Methyl methacrylate (MMA) waa wax muhiim ah oo kiimikaad organic ceeriin iyo monomer polymer, inta badan loo isticmaalo in wax soo saarka ee galaas organic, caag ah, acrylics, daahan iyo alaabta polymer functional farmashiyaha, iwm.

Warshadda Wax-soo-saarka MMA

Sida monomer maaddooyinka, 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 alaabooyin leh sifooyin kala duwan, sida soo saarida polyvinyl chloride (PVC) daro ACR, MBS iyo sida monomer labaad ee wax soo saarka acrylic.

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 ethylene carbonyl synthesis route (habka BASF iyo habka Alpha 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 ah walxaha organic), qadarkeedu waa 2.5 ~ 3.5 jeer ka badan MMA, waana il halis ah oo wasakhowga deegaanka ah;

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 waa oxidized by ammonia si loo helo MAN, taas oo ka falcelisa sulfuric acid si ay u soo saarto methacrylamide, ka dibna la falgala sulfuric acid iyo methanol si loo soo saaro MMA. Dariiqa 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 ee gudaha 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 tignoolajiyada wax soo saarka nadiifka ah ee MMA, iyo bishii Diseembar 2017, waxay dhammaysay oo ay gelisay hawlgal 50,000-ton MMA warshad warshadeed oo ku taal Yuangng Hudo. Gobolka, jebinta monoboliga tignoolajiyada ee Japan oo noqday 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 farsamada ayaa ka kooban falcelin laba-tallaabo ah, ie oksaydhka isobutylene ama tert-butanol ee wajiga gaaska ee hoos yimaada ficilka Mo-Bi composite oxide catalyst si loo soo saaro methacrolein (MAL), oo ay ku xigto oxidative esterification ee MAL ee marxaladda dareeraha ah ee hoos yimaada ficilka Pd-Pb kicinta si ay u soo saarto dariiqa MMA si toos ah. 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, hay'adaha cilmi-baarista gudaha bilaabay kobcinta cilmi-baarista aaggan, iyada oo dhowr qaybood oo kala ah Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University iyo Harbin Engineering University diiradda saaraya horumarinta iyo hagaajinta Pd-Pb ee cilmi-baadhayaasha, iwm Ka dib markii 2015 ee catalysts gudaha - Nini, wakiil kale oo ka mid ah 2015 ee cilmi-baarista gudaha. taas oo ah Dalian Institute of Chemical Engineering, Akadeemiyada Sayniska Shiinaha, ayaa horumar weyn ka samaysay daraasadda tijaabada yar, waxay dhamaystirtay hagaajinta habka diyaarinta nano-dahab ee diyaarinta, baaritaanka xaaladda falcelinta iyo cusboonaysiinta qumman ee imtixaanka qiimeynta hawlgalka muddada-dheer, oo hadda si firfircoon ula shaqeyneysa shirkadaha si ay u horumariyaan farsamada 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 loo soo saaro MAA, iyo MAA waa la kala soocay oo la nadiifiyaa si loo soo saaro MMA by esterification with 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 nidaamka Lucite Alpha xaaladaha hawlgalka waa mid khafiif ah, wax-soo-saarka alaabadu waa sarreeyaa, maalgashiga dhirta iyo kharashka alaabta ceeriin waa yar yahay, miisaanka hal unug waa sahlan tahay in la sameeyo, hadda kaliya Lucite ayaa si gaar ah u xakameynaya tiknoolajiyada adduunka oo aan loo wareejin 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-saleysan kaarboonylation-ka-soo-baxa, kaas oo leh sifooyinka dhaqdhaqaaqa sare, xulashada sare (99.9%) iyo nolosha adeegga dheer, iyo 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, ganacsiyada gudaha waxay ku maalgaliyeen xamaasad weyn horumarinta tignoolajiyada ee methyl propionate iyo uumiga formaldehyde ee MMA, waxayna horumar weyn ka sameeyeen kobcinta iyo horumarinta habka falcelinta sariirta go'an, laakiin nolosha kicinta wali ma gaarin shuruudaha codsiyada warshadaha.


Waqtiga boostada: Abriil-06-2023