Methyl methacrylate (MMA) ke ntho ea bohlokoa ea lik'hemik'hale tse tala le polymer monomer, haholo-holo e sebelisoang ha ho etsoa likhalase tsa tlhaho, li-plastiki tse bōpang, li-acrylics, li-coatings le lisebelisoa tsa polymer tse sebetsang ka meriana, joalo-joalo Ke thepa e phahameng ea ho qetela bakeng sa aerospace, tlhahisoleseding ea elektronike, fiber optical, robotics le masimo a mang.

E le monoma ea lintho tse bonahalang, MMA e sebelisoa haholo-holo tlhahisong ea polymethyl methacrylate (eo hangata e tsejoang e le plexiglass, PMMA), hape e ka kopanngoa le metsoako e meng ea vinyl ho fumana lihlahisoa tse nang le thepa e fapaneng, joalo ka ho etsa li-additives tsa polyvinyl chloride (PVC) ACR, MBS le e le monoma ea bobeli ha ho etsoa li-acrylic.

Hona joale, ho na le mefuta e meraro ea mekhoa e hōlileng tsebong bakeng sa tlhahiso ea MMA lapeng le linaheng tse ling: tsela ea methacrylamide hydrolysis esterification (mokhoa oa acetone cyanohydrin le mokhoa oa methacrylonitrile), tsela ea isobutylene oxidation (mokhoa oa Mitsubishi le mokhoa oa Asahi Kasei) le tsela ea ethylene carbonyl synthesis (mokhoa oa BASF le Lucite).

1, Methacrylamide hydrolysis esterification tsela
Tsela ena ke mokhoa o tloaelehileng oa tlhahiso ea MMA, ho kenyelletsa le mokhoa oa acetone cyanohydrin le mokhoa oa methacrylonitrile, ka mor'a methacrylamide bohareng hydrolysis, esterification synthesis ea MMA.

(1) Acetone cyanohydrin mokhoa (ACH mokhoa)

Mokhoa oa ACH, o qalileng pele ke US Lucite, ke mokhoa oa pele oa tlhahiso ea indasteri oa MMA, hape ke mokhoa o ka sehloohong oa tlhahiso ea MMA lefatšeng hona joale. Mokhoa ona o sebelisa acetone, hydrocyanic acid, sulfuric acid le methanol e le lisebelisoa tse tala, 'me mehato ea karabelo e kenyelletsa: cyanohydrinization reaction, amidation reaction le hydrolysis esterification reaction.

Ts'ebetso ea ACH e holile tsebong, empa e na le mefokolo e latelang e tebileng:

○ Tšebeliso ea hydrocyanic acid e chefo haholo, e hlokang mehato e tiileng ea tšireletso nakong ea polokelo, lipalangoang le tšebeliso;

○ Ka tlhahiso ea masala a mangata a asiti (motsoako o nang le asiti ea sulfuric le ammonium bisulfate e le likaroloana tse kholo le tse nang le lintho tse itseng tse phelang), tseo palo ea tsona e leng makhetlo a 2.5~3.5 ho feta a MMA, 'me ke mohloli o matla oa tšilafalo ea tikoloho;

o Ka lebaka la tšebeliso ea sulfuric acid, lisebelisoa tse thibelang ho bola lia hlokahala, 'me kaho ea sesebelisoa e theko e boima.

(2) mokhoa oa Methacrylonitrile (mokhoa oa MAN)

Asahi Kasei o hlahisitse ts'ebetso ea methacrylonitrile (MAN) e thehiloeng tseleng ea ACH, ke hore, isobutylene kapa tert-butanol e oxidized ke ammonia ho fumana MAN, e sebetsanang le sulfuric acid ho hlahisa methacrylamide, e ntan'o itšoara ka sulfuric acid le methanol ho hlahisa MMA. tsela ea MAN e kenyelletsa ammonia oxidation reaction, amidation reaction le hydrolysis esterification reaction, mme e ka sebelisa boholo ba lisebelisoa tsa semela sa ACH. Karabelo ea hydrolysis e sebelisa sulfuric acid e feteletseng, 'me lihlahisoa tsa methacrylamide tse mahareng li batla li le 100%. Leha ho le joalo, mokhoa ona o na le lihlahisoa tse chefo haholo tsa hydrocyanic acid, hydrocyanic acid le sulfuric acid li senya haholo, litlhoko tsa thepa ea karabelo li phahame haholo, athe likotsi tsa tikoloho li phahame haholo.

2. Tsela ea Isobutylene oxidation
Isobutylene oxidation e 'nile ea e-ba tsela ea theknoloji e ratoang bakeng sa lik'hamphani tse kholo lefatšeng ka lebaka la ts'ebetso ea eona e phahameng le ts'ireletso ea tikoloho, empa moeli oa eona oa tekheniki o phahame,' me ke Japane feela e kileng ea e-ba le theknoloji lefatšeng 'me ea thibela theknoloji ho ea Chaena. Mokhoa ona o kenyelletsa mefuta e 'meli ea ts'ebetso ea Mitsubishi le ts'ebetso ea Asahi Kasei.

(1) Ts'ebetso ea Mitsubishi (mokhoa oa mehato e meraro ea isobutylene)

Mitsubishi Rayon ea Japane e hlahisitse mokhoa o mocha oa ho hlahisa MMA ho tsoa ho isobutylene kapa tert-butanol e le lisebelisoa tse tala, oxidation ea mehato e 'meli e khethiloeng ke moea ho fumana methacrylic acid (MAA), ebe e tšeloa ka methanol. Kamora nts'etsopele ea indasteri ea Mitsubishi Rayon, Khamphani ea Asahi Kasei ea Japane, Kyoto Monomer Company ea Japane, Korea Lucky Company, joalo-joalo e se e lekile kholo ea indasteri ka ho latellana. The malapeng Shanghai Huayi Group Company invested e ngata batho le matlotlo a lichelete, 'me ka mor'a lilemo tse 15 tsa boiteko bo tsoelang pele le unremitting ea meloko e' meli, e ka katleho ntshetswa pele ka boikemelo tse peli-mohato oxidation le esterification ea isobutylene hloekileng tlhahiso MMA thekenoloji, 'me ka December 2017, e ile ea qeta le ho kenya tshebetsong 50,000 khamphani e kopanetsweng ea indasteri ea Donghuang Yuven Huven Huven Heze, Profinseng ea Shandong, e senya puso ea theknoloji ea Japane le ho ba eona feela k'hamphani e nang le theknoloji ena Chaena. theknoloji, e boetse e etsa hore Chaena e be naha ea bobeli ea ho ba le theknoloji e tsoetseng pele ea indasteri bakeng sa tlhahiso ea MAA le MMA ka oxidation ea isobutylene.

(2) Asahi Kasei tshebetso (isobutylene mehato e 'meli)

Asahi Kasei Corporation ea Japane ke khale e ikemiseditse ho ntshetsopele ya mokgwa o otlolohileng wa esterification bakeng sa tlhahiso ya MMA, e ileng ya ntshetswa pele ka katleho mme ya kenngwa tshebetsong ka 1999 ka semela sa indasteri sa dithane tse 60,000 Kawasaki, Japane, mme hamorao sa atoloswa ho fihla ho dithane tse 100,000. Tsela ea tekheniki e na le karabelo ea mehato e 'meli, ke hore, oxidation ea isobutylene kapa tert-butanol mokhahlelong oa khase tlas'a ts'ebetso ea Mo-Bi composite oxide catalyst ho hlahisa methacrolein (MAL), e lateloang ke oxidative esterification ea MAL mokhahlelong oa mokelikeli tlas'a ts'ebetso ea Pd-Pb MMA oxidative ka kotloloho, mohato tseleng ena ho hlahisa MMA. Mokhoa oa ts'ebetso oa Asahi Kasei o bonolo, o na le mehato e 'meli feela ea karabelo le metsi feela e le sehlahisoa, se nang le botala le tikoloho, empa moralo le ho lokisoa ha catalyst ho thata haholo. Ho tlalehoa hore Asahi Kasei's oxidative esterification catalyst e ntlafalitsoe ho tloha molokong oa pele oa Pd-Pb ho isa molokong o mocha oa Au-Ni catalyst.

Ka mor'a indasteri ea theknoloji ea Asahi Kasei, ho tloha 2003 ho ea ho 2008, litsi tsa lipatlisiso tsa malapeng li ile tsa qala ho etsa lipatlisiso sebakeng sena, tse nang le lihlopha tse 'maloa tse kang Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Univesithi ea Tianjin le Harbin Engineering University e lebisang tlhokomelo ho nts'etsopele le ntlafatso ea li-catalysts tsa Pd-Pb, joalo-joalo Ka mor'a 201 ho pota-pota, moemeli oa 201-Ni o ile a qala ho pota-pota ka Aus5-Ni. eo e leng Dalian Institute of Chemical Engineering, Sechaena Academy of Sciences, e entse tsoelo-pele e kholo thutong e nyenyane ea sefofane, e phethile ho ntlafatsa ts'ebetso ea ho lokisa li-catalyst tsa nano-khauta, tlhahlobo ea boemo ba karabelo le tlhahlobo ea tlhahlobo ea tlhahlobo ea nako e telele ea potoloho, 'me hona joale e sebelisana ka mafolofolo le likhoebo ho ntshetsa pele theknoloji ea indasteri.

3, Ethylene carbonyl synthesis tsela
Theknoloji ea ethylene carbonyl synthesis route industrialization e kenyelletsa ts'ebetso ea BASF le ts'ebetso ea ethylene-propionic acid methyl ester.

(1) mokhoa oa ethylene-propionic acid (mokhoa oa BASF)

Tshebetso ena e na le mehato e mene: ethylene ke hydroformylated ho fumana propionaldehyde, propionaldehyde e condensed le formaldehyde ho hlahisa MAL, MAL ke moea oxidized ka tubula fixed-bed reactor ho hlahisa MAA, 'me MAA e arohane le ho hloekisoa ho hlahisa MMA ka esterification ka methanol. Karabelo ke mohato oa bohlokoa. Ts'ebetso e hloka mehato e mene, e batlang e le boima 'me e hloka lisebelisoa tse phahameng le litšenyehelo tse phahameng tsa lichelete, athe molemo ke theko e tlaase ea thepa e tala.

Likhatelo-pele tsa malapeng le tsona li entsoe ntlafatsong ea theknoloji ea ethylene-propylene-formaldehyde synthesis ea MMA. Ka 2017, Shanghai Huayi Group Company, ka tšebelisano-'moho le Nanjing NOAO New Materials Company le Univesithi ea Tianjin, ba qetile teko ea lifofane ea lithane tse 1,000 tsa condensation ea propylene-formaldehyde ka formaldehyde ho methacrolein le nts'etsopele ea sephutheloana sa ts'ebetso bakeng sa semela sa indasteri sa 90,000-ton. Ntle le moo, Setsi sa Boenjiniere ba Ts'ebetso ea Setsi sa Setsi sa Sechaena sa Mahlale, ka tšebelisano le Henan Energy le Chemical Group, se phethetse setsi sa liteko sa liindasteri sa lithane tse 1,000 mme se fihletse ts'ebetso e tsitsitseng ka 2018.

(2) Ts'ebetso ea Ethylene-methyl propionate (ts'ebetso ea Lucite Alpha)

Maemo a ts'ebetso ea ts'ebetso ea Lucite Alpha a bonolo, lihlahisoa tsa lihlahisoa li phahame, matsete a limela le litšenyehelo tsa thepa e tala li tlaase, 'me tekanyo ea yuniti e le' ngoe e bonolo ho e etsa e kholo, hona joale ke Lucite feela ea nang le taolo e khethehileng ea thekenoloji ena lefatšeng 'me ha e fetisetsoe lefatšeng le ka ntle.

Mokhoa oa Alpha o arotsoe ka mehato e 'meli:

Mohato oa pele ke karabelo ea ethylene e nang le CO le methanol ho hlahisa methyl propionate

sebelisa palladium e thehiloeng homogeneous carbonylation catalyst, e nang le litšobotsi tsa mosebetsi o phahameng, selectivity phahameng (99,9%) le bophelo bo bolelele tšebeletso, 'me karabelo e etsoa tlas'a maemo a bonolo, e leng ka tlaase ho moo senya ho sesebediswa le ho fokotsa kaho motse-moholo letsete;

Mohato oa bobeli ke karabelo ea methyl propionate e nang le formaldehyde ho theha MMA

Ho sebelisoa catalyst ea mekhahlelo e mengata, e nang le khetho e phahameng ea MMA. Lilemong tsa morao tjena, likhoebo tsa malapeng li tsetetse cheseho e kholo ho nts'etsopele ea thekenoloji ea methyl propionate le formaldehyde condensation ho MMA, 'me ba entse tsoelo-pele e kholo ho nts'etsopele ea ts'ebetso ea li-catalyst le bethe e tsitsitseng, empa bophelo bo susumetsang ha bo e-s'o fihlele litlhoko tsa likopo tsa indasteri.