I-Methyl methacrylate (MMA) iyi-organic amakhemikhali eluhlaza okokusebenza okubalulekile kanye ne-polymer monomer, ikakhulukazi esetshenziswa ekukhiqizeni ingilazi ephilayo, amapulasitiki okubumba, ama-acrylics, ama-coatings kanye nezinto zokwakha ze-polymer ezisebenzayo zemithi, njll. Kuyinto ephezulu yokugcina i-aerospace, ulwazi lwe-elekthronikhi, i-fiber optical, amarobhothi kanye neminye imikhakha.

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

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 kanye nenqubo ye-Asahi Kasei) kanye ne-ethylene carbonyl synthesis umzila (indlela ye-BASF kanye ne-Lucite Al-Lucite).

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 liwumthombo ongathi sína wokungcoliswa 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 ifakwe i-ammonia ukuze ithole i-MAN, esabela nge-sulfuric acid ukuze ikhiqize i-methacrylamide, ebese isabela nge-sulfuric acid kanye ne-methanol ukukhiqiza 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 uphakeme, 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. I-Shanghai Huayi Group Company yasekhaya itshale izinsiza eziningi zabantu kanye nezezimali, kwathi ngemuva kweminyaka eyi-15 yemizamo eqhubekayo nengapheli yezizukulwane ezimbili, yathuthuka ngempumelelo ngokuzimela i-oxidation enezinyathelo ezimbili kanye ne-esterification ye-isobutylene ehlanzekile yokukhiqiza ubuchwepheshe be-MMA, kwathi ngoDisemba 2017, yaqeda futhi yafaka ukusebenza kwenkampani yezimboni ezingama-50,000 e-Donghung Huven MMA ehlangene imboni yayo ye-Donghung Huven. UHeze, eSifundazweni SaseShandong, wephula ukubusa kobuchwepheshe base-Japan futhi waba ukuphela kwenkampani enalobu buchwepheshe e-China. 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), elandelwa yi-oxidative esterification ye-MAL esigabeni soketshezi ngaphansi kwesenzo se-Pd-Pb MMA i-oxidative ekhiqiza ngokuqondile i-oxidative ye-MMA. ngena kulo mzila ukuze ukhiqize 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.

Ngemva kwezimboni Asahi Kasei ubuchwepheshe, kusukela ngo-2003 kuya ku-2008, izikhungo zocwaningo ezifuywayo waqala boom ucwaningo kule ndawo, nge amayunithi eziningana ezifana Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University kanye Harbin Engineering University egxile ekuthuthukisweni nasekuthuthukisweni Pd-Pb catalysts, njll Ngemva 201 kocwaningo ummeleli we-Aust-Ni waqala ngo-201, omele ucwaningo lwasekhaya lwe-Aust5, njll. okuyi-Dalian Institute of Chemical Engineering, i-Chinese Academy of Sciences, yenze inqubekelaphambili enkulu ocwaningweni oluncane lomshayeli, yaqeda ukwenziwa kahle kwenqubo yokulungiselela i-nano-gold catalyst, ukuhlolwa kwesimo sokusabela kanye nokuhlolwa okuqondile kokuthuthukiswa kokusebenza komjikelezo omude, futhi manje ibambisana 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-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 kanye nezindleko zempahla eluhlaza ziphansi, futhi isikali seyunithi eyodwa kulula ukwenza esikhulu, okwamanje uLucite kuphela onokulawula okukhethekile kwalobu buchwepheshe emhlabeni futhi akadluliswanga emhlabeni wangaphandle.

Inqubo ye-Alpha ihlukaniswe ngezinyathelo ezimbili:

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

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

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

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