Maitiro eCumene ndiwo anotonga kugadzirwa kwePhenol-Acetone pasi rose, asi maitiro ayo akaomarara uye matanho ekunyungudutsa anoda kutariswa kwakanyatsojeka panguva chaiyo. Kuyerwa kwehuwandu hwemvura hakugone kutaurwa pano: kunotevera ipapo ipapo kuumbwa kwemvura muchikamu chekupatsanurwa kwemafuta, kucheneswa kweacetone, uye matanho ekuchenesa phenol, zvichiita kuti zvionekwe nekukurumidza kuchinja kwetsvina kana kusagadzikana kwemaitiro. Ruzivo urwu runotungamira zvakananga kugadziriswa kwemaparameter ekunyungudutsa, runoita kuti kuchena kwechigadzirwa kusvike pazvinodiwa nemaindasitiri, uye runoderedza njodzi dzekuchengetedza senge tower coking kana kusagadzikana kwehydroperoxide kuora - kuzadza mukaha uyo usingakwanise kugadzirisa kunze kwesampuru, nekunonoka kwayo uye njodzi dzekudonha,.
Pfupiso yeMaitiro eCumene ekugadzira Phenol neAcetone
Maitiro ekugadzira cumene, anozivikanwa seHock process, ndiyo nzira huru yeindasitiri yekugadzira phenol neacetone kubva kubenzene nepropylene. Ine matanho matatu makuru: alkylation yebenzene kuti igadzire cumene, oxidation yecumene kuita cumene hydroperoxide, uye acid-catalyzed decomposition yeiyi hydroperoxide kuti ibudise phenol neacetone.
Pakutanga, benzene inopindirana nepropylene mumamiriro ezvinhu ane acidic—kazhinji inoshandisa ma catalysts emazuva ano e zeolite—kuumba cumene. Kusarudza kwakakosha padanho rino; ma process parameter akadai setembiricha uye benzene-to-propylene ratios zvinodzorwa zvakasimba kuti zvidzivise polyalkylation isingadiwe. Kusarudza kwakanyanya kwema catalysts emazuva ano kunoderedza marara uye kuderedza kukanganisa kwezvakatipoteredza, chinhu chikuru chaunofanira kufunga nezvacho mumamiriro ekunze emazuva ano.
Chirimwa cheCumene
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Kuoxidation kwecumene kunoitwa nemhepo, zvichigadzira cumene hydroperoxide kuburikidza ne radical chain reaction. Iyi intermediate ndiyo inonyanya kukosha mukuita asi inounza njodzi huru dzekushanda. Cumene hydroperoxide inogona kuora zvakanyanya uye inogona kuputika pasi pekudzora tembiricha isingakoshi, nokudaro ichida dziviriro yakasimba yeinjiniya munzvimbo dzese dzekuchengetera nedzekuita.
Hydroperoxide inobva yatanga kupatsanurwa neacid-catalyzed cleavage—inowanzo shandiswa nesulfuric acid—zvichikonzera kugadzirwa kwephenol neacetone panguva imwe chete muhuwandu hwe1:1 molar. Huremu uhwu hunotsanangura kudyidzana kwehupfumi hwemaitiro aya, sezvo kuchinja-chinja mukudiwa kana mutengo wemusika wechimwe chigadzirwa kunokanganisa kugona kwechimwe. Phenol neacetone zvinogadzirwa pamwe chete mumamiriyoni ematani pagore, uye maitiro ecumene anosvika 95% yekugadzirwa kwephenol pasi rose kusvika muna 2023. Zvigadzirwa, zvakaita sealpha-methylstyrene, zvinodzokororwazve muhurongwa, zvichiwedzera kushanda zvakanaka kwezvinhu.
Kusarudzwa kwecumene hydroperoxide senzira huru yepakati kunobatanidza makemikari ekushanda uye zvivakwa. Kuora kwayo kwakadzorwa kwakakosha pakubudirira kukuru uye kuvimbika kwemaitiro. Hydroperoxide decomposition catalysts uye optimized reactor design zvakawedzera mwero wekushandura uku zvichidzvinyirira njodzi dzemigumisiro. Kushanda kwemakoramu ekugadzira crude distillation nemayuniti ekuchenesa acetone kunoratidzawo hunyanzvi hwemaindasitiri ekugadzira distillation akabatanidzwa pasi pe primary reaction loop. Kupatsanurwa uku kunotongwa nekugadzirwa kwakasimba kwemakoramu ekugadzira distillation uye nzira dzekushanda dzekutsigira maitiro ekuchenesa ketone anoenderana nemitemo yemhando yechigadzirwa.
Maitiro eCumene ane matambudziko akati wandei ekushanda uye ekuchengetedza akasiyana nemakemikari ayo. Pakati peaya pane manejimendi chaiwo ekugadzirisa maitiro akasimba, kudzivirira kuunganidzwa kwehydroperoxide, uye kudzora kuburitswa kwemhepo inobvira kana ine chepfu mukati memiganhu yezvakatipoteredza inoenderana. Kuiswa kwemaindasitiri kunoda ma reactors akasarudzika, kutarisa kwepamusoro, uye masisitimu ekukurumidzira nekuda kwehunhu hune njodzi hwecumene hydroperoxide uye kupisa kwakanyanya kwenzira dzekushanda. Kunyangwe nemaitiro emazuva ano ekuwedzera uye kudzora, ruzivo rwenjodzi runoda kutariswa nguva dzose, kudzidziswa kwevashandisi, uye ongororo yakakwana yekuchengetedzwa kwemaitiro.
Pasinei nekutsvagurudza kuri kuitwa pamusoro penzira dzekugadzira dzimwe phenol, kugona kwenzira yecumene kugadzira phenol neacetone zvine purity yakakwira pamwe chete nehurongwa hwakabatanidzwa hwekuchenesa nekudzorera hunoita kuti ive muenzaniso wakanaka muindasitiri. Kubatana kwayo mumusika, chemistry, uye process engineering ndiko kuri kuumba musika wepasi rose wephenol neacetone kusvika nhasi.
Maitiro uye Kudzora Kuora kweCumene Hydroperoxide
Kuora Kwekupisa Kinetics uye Nzira
Cumene hydroperoxide (CHP) ndiyo inonyanya kukosha mukugadzirwa kwe phenol-acetone. Kuora kwayo kunotsigira kushandurwa kwe cumene kuita phenol ne acetone, makemikari maviri eindasitiri anodiwa zvikuru. Kuora kunotanga nekuparadzaniswa kwe homolytic kwe O–O bond mu CHP, zvichigadzira cumyloxy radicals. Aya ma radicals anokurumidza kupinda mu β-scission, achigadzira acetone ne phenol, izvo zvinotarisirwa kuitwa mukugadzirwa kwe cumene.
Maitiro ekuita reaction akaomarara uye anosiyana nemaitiro ari nyore ekutanga. Differential scanning calorimetry (DSC) uye integral kinetic models (Flynn-Wall-Ozawa naKissinger-Akahira-Sunose) zvinoratidza avhareji yesimba rekuita activation re ~122 kJ/mol, ne reaction order iri pedyo ne 0.5, zvichiratidza maitiro akasiyana-siyana. Nzira iyi inosanganisira chain reactions inosanganisira cumyl peroxy uye cumyloxy radicals, izvo zvinogona kuita activist kuti zvigadzire byproducts dzakadai se acetophenone, α-methylstyrene, uye methane.
Mamiriro ekushanda, anosanganisira tembiricha, kumanikidzwa, uye huwandu hweCHP, zvinoumba zvakanyanya kusarudza uye goho mukugadzirwa kweacetone nephenol. Kupisa kwakanyanya kunowedzera kutanga kwe radical, zvichiwedzera mwero wekuchinja kwese asi zvingangoderedza kusarudza nekukurudzira makwikwi emakwikwi. Kusiyana neizvi, kumanikidzwa kuri pakati nepakati uye huwandu hwakanaka hweCHP zvinokurudzira kuumbwa kwephenol neacetone uku zvichideredza kugadzirwa kwezvigadzirwa. Kuwedzerwa kwemaitiro—kushandisa kudzora kupisa kwakaringana—kunoramba kuri chikamu chakakosha chekugadzirwa kwephenol neacetone kwakachengeteka, kunobereka goho guru, nekutarisa kwenguva chaiyo kuburikidza ne inline density metres, senge idzo dzakagadzirwa neLonnmeter, zvichipa mhinduro yakavimbika yemaitiro mukati memaitiro ekugadzira ecumene.
Zvinokonzera uye Kugadzikana kweMakemikari
Kuora kweCatalytic kunogadzira kushanda zvakanaka uye kuchengetedzeka kwemaitiro ecumene. Zvinhu zvinokonzeresa kuodzwa kwechinhu zvakaita sesodium hydroxide (NaOH) zvinoderedza zvakanyanya tembiricha yekutanga kuora uye simba reCHP, zvichikonzera kushanduka nekukurumidza asiwo kuwedzera njodzi yekuchinja kwechinhu. Zvinhu zvine acid, zvinosanganisira sulfuric acid (H₂SO₄), zvinokurumidzisawo kuora, kunyangwe nenzira dzakasiyana dzemakanika, zvichiwanzo shandura hupenyu hwenguva refu uye zvichikanganisa musanganiswa wechigadzirwa uye kuwanda kwechigadzirwa.
Kusarudzwa kwe catalyst kunokanganisa zvakananga mwero wekushandurwa, kudzikiswa kwezvigadzirwa zve byproducts, uye kuchengetedzeka kwekushanda. Pakugadzirwa kwe phenol ne acetone, huwandu hwakadzorwa hweNaOH hunowanzo shandiswa mumaindasitiri, sezvo huchinyatso kurudzira kuparara kweCHP uye hunoita kuti zvigadzirwa zvinodiwa zvisarudzwe zvakanyanya. Zvisinei, catalyst yakawandisa inogona kukurudzira kupararira kwecheni kusingadzoreki, zvichiwedzera njodzi yekupisa uye kuumbwa kwezvigadzirwa zve byproduct zvine njodzi, zvakaita se α-methylstyrene ne acetophenone. Kuyera catalyst kwakachengeteka uye kwakarongeka, pamwe chete nekuongorora kwakarurama kwemaitiro, saka zvakakosha mukuora kwe cumene hydroperoxide.
Kutarisira Kuchengetedzeka Mukuora
CHP haina kugadzikana pakupisa uye ine njodzi huru panguva yekubata nekuora. Izvi zvinosanganisira mukana wayo wekukurumidza kuita exothermic reactions, mukana wekuti iite catalytic runaway, uye kukanganiswa nekusvibiswa nenzvimbo dzinopisa dzemunzvimbo. Kana CHP ikasadzorwa, kuora kweCHP kunogona kukonzera kuunganidzwa kwedzvinyiriro, kuputika kwemidziyo, uye kuburitsa utsi hune njodzi.
Kuchengetedza kugadzikana kwehurongwa kunoshandisa nzira dzakasiyana-siyana dzakakosha. Zvishandiso zvekutarisa zviri mukati, zvakaita seLonnmeter inline density metres, zvinopa ruzivo rwechokwadi nezvema profiles e concentration uye process temperature state, zvichiita kuti pave nekuona mamiriro asina kujairika panguva yakakodzera. Maitiro akavharwa anoderedza kusvibiswa uye kusvibiswa. Kudzora tembiricha yekuchengetera CHP, kushandisa mhepo isina kusimba (senge nitrogen), uye kudzivirira catalyst overdose kunoderedza mukana wekuti zvinhu zvisaitike. Kuongororwa kweCalorimetric predictive (kushandisa adiabatic calorimetry) kunoshandiswa zvakanyanya kufungidzira kutanga kwekuora pasi pemamiriro ezvinhu chaiwo uye kugadzirisa maitiro e emergency.
Kugadzira maitiro kunosanganisira masisitimu ekuparadzanisa uye ekuburitsa mweya kuti atarisire kukwira kwesimba, nepo zvinhu zvinodzora tembiricha uye zvinovhara zvinoderedza mukana wekupisa zvakanyanya. Maitiro ekuora anowanzoitwa pasi pekuyerera kunodzorwa, mukati memareactor akagadzirirwa kubvisa kupisa nekukurumidza. Matanho aya anovimbisa kuti kuora kweCHP pakupisa—kwakakosha pakugadzirwa kweacetone nephenol—kunoramba kuri kushanda zvakanaka uye kwakachengeteka mukati mehurongwa hwecumene.
Kugadzirisa Maitiro muCumene Magadzirirwo Ekugadzira
Kuvandudza Goho uye Kushanda Nesimba Zvakanaka
Kubatanidzwa kwekupisa inzira huru mukugadzirwa kwecumene yekuwedzera kushanda zvakanaka kwekupisa. Nekudzoreredza uye kushandisazve simba rekupisa kubva munzizi dzinopisa zvakanyanya, zvirimwa zvinogona kupisa zvekudya, kuderedza kushandiswa kwekunze, uye kuderedza mari yekushandisa. Nzira dzinonyanya kushanda dzekubatanidza kupisa dzinowanzo sanganisira dhizaini nekugadzirisa manetwork eheat exchanger (HENs), achitungamirirwa nekuongorora kwepinch kuti arongedze macurve anopisa neanotonhora ecomposite kuti pave nekupisa kwakanyanya kunodzoserwa. Semuenzaniso, kugadzirisa mabasa ekupisa ereboiler necondenser mukati mezvikamu zvedistillation nepreheat kunogona kuchengetedza simba zvakanyanya uye kuderedza kuburitswa kwegasi rinopisa pasi kunokonzerwa nekugadzirwa kwemhepo. Zvidzidzo zvemaindasitiri zviripo parizvino zvakashuma kudzikiswa kwemagetsi kusvika ku25%, nerubatsiro rwakananga mumutengo wesimba uye kutevedzera nharaunda.
Chimwe chinhu chakakosha pakugadzirisa zvinhu ndechekudzokorodza chikafu. Mukuita kwecumene, kushandurwa kwakakwana kwebenzene nepropylene hakuwanzoitika muchikamu chimwe chete chereactor. Nekudzokorodza benzene necumene zvisina kugadziriswa, maitiro aya anowedzera kushandurwa kwereactant kunobudirira uye anoshandisa zviwanikwa zvecatalyst zvinobudirira. Maitiro aya haangoderedzi kurasikirwa kwezvinhu zvakabikwa chete asiwo anobatsira pakukura kwegoho rezvirimwa. Dhizaini inoshanda yekudzokorora loop inotarisa kuderedza kudonha kwepressure, kutarisa kuumbwa kwenguva chaiyo, uye kuyera kuyerera kwakaringana. Kugadziriswa kwekugadzirisa zvakare kunoderedzawo njodzi yekusvibiswa kwecatalyst uye kunowedzera hupenyu hwecatalyst cycle, zvichideredza nguva yekushanda uye mari yekutsiva catalyst.
Zvishandiso zvekuongorora maekisesaizi zvakaita seAspen Plus neMATLAB zvinogonesa kuongororwa kwakadzama kwechikamu chega chega chemuti. Zvidzidzo zvinosimbisa kuti kurasikirwa kukuru kweekisesaizi—uye nekudaro mukana wekuvandudza—zviri muzvikamu zvekudiridza nekuparadzanisa zvinopisa zvakanyanya. Saka, kunangwa kwezvikamu izvi kunotungamirirwa nehuwandu, kunotungamirirwa nekuenzanisa, ndiko kunonyanya kukosheswa pakutsvaga kugadzirisa kuyerera kwesimba uye kuderedza kusachinjika kwemuti wese.
Kushanda kweReactor neDistillation Column
Kugadzirisa saizi nedhizaini yereactor kwakakosha kuti mari yemuchina ienderane nekushanda zvakanaka. Huwandu hwereactor, nguva yekugara, uye catalyst loading zvinofanirwa kugadziriswa kuti zvive nechokwadi chekuti shanduko huru dze single-pass pasina njodzi yekudonha kwakanyanya kwepressure kana kushandiswa zvakanyanya kwemagetsi. Semuenzaniso, kuwedzera dhayamita yereactor kunogona kuderedza kudonha kwepressure asi kunogona kukonzera kusasanganiswa zvakanaka, nepo reactor dzakareba dzichivandudza kushandurwa kusvika padanho rekudzikira kwekudzoka nekuda kwemiganhu ye reaction equilibrium uye kugadzirwa kwechigadzirwa.
Kune distillation column iri pasi, kunyanya distillation isina kuchena, kugadzirisa reflux ratio, nzvimbo yekudyisa, spacing yetireyi, uye column pressure zvinoita kuti cumene iparadzaniswe zvakanyanya kubva kune benzene isina kugadziriswa, polyisopropylbenzene, nezvimwe zvigadzirwa. Kugadziriswa kwe distillation kwakanaka hakungowedzere kudzoreredzwa kwecumene chete asiwo kunoderedza mutoro we reboilers nema condenser, zvichishandura zvakananga kudzikiswa kwemari yesimba. Kushandiswa kwema side drawers kana ma split-feed designs kunogona kuvandudza kuparadzaniswa pakati pezvinhu zvinofashaira zvakaita se acetone ne cumene, zvichitsigira kugadzirwa kwe high-purity phenol ne acetone zvinodiwa nemusika we phenol ne acetone.
Hunhu hwesimba remuchina wekudiridza hunoratidzwa pazasi, hunoratidza kupinda kwesimba paboiler uye kubuda pacondenser, pamwe nezvikamu zvakabatanidzwa zvekudzoreredza kupisa padivi zvichideredza kudiwa kwese kwemidziyo yekudziyisa nekutonhodza.
Kugadzira Zvinhu Zvitsva muReactor Design
Maitiro ekuwedzera mashandiro munguva pfupi yapfuura ari kuchinja tekinoroji yecumene reactor. Kushandiswa kwema microbubble nema miniaturized reactor systems kunowedzera kubatana pakati pe reactants, zvichiita kuti pave nekukurumidzira kutamiswa kwehuwandu uye kusarudza kwakanyanya. Aya mafomati asina kujairika eactants anogona kushanda panguva shoma yekugara uku achichengetedza kana kupfuura zvinangwa zvekushandura, nokudaro achideredza simba rinodiwa payuniti imwe neimwe yechigadzirwa chakagadzirwa.
Ma microbubble reactors anopa simba guru pamusoro pekupisa kwakanyanya uye anoderedza kugadzirwa kwezvinhu zvinorema zvinogona kukuvadza ma catalysts kana kuita kuti kupatsanurwa kwemvura kuome. Izvi zvinovandudza kuchengetedzeka—nekuderedza nzvimbo dzinopisa uye kukwira kwesimba—uye zvinoderedza kukanganiswa kwezvakatipoteredza kuburikidza nekuderedza kusvibiswa kwemhepo, kupisa kwemarara, uye kushandiswa kwezvikafu zvakawandisa. Pamusoro pezvo, ma miniaturized reactors anogonesa ma decentralized, modular plant architectures, achikwira nemutengo wakaderera kuti aenderane nekuchinja kwemusika kudiwa kwe phenol ne acetone production.
Izvi zvitsva zviri kugadzira chiyero chitsva chekushanda zvakanaka kwereactor uye kuchengetedzeka kwemaitiro mukuora kwecumene oxidation uye hydroperoxide, kugadzirisa kugadzirwa kwephenol-acetone pamwe nekusangana nezvinodiwa zvakanyanya pakuchena kwechigadzirwa zvinodikanwa munzira dzekuchenesa acetone uye maitiro ekuchenesa ketone.
Nekushandisa nzira idzi dzekugadzirisa mashandiro, vagadziri vanogona kuwana chiyero chepamusoro pakati pekushandisa simba zvakanaka, kushandiswa kwemiti, zvinangwa zvekuchena, uye kugara kwenguva refu pasina kukanganisa mitemo yakasimba yekuchengetedza maitiro ecumene.
Kugadziriswa kweDownstream: Kuparadzaniswa kwePhenol neAcetone
Kuparadzanisa phenol neacetone mushure mekuora kwecumene hydroperoxide kunoda matanho akaomarara ekunyungudutsa nekucheneswa. Kutarisira simba nekudzoreredza chigadzirwa zvakanaka kunoumba dhizaini yemaitiro uye maitiro ekushanda mukugadzirwa kwephenol neacetone yakakura.
Kutevedzana kwekuparadzaniswa kwechigadzirwa
Chikamu chepasi chinotanga nekuchenesa crude reactor output, ine phenol, acetone, mvura, α-methylstyrene, cumene, benzene, nezvimwe zvinhu zvidiki zvinobva mureactor. Pakubuda mureactor, musanganiswa wacho unobviswa simba uye kupatsanurwa kwechikamu kunoitwa kana paine mvura yakawanda.
Chinhu chekutanga chinotarirwa pakupatsanurwa kweacetone kubviswa. Nekuda kweacetone iri kufashaira zvishoma (56 °C), inowanzo sanganiswa pamusoro pechinhu chose chinobva pane chimwe chikamu cheorganic chinofashaira zvakanyanya. Izvi zvinoitwa muchikamu che distillation chisina kuchena, uko acetone, mvura, uye tsvina yechiedza inoenda pamusoro, uye phenol ine makemikari akakora inoramba iri chigadzirwa chepasi. Acetone iri pamusoro inogona kunge ichiri nemvura uye zvimwe zviratidzo zvemamwe magumo echiedza, saka inogona kuomeswa nekucheneswa mushure mezvo—kuburikidza ne azeotropic kana extractive distillation kana kuchena kwakanyanya kuchidikanwa—kunyange zvazvo distillation yenguva dzose yakakwana mumabasa mazhinji ekutengeserana.
Zvisaririra zvephenol zvakapfuma zvinonatswa zvakare muzvikamu zve distillation columns. Chekutanga chinobvisa magumo echiedza akadai se residual acetone, benzene, uye magasi akanyungudutswa. Chikamu chinotevera chephenol chinopa kupatsanurwa kukuru, zvichiburitsa phenol yakachena uye kupatsanura zvigadzirwa zvinofashaira zvakanyanya pasi pechikamu. Mumarongerwo mazhinji, zvigadzirwa zvinokosha zvakaita se α-methylstyrene zvinodzoserwawo nematanho ekudhonza kana anotevera ekudhirowa. Zvikamu izvi zvinoshandiswa pakumanikidzwa kwakaverengerwa uye purogiramu yekupisa kuti zviwedzere kushanda zvakanaka kwekuparadzanisa uye kuderedza kurasikirwa kwechigadzirwa.
Kugadzirwa kweKoramu yeDistillation uye Crude Distillation Koramu
Makoramu ekunyungudutsa ndiwo akakosha pakucheneswa kweacetone nephenol. Magadzirirwo awo uye mashandiro awo anokanganisa zvakananga kuchena, goho, uye kushandiswa kwesimba mukati mekugadzirwa kwecumene.
Pakubvisa acetone, crude distillation column inofanira kupa mukana wekuparadzanisa zvakanyanya zvichitevera musiyano uripo pakati peacetone nephenol. Makoramu marefu ane matireyi anoshanda zvakanaka kana kurongedza kwepamusoro-soro anoshandiswa. Kubatanidzwa kwesimba kwakakosha; kupisa kubva pamusoro pemhepo kunogona kupisa mafeeds kana kudzoserwa muma reboiler circuits, zvichideredza kushandiswa kwesimba rose sezvinoratidzwa nezvidzidzo zve process simulation zvichishuma kudzikira kwe15% mukushandiswa kwesimba rakati mushure mekushandisa kupisa muzvirimwa zvikuru ([Chemical Engineering Progress, 2022]).
Matambudziko ekushanda anosanganisira kuumbwa kweazeotrope, kunyanya pakati peacetone nemvura. Kunyangwe izvi zvichigona kuomesa kupatsanurwa zvachose, kusagadzikana kwemaindasitiri kunowanzo batsira kugadziriswa kwetsika. Kudzora kumanikidzwa kwakakosha kudzivirira kurasikirwa neacetone uye kuchengetedza simba rekutyaira rethermodynamic. Kudzora tembiricha kwakanyatsojeka kumusoro nepasi kunoita kuti zvinhu zvinonangwa zviwanikwe pasina kupisa zvakanyanya.
Kunyungudika kwePhenol kunosangana nematambudziko ayo. Kufashaira kwakanyanya kwePhenol uye kugona kwayo kuoxidation zvinoreva kuti zvinhu zviri mukati me column zvinofanira kuramba ngura, kazhinji zvichishandisa alloys dzakakosha. Kumanikidzwa kwe column kunogadziriswa kuti kuenzanise mutengo wesimba uye kuderedza njodzi dzekuora. Zvigadzirwa zvinokurumidza kupiswa ne thermal polymerization, zvakaita se α-methylstyrene, zvinobviswa nekukurumidza uye zvinotonhodzwa kuti zvidzivise mhedzisiro.
Kudzora maitiro kwakanyatsogadzirwa uye zvishandiso zvekuyera mukati memutsara—zvakadai seLonnmeter inline density uye viscosity metres—zvinoshandiswa nguva dzose kugadzirisa mashandiro ekoramu, zvichiita kuti zvinangwa zvekuchena uye zviyero zvekoramu zvirambe zvichisangana.
Kubatanidzwa neHydroperoxide Decomposition uye Kudzorerwa kweChigadzirwa
Kubatanidzwa kwezvikamu zvekuora, kupatsanura, uye kuchenesa kwakakosha pakuita kwecumene. Mvura inobuda muropa inoenda zvakananga pakupatsanurana kwemvura. Kutamiswa nekukurumidza kunoderedza mhedzisiro isina kunaka kana polymerization.
Danho rega rega rekuparadzanisa rakabatana zvakasimba kune rinotevera. Acetone yepamusoro inounganidzwa nekukurumidza kudzivirira kurasikirwa nemhepo. Phenol uye mativi emvura anobuda anozopinda mumatanho avo ekuchenesa. Kana zvigadzirwa zvinokosha zvadzorerwa, mafambiro azvo anotorwa mushure mekuongorora kwakadzama kwechikamu uye kuumbwa.
Chinhu chakakosha ndechekudzivisa kusvibiswa pakati pemagumo echiedza (acetone/chikamu chemvura) uye zvinosvibisa zvinorema (cumene isina kugadziriswa, tars). Izvi zvinoitwa kuburikidza nematanho akawanda ekuenzanisa kwemvura-mvura mukati memakoramu uye kushandiswa kwemvura inoyerera. Mapaipi nemidziyo yeropa zvakagadzirwa kuderedza kubatwa uye kupfupika kwemhepo.
Mwero wekudzoreredzwa kweacetone nephenol unodarika 97% mumiti yakagadziriswa, nekurasikirwa kunowanzo konzerwa nekubuda kwemvura munzizi dzisingadzivisike uye kudonha kwemvura. Mvura yakasviba inogadzirwa mukati mekuita uku, ine zvinhu zvakasikwa zvakanyungudutswa, inochengetwa yoga uye inoendeswa kune masisitimu ekurapa epamusoro kuti ienderane nezvinodiwa nemutemo.
Kubatanidzwa kwakanaka kunoenderana nekutarisa nguva dzose zvinhu zvakakosha: kuwanda uye kuverengerwa kwe viscosity kubva pamamita akafanana neaya anobva kuLonnmeter, kusimbisa mhando yekudya uye kuchena kwechigadzirwa munguva chaiyo, zvichiita kuti pave nekudzora mhinduro kuti pave nekukosha kwakanyanya uye kuchengetedzeka kwekushanda.
Kugadzirwa kwemaitiro anoshanda mukugadzirwa kwephenol-acetone kunoenderana nekupatsanurwa kwakasimba, kunyungudutswa kwesimba kwakagadziriswa, kubatanidzwa kwakasimba kwekuita nekucheneswa, uye kutarisa nguva dzose mukati memutsara, zvichitsigira kuchengetedzwa kwemaitiro uye kunaka kwechigadzirwa.
Maitiro Epamusoro Ekuchenesa Acetone
Kucheneswa kweacetone mushure mekugadzirwa pamwe chete kwephenol-acetone kuburikidza nemaitiro ecumene kunoumbwa nezvinodiwa zvemhando yepamusoro yechigadzirwa. Kusarudza nzira yakakodzera yekuchenesa acetone kunoenderana nezvinodiwa zvekupedzisira zvekuchena, miganhu yemutemo, uye chimiro chekusachena chinogadzirwa panguva yekuora kwecumene hydroperoxide uye maitiro ekumusoro.
Nheyo Dzakakosha Mukuchenesa Acetone
Acetone isina kuchena inobva kucumene oxidation ine huwandu hwakawanda hwemvura, phenol, α-methylstyrene, cumene, acetophenone, carboxylic acids, aldehydes, nezvimwe zvinhu zve organics zvine oxygen. Kucheneswa kwetsvina uku kunonangwa kubviswa. Musana unogadzirwa ne distillation:
- Makoramu ekutanga anobvisa tsvina inorema uye inofashaira zvakanyanya—kunyanya phenol, α-methylstyrene, acetophenone, uye zvinhu zvinogadzira tar—nekubvisa pasi. Chikamu chepakati chine acetone-water azeotrope, nepo magumo echiedza (senge cumene isina kugadziriswa) anogona kupatsanurwa pamusoro muzvikamu zvinotevera.
Kunyungudutsa kweAzeotropic kunowanzo kuve kwakakosha pakupatsanura musanganiswa weacetone nemvura yakaoma, uchishandisa hydrocarbon entrainer kukanganisa chimiro cheazeotropic uye kuwedzera kuchena kweacetone. Kana tsvina ine poindi dzakafanana dzekufashaira, kunyungudutsa kwemvura inonyungudutsa—nemaglycols kana zvinonyungudutsa zvakagadzirwa—kunoiswa. Pano, chinhu ichi chinogadzirisa kusagadzikana, zvichiita kuti zvive nyore kupatsanurana kwezvinhu zvakasikwa zvine hukama uye kuwedzera kugona kweacetone.
Kunze kwekunyungudutsa, matanho ekuchenesa anobvisa phenol yakasara uye polar compounds. Kabhoni yakakangwa, silica gel, uye ion-exchange resins zvinoshanda zvakanaka pakati pezvikamu zvemakoramu kana mushure mezvikamu zvemakoramu. Kana paine acidic organics, maitiro acho anogona kusanganisira neutralization ne caustic soda zvichiteverwa nekushambidzwa nemvura kubvisa munyu nemaacids usati wanyungudutsa.
Acetone ine kuchena kwakanyanya (≥99.5 wt% yezvinodiwa zvakawanda zvemaindasitiri kana murabhoritari) inowanzo pinda muchikamu chekupedzisira che "kupukuta" ichisanganisa fine filtration uye adsorption yepamusoro kuti ive nechokwadi chekuti zvinodiwa zvemvura (<0.3 wt%), phenol (<10 ppm), heavy aromatics (<100 ppm), uye total non-volatiles (<20 ppm) zvinosangana. Izvi zvakakosha kune electronics kana pharmaceutical-grade acetone.
Kugadzirisa uye Kugadzirisa Matambudziko muDistillation
Kubudirira kwemaitiro ekunyungudutsa acetone kunoenderana nekugadzirwa kwemakoramu ekunyungudutsa kwakanyatsojeka uye mashandiro akarongwa. Makoramu ekupatsanura anoshandiswa saizi uye anoshandiswa kukurudzira kutamiswa kwakasimba kwehuwandu uye kupatsanurwa kwakanaka. Nzira dzakasiyana siyana dzinowedzera kuchena uye goho:
- Makoramu marefu ane matireyi akawanda kana kurongedza kwakarongeka zvine simba guru kunoita kuti pave nekupatsanurwa kwakapinza, kunyanya kana nzvimbo dzekufashaira dzeacetone-water kana acetone-cumene dziri pedyo.
- Kubatanidzwa kwekupisa pakati pema reboilers nema condenser (semuenzaniso, kuburikidza nekudzoreredza utsi kana kuti ma heat exchangers) kunoderedza kushandiswa kwesimba uye kudzikamisa tembiricha, izvo zvinotsigira kupatsanurwa kunogara kuripo.
- Kugadziriswa kwakanyatsojeka kwehuwandu hwe reflux uye huwandu hwekubvisa chigadzirwa, zvichitungamirirwa nekutarisa huwandu uye maumbirwo acho mumutsara (nezvishandiso zvakaita seLonnmeter inline density metres), zvinogonesa kugadzirisa nekukurumidza uye kunanga chigadzirwa nemazvo, zvichiita kuti batch yega yega isvike padanho rakasimba rekuchena.
Matambudziko anowanzoitika ekugadzira simbi anosanganisira mafashamo emumakomba, furo, uye kuunganidzwa kwezvisaririra:
Kufashamira kwemvura mumitsetse kunoitika kana mwero wekuyerera kwemvura wakakwira zvakanyanya—mvura inokwira kumusoro kwete pasi, zvichideredza zvakanyanya kushanda kwekuparadzanisa. Kugadzirisa izvi kunoda kuderedza kubuda kwemvura kana kugadzirisa reflux ratios. Kufuro kunobva mukumhanya kwakanyanya kwemhepo kana kubva pakuvapo kwezvinhu zvinoshanda pamusoro (semuenzaniso, tars kana phenol traces). Mishonga inorwisa furo, kutarisisa makoramu, uye kuisa ma process streams mumitsara kunogona kuderedza furo rinogara riripo.
Kuunganidzwa kwezvisaririra, zvinowanzoonekwa mumatireyi akaderera kana muchina wekugadzirisazve wedhiziri, kunobva muzvigadzirwa zve oligomerization kana tara. Kubviswa kwechigadzirwa chepasi nguva nenguva, kuchenesa nguva dzose, uye kuchengetedza tembiricha mukati memiganhu kunoderedza kuumbwa kwetara uye kunoita kuti koramu igare kwenguva refu.
Pakuparadzanisa azeotropes kana kugadzirisa tsvina inofashaira zvakanyanya, matireyi echinyakare anogona kutsiviwa nezvinhu zvekurongedza zvinoshanda zvakanyanya. Tembiricha uye mapurofiti ari mukoramu anochengetwa mukati memahwindo akasimba. Zvishandiso zveotomatiki—zvakadai sekuyera huwandu hwezvinhu zviri mukati—zvinogonesa vashandisi kukurumidza kuona chigadzirwa chisina kutsanangurwa uye kupindura panguva chaiyo, zvichiwedzera kushanda zvakanaka uye goho.
Chati iri nyore inoratidza kunyungudika kweacetone muzvikamu zvakawanda uye kucheneswa kwekugadzirwa kwephenol neacetone (kudhirowa kwako pachako zvichibva pamaitiro akajairwa)
Kubatanidzwa kwenzira idzi dzepamusoro dzekuchenesa acetone kunovimbisa kubatwa kwakachengeteka kwezvigadzirwa zvinobva mukugadzirwa kwecumene, kutevedzera mitemo yemusika weacetone nephenol, uye kudzikira kwekukanganiswa kwezvakatipoteredza.
Zvinokonzera Kuvandudzwa Kwemaindasitiri uye Kugara Kwenguva Refu
Mukugadzirwa kweCumene, kubatanidza zvakasimba dhizaini yemaitiro, catalysis, uye sarudzo dzekuparadzanisa nekushanda zvakanaka kwezviwanikwa zvakakosha. Dhizaini yemaitiro akabatanidzwa inoronga reaction engineering, tekinoroji yekuparadzanisa, uye kudzoreredza simba kuti iwedzere goho uye kuderedza marara padanho rega rega rekugadzirwa pamwe chete kwephenol-acetone. Nekushandisa masisitimu epamusoro ecatalytic, akadai se solid solid acid catalysts (kusanganisira zeolites uye heteropolyacids), vashandisi vanowana sarudzo yakakwira mukuora kwecumene hydroperoxide, zvichideredza kuumbwa kwezvigadzirwa zvakaita seα-methylstyrene neacetophenone. Kuwedzerwa uku kwekusarudza hakungogadzirisi goho remaitiro chete asiwo kunotsigira kugara kwenguva refu kuburikidza nekuderedzwa kwenzira dzemarara.
Pakusarudza macatalyst ekuora kwehydroperoxide, kuwedzera kwemaitiro kunoita basa guru. Semuenzaniso, nzira dzehybrid catalytic, dzinosanganisa zvinhu zve catalysis yakafanana uye yakasiyana, dziri kuwana simba nekuda kwekuwedzera kwekushanda kwadzo uye hupenyu hwadzo hwe catalyst hwakareba. Kunyange zvakadaro, dhizaini ye catalyst inofanira kuyananisa kushanda kwakanyanya uye kugadzikana pakurwisa nyaya dzakadai sekubikwa kwemvura uye chepfu netsvina, zvichiita kuti pave nekuchinjana kushoma kwe catalyst uye mutoro wezvakatipoteredza kubva mukurasa catalyst yakapedzwa. Kuvandudzwa kuri kuenderera mberi kwe catalyst kunokanganisa zvakananga kushanda zvakanaka kwezviwanikwa, kuderedza kurasikirwa kwezvinhu zvakabikwa uye kuderedza kudiwa kwemagetsi.
Kubatanidzwa kwemagadzirirwo emaprocess, kunyanya panguva yekuchenesa acetone uye maitiro ekugadzira acetone, kuchiri kukosha pakugadzirisa maindasitiri. Kuitwa kwemagadzirirwo ema column epamusoro ekugadzira distillation—akadai sekuparadzanisa madziro—uye kupatsanurana kwe membrane-based based spenditures kunogonesa mashandiro anochengetedza mari uye anogara kwenguva refu. Kupatsanura madziro, semuenzaniso, kunoita kuti kushanda kwema column ekugadzira distillation kuve nyore, zvichikonzera kuchengetedza simba kusvika 25% pane zvechinyakare zve multi-column setups, ukuwo zvichisunungura nzvimbo yemiti chaiyo. Uyezve, nzira dzakaoma dzekubatanidza kupisa, dzichitungamirirwa nematekiniki akadai sekuongorora pinch, dzakaratidza kudzikiswa kwekushandiswa kwemhepo inopfuudza 20%, sezvinoratidzwa mukuvandudzwa kwenzvimbo dzekugadzira phenol ne acetone. Matanho aya anoshandura kudzikira kwemhepo inotonhorera uye kudzikira kwekuvimba nemhepo inobva mumafuta efossil.
Kubatanidzwa kwemvura nekupisa kunowedzera kushanda zvakanaka kwezviwanikwa mukuita kwe cumene oxidation uye matanho anotevera ekuparadzanisa. Masisitimu ekushandisazve Cascade uye nzvimbo dzekudzima dzakaiswa zvine hungwaru zvinogona kuderedza kubuda kwemvura yakasviba kusvika ku40%, zvichigadzirisa huwandu uye kusvibiswa kwetsvina. Izvi zvinonyanya kukosha pakutevedzera mitemo iri kuchinja mumisika mikuru ye phenol ne acetone, uko mitemo yekubuda kwetsvina uye kuburitswa kwekabhoni iri kusimba.
Kufunga nezvemitemo nezvakatipoteredza kwakanyanya kunzwisiswa mukugadzirwa pamwe chete kwephenol-acetone uchishandisa maitiro ecumene. Kudzora kwakasimba pamishonga ine njodzi—senge cumene hydroperoxide—kunorayira kudzora kwakarurama kwemaitiro uye kutarisa kuchengetedzeka panguva chaiyo panguva yekushanda kune njodzi huru. Mitemo yezvakatipoteredza, kunyanya munzvimbo dzekuNorth America neEurope, inowedzera zvinodiwa zvekurapa tsvina, kudzora kuburitsa, uye kudzokorodza solvent/kupisa. Maitiro ekutevedzera mitemo anowanikwa mukugadzirwa kwekutanga kwemaitiro, kazhinji kunosanganisira metrics yesimba remaitiro uye ongororo yehupenyu iyo inoumba zvakananga marongerwo emiti uye kusarudzwa kwetekinoroji.
Kutarisa nguva chaiyo uye kugadzirisa maitiro zvakakosha pakuchengetedza kushanda zvakanaka uye kuderedza kurasikirwa kwemaitiro kusingadzivisike. Mita dze inline density uye viscosity metres kubva kuLonnmeter, semuenzaniso, zvinogonesa kudzora nguva dzose, mukati menzvimbo ye reaction uye separation parameters mukati mekugadzira acetone nephenol. Nekutevera zvakanyatsonaka huwandu hwezvigadzirwa nezvigadzirwa, vashandisi vanogona kugadzirisa zvinhu zvakakosha - zvakaita se reflux ratios, cut points mu distillation, uye catalyst dosing - nokudaro kuderedza kushandiswa kwesimba uye kuderedza huwandu hwezvinhu zvisiri spec kana marara.
Kushandisa matekiniki ekugadzira zvinhu zvemaindasitiri, zvichitsigirwa nedata remasensa renguva chaiyo, zvinokurumidzisawo kugadzirisa matambudziko nekudzima mhinduro kana paine mamiriro ezvinhu asina kunaka. Nekudzikira kwekushanduka-shanduka kwemakwikwi uye kuwedzera kugona kudzokororwa kwebatch, vashandi vanowana kuchengetedza mari zvakananga, kudzikira kwezvinhu zvakabikwa, uye kutyorwa kwemitemo yezvakatipoteredza kushoma. Nekuda kweizvozvo, kugadzirisa maitiro munguva chaiyo, kuchikonzereswa nehunyanzvi hwekuyera hwakakwana, hunoramba huchikosha pakugadzirwa kwephenol neacetone zvinokwikwidzana, zvinoenderana, uye zvinogara kwenguva refu.
Mibvunzo Inowanzo bvunzwa (Mibvunzo Inowanzo bvunzwa)
Chii chinonzi maitiro ecumene uye nei zvichikosha pakugadzirwa pamwe chete kwephenol-acetone?
Maitiro eCumene, anozivikanwawo seHock process, inzira yeindasitiri yekugadzira phenol neacetone pamwe chete muchikamu chimwe chete chakabatanidzwa. Inotanga nealkylation, apo benzene inopindirana nepropylene kugadzira cumene ichishandisa solid acid catalysts dzakadai sezeolites kana phosphoric acid. Cumene inozosanganiswa nemhepo kuti igadzire cumene hydroperoxide. Iyi intermediate inopinda muacid-catalyzed cleavage, ichiburitsa phenol neacetone muchiyero chaicho che1:1 molar. Maitiro aya akakosha nekuti anotonga kugadzirwa kwephenol neacetone pasi rose, zvichipa kugona kukuru kwekukohwa uye kubatanidzwa kwezviwanikwa. Inenge 95% yephenol yepasi rose inogadzirwa kuburikidza nemaitiro aya kubva muna 2023, zvichisimbisa kukosha kwayo muindasitiri nehupfumi.
Kuora kwecumene hydroperoxide kunokanganisa sei kuchengetedzeka uye goho remushonga?
Kuora kwecumene hydroperoxide kunonyanya kupisa, zvichiburitsa kupisa kwakawanda. Kana kukasatarisirwa zvakanaka, kunogona kukonzera kupisa, kuputika, kana moto—zvichinyanya kuomera pakugadzira uye kushanda zvakanaka. Kusarudza nekungwarira macatalyst ekuora kwehydroperoxide uye kudzora mamiriro ekuita kwakakosha pakushanda kwakachengeteka. Kutarisa tembiricha uye mwero wekuita kunoita kuti phenol neacetone zvirambe zviripo ukuwo zvichideredza kugadzirwa kwezvigadzirwa zvitsva uye njodzi dzekuchengetedza. Maitiro akanakisa eindasitiri anosanganisira kutarisa system nguva dzose, kudzimwa kwechimbichimbi, uye dhizaini yereactor yakasimba yekubata exothermicity uye kudzivirira chero kumanikidzwa kunowedzera.
Koramu yekubikisa isina kuchekwa inoita basa rei mukugadzirwa kwecumene?
Koramu yekudiridza isina kucheneswa chinhu chakakosha mushure mekutsemuka kwehydroperoxide. Inoparadzanisa phenol, acetone, cumene isina kugadziriswa, uye zvigadzirwa zvidiki. Kushanda zvakanaka kwekoramu yekudiridza isina kucheneswa kunowedzera kudzoreredzwa kwechigadzirwa, kunoderedza kushandiswa kwesimba, uye kugadzira nzizi dzinopinda zvakananga mumatanho ekuchenesa gare gare. Dhizaini uye mashandiro ekoramu yekudiridza inofanirwa kuverengera nzvimbo dzinofashaira dzezvinhu zvakasiyana-siyana, zvichida kunyatsoongorora tembiricha nekudzora kumanikidzwa. Kukundikana kwekudiridza kunogona kukonzera kurasikirwa kwechigadzirwa, kusvibiswa, kana mari yakawanda yekushandisa.
Sei kucheneswa kweacetone kuchidikanwa pakugadzirwa kwephenol-acetone?
Acetone inowanikwa kubva mukuita kwecumene ine tsvina dzakasiyana-siyana: zvigadzirwa zve side-reaction (zvakaita se methyl isobutyl ketone, isopropanol), mvura, uye organic acids zvinoumbwa panguva yekuoxidation nekucheka. Kucheneswa kwakasimba kunodiwa kuitira kuti acetone isangane nezvinodiwa zvemaindasitiri zvekushandisa mumishonga, zvinonyungudutsa, uye mapurasitiki. Maitiro ekuchenesa, akadai se tight-fractionation kuburikidza ne distillation columns, anobvisa tsvina iyi. Acetone yakachena inowedzerawo mutengo wemusika, zvichisimbisa chikonzero chehupfumi chekuchenesa zvinobudirira.
Kubatanidzwa kwemaprocess uye kuvandudzwa kwemareactor kunogona sei kuvandudza hunhu hwehupfumi nenharaunda hweCumene?
Kubatanidzwa kwemaitiro kunoshandisa mikana yekudzoreredza kupisa, kudzokorodza zvinhu zvisina kugadziriswa, uye kurerutsa mashandiro eyuniti kuderedza kushandiswa kwesimba. Semuenzaniso, kubatanidza kutumira kunze kwekupisa kwe reaction kana kusanganisa distillation sequences kunogona kuderedza mari yemafuta nemagetsi. Kushandiswa kwekuvandudzwa kwakaita se microbubble reactors kwakaratidza kuvandudza kutamiswa kwehuwandu, kusimudzira kushanda zvakanaka kwe oxidation, uye kuderedza kugadzirwa kwemarara. Izvi zvitsva pamwe chete zvinoderedza kukanganiswa kwezvakatipoteredza nekuderedza kuburitswa kwemhepo uye kugadzirwa kwemvura yakasviba, ukuwo zvichideredzawo mari yekugadzirisa, zvichiita kuti kugadzirwa kwe phenol-acetone kuve kwakasimba uye kwakasimba mune zvemari.
Nguva yekutumira: Zvita-19-2025
