I-Methyl methacrylate (MMA) yinto ebalulekileyo ye-organic khemikhali ekrwada kunye ne-polymer monomer, esetyenziswa kakhulu kwimveliso yeglasi ephilayo, iplastiki yokubumba, i-acrylics, i-coatings kunye ne-pharmaceutical functional materials polymer, njl njl. Yinto ephezulu yokugcina i-aerospace, ulwazi lwe-elektroniki, i-fiber optical, i-robotics kunye nezinye iinkalo.

Njengemonoma yezinto, i-MMA isetyenziswa ikakhulu kwimveliso ye-polymethyl methacrylate (eyaziwa ngokuba yi-plexiglass, i-PMMA), kwaye ingaphinda ifakwe kwi-copolymerized kunye nezinye iikhompawundi zevinyl ukufumana iimveliso ezineempawu ezahlukeneyo, ezifana nokuveliswa kwe-polyvinyl chloride (PVC) izongezo ze-ACR, i-MBS kunye ne-monomer yesibini kwimveliso ye-acrylics.

Okwangoku, kukho iintlobo ezintathu zeenkqubo ezivuthiweyo zokuveliswa kwe-MMA ekhaya nakwamanye amazwe: indlela ye-methacrylamide hydrolysis esterification (indlela ye-acetone cyanohydrin kunye nendlela ye-methacrylonitrile), indlela ye-isobutylene oxidation (inkqubo yeMitsubishi kunye nenkqubo ye-Asahi Kasei) kunye ne-ethylene carbonyl synthesis indlela (indlela ye-BASF kunye ne-Lucite Al-Lucite).

1, iMethacrylamide hydrolysis esterification indlela
Le ndlela yindlela yemveli yemveliso ye-MMA, kuquka indlela ye-acetone cyanohydrin kunye nendlela ye-methacrylonitrile, zombini emva kwe-hydrolysis ye-methacrylamide ephakathi, i-esterification synthesis ye-MMA.

(1) Indlela yeAcetone cyanohydrin (indlela yeACH)

Indlela ye-ACH, eyaphuhliswa okokuqala yi-US Lucite, yindlela yokuqala yokuveliswa kwemveliso ye-MMA, kwaye ikwayinkqubo yemveliso ye-MMA ephambili kwihlabathi ngoku. Le ndlela isebenzisa i-acetone, i-hydrocyanic acid, i-sulfuric acid kunye ne-methanol njengezinto ezibonakalayo, kunye namanyathelo okuphendula abandakanya: i-cyanohydrinization reaction, i-amidation reaction kunye ne-hydrolysis esterification reaction.

Inkqubo ye-ACH ikhulile ngokobuchwepheshe, kodwa ineziphene zilandelayo:

○ Ukusetyenziswa kwe-hydrocyanic acid enetyhefu kakhulu, efuna amanyathelo okhuseleko angqongqo ngexesha logcino, uthutho kunye nokusetyenziswa;

○ Ngokuveliswa kwentsalela yesixa esikhulu se-asidi (unyibiliko olune-asidi yesulfuric kunye ne-ammonium bisulfate njengenxalenye engundoqo kwaye iqulethe isixa esincinci sezinto eziphilayo), ubungakanani bayo buyi-2.5~3.5 umphinda-phindene we-MMA, kwaye ingumthombo omandundu wongcoliseko lokusingqongileyo;

o Ngenxa yokusetyenziswa kwe-asidi ye-sulfuric, izixhobo zokulwa ne-corrosion ziyafuneka, kwaye ukwakhiwa kwesixhobo kuyabiza.

(2) Indlela yeMethacrylonitrile (indlela ye-MAN)

U-Asahi Kasei uye waphuhlisa inkqubo ye-methacrylonitrile (MAN) esekelwe kwindlela ye-ACH, oko kukuthi, i-isobutylene okanye i-tert-butanol i-oxidized yi-ammonia ukuze ifumane i-MAN, ephendula nge-asidi ye-sulfuric ukuvelisa i-methacrylamide, ethi emva koko iphendule nge-asidi ye-sulfuric kunye ne-methanol ukuvelisa i-MMA. indlela ye-MAN iquka i-ammonia oxidation reaction, i-amidation reaction kunye ne-hydrolysis esterification reaction, kwaye inokusebenzisa izixhobo ezininzi zesityalo se-ACH. Impendulo ye-hydrolysis isebenzisa i-asidi ye-sulfuric engaphezulu, kwaye isivuno se-methacrylamide ephakathi siphantse sibe yi-100%. Nangona kunjalo, indlela inetyhefu kakhulu yeemveliso ze-hydrocyanic acid, i-hydrocyanic acid kunye ne-sulfuric acid ziyonakalisa kakhulu, iimfuno zezixhobo zokusabela ziphezulu kakhulu, ngelixa iingozi zokusingqongileyo ziphezulu kakhulu.

2, indlela ye-Isobutylene oxidation
I-Isobutylene oxidation ibe yindlela yobuchwepheshe ekhethwayo kwiinkampani ezinkulu zehlabathi ngenxa yokusebenza kwayo okuphezulu kunye nokukhuselwa kokusingqongileyo, kodwa umda wayo wobugcisa uphezulu, kwaye yiJapan kuphela eyayinobuchwephesha emhlabeni kwaye yavala iteknoloji ukuya eChina. Indlela ibandakanya iintlobo ezimbini zenkqubo yeMitsubishi kunye nenkqubo ye-Asahi Kasei.

(1) Inkqubo yeMitsubishi (indlela ye-isobutylene enamanyathelo amathathu)

I-Mitsubishi Rayon yaseJapan iphuhlise inkqubo entsha yokuvelisa i-MMA ukusuka kwi-isobutylene okanye i-tert-butanol njengento ekrwada, i-oxidation enamanyathelo amabini akhethiweyo ngomoya ukufumana i-methacrylic acid (MAA), kwaye emva koko i-esterified nge-methanol. Emva koshishino lweMitsubishi Rayon, iJapan Asahi Kasei Company, Japan Kyoto Monomer Company, Korea Lucky Company, njl. Inkampani yasekhaya yaseShanghai Huayi Group ityale imali eninzi yabantu kunye nemali, kwaye emva kweminyaka eli-15 yemizamo eqhubekayo nengapheliyo yezizukulwana ezibini, iphuhlise ngempumelelo ngokuzimeleyo inyathelo elibini le-oxidation kunye ne-esterification ye-isobutylene imveliso ecocekileyo ye-MMA yobugcisa, kwaye ngoDisemba 2017, yagqiba kwaye yafaka i-50,000 yenkampani ye-industrial ye-50,000 ye-industrial ye-Donghung-toni ye-MMA e-Donghung-toni ye-MMA UHeze, kwiPhondo laseShandong, ukwaphula iteknoloji ye-monopoly yaseJapan kwaye ibe yinkampani kuphela enobu buchwepheshe eChina. itekhnoloji, kwakhona yenza i-China ilizwe lesibini ukuba neteknoloji yezoshishino yokuvelisa i-MAA kunye ne-MMA nge-oxidation ye-isobutylene.

(2) Inkqubo ye-Asahi Kasei (inkqubo ye-isobutylene yamanyathelo amabini)

I-Asahi Kasei Corporation yaseJapan kudala izibophelele kuphuhliso lwendlela ye-esterification ethe ngqo yokuveliswa kwe-MMA, eyaphuhliswa ngempumelelo yaza yasetyenziswa ngo-1999 kunye neplanti yoshishino yeetoni ezingama-60,000 eKawasaki, eJapan, kwaye kamva yandiswa ukuya kwiitoni eziyi-100,000. Indlela yobugcisa iquka ukusabela kwamanyathelo amabini, oko kukuthi i-oxidation ye-isobutylene okanye i-tert-butanol kwisigaba segesi phantsi kwesenzo se-Mo-Bi composite oxide catalyst ukuvelisa i-methacrolein (MAL), ilandelwa yi-oxidative esterification ye-MAL kwisigaba solwelo phantsi kwesenzo se-Pd-Pb ye-MMA ye-oxidative ngokuthe ngqo ukuvelisa i-oxidative ye-MMA ngqo. inyathelo kule ndlela ukuvelisa iMMA. Indlela yenkqubo ye-Asahi Kasei ilula, kunye namanyathelo amabini kuphela okuphendula kunye namanzi kuphela njengemveliso, eluhlaza kunye nokusingqongileyo, kodwa ukuyila kunye nokulungiswa kwe-catalyst kufuna kakhulu. Kuxelwa ukuba i-Asahi Kasei ye-oxidative esterification catalyst iye yaphuculwa ukusuka kwisizukulwana sokuqala sePd-Pb ukuya kwisizukulwana esitsha se-Au-Ni catalyst.

Emva koshishino lweteknoloji ye-Asahi Kasei, ukususela ngo-2003 ukuya ku-2008, amaziko ophando lwasekhaya aqala uphando oluphezulu kule ndawo, kunye neeyunithi ezininzi ezifana neYunivesithi yaseHebei Normal, iZiko leNjineli yeNkqubo, i-Chinese Academy yeSayensi, iYunivesithi yaseTianjin kunye neYunivesithi yaseHarbin Engineering egxile kuphuhliso kunye nokuphuculwa kwe-Pd-Pb catalysts, njl apho yiDalian Institute of Chemical Engineering, Chinese Academy of Sciences, wenze inkqubela enkulu kuphononongo olulingwayo oluncinci, lugqibe ukulunga kwenkqubo yokulungiselela i-nano-gold catalyst, ujongo lwemeko yokusabela kunye novavanyo lokuvavanya ukusebenza komjikelo oluthe nkqo, kwaye ngoku ngokukhutheleyo usebenzisana namashishini ukuphuhlisa iteknoloji yoshishino.

3, Indlela ye-ethylene carbonyl synthesis
Itekhnoloji ye-ethylene carbonyl synthesis route industrialization ibandakanya inkqubo ye-BASF kunye nenkqubo ye-ethylene-propionic acid methyl ester.

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

Inkqubo iqulethwe ngamanyathelo amane: i-ethylene i-hydroformylated ukufumana i-propionaldehyde, i-propionaldehyde igxininiswe nge-formaldehyde ukuvelisa i-MAL, i-MAL i-air oxidized kwi-tubular fixed-bed reactor ukuvelisa i-MAA, kwaye i-MAA ihlukaniswe kwaye ihlanjululwe ukuvelisa i-MMA nge-esterification nge-methanol. Ukusabela linyathelo eliphambili. Inkqubo idinga amanyathelo amane, anzima kwaye afuna izixhobo eziphezulu kunye neendleko eziphezulu zotyalo-mali, ngelixa inzuzo yindleko ephantsi yezinto eziluhlaza.

Ukuphumelela kwasekhaya kuye kwenziwa kuphuhliso lwetekhnoloji ye-ethylene-propylene-formaldehyde synthesis ye-MMA. Ngo-2017, i-Shanghai Huayi Group Company, ngokubambisana neNanjing NOAO New Materials Company kunye neYunivesithi yaseTianjin, igqibe uvavanyo lokulinga lwe-1,000 yeetoni ze-propylene-formaldehyde condensation kunye ne-formaldehyde kwi-methacrolein kunye nokuphuhliswa kwepakethe yenkqubo ye-90,000-toni yesityalo soshishino. Ukongezelela, iZiko loBunjineli beNkqubo ye-Chinese Academy yeSayensi, ngokubambisana ne-Henan Energy kunye ne-Chemical Group, igqibe isityalo sokulinga soshishino lwe-1,000-toni kwaye iphumelele ngempumelelo ukusebenza okuzinzile kwi-2018.

(2) Inkqubo ye-Ethylene-methyl propionate (inkqubo yeLucite Alpha)

Iimeko zokusebenza zenkqubo ye-Lucite Alpha zilula, isivuno semveliso siphezulu, utyalo-mali lwezityalo kunye neendleko zempahla ekrwada ziphantsi, kwaye isikali seyunithi enye kulula ukwenza enkulu, okwangoku kuphela uLucite unolawulo olukhethekileyo lobu buchwepheshe kwihlabathi kwaye aludluliswanga kwihlabathi langaphandle.

Inkqubo yeAlfa yahlulwe yangamanyathelo amabini:

Isinyathelo sokuqala kukusabela kwe-ethylene kunye ne-CO kunye ne-methanol ukuvelisa i-methyl propionate

usebenzisa i-palladium-based homogeneous carbonylation catalyst, eneempawu zomsebenzi ophezulu, ukukhetha okuphezulu (99,9%) kunye nobomi benkonzo ende, kunye nokusabela kuqhutyelwa phantsi kweemeko ezinobunono, okungenakonakala kwisixhobo kunye nokunciphisa utyalo-mali lwenkunzi yokwakha;

Isinyathelo sesibini kukusabela kwe-methyl propionate kunye ne-formaldehyde ukwenza i-MMA

I-catalyst ye-proprietary multi-phase catalyst isetyenzisiweyo, enokukhethwa kwe-MMA ephezulu. Kwiminyaka yakutshanje, amashishini asekhaya atyale intshiseko enkulu kuphuhliso lwetekhnoloji ye-methyl propionate kunye ne-formaldehyde condensation kwi-MMA, kwaye enze inkqubela phambili enkulu ekuphuhlisweni kwenkqubo ye-catalyst kunye ne-fixed-bed-bed reaction, kodwa ubomi be-catalyst abukafikeleli kwiimfuno zezicelo zoshishino.