Methyl methacrylate (MMA) nigikoresho cyingenzi cyibikoresho ngengabuzima hamwe na polymer monomer, bikoreshwa cyane mugukora ibirahuri kama, kubumba plastike, acrylics, coatings hamwe nibikoresho bya farumasi bikora bya polymer, nibindi.

Nka monomer yibikoresho, MMA ikoreshwa cyane cyane mugukora polymethyl methacrylate (bakunze kwita plexiglass, PMMA), kandi irashobora kandi gukoporora hamwe nibindi bikoresho bya vinyl kugirango ibone ibicuruzwa bifite imitungo itandukanye, nko gukora polyvinyl chloride (PVC) inyongeramusaruro ACR, MBS ndetse na monomer ya kabiri mugukora acrylics.

Kugeza ubu, hari ubwoko butatu bwibikorwa bikuze kugirango habeho umusaruro wa MMA mugihugu ndetse no mumahanga: inzira ya methacrylamide hydrolysis esterification inzira (uburyo bwa acetone cyanohydrin nuburyo bwa methacrylonitrile), inzira ya okiside ya isobutylene (inzira ya Mitsubishi na Asahi Kasei inzira) hamwe na Ethylene carboneyl synthesis (inzira ya BASF) na Lucite Alpha.

1 、 Inzira ya methacrylamide hydrolysis esterification inzira
Iyi nzira nuburyo gakondo bwa MMA bwo kubyaza umusaruro, harimo uburyo bwa acetone cyanohydrin nuburyo bwa methacrylonitrile, haba nyuma ya methacrylamide hagati ya hydrolysis, synthesis ya esterification ya MMA.

(1) Uburyo bwa Acetone cyanohydrin (uburyo bwa ACH)

Uburyo bwa ACH, bwatunganijwe bwa mbere na Amerika Lucite, nuburyo bwambere bwo gutunganya inganda za MMA, kandi nuburyo bukoreshwa cyane muri MMA ku isi muri iki gihe. Ubu buryo bukoresha acetone, aside hydrocyanic, aside sulfurike na methanol nk'ibikoresho fatizo, kandi intambwe zo kubyitwaramo zirimo: cyanohydrinisation reaction, amidation reaction na hydrolysis esterification reaction.

Inzira ya ACH irakuze mubuhanga, ariko ifite ibibi bikurikira:

Use Gukoresha aside hydrocyanic ifite ubumara bukabije, bisaba ingamba zikomeye zo kubarinda mugihe cyo kubika, gutwara no gukoresha;

Gukomoka ku musemburo mwinshi wa aside (igisubizo cyamazi hamwe na acide sulfurike na bisulfate ya ammonium nkibice byingenzi kandi bikubiyemo ibintu bike kama kama), ubwinshi bwikubye inshuro 2,5 ~ 3,5 za MMA, kandi ni isoko ikomeye yangiza ibidukikije;

o Bitewe no gukoresha aside sulfurike, harasabwa ibikoresho byo kurwanya ruswa, kandi kubaka igikoresho bihenze.

(2) Uburyo bwa Methacrylonitrile (Uburyo bwa MAN)

Asahi Kasei yateje imbere methacrylonitrile (MAN) ishingiye ku nzira ya ACH, ni ukuvuga isobutylene cyangwa tert-butanol ihindurwamo na ammonia kugirango ibone MAN, ikora na aside sulfurike ikora methacrylamide, hanyuma igakora na acide sulfurique na metani kugirango ikore MMA. inzira ya MAN ikubiyemo reaction ya ammonia, reaction ya amidation na hydrolysis esterification reaction, kandi irashobora gukoresha ibikoresho byinshi byuruganda rwa ACH. Hydrolysis reaction ikoresha aside irike ya sulfurike, kandi umusaruro wa methacrylamide uri hagati ni 100%. Nyamara, uburyo bufite aside irike cyane ya hydrocyanic aside, aside hydrocyanic na aside sulfurike irashobora kwangirika cyane, ibikoresho byibisubizo birakenewe cyane, mugihe ibyangiza ibidukikije ari byinshi.

2 route Inzira ya okiside ya Isobutylene
Okiside ya Isobutylene niyo nzira y’ikoranabuhanga yatoranijwe ku masosiyete akomeye ku isi kubera imikorere yayo myiza no kurengera ibidukikije, ariko urwego rwayo rwa tekinike ni rwinshi, kandi Ubuyapani bwonyine ni bwo bwigeze kugira ikoranabuhanga ku isi kandi buhagarika ikoranabuhanga mu Bushinwa. Uburyo bukubiyemo ubwoko bubiri bwibikorwa bya Mitsubishi na Asahi Kasei.

(1) Inzira ya Mitsubishi (uburyo bwa isobutylene intambwe eshatu)

Umuyapani Mitsubishi Rayon yateguye uburyo bushya bwo gukora MMA muri isobutylene cyangwa tert-butanol nk'ibikoresho fatizo, intambwe ebyiri zo guhitamo okiside ikoresheje umwuka kugirango ibone aside methacrylic (MAA), hanyuma igereranywa na methanol. Nyuma yinganda za Mitsubishi Rayon, Ubuyapani Asahi Kasei, Ubuyapani Kyoto Monomer Company, Korea Lucky Company, nibindi byabonye inganda murindi. Isosiyete yo mu gihugu cya Shanghai Huayi yo mu gihugu yashoye imari myinshi y’abantu n’imari, kandi nyuma y’imyaka 15 y’imbaraga zidahwema kandi zidatezuka z’ibisekuru bibiri, yateje imbere mu bwigenge intambwe ebyiri za okiside hamwe no guha agaciro isobutylene ikora neza ikoranabuhanga rya MMA, maze mu Kuboza 2017, ryuzuza kandi rishyira mu bikorwa uruganda rukora inganda rwa MMA rufite toni 50.000 mu isosiyete ikora imishinga ya Dongming Huayi Yuhuang iherereye mu Ntara ya Heop, mu karere ka Heop, iri koranabuhanga mu Bushinwa. ikoranabuhanga, kandi bituma Ubushinwa bugira igihugu cya kabiri gifite ikoranabuhanga ryateye imbere mu gukora MAA na MMA hakoreshejwe okiside ya isobutylene.

(2) Inzira ya Asahi Kasei (isobutylene intambwe ebyiri)

Isosiyete y’Ubuyapani Asahi Kasei imaze igihe kinini yiyemeje guteza imbere uburyo bwa esterification butaziguye bwo gukora MMA, yatejwe imbere kandi ishyirwa mu bikorwa mu 1999 hamwe n’uruganda rw’inganda rwa toni 60.000 i Kawasaki, mu Buyapani, nyuma rugera kuri toni 100.000. Inzira ya tekiniki igizwe nintambwe ebyiri, ni ukuvuga okiside ya isobutylene cyangwa tert-butanol mugice cya gaze ikorwa na Mo-Bi composite oxyde cataliste kugirango ikore methacrolein (MAL), ikurikirwa na esterifisifike ya MAL mugice cyamazi ikorwa na catalizike ya PMA kugirango itange MMA muburyo butaziguye, aho MID itera intambwe ya MMA. Uburyo bwa Asahi Kasei buroroshe, hamwe nintambwe zibiri gusa zo kubyitwaramo namazi gusa nkibicuruzwa, bibisi kandi bitangiza ibidukikije, ariko gushushanya no gutegura catalizator birasaba cyane. Biravugwa ko catisale ya Asahi Kasei ya okiside ya esterifike yazamuwe kuva mu gisekuru cya mbere cya Pd-Pb kugeza ku gisekuru gishya cya catalizike ya Au-Ni.

Nyuma y’inganda zikoranabuhanga rya Asahi Kasei, kuva 2003 kugeza 2008, ibigo byubushakashatsi bwimbere mu gihugu byatangiye ubushakashatsi muri kariya gace, hamwe n’ibice byinshi nka kaminuza isanzwe ya Hebei, Ishuri Rikuru ry’Ubwubatsi, Ishuri Rikuru ry’Ubushinwa, Ishuri Rikuru ry’Ubushinwa, Kaminuza ya Tianjin na Harbin Engineering University byibanda ku iterambere no guteza imbere catalizike ya Pd-Pb, n’ibindi. iterambere ryinshi mubushakashatsi buto bw'icyitegererezo, bwarangije kunoza gahunda yo gutegura catalizator ya nano-zahabu, kugenzura uko ibintu byifashe no kuzamura vertical igeragezwa ryigihe kirekire, kandi ubu irakorana cyane ninganda guteza imbere ikoranabuhanga mu nganda.

3 、 Inzira ya synthesis ya Ethylene
Tekinoroji ya Ethylene carbone synthesis inzira yinganda zirimo inzira ya BASF hamwe na Ethylene-propionic aside methyl ester inzira.

(1) uburyo bwa aside ya Ethylene-propionic (inzira ya BASF)

Inzira igizwe nintambwe enye: Ethylene ni hydroformylated kugirango ibone propionaldehyde, propionaldehyde ihujwe na formaldehyde kugirango itange MAL, MAL ihumeka umwuka mubyuma byuburiri bwigitanda kugirango ubyare umusaruro MAA, kandi MAA iratandukanijwe kandi isukurwa kugirango ikore MMA hamwe na methanol. Igisubizo nintambwe yingenzi. Inzira isaba intambwe enye, zisa naho zigoye kandi zisaba ibikoresho bihanitse nigiciro kinini cyishoramari, mugihe inyungu nigiciro gito cyibikoresho fatizo.

Iterambere ryimbere mu gihugu naryo ryakozwe mugutezimbere ikoranabuhanga rya Ethylene-propylene-formaldehyde synthesis ya MMA. 2017, Isosiyete ya Groupe ya Shanghai Huayi, ku bufatanye na Nanjing NOAO Sosiyete nshya y’ibikoresho na kaminuza ya Tianjin, barangije ikizamini cy’icyitegererezo cya toni 1.000 za propylene-formaldehyde hamwe na formaldehyde kuri methacrolein no guteza imbere gahunda yo gutunganya uruganda rukora toni 90.000. Byongeye kandi, Ishuri Rikuru ry’Ubwubatsi ry’Ishuri Rikuru ry’Ubumenyi ry’Ubushinwa, ku bufatanye na Henan Energy na Chemical Group, barangije uruganda rw’indege rwa toni 1.000 kandi rugera ku bikorwa bihamye muri 2018.

(2) Inzira ya Ethylene-methyl propionate (inzira ya Lucite Alpha)

Ibikorwa bya Lucite Alpha nibikorwa byoroheje, umusaruro wibicuruzwa ni mwinshi, ishoramari ryibimera nigiciro cyibikoresho biri hasi, kandi igipimo cyikintu kimwe cyoroshye gukora kinini, kuri ubu Lucite wenyine niwe ufite ubushobozi bwihariye bwikoranabuhanga kwisi kandi ntabwo yimuriwe hanze.

Inzira ya Alpha igabanijwemo intambwe ebyiri:

Intambwe yambere ni reaction ya Ethylene hamwe na CO na methanol kugirango itange methyl propionate

ukoresheje palladium ishingiye kuri homogeneous carbonylation catalizator, ifite ibiranga ibikorwa byinshi, guhitamo byinshi (99.9%) hamwe nigihe kirekire cyo gukora, kandi reaction ikorwa mubihe byoroheje, bikaba bitangirika kubikoresho kandi bikagabanya ishoramari ryubwubatsi;

Intambwe ya kabiri ni reaction ya methyl propionate hamwe na formaldehyde yo gukora MMA

Umutungo wibyiciro byinshi byifashishwa, bifite amahitamo menshi ya MMA. Mu myaka yashize, ibigo byimbere mu gihugu byashize imbaraga nyinshi mugutezimbere ikoranabuhanga rya methyl propionate na formaldehyde ya MMA, kandi byateye intambwe ishimishije mugutezimbere no gutunganya uburiri buteganijwe, ariko ubuzima bwa catalizator butaragera kubisabwa mubikorwa byinganda.