Methyl methacrylate (MMA) o se vailaʻau faʻalaʻau faʻalaʻau mea mata ma polymer monomer, e masani ona faʻaaogaina i le gaosiga o tioata faʻapitoa, faʻapipiʻi palasitika, acrylics, coatings ma mea tau vailaʻau polymer aoga, ma isi. fa'amatalaga, fiber opitika, robotics ma isi matā'upu.

I le avea ai o se monomer meafaitino, MMA e masani ona faʻaaogaina i le gaosiga o le polymethyl methacrylate (e masani ona taʻua o le plexiglass, PMMA), ma e mafai foi ona faʻapipiʻiina ma isi vailaʻau vinyl e maua ai oloa e iai mea eseese, e pei o le gaosiga o le polyvinyl chloride (PVC). ) faʻaopoopoga ACR, MBS ma o se monomer lona lua i le gaosiga o acrylics.

I le taimi nei, e tolu ituaiga o faiga matutua mo le gaosiga o le MMA i le fale ma fafo: methacrylamide hydrolysis esterification auala (acetone cyanohydrin method ma methacrylonitrile method), isobutylene oxidation auala (Mitsubishi process ma Asahi Kasei process) ma ethylene carbonyl synthesis auala ( Auala BASF ma metotia Lucite Alpha).

1, Methacrylamide hydrolysis auala esterification
O lenei auala o le auala masani o le gaosiga o le MMA, e aofia ai le acetone cyanohydrin method ma le methacrylonitrile method, i le maeʻa ai o le methacrylamide intermediate hydrolysis, esterification synthesis o MMA.

(1) Acetone cyanohydrin auala (ACH method)

O le auala ACH, muamua na atiaʻe e le US Lucite, o le auala muamua o gaosiga o fale gaosi oloa a le MMA, ma o le faʻaogaina o le gaosiga o le MMA i le lalolagi i le taimi nei. O lenei metotia e faʻaaogaina ai le acetone, hydrocyanic acid, sulfuric acid ma le methanol e fai ma mea mataʻutia, ma o laʻasaga faʻaalia e aofia ai: cyanohydrinization reaction, amidation reaction and hydrolysis esterification reaction.

O le fa'agasologa o le ACH e matua fa'atekinolosi, ae o lo'o i ai fa'afitauli matuia nei:

○ Le faʻaaogaina o le hydrocyanic acid e sili ona oona, lea e manaʻomia ai ni puipuiga malosi i le taimi o le teuina, felauaiga ma le faʻaaogaina;

○ E ala i le gaosia o se aofaiga tele o mea o totoe o le acid (vaivai vai ma le sulfuric acid ma le ammonium bisulfate e avea ma vaega autu ma o loʻo i ai se vaega itiiti o mea faʻalaʻau), o le aofaʻi o le 2.5 ~ 3.5 taimi o le MMA, ma o se ogaoga. puna o le faaleagaina o le siosiomaga;

o Ona o le faʻaaogaina o le sulfuric acid, e manaʻomia ai mea e faʻafefe ai mea, ma e taugata le fausiaina o le masini.

(2) Methacrylonitrile auala (Metotia MAN)

Ua fausia e Asahi Kasei le faagasologa o le methacrylonitrile (MAN) e faavae i luga o le auala ACH, o lona uiga, o le isobutylene poʻo le tert-butanol e faʻamaʻiina e le ammonia e maua ai le MAN, lea e tali atu i le sulfuric acid e maua ai le methacrylamide, ona faʻafefe ai lea ma le sulfuric acid ma le methanol e maua ai. MMA. O le auala MAN e aofia ai le ammonia oxidation reaction, amidation reaction and hydrolysis esterification reaction, ma e mafai ona fa'aogaina le tele o meafaigaluega a le fale ACH. O le fa'aogaina o le hydrolysis e fa'aaogaina ai le sili atu o le sulfuric acid, ma o le fua o le methacrylamide intermediate e toetoe lava 100%. Ae ui i lea, o le metotia o loʻo i ai mea e sili ona oona o le hydrocyanic acid, o le hydrocyanic acid ma le sulfuric acid e matua pala, o mea e manaʻomia e tali atu e maualuga tele, ae o le siosiomaga e maualuga tele.

2、 auala fa'ama'i ole isobutylene
O le Isobutylene oxidation o le auala faʻatekonolosi sili lea mo kamupani tetele i le lalolagi ona o lona maualuga maualuga ma le puipuiga o le siosiomaga, ae o lona tulaga faʻapitoa e maualuga, ma e naʻo Iapani na i ai le tekonolosi i le lalolagi ma poloka le tekonolosi i Saina. O le metotia e aofia ai ituaiga e lua o le Mitsubishi process ma Asahi Kasei process.

(1) Mitsubishi process (isobutylene tolu-laasaga auala)

O le Mitsubishi Rayon a Iapani na atiina ae se faiga fou e gaosia ai le MMA mai le isobutylene poʻo le tert-butanol e avea ma mea mata, lua-laasaga filifilia faʻamaʻi e ala i le ea e maua ai le methacrylic acid (MAA), ona faʻamasimaina lea i le methanol. Ina ua uma le alamanuia o Mitsubishi Rayon, Iapani Asahi Kasei Kamupani, Iapani Kyoto Monomer Kamupani, Korea Lucky Kamupani, ma isi ua iloa alamanuia tasi ma le isi. O le Shanghai Huayi Group Company na teu faafaigaluegaina le tele o tagata ma punaoa tau tupe, ma ina ua mavae le 15 tausaga o taumafaiga faifaipea ma le le mafaagaloina o augatupulaga e lua, na ia atiina ae tutoatasi le lua-laasaga oxidation ma esterification o isobutylene mama gaosiga MMA tekinolosi, ma ia Tesema 2017 , na maeʻa ma faʻaaogaina se fale gaosi oloa 50,000-ton MMA i lana kamupani faʻapisinisi faʻatasi Dongming Huayi Yuhuang o loʻo i totonu. Heze, Itumalo o Shandong, talepeina le pule faʻatekonolosi a Iapani ma avea ai ma kamupani e tasi i lenei tekinolosi i Saina. tekinolosi, ma avea ai foi Saina ma atunuu lona lua e maua le tekinolosi alamanuia mo le gaosiga o le MAA ma le MMA e ala i le oxidation o isobutylene.

(2) Asahi Kasei fa'agasologa (isobutylene lua-laasaga fa'agasologa)

O le Faalapotopotoga a Asahi Kasei a Iapani ua leva ona tuuto atu i le atinaʻeina o auala esterification tuusaʻo mo le gaosiga o le MMA, lea na faʻaleleia lelei ma faʻaaogaina i le 1999 ma se fale gaosi oloa 60,000-ton i Kawasaki, Iapani, ma mulimuli ane faʻalauteleina i le 100,000 tone. O le auala faʻapitoa e aofia ai se tali e lua-laasaga, e pei o le faʻamaʻiina o le isobutylene poʻo le tert-butanol i le vaega o le kesi i lalo o le gaioiga a le Mo-Bi composite oxide catalyst e maua ai le methacrolein (MAL), sosoo ai ma le esterification oxidative o MAL i le vaega vai i lalo o le gaioiga a le Pd-Pb catalyst e gaosia saʻo MMA, lea o le esterification oxidative o MAL o le laasaga autu i lenei auala e maua ai le MMA. Ole auala ole faiga ole Asahi Kasei e faigofie, e na o le lua laasaga ole tali atu ma naʻo le vai e fai ma mea faʻapitoa, lea e lanu meamata ma faʻafeiloaʻi le siosiomaga, ae o le mamanu ma le sauniuniga o le catalyst e matuaʻi manaʻomia. Ua lipotia mai o Asahi Kasei's oxidative esterification catalyst ua faaleleia mai le uluai augatupulaga o le Pd-Pb i le tupulaga fou o Au-Ni catalyst.

Ina ua maeʻa le gaosiga o tekinolosi a Asahi Kasei, mai le 2003 i le 2008, na amata ai e le au suʻesuʻe faʻapitonuʻu se faʻalauteleina o suʻesuʻega i lenei vaega, ma le tele o iunite e pei o le Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University ma Harbin Engineering University o loʻo taulaʻi atu. i luga o le atinae ma le faaleleia o Pd-Pb catalysts, ma isi. Ina ua mavae 2015, suesuega i totonu o le lotoifale i Au-Ni catalysts amata le isi taamilosaga o le boom, sui o lea Dalian Inisetiute o Inisinia Kemisi, Saina Academy o Saienisi, ua faia tele le alualu i luma i le suesuega pailate laiti, faamaeaina le optimization o nano-auro catalyst faagasologa sauniuniga, tali tulaga suʻesuʻe ma faʻaleleia tūsaʻo umi-taamilosaga suʻega suʻega suʻega, ma o loʻo galulue faʻatasi nei. fa'atasi ai ma atina'e e atia'e tekinolosi fa'apisinisi.

3. Ethylene carbonyl ala fa'apipi'i
O le tekinolosi o le ethylene carbonyl synthesis auala alamanuia e aofia ai le faagasologa BASF ma le ethylene-propionic acid methyl ester process.

(1) auala ethylene-propionic acid (fa'agasologa BASF)

O le faagasologa e aofia ai laasaga e fa: ethylene ua hydroformylated e maua ai le propionaldehyde, propionaldehyde ua condensed ma formaldehyde e maua ai MAL, MAL o le ea oxidized i totonu o se tubular reactor moega-maua e maua ai MAA, ma MAA ua tuueseeseina ma faamamaina e maua ai le MMA esterification ma methanol. O le tali o le laasaga autu. O le faagasologa e manaʻomia ai ni laasaga se fa, lea e fai si faigata ma e manaʻomia ai meafaigaluega maualuga ma le maualuga o tupe faʻaalu, ae o le lelei o le tau maualalo o mea mata.

Ua faia fo'i fa'alavelave fa'ale-lotoifale i le atina'eina o tekonolosi o le ethylene-propylene-formaldehyde synthesis o le MMA. 2017, Shanghai Huayi Group Company, i le galulue faatasi ma Nanjing NOAO New Materials Company ma le Iunivesite o Tianjin, faamaeaina se suega pailate o 1,000 tone o propylene-formaldehyde condensation ma formaldehyde i methacrolein ma le atinae o se afifi faagasologa mo se fale gaosi oloa 90,000 tone. E le gata i lea, o le Institute of Process Engineering a le Chinese Academy of Sciences, i le galulue faatasi ai ma le Henan Energy and Chemical Group, na maeʻa le 1,000 tone pailate fale gaosi oloa ma ausia manuia le faʻagaioiga mautu i le 2018.

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

Lucite Alpha faʻagasologa o tulaga faʻagaioia e agamalu, e maualuga le gaosiga o oloa, faʻafaigaluegaina o laʻau ma tau o mea mataʻutia e maualalo, ma o le fua o se iunite e tasi e faigofie ona fai tele, i le taimi nei naʻo Lucite e iai le pule faʻapitoa o lenei tekinolosi i le lalolagi ma e le o. siitia atu i le lalolagi i fafo.

O le faagasologa o le Alpha ua vaevaeina i ni laasaga se lua:

Ole laasaga muamua ole tali ole ethylene ile CO ma le methanol e maua ai le methyl propionate

faʻaaogaina palladium-based homogeneous carbonylation catalyst, o loʻo i ai uiga o le maualuga o le gaioiga, maualuga le filifilia (99.9%) ma le umi o le auaunaga, ma o le tali e faia i lalo o tulaga agamalu, lea e faʻaitiitia ai le pala i le masini ma faʻaitiitia ai le faʻafaigaluegaina o tupe faavae. ;

O le laasaga lona lua o le tali atu o le methyl propionate ma le formaldehyde e fausia ai le MMA

O lo'o fa'aaogaina se fa'ato'aga fa'a-vaega fa'apitoa, lea e maualuga le filifilia o le MMA. I tausaga talu ai nei, o pisinisi i totonu o le atunuu na teufaafaigaluegaina le naunautaiga tele i le atinaʻeina o tekonolosi o le methyl propionate ma le formaldehyde condensation i le MMA, ma ua faia le alualu i luma tele i le faʻaogaina ma le faʻaogaina o le faʻaogaina o le moega, ae e leʻi oʻo atu le ola faʻamalosi i manaʻoga mo pisinisi. talosaga.