Methyl methacrylate (MMA) nigikoresho cyingenzi cya chimique chimique na polymer monomer, ikoreshwa cyane cyane mugukora ibirahuri kama, plastike ibumba, acrylics, coatings hamwe nibikoresho bya farumasi ikora, nibindi nibikoresho byo murwego rwohejuru kubirere, elegitoroniki amakuru, fibre optique, robotike nizindi nzego.

Nka monomer yibikoresho, MMA ikoreshwa cyane mugukora polymethyl methacrylate (bakunze kwita plexiglass, PMMA), kandi irashobora no gukoporora hamwe nibindi bikoresho bya vinyl kugirango ibone ibicuruzwa bifite imitungo itandukanye, nko gukora chloride polyvinyl (PVC) ) inyongera ACR, MBS kandi nka monomer wa 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 synthesis ya Ethylene carboneyl (inzira) Uburyo bwa BASF nuburyo bwa 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;

By-umusaruro mwinshi wa aside isigara (igisubizo cyamazi hamwe na acide sulfurike na bisulfate ya ammonium nkibice byingenzi kandi birimo ibintu bike kama kama), ubwinshi bwikubye inshuro 2,5 ~ 3,5 za MMA, kandi birakomeye isoko yo guhumanya 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 acide sulfurike ikora methacrylamide, hanyuma igakora na acide sulfurique na methanol kugirango itange umusaruro 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 bwa Mitsubishi na Asahi Kasei inzira.

(1) Inzira ya Mitsubishi (isobutylene uburyo butatu)

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’ingufu zidahwema kandi zidatezuka z’ibisekuru bibiri, yateye imbere mu bwigenge ibyiciro bibiri bya okiside hamwe no guha agaciro isobutylene ikora neza ikoranabuhanga rya MMA, no mu Kuboza 2017 , yarangije itangira gushyira mu bikorwa uruganda rukora inganda rwa toni 50.000 MMA mu isosiyete ikora imishinga ihuriweho na Dongming Huayi Yuhuang iherereye i Heze, mu Ntara ya Shandong, isenya monopoliya y’ikoranabuhanga mu Buyapani maze iba sosiyete yonyine ifite ikoranabuhanga 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 umusaruro wa MMA, watejwe imbere kandi ushyirwa mu bikorwa mu 1999 hamwe n’uruganda 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 okiside ya okiside ya MAL muri icyiciro cyamazi munsi ya catalizike ya Pd-Pb kugirango itange MMA itaziguye, aho okiside ya okiside ya MAL nintambwe yingenzi muriyi nzira yo kubyara 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 z’ikoranabuhanga rya Asahi Kasei, kuva mu 2003 kugeza 2008, ibigo by’ubushakashatsi mu gihugu byatangiye ubushakashatsi muri kariya gace, hamwe n’ibice byinshi nka kaminuza isanzwe ya Hebei, Institute of Process Engineering, Ishuri Rikuru ry’Ubushinwa, Kaminuza ya Tianjin na kaminuza ya Harbin Engineering. ku iterambere no kunoza catalizike ya Pd-Pb, nibindi. Nyuma yumwaka wa 2015, ubushakashatsi bwakozwe murugo kuri catalizike ya Au-Ni bwatangiye Ikindi cyiciro cy’iterambere, uhagarariye akaba ari ikigo cya Dalian Institute of Chemical Engineering, Academy of Science, Ubushinwa, cyateye intambwe nini muri ubushakashatsi buto bw'icyitegererezo, bwarangije gutezimbere gahunda ya nano-zahabu yo gutegura catalizator, kugenzura uko ibintu byifashe no kuzamura vertical verisiyo yikizamini cyo gusuzuma ibikorwa, 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.

(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 mubitereko byuburiri bwigitanda kugirango ikore MAA, kandi MAA iratandukanijwe kandi isukurwa kugirango ikore MMA hamwe na esterification hamwe 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, Shanghai Huayi Group Company, ku bufatanye na Nanjing NOAO Sosiyete Nshya y’ibikoresho na kaminuza ya Tianjin, barangije ikizamini cy’icyitegererezo cya toni 1.000 za kondine ya propylene-formaldehyde hamwe na fordehide 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 sibyo. bimuriwe 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 cataliste, ifite ibiranga ibikorwa byinshi, guhitamo byinshi (99.9%) hamwe nigihe kirekire cyo gukora, kandi reaction ikorwa mubihe byoroheje, bikaba bitangirika kubikoresho kandi bigabanya 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 nini mugutezimbere ibikorwa bya catalizator hamwe nigitanda gihamye, ariko ubuzima bwa cataliste ntiburagera kubisabwa mubikorwa byinganda Porogaramu.