The PONA K. 7890A HP min 523 Agilent an mL and 30 an were (FID) on air detector analyzed ionization were flame 0.5 a products with hydrogenation equipped and esterification The analysis Product 2.4 2 μ hssrto a odce t7 naMcoeiisTitr30 paau.Pirt h measu- the to Prior apparatus. 3000 Tristar Micromeritics a on K 77 at conducted was physisorption ) uigteaayi,teflwrt fteN the of rate flow the analysis, the During m). × θ 100%. p nlswr cne rm1 o70 to 10 from scanned were angles tleeslhncai aayt nccoeeeetrfiainwt omcacid. formic with esterification cyclohexene in catalysts acid sulphonic -toluene –1 13 n anandfr1 i.Teclm eprtr a ute asdt 1 ta at K 513 to raised further was temperature column The min. 15 for maintained and –1 spotdi iue2,teeulbimcneso fccoeeedcesswt the with decreases cyclohexene of conversion equilibrium the 2a, Figure in plotted As n 0 Lmin mL 400 and × –1 100%. α n anandfr5 min. 50 for maintained and aito ( radiation λ –1 .51 m.Tetb otg a 0k,adtecretws40 was current the and kV, 40 was voltage tube The nm). 0.15418 = epciey h eprtrso h netradFDwr both were FID and injector the of temperatures The respectively. , o 22 13 t10 at 3 PW npriua,Sh n hrarpre htAmberlyst that reported Sharma and Saha particular, In n h hroyai rpriso ylhxlacetate cyclohexyl of properties thermodynamic the and 2 22-24 are a a . Lmin mL 0.2 was gas carrier o 4 12 min O mels 5i omrilyaalbe strongly available, commercially a is 15 Amberlyst 40 -1 uftdzroi,adinecag eis have resins, ion-exchange and zirconia, sulfated , E hrceiainadeeetlmapping elemental and characterization TEM . –1 h o ae fH of rates flow The . 3 ouinadheated and solution 25 × Chakrabarti 0% The 100%. × 100%. 2 and Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. nraigtecnet fC hl xn h n imlrrtoa :2 h ovrino ylhxlacetate cyclohexyl of conversion the 2, 1: Cu at the the ratio over molar on Si maximum ratios Zn: a molar the reaching fixing Cu/Zn drastically, while the increased Cu and of contents Cu Cu the the increasing of over contents S3, Table the in of rized Cu/ZnO/SiO effects the of the performances catalytic examined systematically intramolecular/intermolecular undesired we products. considerable Firstly, to hydrogenation lead are the not of of that would isomerization capable catalysts and or nature is chromite dehydration in ZnO copper acidic conventional weakly background. the also industrial but replace significant which to environment. with Cu. purpose, the nanoparticles choice, reaction to this on hazardous Cu of a for based stabilizing catalysts for catalysts mostly and metal-based considered The are noble dispersing be of the alcohols, to best limited. than to factor cost-effective the is esters important more to hydrogenation of are explored conversion ester catalysts selective based been from highly not alcohols the also of allow has production cyclohexanol the Cu/ZnO/SiO to the allowing acetate developed we cyclohexyl knowledge, of our hydrogenation cyclohexanol the to hydration. Since acetate cyclohexene than cyclohexyl advantageous of more Hydrogenation kinetically 3.2 and ( thermodynamically both energy is activation acid apparent mol acetic kJ much the is 60.0 Moreover, derived cyclohexene is hydration. parameters of acid acid. constant reaction acetic acetic equilibrium the with adsorption of cyclohexene S2, the Table that active that Langmuir–Hinshelwood– same in show than the the using model compiled smaller on 3 kinetics As Figure factor acid LHHW-type in key acetic the model. data the to from reaction kinetics is respect the type of cyclohexene with sulfonic results (LHHW) cyclohexene of the fitting Hougen–Watson of adsorption with the adsorption the by tightly weak substantiated Hence, interact is The can sites bonding. reaction. acid hydrogen the acetic via limits rate that much 15 reaction that adsorbs considering Amberlyst cyclohexene the 15, on that Besides, Amberlyst plausible groups is temperature. on acid It reaction acid ratio. the acetic cyclohex- acid/cyclohexene in than acetic of K-increment the weaker have rate 10 in diffusion esterification increase a internal the the with and with affects doubles decreases external drastically general and of temperature in ratios effects reaction which The acid/cyclohexene The ene, acetic S1). S2). various (Figure (Figure at reactor eliminated esterification fixed-bed been cyclohexene a cyclohexene of on rates than temperatures reaction favorable reaction the more shows thermodynamically 3 Figure is acid acetic with cyclohexene hydration. of esterification that mol J the esterification that the noted derived: for be ln are parameters should between acetate thermodynamic relationship cyclohexyl following linear to the –42.8 acid good = line, acetic a the with obtained of we cyclohexene slope 2A, of and Figure intercept in the data From the 2B). of basis the On ( constant as: equilibrium expressed reaction be the can between relationship have the by-products investigated, ( These change enthalpy the catalyst. that acid Assuming hydration. the cyclohexene of in the to identified presence Nevertheless, slightly been the K. also 12.7% decreases in of which 373 cyclohexene conversion K, of the at than oligomerization/isomerization 343 85.1% higher at much hydration. to still 99.7% cyclohexene decreases is as of K which route 373 K, at the ratio 333 via stoichiometric at the at 93.5% conversion to cyclohexene amounts conversion clohexene –1 ± t33Kad73 mol J 7339 and K 333 at 26 . mol J 8.0 hrfr,teeeprmna eut usataeta h seicto fccoeeewith cyclohexene of esterification the that substantiate results experimental these Therefore, –1 K –1 Δ and , G o 0 27,31 Zn o hsrato sfrmr eaieta htfrccoeeehdain(365 hydration cyclohexene for that than negative more far is reaction this for Δ 1 G –1 Si SiO o Δ 2 t33K acltdb S50sfwr) nmiuul confirming unambiguously software), HSC5.0 by calculated K, 373 at 2808+42.8 + –22860.8 = aaytwtotC,tehdoeainrato i o cu.When occur. not did reaction hydrogenation the Cu, without catalyst H 2 8 a dpe stespot ic ti o nyal odses Cu, disperse to able only not is it since support, the as adopted was o nadto,teslciiyt ylhxlaeaermisa high as remains acetate cyclohexyl to selectivity the addition, In n nrp hne( change entropy and ) 2 –1 aayt ntehdoeaino ylhxlaeae ssumma- As acetate. cyclohexyl of hydrogenation the in catalysts hc slwrta the than lower is which , 7 2 < aayt o hsproe h ubro aaytsystems catalyst of number The purpose. this for catalysts 8 t33Kadaoeoigt h curneo the of occurrence the to owing above and K 363 at 98% 5 T 1 Zn mol J 1 Si 2 –1 Δ aayt aietn htC steactive the is Cu that manifesting catalyst, Δ S ntetmeauerneo 3–7 .It K. 333–373 of range temperature the in H o r osati h eprtr range temperature the in constant are ) o E –22860.8 = a K f7. Jmol kJ 71.2 of n h ecintemperature reaction the and ) E a fteetrfiainof esterification the of ) ± 27–29 854Jmol J 2825.4 K –1 eie,teCu- the Besides, n 1/ and o cyclohexene for 30 hc san is which T –1 (Figure , Δ S 27 o Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. hnei aaytt ombscatv ie n h mrvmn ftesraeae ftecatalyst. the of area textural surface the the as of such improvement aspects, the Cu several and the from sites Cu of originated active as properties basic be physicochemical (denoted form basic to Cu The to reported to catalyst relative been in have La Cu change oxide of the lanthanum fraction modified of molar situ effects 0.1 in adding ether. we by cyclohexyl selectivity, process and the cyclohexane, improve acetate, further h ethyl was 0.5 To H including of ratio MPa, by-products (WHSV) 5.0 Cu/Zn velocity acid-catalyzed K, space optimal 483 the hourly of of An weight conditions amounts and reaction 30, 1. identical of under ratio 1: 98.3% molar of sufficient there at selectivity no ratio, cyclohexanol occurred was highest Cu/Zn ratio the there low molar ratio, At Cu/Zn Cu/Zn shape. optimal CuZn–SiO high Cu/ZnO/SiO volcanic the an at for a thus while identified in hydrogenation, Cu, also evolved ester disperse acetate for to cyclohexyl centers Cu/ZnO/Al ZnO of active the conversion sufficient effect on the no similar observed 2, was A was cyclohexyl 2: activity of Cu. at hydrogenation conversion excessive ratio the the of acetate. on Cu, agglomeration ethyl Cu of of the hydrogenation of contents to content the attributed the increasing is of which further monotonically, When declined acetate hydrogenation. ester for center epciey hc a con o h ihcneso fccoey ctt hnicesn h WHSV the increasing when acetate cyclohexyl of conversion high Cu the the for on account may which respectively, Moreover, 4). Figure and S3 (Table conversion the on up effect h selectivity adverse 1.1 cyclohexanol to an 0.5 Cu the acid-catalyzed impose from improved the WHSV not which of the did acetate, occurrence increasing while the cyclohexyl suppressed 99.7%, of further hydrogenation to oxide lanthanum the of during basicity reactions the anticipated, As S4. rcs,weestelte smr hntieo hto h otecetpeo yrgnto process. hydrogenation phenol producing efficient in most manner. advantageous the green highly and of is efficient, that process safe, hydration esterification–hydrogenation of cyclohexene a cyclohexene selective twice in the most than cyclohexanol the that more of evident that is is as to and latter It process, comparable 99.4% esterification–hydrogenation the is of cyclohexene former whereas novel economy The the atom process, 1. Zn. for overall Figure of 34.6% the in of that demonstrated out pass as hand, also per figured preference other cyclohexanol we a of the above, such yield is On demonstrated show the Zn 5I. results not that experimental Figure does reveals the by and From 5F substantiated homogeneous SiO particles and additionally is on bright 5D La is randomly Figures the of distributed conclusion Figures than distribution with that This rather of the 5G conclusion Cu. overlapping Cu Figure with the to the of vicinity strongly to is Comparison in interacts 5I leads Cu. or Figure readily on from and 5F preferentially originated La, located Figure are and spectroscopic with 5D Zn, 5D Figure Cu, dispersive in Si, Figure of of microscopic-energy mappings Comparison EDS electron 5E–5H. corresponding transmission the are Cu scanning 5H the of the images present (STEM–EDS) XRD. 5D–5I from derived histogram Figures size distribution crystallite size particle the and with image well TEM agrees The Cu result. 2.08 XRD the of the of spacing with consistent interplanar is the which Cu with in identified, the fringes formula lattice for Scherrer Cu(111) the nm the by 14.8 calculated and Cu nm of 18.0 sizes are crystallite broadening The line dispersion. X-ray high of and/or terms loading Cu the low on its La to to relating phase 2 The at catalysts. peak ( broad Cu the metallic from aside that show Cu the of codn oTbeS,teseicsraeae ( area surface specific the S4, Table to According 1 Zn 1 Si 1 2 1 1 Zn La Zn Zn fcc 0.1 1 2 1 1 Si Si Si aayt netgtd h Cu the investigated, catalysts aayt(al S3). (Table catalyst 2 u CD 403)wr dnie,idctn htZOi nteaopossaeo both on state amorphous the in is ZnO that indicating identified, were 04-0836) JCPDS Cu, 2 2 La La aayt h R atrso h Cu the of patterns XRD The catalyst. 0.1 0.1 aayti iue5 hw htteaeaepril ieo ui 58n,which nm, 15.8 is Cu of size particle average the that shows 5C Figure in catalyst aayt h RE mg fteCu the of image HRTEM The catalyst. 32 1 2 Zn hnatrn h uZ oa ai hl xn h C n:S molar Si Zn): + (Cu the fixing while ratio molar Cu/Zn the altering When iealcctlssi h yrgnto fmty acetate. methyl of hydrogenation the in catalysts bimetallic 1 Si 2 –1 La i o hnesgicnl h ovrinadslciiyoe the over selectivity and conversion the significantly change not did θ 0.1 f˜25 of 1 aayt iue5 steHAFSE mg,Fgrs5E– Figures image, HAADF–STEM the is 5D Figure catalyst. 1 Zn Zn 1 1 Zn 1 o Si Si S 1 rmaoposSiO amorphous from 2 2 Si BET La aaytdslydtehgetcneso f9.%and 99.5% of conversion highest the displayed catalyst 6 2 0.1 La fteCu the of ) 1 aaytwsas o icre,wihi attributed is which discerned, not also was catalyst 0.1 Zn n Cu and 1 Si 1 1 Zn 2 ,wieteltiefigso n eenot were ZnO of fringes lattice the while A, ˚ Zn n Cu and 1 1 Si 1 –1 1 Si Zn Zn 2 1 satcptd hr eeol trace only were there anticipated, As . 2 La Zn 1 1 aaytdrn h co-precipitation the during catalyst 2 Si Si 0.1 1 nytedffato ek u to due peaks diffraction the only , 1 Zn 2 Si 2 1 aayti iue5 hw only shows 5B Figure in catalyst La Zn aayt r rsne nTable in presented are catalysts 2 1 Si 0.1 n Cu and 1 2 Si La aayti agrta that than larger is catalyst 2 La 0.1 0.1 aayt nFgr 5A Figure in catalysts 1 2 2 Zn infigta ZnO that signifying , O .Temodification The ). 3 1 Si aayt o the for catalysts 2 La 33 0.1 mn the Among catalysts, 2 /ester 34,35 Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. tde eie htccoeeeetrfiaini hroyaial n ieial oefvrbethan favorable more kinetically Cu and the thermodynamically And of is production esterification the hydration. for cyclohexene process cyclohexene intermediate esterification–hydrogenolysis that the cyclohexene verified cyclohexanol, novel studies of the production of the feasibility for selectivity the ethanol demonstrated the successfully addition, We In average. on span. 99.4% reaction always CONCLUSIONS whole of 4. is the selectivity acetate during the average cyclohexyl and on successive 99.8% of 99.5% always the of conversion is is conversion into the selectivity the fed that cyclohexanol to directly the shows rise was and 6B reactor 100%, no Figure to distillation with hydrogenation. close reactive stream for the on reactor h from 1000 fixed-bed produced than acetate more cyclohexyl for The smoothly proceeds reaction deactivation. the distillation of Moreover, reactive indication 6A). t/a the (Figure 8000 On to improved ˜99.0% of S4). further for of capacity (Figure is reactor conversion a SINOPEC fixed-bed cyclohexene Company, a with the Petrochemical with unit reactor, conjugation Baling demonstration in at esterification pilot-scale hydrogenation cyclohexene are a for ester reactor reactor established distillation distillation we reactive in reactive the presented Then, the in are using S3. profiles reactor Figure composition distillation scope and reactive in the temperature the illustrated of for corresponding out parameters the are esterifi- And operation which cyclohexene S5. optimized optimized, Table for The experimentally thermodynamic built work. further was present experimental were reactor the in above parameters distillation of rate operation reactive the the a reaction of which simulations, and on basis Plus conversion cation, Aspen the the and On data between disentangled. kinetic conflict and be reaction. im- intrinsic exothermic cannot limitation the the esterification thermodynamic reactor, for the cyclohexene rate fixed-bed reaction through or high breaking the reaction reactor of retaining this slurry-phase capable while transferred conversion is we the which esterification, on reactor, cyclohexene posed distillation of reactive characteristics a reaction onto the of account into Taking esterification–hydrogenation cyclohexene Pilot-scale 3.3 .Wisre ,Ap J nutilOgncCeity t d,WlyVH Weinheim, nylon? Wiley-VCH, to ed., way using acid 4th cleaner adipic to A cyclohexene Chemistry, of oxidation M. Organic Green liquid: Poliakoff ionic Industrial task-specific MM. R, the Hashemi HJ. of Mokaya M, function catalytic Vafaeezadeh Arpe Dual 4. K, 2. https://www.marketsandmarkets.com/PressReleases/caprolactam.asp. Weissermel 2003. 1. cited Literature China Natu- SINOPEC, the of (2012CB224800), Program China Development of Technology Program and Research (20872035), Basic China National (S411063). of the Foundation by Science supported ral was work This safe, a in benzene from ACKNOWLEDGMENTS nylon-6 of manufacture the for process manner. next-generation green a and not process of efficient, process Raja’s development and gap this Thomas the to the exhibits and Moreover, for cyclohexanone cyclohexene bridges also to elegantly of but hydrogenation work transformation unit. partial This one-step process, benzene of demonstration hydration process. of hydrogenation cyclohexene process pilot-scale phenol Asahi’s the the the a to between than on comparable efficiency economy catalytic term higher atom much long overall process a high esterification–hydrogenation shows in cyclohexene only The smoothly cyclohexanol. operated to was acetate cyclohexyl of hydrogenation 1 Zn 1 Si 2 La ε 0.1 - arlca,tu opeigtels ehooia puzzle technological last the completing thus caprolactam, aaytaoddhg ovrinadslciiyi the in selectivity and conversion high afforded catalyst 7 > > 9 uigmr hn10 nsra,giving stream, on h 1000 than more during 99% 92 ihhg eetvt occoey acetate cyclohexyl to selectivity high with 99.2% Nature. ε - arlca.Tebench-scale The caprolactam. 054714-24 3. 2005;437:1243-1244. 36 nconventional On Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. 6 eJ,HagJ,LnH,CoK,SaY iei-hroyai nlsso h eciedistillation reactive the of analysis catalyst. Kinetic-thermodynamic aeolite Y. the Sha using KT, hydration Cao cyclohexene HD, the Lin of JL, process Huang JC, in Ye cyclohexene 26. with acid catalysts. methacrylic as and resins + acid ion-exchange water acrylic reactors: + acid, 278. formic column cyclohexene of distillation + Esterification and cyclohexane MM. batch system Sharma ester. the B, cyclohexyl Saha for acid set 25. formic data + hetero- LLE acid in and formic determination VLE + mechanism K. cyclohexanol of Sundmacher challenge F, Steyer The 24. olefins: of 2015. esterification Raton, Direct Boca S. catalysis. Press, Fisher geneous CRC JC, Catalysis, Gee Acid alcohols 23. Solid to Y. esters of Ono Hydrogenation H, on M. Hattori nanoparticles Beller 22. K, Ru complexes. Junge BN. pincer A, Zong manganese Spannenberg B, defined HJ, by Jiao Sun M, catalyzed MH, Garbe Qiao S, Elangovan KN, Fan 21. Y, Pei SH, process Xie different cyclohexene. HZ, TiO to of P25 Bi Evaluation of RF, K. junction Dou Sundmacher rutile/anatase GB, RJ, Zhou Meier cyclohexanol. to C, 20. cyclohexene Fellay of RPM, hydration Guit indirect the H, for Freund concepts RA, process distillation Imam simulations. catalytic 19. novel process a complementary of and Development experiments K. plant Dev. Sundmacher Mini Res H, production: Freund cyclohexanol A, Katariya for and R, acid formic Kumar with 18. cyclohexene kinetics. of esters?Reaction esterification the via of production hydration Cyclohexanol K. subsequent Sundmacher F, Steyer and 17. acetate methyl of Transesterification 15. catalyzed J. berlyst heterogeneously Gmehling of E, Bo˙zek-Winkler kinetics 16. reaction and equilibrium Chemical esterification. H. acetate Hasse catalysts. M, as with Schmitt titanate acrylate tetrabutyl 15 cyclohexyl and resins of ion- Transesterification exchange by ion M. clay, catalysis Streat treated B, acetate: Saha cyclohexyl via 14. cyclohexene clay. from acid-treated Cyclohexanol and MM. resin Sharma exchange efficiency. A, synthetic Chakrabarti for search 13. economy?A atom The production. BM. phenol Trost - 12. processes catalyst. catalytic acid Industrial Pd–Lewis RJ. Schmidt supported treat- 11. alkali dual by a over performance cyclohexanone catalyst to 2009;326(5957):1250-1252. Improved hydrogenation ZSM-5: phenol zeolite Selective over cyclohexene of ment. Hydration zeolites. approach. SH. with simulation Wang cyclohexene explosion an of catalysts. - process acid revisited solid Flixborough with KA. clohexene Malo T, Mater. Solberg Hazardous BH, Hjertager S, Høiset of production H 30% ec ie ehCatal. Mech Kinet React 2 O 2 2011;15(3):527-539. . hmEgJ. Eng Chem n n hmRes. Chem Eng Ind ε - Catal. J arlca peusro nylon-6). of (precursor caprolactam 007(-)19 .ZagH aaaiS,Sam M rda .Hdaino cy- of Hydration T. Sridhar MM, Sharma SM, Mahajani H, Zhang 7. 2000;77(1-3):1-9. Catal. J n n hmRes. Chem Eng Ind 2015;332:119-126. 03212427 .Toa M aaR eino gen n-tpcatalytic one-step “green” a of Design R. Raja JM, Thomas 5. 2013;221:254-257. 2015;331:13-24. 2006;45(20):6648-6654. 06192:7-8.1.LuH,JagT a X in G huYX. Zhou SG, Liang BX, Han T, Jiang HZ, Liu 10. 2016;119(2):671-683. 2 otolddpsto n yeg nprilhdoeaino benzene of hydrogenation partial in synergy and deposition Controlled : hmEgSci. Eng Chem ec Polym. React aa uvJpn. Surv Catal 2006;45(12):4123-4132. ne hmItEd. Int Chem Angew 025()3532 .Ihd .Lqi-hs hydration Liquid-phase H. Ishida 8. 2002;57(3):315-322. 921() 107-115. 1992;18(2): 8 n n hmRes. Chem Eng Ind rcNt cd Sci. Acad. Natl Proc 9712126 .Mn J agY,Wn SG, Wang YQ, Wang FJ, Meng 9. 1997;1:241-246. hmEgData. Eng Chem J hnJCe Eng. Chem J Chin r rcs e Dev. Res Process Org Science. plCtlA. Catal Appl n ec uc Polym. Funct React btnlad2ehleao:acid- 2-ethylhexanol: and -butanol 2016;55(49):15364-15368. ec uc Polym. Funct React 2007;46(4):1099-1104. 91 254(5037):1471-1477. 1991; 05123)172176 6. 2005;102(39):13732-13736. n 2005;50(4):1277-1282. btnlctlzdb Am- by catalyzed -butanol 2005;280(1):89-103. 2011;19(5):808-814. 2013;17(3):343-358. 1999;40(1):13–27. 1996;28(3):263- r Process Org n Science. -hexyl J Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. aiu ecintmeaue.Tecre r iuae yteLH-yekntc model. kinetics Cu LHHW-type 4 the by simulated FIGURE are curves The temperatures. reaction various ln of plot 3 a FIGURE (B) and esterification, cyclohexene in conversion benzene. from 2 process esterification–hydrogenation FIGURE cyclohexene novel the and processes industrial current the 1 FIGURE distillation. CAPTIONS reactive FIGURE Ni-La Modelling anti-coking R. and Krishna methane. R, dispersed Taylor of highly 36. reforming A dioxide S. carbon Kawi dry from KKM, production Cu/SiO Leong LY, glycol. oxide-modified Mo ethylene Lanthanum 35. to YZ. oxalate Yuan dimethyl XP, of Duan hydrogenation JW, 2013;3(12):2738-2749. chemoselective Zheng ethanol. for HQ, CuZn–SiO catalyst to Lin effective performance acetate XL, An methyl XB. Zheng of Ma 34. hydrogenation SP, the Wang for JH, method Zhou Res. alcohol. precipitation Chem Y, to Wang hydrolysis acetate B, by ethyl Shan prepared of YJ, hydrogenation Zhao for 33. catalyst Cu–Al promoted Zn structural L. of Chem. investigations Shi general situ YM, A In Zhu JM. BS. 32. Clausen Basset of H, Y, Topsøe hydrogenolysis catalysts. NY, efficient Cu/ZnO Saih Topsøe for in MN, AM, catalysts changes Molenbroek Hedhili Ir) JD, and DH, Grunwaldt Rh Anjum 31. syngas Ru, SS, via = (M ethanol Sangaru M–Sn of M, bimetallic Synthesis Harb of XB. ester. synthesis Ma HB, the SP, Zhu Wang for J, AK, approach Lv Samal L, Zhao 30. S, Zhao Cu/SiO YJ, of KN. Zhao Cu/SiO Fan hydrogenation HR, on Yue HL, in JL, Xu performance Gong W, catalytic Shen 29. and HX, glycol. structure, Li ethylene Texture, SR, to Yan oxalate method: MH, dimethyl Qiao ammonia-evaporation PJ, the alcohols. Guo by to LF, esters Chen of hydrogenolysis 28. catalytic The NW. Cant DL, 1994;36(4):645-683. Trimm T, Turek 27. pnigESmpig f()S,()C,()Z,()L,ad()teoelpigo hs lmnso the of elements these of overlapping the (I) and corre- La, the (H) and Zn, image (G) HAADF–STEM Cu, the (F) (D) Si, histogram, (E) Cu distribution of size mappings particle EDS and sponding image TEM the (C) 5 FIGURE h eetvte occoeao n tao ntehdoeaino ylhxlaeaeo h pilot-scale and the acetate on cyclohexyl acetate of cyclohexyl conversion of the hydrogenation of the evolutions in long-term ethanol of the top and the (B) cyclohexanol at and reactor. to feed kg, acid distillation selectivities acetic 2.65 reactive the pressure, pilot-scale of ambient h the at loading kg reflux on catalyst 2.59 total acid at W, acetic 1050 column of with the duty cyclohexene reboiler of conditions: esterification Reaction the in acetate 6 FIGURE 1 1 Zn Zn aa c Technol. Sci Catal 1 1 2014;20(4):2341-2347. Si Si 2 2 La La 2 2018;57(13):526-4534. aayt ihblne Cu balanced with catalysts A h R atrso h Cu the of patterns XRD The (A) 0.1 0.1 A h ogtr vltoso h ovrino ylhxn n h eetvt ocyclohexyl to selectivity the and cyclohexene of conversion the of evolutions long-term The (A) nuneo h ctcai/ylhxn oa ai nteetrfiainrt fccoeeeat cyclohexene of rate esterification the on ratio molar acid/cyclohexene acetic the of Influence oprsno h vrl tmeooyadprps il fccoeao/ylhxnn of cyclohexanol/cyclohexanone of yield pass per and economy atom overall the of Comparison A ffcso ecintmeaueadaei cdccoeeemlrrtoo cyclohexene on ratio molar acid/cyclohexene acetic and temperature reaction of Effects (A) catalyst. catalyst. h hoaormo h yrgnto rdcso ylhxlaeaeoe the over acetate cyclohexyl of products hydrogenation the of chromatogram The –1 2017;7(3):581-586. ylhxn eda h ideo h aayi eto t35 gh kg 3.54 at section catalytic the of middle the at feed cyclohexene , Catal. J Catal. J 2000;194(2):452-460. 0 -Cu + 2008;257:172-180. 1 Zn sites. 1 Si 2 mCe Soc. Chem Am J 9 n Cu and hmEgSci. Eng Chem aa c Technol. Sci Catal K 1 Zn gis 1/ against 1 Si 2 La 2012;134(34):13922-13925. 0.1 2000;55(22):5183-5229. T aayt,()teHTMimage, HRTEM the (B) catalysts, . 2 2014;4(7):2107-2114. O 3 /SiO 2 2 2 aa e-c Eng. Rev-Sci Catal aaytfrsyngas for catalyst iealccatalyst bimetallic aayt prepared catalysts –1 2 C Catal. ACS n total and , sahigh- a as n Eng Ind J n Eng Ind Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. IUE2 FIGURE 1 FIGURE H MPa, 6.2 of pressure K, 473 of temperature conditions: min Reaction reactor. fixed-bed –1 ylhxlaeaefe aeo 7 h g 870 of rate feed acetate cyclohexyl , –1 n aaytlaigo . kg. 1.0 of loading catalyst and , 10 2 o aeo 0 L 100 of rate flow Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. IUE3 FIGURE 11 Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. IUE5 FIGURE 4 FIGURE 12 Posted on Authorea 7 Jul 2020 — The copyright holder is the author/funder. All rights reserved. No reuse without permission. — https://doi.org/10.22541/au.159415187.76445216 — This a preprint and has not been peer reviewed. Data may be preliminary. trigfo benzene. from starting 2 SCHEME hydrogenation. phenol (3) and hydration, cyclohexene (2) oxidation, cyclohexane (1) benzene: from ing 1 SCHEME 6 FIGURE h oe ylhxn seicto–yrgnto rcs o h rdcino cyclohexanol of production the for process esterification–hydrogenation cyclohexene novel The he yia nutilzdpoessfrtepouto fccoeao/ylhxnn start- cyclohexanol/cyclohexanone of production the for processes industrialized typical Three 13