Methyl methacrylate (MMA) yakakosha organic makemikari raw material uye polymer monomer, inonyanya kushandiswa mukugadzira organic glass, molding plastics, acrylics, coatings uye pharmaceutical functional polymer materials, nezvimwewo. ruzivo, optical fiber, marobhoti uye mamwe minda.

Sechinhu monomer, MMA inonyanya kushandiswa mukugadzirwa kwepolymethyl methacrylate (inowanzo zivikanwa se plexiglass, PMMA), uye inogona zvakare kugadzirwa nemamwe mavhinyl compounds kuti iwane zvigadzirwa zvine zvinhu zvakasiyana, sekugadzira polyvinyl chloride (PVC). ) additives ACR, MBS uye sechipiri monomer mukugadzirwa kwema acrylics.

Parizvino, kune marudzi matatu emaitiro akakura ekugadzirwa kweMMA kumba nekune dzimwe nyika: methacrylamide hydrolysis esterification nzira (acetone cyanohydrin nzira uye methacrylonitrile nzira), isobutylene oxidation nzira (Mitsubishi process uye Asahi Kasei process) uye ethylene carbonyl synthesis nzira ( BASF nzira uye Lucite Alpha nzira).

1, Methacrylamide hydrolysis esterification nzira
Iyi nzira ndiyo yechinyakare MMA yekugadzira nzira, kusanganisira iyo acetone cyanohydrin nzira uye methacrylonitrile nzira, zvese mushure memethacrylamide yepakati hydrolysis, esterification synthesis yeMMA.

(1) Acetone cyanohydrin nzira (ACH nzira)

Iyo nzira yeACH, yakatanga kugadzirwa neUS Lucite, ndiyo yekutanga nzira yekugadzira maindasitiri yeMMA, uye zvakare ndiyo yakajairwa kugadzirwa kweMMA munyika parizvino.Iyi nzira inoshandisa acetone, hydrocyanic acid, sulfuric acid uye methanol semidziyo, uye matanho ekuita anosanganisira: cyanohydrinization reaction, amidation reaction uye hydrolysis esterification reaction.

Iyo ACH maitiro akakura muhunyanzvi, asi ane zvinotevera zvakakomba zvakashata:

○ Kushandiswa kweiyo yakanyanya muchetura hydrocyanic acid, inoda matanho ekudzivirira akasimba panguva yekuchengetera, yekufambisa uye kushandiswa;

○ Nekugadzirwa kweasidhi yakawanda yakasara (mushonga wemvura une sulfuric acid uye ammonium bisulfate sezvikamu zvikuru uye zvine hushoma hwezvinhu zvakasimukira), huwandu hwacho hunoita 2.5~3.5 nguva yeMMA, uye ihombe. kunobva kusvibiswa kwezvakatipoteredza;

o Nekuda kwekushandiswa kwe sulfuric acid, anti-corrosion midziyo inodiwa, uye kuvakwa kwechigadzirwa kunodhura.

(2) Methacrylonitrile nzira (MAN nzira)

Asahi Kasei akagadzira nzira ye methacrylonitrile (MAN) yakavakirwa panzira yeACH, kureva, isobutylene kana tert-butanol yakashongedzwa neammonia kuti iwane MUNHU, inopindirana ne sulfuric acid kugadzira methacrylamide, iyo inobva yasangana ne sulfuric acid uye methanol kugadzira. MMA.iyo MAN nzira inosanganisira ammonia oxidation reaction, amidation reaction uye hydrolysis esterification reaction, uye inogona kushandisa yakawanda yemidziyo yeACH chirimwa.Iyo hydrolysis reaction inoshandisa yakawandisa sulfuric acid, uye goho repakati methacrylamide rinenge 100%.Nekudaro, iyo nzira ine yakanyanya muchetura hydrocyanic acid ne-zvigadzirwa, hydrocyanic acid uye sulfuric acid inoparadza zvakanyanya, maitiro emidziyo zvinodiwa akakwira zvakanyanya, nepo njodzi dzezvakatipoteredza dzakanyanya.

2, Isobutylene oxidation nzira
Isobutylene oxidation yanga iri nzira inofarirwa tekinoroji kumakambani makuru pasirese nekuda kwehunyanzvi hwayo hwepamusoro uye kuchengetedza kwezvakatipoteredza, asi tekinoroji yayo yakakwira, uye Japan chete yakambove nehunyanzvi munyika uye yakavharira tekinoroji kuChina.Iyo nzira inosanganisira maviri marudzi eMitsubishi maitiro uye Asahi Kasei maitiro.

(1) Mitsubishi maitiro (isobutylene-nhanho nhatu nzira)

Mitsubishi Rayon yekuJapan yakagadzira nzira nyowani yekugadzira MMA kubva kuisobutylene kana tert-butanol seyakagadzirwa, nhanho mbiri-inosarudza oxidation nemhepo kuti iwane methacrylic acid (MAA), uyezve esterified nemethanol.Mushure mekugadzirwa kwemaindasitiri kweMitsubishi Rayon, Japan Asahi Kasei Kambani, Japan Kyoto Monomer Kambani, Korea Lucky Kambani, nezvimwe.Imba yeShanghai Huayi Group Kambani yakaisa mari yakawanda yevanhu nemari, uye mushure memakore gumi nemashanu ekuenderera mberi uye kusingadzoreki kuedza kwezvizvarwa zviviri, yakabudirira kuvandudza yakazvimiririra nhanho mbiri oxidation uye esterification ye isobutylene yakachena kugadzirwa kweMMA tekinoroji, uye muna Zvita 2017. , yakapedzisa nekuisa 50,000-ton MMA industry plant mukambani yayo yemubatanidzwa Dongming Huayi Yuhuang iri muHeze, Shandong Province, ichityora tekinoroji yeJapan uye ikava iyo yega kambani ine tekinoroji iyi muChina.tekinoroji, zvichiitawo kuti China ive nyika yechipiri kuve nehunyanzvi hwekugadzira MAA neMMA neoxidation yeisobutylene.

(2) Asahi Kasei maitiro (isobutylene maviri-nhanho maitiro)

Asahi Kasei Corporation yekuJapan yakagara yakazvipira mukuvandudza nzira yakananga esterification yekugadzirwa kweMMA, iyo yakabudirira kugadzirwa uye yakaiswa mukushanda muna 1999 ine 60,000-matani maindasitiri chirimwa muKawasaki, Japan, uye yakazowedzerwa kusvika 100,000 matani.Iyo tekinoroji nzira ine nhanho mbiri yekuita, kureva, oxidation ye isobutylene kana tert-butanol muchikamu chegasi pasi pekuita kweMo-Bi composite oxide catalyst kugadzira methacrolein (MAL), ichiteverwa neiyo oxidative esterification yeMAL mu fluid chikamu pasi pekuita kwePd-Pb catalyst kugadzira MMA zvakananga, uko oxidative esterification yeMAL ndiyo nhanho yakakosha munzira iyi kugadzira MMA.Iyo Asahi Kasei process nzira iri nyore, ine matanho maviri chete ekuita uye chete mvura seyakagadzirwa-chigadzirwa, icho chakasvibira uye chinoenderana nemamiriro ekunze, asi dhizaini uye kugadzirira kweiyo catalyst inoda zvakanyanya.Zvinonzi Asahi Kasei's oxidative esterification catalyst yakagadziridzwa kubva kuchizvarwa chekutanga chePd-Pb kusvika kuchizvarwa chitsva cheAu-Ni catalyst.

Mushure mekugadzirwa kwehunyanzvi hweAsahi Kasei tekinoroji, kubva 2003 kusvika 2008, masangano ekutsvagisa mudzimba akatanga tsvakiridzo munzvimbo ino, aine zvikamu zvakati wandei seHebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University uye Harbin Engineering University inotarisisa. pakuvandudzwa nekuvandudzwa kwePd-Pb catalysts, nezvimwewo. Mushure megore ra2015, tsvakurudzo yemumba pamusoro peAu-Ni catalysts yakatanga Imwe denderedzwa rekusimudzira, mumiririri wayo ari Dalian Institute of Chemical Engineering, Chinese Academy of Sciences, yakafambira mberi zvikuru. chidzidzo chidiki chemutyairi wendege, chakapedza kukwidziridzwa kwenano-goridhe catalyst gadziriro, reaction yemamiriro ekuongorora uye yakatwasuka kukwidziridzwa kwerefu-kutenderera oparesheni yekuongorora bvunzo, uye ikozvino iri kushanda nesimba pamwe nemabhizinesi kuvandudza maindasitiri tekinoroji.

3, Ethylene carbonyl synthesis nzira
Iyo tekinoroji ye ethylene carbonyl synthesis nzira maindasitiri inosanganisira BASF maitiro uye ethylene-propionic acid methyl ester maitiro.

(1) ethylene-propionic acid nzira (BASF maitiro)

Maitiro acho ane matanho mana: ethylene is hydroformylated kuti iwane propionaldehyde, propionaldehyde yakanyungudutswa ne formaldehyde kugadzira MAL, MAL imhepo oxidized mu tubular fixed-bed reactor kuti ibudise MAA, uye MAA inoparadzaniswa uye inocheneswa kugadzira MMA ne esterification ne. methanol.Kuita ndiyo danho rinokosha.Maitiro acho anoda nhanho ina, iyo inorema uye inoda yakakwirira michina uye yakakwirira mari yekudyara, nepo mukana wacho uri mutengo wakaderera wezvigadzirwa.

Kubudirira kwemumba kwakaitwawo mukuvandudza tekinoroji ye ethylene-propylene-formaldehyde synthesis yeMMA.2017, Shanghai Huayi Group Kambani, mukubatana neNanjing NOAO New Materials Company uye Tianjin University, vakapedza kuyedza kwe1,000 matani epropylene-formaldehyde condensation ne formaldehyde kune methacrolein uye kugadzirwa kwepakeji yehurongwa hwe90,000-ton indasitiri chirimwa.Pamusoro pezvo, iyo Institute of Process Injiniya yeChinese Academy yeSainzi, yakabatana neHenan Energy neChemical Group, yakapedza 1,000-ton indasitiri yekutyaira chirimwa uye yakabudirira kushanda kwakagadzikana muna 2018.

(2) Ethylene-methyl propionate maitiro (Lucite Alpha maitiro)

Lucite Alpha maitiro ekushanda ane hunyoro, goho rechigadzirwa rakakwira, kudyara kwekudyara uye mitengo yemidziyo yakaderera, uye chiyero chechikamu chimwe chiri nyore kuita hombe, parizvino Lucite chete ndiye ane hunyanzvi hwekutonga tekinoroji iyi munyika uye haasi kutamisirwa kunyika yekunze.

Iyo Alpha process yakakamurwa kuita matanho maviri:

Nhanho yekutanga ndeyekuita kwe ethylene ine CO uye methanol kugadzira methyl propionate

kushandisa palladium-yakavakirwa homogeneous carbonylation catalyst, iyo ine hunhu hwekuita kwepamusoro, kusarudzwa kwepamusoro (99.9%) uye hupenyu hurefu hwebasa, uye maitiro anoitwa pasi pemamiriro akapfava, ayo asinganyanyi kukuvadza kune mudziyo uye anoderedza kuvakwa kwekudyara kwemari. ;

Nhanho yechipiri ndeyekuita kwemethyl propionate ine formaldehyde kuumba MMA

A proprietary multi-phase catalyst inoshandiswa, iyo ine high MMA selectivity.Mumakore achangopfuura, mabhizinesi epamba akadyara chishuwo chikuru mukuvandudza tekinoroji yemethyl propionate uye formaldehyde condensation kuMMA, uye akafambira mberi zvikuru mukusimudzira uye yakagadziriswa mubhedha reaction process process, asi iyo catalyst hupenyu hausati hwasvika kune zvinodiwa zveindasitiri. applications.