Methyl methacrylate (MMA) inokosha organic kemikari raw material uye polymer monomer, inonyanya kushandiswa mukugadzirwa kwegirazi reorganic, molding plastiki, acrylics, coatings uye pharmaceutical functional polymer zvinhu, etc. Icho chinhu chepamusoro-chepamusoro-chepamusoro-soro ye aerospace, ruzivo rwemagetsi, optical fiber, robotics nezvimwe minda.

Sechinhu monomer, MMA inonyanya kushandiswa mukugadzirwa kwepolymethyl methacrylate (inowanzozivikanwa se plexiglass, PMMA), uye inogona zvakare kubatanidzwa nemamwe mavhinyl compounds kuti iwane zvigadzirwa zvine zvinhu zvakasiyana-siyana, zvakadai sekugadzira polyvinyl chloride (PVC) additives ACR, MBS uye sechipiri monoma 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 muitiro uye Asahi Kasei muitiro) uye ethylene carbonyl synthesis nzira (BASF nzira uye Lucite Alfabeti).

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 kwehuwandu hukuru hweasidhi yakasara (mushonga wemvura une sulfuric acid uye ammonium bisulfate sezvikamu zvikuru uye zvine hushoma hwezvinhu zvipenyu), huwandu hwayo hunosvika 2.5~3.5 nguva yeMMA, uye ihombe yekusvibisa 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 yakasvibiswa neammonia kuti iwane MAN, iyo inopindirana ne sulfuric acid kuti ibudise 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 Company yakaisa mari yakawanda yevanhu uye mari, uye mushure memakore gumi nemashanu ekuenderera mberi uye kusingaregi kuedza kwezvizvarwa zviviri, yakabudirira kuvandudza yakazvimiririra nhanho mbiri oxidation uye esterification ye isobutylene yakachena kugadzirwa kweMMA tekinoroji, uye muna Zvita 2017, yakapedza nekuisa mukushanda kwe50,000,000 yekambani yemubatanidzwa muIndustria yeDonghu MMA muDonghuang Yunghung. Heze, Shandong Province, kutyora tekinoroji yeJapan uye kuve 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 maviri-nhanho kuita, kureva, oxidation ye isobutylene kana tert-butanol muchikamu chegasi pasi pechiito cheMo-Bi composite oxide catalyst kugadzira methacrolein (MAL), inoteverwa neiyo oxidative esterification yeMAL muchikamu chemvura pasi pekuita kwePd-Pb MMA inokonzeresa iyo inokonzeresa yeMMA inokonzeresa. pinda 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 muna 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 neHarbin Engineering University inotarisa mukusimudzira nekuvandudzwa kwePD-Pb catalysts, nezvimwe. iyo inonzi Dalian Institute of Chemical Engineering, Chinese Academy of Sciences, yakafambira mberi zvikuru muchidzidzo chiduku chemutyairi, yakapedza optimization ye nano-goridhe catalyst gadziriro yekugadzirira, maitiro ekuongorora mamiriro uye vertical upgrade refu-cycle operation evaluation test, uye iye zvino ari kushanda nesimba pamwe chete nemabhizinesi kuvandudza tekinoroji yeindasitiri.

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)

Nzira yacho ine matanho mana: ethylene inonzi hydroformylated kuti iwane propionaldehyde, propionaldehyde inogadziriswa ne formaldehyde kuti ibudise MAL, MAL inogadzirwa nemhepo mu tubular fixed-bed reactor kuti ibudise MAA, uye MAA inoparadzaniswa uye inonatswa kuti ibudise MMA ne esterification ine 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 maitiro akapfava, goho rechigadzirwa rakakwira, kudyara kwekudyara uye mari yemidziyo yakaderera, uye chiyero chechikamu chimwe chiri nyore kuita chakakura, parizvino Lucite chete ndiye ane hutongi hweiyi tekinoroji munyika uye haina kuendeswa kune kunze kwenyika.

Iyo Alpha process yakakamurwa kuita matanho maviri:

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

kushandisa palladium-based homogeneous carbonylation catalyst, iyo ine maitiro ekuita kwepamusoro, high selectivity (99,9%) uye hupenyu hurefu hwebasa, uye maitiro anoitwa pasi pemamiriro ezvinhu akapfava, asinganyanyi kukanganisa kune chigadzirwa uye anoderedza mari yekuvaka mari;

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 bhedha-yekuita maitiro ekuvandudza, asi iyo catalyst hupenyu hausati hwasvika kune zvinodiwa zvekushandiswa kwemaindasitiri.