I-Methyl methacrylate (MMA) iyimpahla ebalulekile yamakhemikhali ephilayo ephilayo kanye ne-polymer monomer, esetshenziswa kakhulu ekukhiqizeni ingilazi ephilayo, amapulasitiki okubumba, ama-acrylics, okokugqoka kanye nezinto zokwakha ze-polymer ezisebenza ekhemisi, njll. Kuyinto esezingeni eliphezulu ye-aerospace, electronics ulwazi, i-fiber optical, amarobhothi neminye imikhakha.

Njenge-monomer yezinto ezibonakalayo, i-MMA isetshenziswa kakhulu ekukhiqizeni i-polymethyl methacrylate (eyaziwa kakhulu ngokuthi i-plexiglass, i-PMMA), futhi ingabuye ihlanganiswe nezinye izinhlanganisela ze-vinyl ukuze kutholwe imikhiqizo enezakhiwo ezahlukene, njengokwenza i-polyvinyl chloride (PVC). ) izithasiselo ze-ACR, i-MBS futhi njenge-monomer yesibili ekukhiqizeni ama-acrylics.

Njengamanje, kunezinhlobo ezintathu zezinqubo ezivuthiwe zokukhiqizwa kwe-MMA ekhaya nakwamanye amazwe: umzila we-methacrylamide hydrolysis esterification (indlela ye-acetone cyanohydrin kanye nendlela ye-methacrylonitrile), umzila we-isobutylene oxidation (inqubo ye-Mitsubishi nenqubo ye-Asahi Kasei) kanye nomzila we-ethylene carbonyl synthesis ( Indlela ye-BASF kanye nendlela ye-Lucite Alpha).

1, umzila we-Methacrylamide hydrolysis esterification
Lo mzila uyindlela yokukhiqiza ye-MMA yendabuko, okuhlanganisa indlela ye-acetone cyanohydrin kanye nendlela ye-methacrylonitrile, kokubili ngemva kwe-methacrylamide intermediate hydrolysis, esterification synthesis ye-MMA.

(1) Indlela ye-acetone cyanohydrin (indlela ye-ACH)

Indlela ye-ACH, eyasungulwa okokuqala yi-US Lucite, iyindlela yokuqala yokukhiqiza yezimboni ye-MMA, futhi iyinqubo evamile yokukhiqiza ye-MMA emhlabeni njengamanje.Le ndlela isebenzisa i-acetone, i-hydrocyanic acid, i-sulfuric acid ne-methanol njengezinto zokusetshenziswa, futhi izinyathelo zokusabela zifaka: ukusabela kwe-cyanohydrinization, ukusabela kwe-amidation kanye ne-hydrolysis esterification reaction.

Inqubo ye-ACH ivuthwe ngokobuchwepheshe, kodwa inobubi obulandelayo obulandelayo:

○ Ukusetshenziswa kwe-hydrocyanic acid enobuthi obukhulu, edinga izinyathelo zokuvikela eziqinile ngesikhathi sokugcinwa, ukuthuthwa kanye nokusetshenziswa;

○ Ngokukhiqizwa kwenani elikhulu lezinsalela ze-asidi (ingxube enamanzi ene-sulfuric acid ne-ammonium bisulfate njengezingxenye eziyinhloko futhi equkethe inani elincane lezinto eziphilayo), inani layo eliphindwe izikhathi ezingu-2.5~3.5 kune-MMA, futhi liyingozi kakhulu. umthombo wokungcola kwemvelo;

o Ngenxa yokusetshenziswa kwe-sulfuric acid, imishini yokulwa nokugqwala iyadingeka, futhi ukwakhiwa kwedivayisi kuyabiza.

(2) Indlela ye-Methacrylonitrile (indlela ye-MAN)

U-Asahi Kasei uthuthukise inqubo ye-methacrylonitrile (MAN) esekelwe emzileni we-ACH, okungukuthi, isobutylene noma i-tert-butanol i-oxidized yi-ammonia ukuze ithole i-MAN, esabela nge-sulfuric acid ukuze ikhiqize i-methacrylamide, ebese isabela nge-sulfuric acid ne-methanol ukuze ikhiqize. I-MMA.umzila we-MAN uhlanganisa ukusabela kwe-ammonia oxidation, ukusabela kwe-amidation kanye ne-hydrolysis esterification reaction, futhi ungasebenzisa iningi lempahla yesitshalo se-ACH.Ukusabela kwe-hydrolysis kusebenzisa i-sulfuric acid eyeqile, futhi ukukhiqizwa kwe-methacrylamide ephakathi cishe ku-100%.Kodwa-ke, le ndlela ine-toxic hydrocyanic acid by-products, i-hydrocyanic acid ne-sulfuric acid iyagqwala kakhulu, izidingo zemishini yokusabela ziphezulu kakhulu, kuyilapho izingozi zemvelo ziphezulu kakhulu.

2. Umzila we-Isobutylene oxidation
I-Isobutylene oxidation kube umzila wezobuchwepheshe okhethwayo ezinkampanini ezinkulu emhlabeni ngenxa yokusebenza kahle kwayo okuphezulu nokuvikelwa kwemvelo, kodwa umkhawulo wayo wezobuchwepheshe uphezulu, futhi yiJapane kuphela eyake yaba nobuchwepheshe emhlabeni futhi yavimbela ubuchwepheshe eChina.Indlela ihlanganisa izinhlobo ezimbili zenqubo ye-Mitsubishi kanye nenqubo ye-Asahi Kasei.

(1) Inqubo ye-Mitsubishi (indlela ye-isobutylene enezinyathelo ezintathu)

I-Mitsubishi Rayon yase-Japan ithuthukise inqubo entsha yokukhiqiza i-MMA kusuka ku-isobutylene noma i-tert-butanol njengento eluhlaza, i-oxidation ekhethiwe enezinyathelo ezimbili ngomoya ukuze ithole i-methacrylic acid (MAA), yase ifakwa esterified nge-methanol.Ngemuva kokwakhiwa kwezimboni kweMitsubishi Rayon, iJapan Asahi Kasei Company, Japan Kyoto Monomer Company, Korea Lucky Company, njll. baye basungula izimboni ngokulandelana.Inkampani yasekhaya i-Shanghai Huayi Group Company itshale izimali eziningi zabantu kanye nezezimali, kwathi ngemva kweminyaka engu-15 yemizamo eqhubekayo nengapheli yezizukulwane ezimbili, yathuthuka ngempumelelo ngokuzimela i-oxidation enezinyathelo ezimbili kanye ne-esterification yobuchwepheshe be-MMA yokukhiqiza i-isobutylene ehlanzekile, futhi ngoDisemba 2017. , yaqeda futhi yaqala ukusebenza imboni yezimboni ye-MMA engamathani angu-50,000 enkampanini yayo ehlanganyelwe i-Dongming Huayi Yuhuang eseHeze, eSifundazweni SaseShandong, yaphula ukubusa kobuchwepheshe eJapane futhi yaba ukuphela kwenkampani enalobu buchwepheshe eChina.ubuchwepheshe, futhi okwenza iChina izwe lesibili ukuba nobuchwepheshe obuthuthukisiwe bokukhiqizwa kwe-MAA ne-MMA nge-oxidation ye-isobutylene.

(2) Inqubo ye-Asahi Kasei (inqubo ye-isobutylene enezinyathelo ezimbili)

Inkampani yaseJapan i-Asahi Kasei Corporation kade yazibophezela ekuthuthukiseni indlela eqondile yokukhiqiza i-MMA, eyathuthukiswa ngempumelelo futhi yaqala ukusebenza ngo-1999 ngemboni yezimboni engamathani angama-60,000 eKawasaki, eJapan, futhi kamuva yanwetshwa yaba amathani ayi-100,000.Umzila wezobuchwepheshe uqukethe ukusabela okuyizinyathelo ezimbili, okungukuthi i-oxidation ye-isobutylene noma i-tert-butanol esigabeni segesi ngaphansi kwesenzo se-Mo-Bi composite oxide catalyst ukukhiqiza i-methacrolein (MAL), okulandelwa yi-oxidative esterification ye-MAL isigaba soketshezi ngaphansi kwesenzo se-Pd-Pb catalyst ukukhiqiza i-MMA ngokuqondile, lapho i-oxidative esterification ye-MAL kuyisinyathelo esibalulekile kulo mzila wokukhiqiza i-MMA.Indlela yenqubo ye-Asahi Kasei ilula, enezinyathelo ezimbili kuphela zokusabela kanye namanzi kuphela njengomkhiqizo, oluhlaza futhi ohambisana nemvelo, kodwa ukuklama nokulungiswa kwe-catalyst kufuna kakhulu.Kubikwa ukuthi i-catalyst ye-oxidative esterification ka-Asahi Kasei ithuthukisiwe kusukela esizukulwaneni sokuqala se-Pd-Pb kuya esizukulwaneni esisha se-Au-Ni catalyst.

Ngemuva kokuthuthukiswa kwezimboni kobuchwepheshe be-Asahi Kasei, kusukela ngo-2003 kuya ku-2008, izikhungo zocwaningo lwasekhaya zaqala ukukhula kocwaningo kule ndawo, namayunithi amaningana afana ne-Hebei Normal University, i-Institute of Process Engineering, i-Chinese Academy of Sciences, i-Tianjin University kanye ne-Harbin Engineering University egxile. ekuthuthukisweni nasekuthuthukisweni kwama-catalysts e-Pd-Pb, njll. Ngemva kuka-2015, ucwaningo lwasekhaya mayelana nama-catalysts e-Au-Ni lwaqala Omunye umjikelezo we-boom, omele i-Dalian Institute of Chemical Engineering, i-Chinese Academy of Sciences, wenze inqubekelaphambili enkulu ucwaningo oluncane lomshayeli, luqedele ukulungiselelwa kwenqubo yokulungiselela i-nano-gold catalyst, ukuhlolwa kwesimo sokusabela kanye nokuhlolwa kokusebenza okuqondile komjikelezo omude, futhi manje usebenzisana ngenkuthalo namabhizinisi ukuthuthukisa ubuchwepheshe bezimboni.

3, Umzila we-ethylene carbonyl synthesis
Ubuchwepheshe be-ethylene carbonyl synthesis route industrialization ihlanganisa inqubo ye-BASF kanye nenqubo ye-ethylene-propionic acid methyl ester.

(1) indlela ye-ethylene-propionic acid (inqubo ye-BASF)

Le nqubo iqukethe izinyathelo ezine: i-ethylene i-hydroformylated ukuze ithole i-propionaldehyde, i-propionaldehyde ifinyezwa nge-formaldehyde ukuze ikhiqize i-MAL, i-MAL ifakwe umoya ku-reactor engumbhede ongaguquki weshubhu ukuze ikhiqize i-MAA, futhi i-MAA iyahlukaniswa futhi ihlanzwe ukuze kukhiqizwe i-MMA nge-esterification nge. i-methanol.Ukusabela kuyisinyathelo esibalulekile.Inqubo idinga izinyathelo ezine, okuyinto enzima kakhulu futhi idinga imishini ephezulu kanye nezindleko eziphezulu zokutshala izimali, kuyilapho inzuzo iyizindleko eziphansi zezinto zokusetshenziswa.

Ukuphumelela kwasekhaya kwenziwe nasekuthuthukisweni kobuchwepheshe be-ethylene-propylene-formaldehyde synthesis ye-MMA.Ngo-2017, i-Shanghai Huayi Group Company, ngokubambisana ne-Nanjing NOAO New Materials Company kanye ne-Tianjin University, iqedele ukuhlolwa komshayeli wamathani ayi-1,000 we-propylene-formaldehyde condensation nge-formaldehyde ku-methacrolein kanye nokuthuthukiswa kwephakheji lenqubo yesitshalo sezimboni esingamathani angama-90,000.Ngaphezu kwalokho, i-Institute of Process Engineering ye-Chinese Academy of Sciences, ngokubambisana ne-Henan Energy kanye ne-Chemical Group, iqedele imboni yokuhlola imboni engamathani ayi-1,000 futhi yazuza ngempumelelo ukusebenza okuzinzile ngo-2018.

(2) Inqubo ye-Ethylene-methyl propionate (inqubo ye-Lucite Alpha)

Izimo zokusebenza zenqubo ye-Lucite Alpha zimnene, isivuno somkhiqizo siphezulu, ukutshalwa kwezimali kwezitshalo nezindleko zempahla eluhlaza ziphansi, futhi isikali seyunithi eyodwa kulula ukwenza sikhulu, okwamanje nguLucite kuphela onokulawula okukhethekile kwalobu buchwepheshe emhlabeni futhi akayena. idluliselwe emhlabeni wangaphandle.

Inqubo ye-Alpha ihlukaniswe ngezinyathelo ezimbili:

Isinyathelo sokuqala ukusabela kwe-ethylene nge-CO ne-methanol ukukhiqiza i-methyl propionate

kusetshenziswa i-palladium-based homogeneous carbonylation catalyst, enezici zomsebenzi ophezulu, ukukhetha okuphezulu (99.9%) nempilo ende yesevisi, futhi ukusabela kwenziwa ngaphansi kwezimo ezithambile, ezingonakalisi kancane kudivayisi futhi kunciphisa ukutshalwa kwezimali kwenhlokodolobha yokwakha. ;

Isinyathelo sesibili ukusabela kwe-methyl propionate ne-formaldehyde ukwakha i-MMA

I-proprietary catalyst yezigaba eziningi isetshenziswa, enokukhethwa okuphezulu kwe-MMA.Eminyakeni yamuva nje, amabhizinisi asekhaya atshale isasasa elikhulu ekuthuthukisweni kobuchwepheshe be-methyl propionate kanye ne-formaldehyde condensation ku-MMA, futhi enze inqubekelaphambili enkulu ekuthuthukisweni kwenqubo yokusabela kwe-catalyst kanye ne-fixed-bed-bed-bed, kodwa impilo ye-catalyst ayikafinyeleli izidingo zezimboni. izicelo.