Methyl methacrylate (MMA) waa walxo kiimiko ah oo muhiim ah oo dabiici ah oo ceeriin ah iyo monomer polymer, oo inta badan loo isticmaalo soo saarista dhalada organic, caagagga wax lagu dhejiyo, acrylics, dahaarka iyo agabyada polymer-ka ee farmashiyaha, iwm. macluumaadka, fiber optic, robotics iyo goobo kale.

Maaddaama monomer ah, MMA waxaa inta badan loo isticmaalaa soo saarista polymethyl methacrylate (oo loo yaqaan plexiglass, PMMA), sidoo kale waxaa lagu koobi karaa xeryahooda vinyl kale si loo helo alaab leh sifooyin kala duwan, sida soo saarida polyvinyl chloride (PVC) wax lagu daro ACR, MBS iyo sida monomer labaad ee soo saarista acrylics.

Waqtigan xaadirka ah, waxaa jira saddex nooc oo geeddi-socod qaan-gaar ah oo loogu talagalay soo saarista MMA gudaha iyo dibedda: waddada esterification methacrylamide hydrolysis (habka acetone cyanohydrin iyo habka methacrylonitrile), dariiqa oxidation isobutylene (Habka Mitsubishi iyo habka Asahi Kasei) iyo jidka ethylene carbonyl synthesis Habka BASF iyo habka Lucite Alpha).

1. Methacrylamide hydrolysis wadada esterification
Jidkani waa habka wax soo saarka MMA ee soo jireenka ah, oo ay ku jiraan habka acetone cyanohydrin iyo habka methacrylonitrile, labadaba ka dib methacrylamide dhexdhexaadiyaha hydrolysis, esterification synthesis ee MMA.

(1) Habka cyanohydrin acetone (habka ACH)

Habka ACH, oo ay markii ugu horreysay soo saartay US Lucite, waa habka wax-soo-saarka warshadaha ugu horreeya ee MMA, sidoo kale waa habka wax-soo-saarka MMA ee adduunka hadda.Habkani wuxuu isticmaalaa acetone, hydrocyanic acid, sulfuric acid iyo methanol sida alaabta ceeriin, iyo talaabooyinka falcelinta waxaa ka mid ah: falcelinta cyanohydrinization, falcelinta amidation iyo hydrolysis esterification falcelinta.

Habka ACH waa mid farsamo ahaan u bislaaday, laakiin waxa uu leeyahay faa'iido darrada soo socota:

○ Isticmaalka aashitada hydrocyanic ee sunta ah, taas oo u baahan tallaabooyin ilaalin adag inta lagu jiro kaydinta, gaadiidka iyo isticmaalka;

○ Soo saarista xaddi badan oo haraaga aashitada ah (xalka aqueous leh sulfuric acid iyo ammonium bisulfate sida qaybaha ugu muhiimsan oo ay ku jiraan qadar yar oo maadada organic), qadarkeedu waa 2.5 ~ 3.5 jeer ka MMA, waana halis halis ah. isha wasakhowga deegaanka;

o Isticmaalka sulfuric acid awgeed, qalabka ka hortagga daxalka ayaa loo baahan yahay, dhismaha qalabkuna waa qaali.

(2) Habka Methacrylonitrile (Habka MAN)

Asahi Kasei waxa uu sameeyay habka methacrylonitrile (MAN) ee ku salaysan dariiqa ACH, ie, isobutylene ama tert-butanol waxa oksidhisay ammonia si ay u hesho MAN, kaas oo la falgala sulfuric acid si uu u soo saaro methacrylamide, ka dibna la falgala sulfuric acid iyo methanol si loo soo saaro. MMADariiqa MAN waxaa ka mid ah falcelinta oksaydheynta ammonia, falcelinta amidation-ka iyo falcelinta esterification hydrolysis, waxayna isticmaali kartaa inta badan qalabka warshadda ACH.Dareen-celinta hydrolysis waxay isticmaashaa sulfuric acid xad-dhaaf ah, iyo wax-soo-saarka methacrylamide dhexdhexaadka ah waa ku dhawaad ​​100%.Si kastaba ha ahaatee, habka ayaa leh sunta sunta ah ee hydrocyanic acid by-products, hydrocyanic acid iyo sulfuric acid aad bay u daxaloobaan, shuruudaha qalabka falcelinta ayaa aad u sarreeya, halka khataraha deegaanka ay aad u sarreeyaan.

2. Jidka oksidation isobutylene
Oxidation-ka isobutylene wuxuu ahaa dariiqa teknoolojiyadda ee ay door bidaan shirkadaha waaweyn ee adduunka sababtoo ah waxtarkeeda sare iyo ilaalinta deegaanka, laakiin heerkeeda farsamo ayaa aad u sarreeya, kaliya Japan ayaa mar haysata tignoolajiyada adduunka oo xannibay tignoolajiyada Shiinaha.Habka waxaa ku jira laba nooc oo ah habka Mitsubishi iyo habka Asahi Kasei.

(1) Habka Mitsubishi (habka saddex-tallaabo isobutylene)

Mitsubishi Rayon ee Japan ayaa sameeyay hannaan cusub si uu MMA uga soo saaro isobutylene ama tert-butanol sida walxo ceeriin ah, laba-tallaabo oksaydhation xul ah hawada si loo helo methacrylic acid (MAA), ka dibna lagu nadiifiyo methanol.Ka dib warshadaynta Mitsubishi Rayon, Japan Asahi Kasei Company, Japan Kyoto Monomer Company, Korea Lucky Company, iwm waxay xaqiiqsadeen warshadaynta midba midka kale ka dib.Shirkadda Shanghai Huayi Group Company waxay maalgelisay wax badan oo dhaqaale iyo dhaqaale ah, ka dib 15 sano oo dadaal joogto ah oo aan kala go 'lahayn oo laba jiil, waxay si guul leh u horumarisay si madax-bannaan laba-tallaabo oxidation iyo esterification of isobutylene wax soo saarka nadiif ah technology MMA, iyo December 2017. , waxa ay dhamaystirtay oo ay hawl galisay warshad warshadeed oo 50,000-ton ah oo MMA ah oo ay ku leedahay shirkad ay wada leeyihiin oo lagu magacaabo Dongming Huayi Yuhuang oo ku taal Heze, Gobolka Shandong, iyada oo jebisay kelitaliska tignoolajiyada ee Japan oo noqotay shirkadda kaliya ee tignoolajiyadan ku leh Shiinaha.tignoolajiyada, sidoo kale ka dhigaysa Shiinaha dalka labaad ee haysta tignoolajiyada warshadaha wax soo saarka ee MAA iyo MMA by oksidation of isobutylene.

(2) Habka Asahi Kasei (nidaamka laba-tallaabo isobutylene)

Shirkadda Asahi Kasei ee Japan ayaa muddo dheer u heellan horumarinta habka si toos ah u soo saarista MMA, kaas oo si guul leh loo sameeyay oo la geliyay 1999-kii iyada oo la adeegsanayo warshad 60,000-ton ah oo ku taal Kawasaki, Japan, ka dibna la ballaariyay 100,000 oo tan.Dariiqa farsamo waxa uu ka kooban yahay falcelin laba-tallaabo ah, ie oksaydhka isobutylene ama tert-butanol ee wejiga gaaska ee hoos yimaada ficilka Mo-Bi composite oxide catalyst si uu u soo saaro methacrolein (MAL), oo ay ku xigto oxidative esterification MAL wejiga dareeraha ee hoos yimaada ficilka Pd-Pb kicinta si ay si toos ah u soo saarto MMA, halkaasoo ogaanshaha ogsijiinta ee MAL ay tahay tallaabada ugu muhiimsan ee waddadan si loo soo saaro MMA.Habka geeddi-socodka Asahi Kasei waa mid fudud, oo leh laba tillaabo oo kaliya oo falcelin ah iyo biyo kaliya oo ka mid ah badeecada, taas oo ah cagaar iyo jawi saaxiibtinimo, laakiin naqshadeynta iyo diyaarinta kicinta ayaa aad u baahan.Waxaa la soo wariyay in Asahi Kasei's oxidative esterification kisheeyaha laga cusboonaysiiyay jiilkii ugu horreeyay ee Pd-Pb loona gudbiyay jiilka cusub ee Au-Ni katalist.

Ka dib markii warshadaynta ee tignoolajiyada Asahi Kasei, laga bilaabo 2003 ilaa 2008, machadyada cilmi-baarista gudaha waxay bilaabeen kor u kaca cilmi baarista aaggan, iyada oo qaybo badan oo kala ah Hebei Normal University, Institute of Process Engineering, Academy of Sciences Chinese, Tianjin University iyo Harbin Engineering University Ku saabsan horumarinta iyo hagaajinta Pd-Pb kicinta, iwm ka dib 2015, cilmi-baaris gudaha ah oo ku saabsan Au-Ni catalysts ayaa bilaabay wareeg kale oo kobcin ah, oo wakiil ka ah Machadka Dalian ee injineernimada kiimikada, Akadeemiyada Sayniska Shiinaha, ayaa horumar weyn ka sameeyay daraasad tijaabo ah oo yar, dhamaystirtay hagaajinta habka diyaarinta kicinta nano-dahab, baaritaanka xaaladda falcelinta iyo cusboonaysiinta toosan imtixaanka qiimaynta hawlgalka wareegga dheer, oo hadda waxa ay si firfircoon iskaashi la shirkadaha si ay u horumariyaan technology warshadaha.

3. Jidka synthesis Ethylene carbonyl
Tignoolajiyada ethylene carbonyl synthesis ee dariiqa warshadaynta waxaa ka mid ah habka BASF iyo habka ethylene-propionic acid methyl ester.

(1) Habka ethylene-propionic acid (habsocodka BASF)

Nidaamku wuxuu ka kooban yahay afar tillaabo: ethylene waa hydroformylated si loo helo propionaldehyde, propionaldehyde waxaa lagu ururiyaa formaldehyde si loo soo saaro MAL, MAL waa hawo oksijiin ah oo ku jira reactor sariiro go'an oo tubular ah si ay u soo saarto MAA, MAA waa la kala soocay oo la nadiifiyaa si loo soo saaro MMA by esterification methanol.Falcelintu waa tallaabada muhiimka ah.Nidaamku wuxuu u baahan yahay afar tallaabo, oo ah mid dhib badan oo u baahan qalab sare iyo kharash badan oo maalgashi, halka faa'iidada ay tahay qiimaha hoose ee alaabta ceeriin.

Horumarka gudaha ayaa sidoo kale lagu sameeyay horumarinta tignoolajiyada ethylene-propylene-formaldehyde ee MMA.2017, Shirkadda Shanghai Huayi Group, iyada oo la kaashanaysa shirkadda Nanjing NOAO New Materials Company iyo Jaamacadda Tianjin, waxay dhamaystirtay tijaabo tijaabo ah oo ah 1,000 tan oo ah propylene-formaldehyde uumiga leh formaldehyde ilaa methacrolein iyo horumarinta xirmo geeddi-socod oo loogu talagalay warshad warshadeed oo 90,000-ton ah.Intaa waxaa dheer, machadka injineernimada geeddi-socodka ee Akadeemiyada Sayniska ee Shiinaha, oo kaashanaya Henan Energy iyo Kooxda Kiimikada, waxay dhamaystireen 1,000-ton warshad tijaabo ah oo tijaabo ah waxayna si guul leh u gaareen hawlgal xasilloon 2018.

(2) Habka Ethylene-methyl propionate (Nidaamka Lucite Alpha)

Nidaamka hawlgalka Lucite Alpha waa mid khafiif ah, wax-soo-saarka alaabadu waa sarreeyaa, maalgashiga dhirta iyo kharashka alaabta ceeriin waa hooseeyaa, miisaanka hal unug waa sahlan tahay in la sameeyo, hadda kaliya Lucite ayaa si gaar ah u xakameynaya tiknoolajiyada adduunka oo aan ahayn loo wareejiyo dunida dibadda.

Habka Alpha wuxuu u qaybsan yahay laba tallaabo:

Tallaabada ugu horreysa waa falcelinta ethylene ee CO iyo methanol si loo soo saaro methyl propionate

iyadoo la adeegsanayo palladium-ku-salaysan is-daba-joogga kaarboonylation-ka, kaas oo leh sifooyinka dhaqdhaqaaqa sare, xulashada sare (99.9%) iyo nolosha adeegga dheer, falcelinta waxaa lagu fuliyaa xaalado khafiif ah, taas oo aan waxyeello u lahayn qalabka waxayna yaraynaysaa maalgashiga caasimadda dhismaha. ;

Tallaabada labaad waa falcelinta methyl propionate oo leh formaldehyde si loo sameeyo MMA

Kataliye-waji badan oo iska leh ayaa la isticmaalaa, kaas oo leh xulashada MMA sare.Sanadihii la soo dhaafay, shirkadaha gudaha waxay ku maalgaliyeen xamaasad weyn horumarinta tignoolajiyada ee methyl propionate iyo formaldehyde uumi MMA, waxayna horumar weyn ka sameeyeen kicinta iyo horumarinta habka falcelinta sariirta go'an, laakiin nolosha kicinta wali ma aysan gaarin shuruudaha warshadaha warshadaha. codsiyada.