ʻO Methyl methacrylate (MMA) he mea koʻikoʻi ka mea hoʻokalakupua a me ka polymer monomer, i hoʻohana nui ʻia i ka hana ʻana i nā aniani kūlohelohe, nā plastics molding, acrylics, coatings a me nā mea hana polymer pharmaceutical, etc. He mea kiʻekiʻe no ka aerospace, electronic ʻike, fiber optical, robotics a me nā kahua ʻē aʻe.

Ma ke ʻano he monomer waiwai, hoʻohana nui ʻia ʻo MMA i ka hana ʻana o ka polymethyl methacrylate (ʻike mau ʻia ʻo plexiglass, PMMA), a hiki ke kope pū ʻia me nā pūhui vinyl ʻē aʻe e loaʻa ai nā huahana me nā waiwai like ʻole, e like me ka hana ʻana i ka polyvinyl chloride (PVC). ) nā mea hoʻohui ACR, MBS a ma ke ʻano he monomer lua i ka hana ʻana o nā acrylics.

I kēia manawa, ʻekolu ʻano o nā kaʻina hana makua no ka hana ʻana i ka MMA ma ka home a ma waho: methacrylamide hydrolysis esterification ala (acetone cyanohydrin method a me methacrylonitrile method), isobutylene oxidation ala (Mitsubishi process and Asahi Kasei process) a me ethylene carbonyl synthesis route ( ʻO ke ʻano BASF a me ke ʻano Lucite Alpha).

1、Methacrylamide hydrolysis esterification ala
ʻO kēia ala kaʻina hana MMA kuʻuna, me ke ʻano acetone cyanohydrin a me ke ʻano methacrylonitrile, ʻelua ma hope o ka methacrylamide intermediate hydrolysis, esterification synthesis o MMA.

(1) Acetone cyanohydrin ala (ACH ala)

ʻO ke ala ACH, i hoʻomohala mua ʻia e ka US Lucite, ʻo ia ke ʻano hana hana ʻoihana mua loa o MMA, a ʻo ia hoʻi ke kaʻina hana MMA nui i ka honua i kēia manawa.Hoʻohana kēia ʻano hana i ka acetone, hydrocyanic acid, sulfuric acid a me ka methanol ma ke ʻano he kumu waiwai, a ʻo nā ʻanuʻu hopena e komo pū me: cyanohydrinization reaction, amidation reaction and hydrolysis esterification reaction.

ʻO ke kaʻina hana ACH ua oʻo maoli, akā loaʻa nā pōʻino koʻikoʻi penei:

○ ʻO ka hoʻohana ʻana i ka waika hydrocyanic ʻona loa, kahi e koi ai i nā hana pale koʻikoʻi i ka wā o ka mālama ʻana, ka lawe ʻana a me ka hoʻohana ʻana;

○ Ma ka hana ʻana i ka nui o ke koena waikawa (ka hopena wai me ka sulfuric acid a me ka ammonium bisulfate ma ke ʻano nui a loaʻa kahi mea liʻiliʻi o nā mea organik), ʻo ka nui o ia mea he 2.5 ~ 3.5 mau manawa o MMA, a he koʻikoʻi koʻikoʻi. kumu o ka haumia kaiapuni;

o Ma muli o ka hoʻohana ʻana i ka sulfuric acid, pono nā mea hana anti-corrosion, a ʻoi aku ke kumukūʻai o ke kūkulu ʻana i ka mea hana.

(2) Methacrylonitrile ala (MAN)

Ua hoʻomohala ʻo Asahi Kasei i ke kaʻina hana methacrylonitrile (MAN) e pili ana i ke ala ACH, ʻo ia hoʻi, ua hoʻoheheʻe ʻia ka isobutylene a i ʻole tert-butanol e ka amonia no ka loaʻa ʻana o MAN, ka mea e hana ai me ka sulfuric acid e hana i ka methacrylamide, a laila e hana me ka sulfuric acid a me ka methanol e hana ai. MMA.ʻO ke ala MAN e loaʻa ana i ka hopena ammonia oxidation, amidation reaction a me hydrolysis esterification reaction, a hiki ke hoʻohana i ka hapa nui o nā lako o ka mea kanu ACH.Hoʻohana ka hopena hydrolysis i ka waikawa sulfuric nui, a ʻo ka hua o ka methacrylamide waena he aneane 100%.Eia nō naʻe, ʻoi aku ka nui o nā huahana hydrocyanic acid, hydrocyanic acid a me sulfuric acid he corrosive loa, ʻoi aku ka kiʻekiʻe o ka pono o nā mea hana, ʻoiai ke kiʻekiʻe loa nā pōʻino o ke kaiapuni.

2、 Isobutylene oxidation ala
ʻO ka Isobutylene oxidation ke ala ʻenehana i makemake ʻia no nā ʻoihana nui o ka honua ma muli o kona kiʻekiʻe kiʻekiʻe a me ka mālama ʻana i ke kaiapuni, akā kiʻekiʻe kona paepae ʻenehana, a ʻo Iapana wale nō i loaʻa i ka ʻenehana i ka honua a kāohi i ka ʻenehana i Kina.Aia i loko o ke kaʻina hana ʻelua ʻano kaʻina hana Mitsubishi a me ka hana ʻo Asahi Kasei.

(1) Kaʻina hana Mitsubishi (isobutylene ʻekolu-ʻanuʻu ala)

Ua hoʻomohala ʻo Mitsubishi Rayon o Iapana i kahi kaʻina hana hou e hana ai i ka MMA mai ka isobutylene a i ʻole tert-butanol ma ke ʻano he mea maka, ʻelua ʻanuʻu koho ʻoki ʻia e ka ea no ka loaʻa ʻana o ka methacrylic acid (MAA), a laila esterified me ka methanol.Ma hope o ka hana ʻana o Mitsubishi Rayon, Japan Asahi Kasei Company, Japan Kyoto Monomer Company, Korea Lucky Company, etc.ʻO ka Shanghai Huayi Group Company i hoʻokomo i ka nui o nā kumu waiwai kanaka a me ke kālā, a ma hope o 15 mau makahiki o ka hoʻomau a me ka hoʻomau ʻole ʻana o nā hanauna ʻelua, ua hoʻomohala kūʻokoʻa ia i ka ʻelua-ʻanuʻu oxidation a me ka esterification o ka isobutylene maʻemaʻe hana ʻenehana MMA, a ma Dekemaba 2017 , ua hoʻopau a hoʻokomo i ka hana ʻoihana ʻoihana MMA 50,000-ton i kāna hui hui ʻo Dongming Huayi Yuhuang aia ma Heze, Shandong Province, e uhaki ana i ka monopoly ʻenehana o Iapana a lilo ʻo ia wale nō ka hui me kēia ʻenehana ma Kina.ʻenehana, ʻo ia hoʻi ʻo Kina ka lua o ka ʻāina i loaʻa ka ʻenehana ʻenehana no ka hana ʻana o MAA a me MMA ma o ka oxidation o isobutylene.

(2) ʻO ke kaʻina hana ʻo Asahi Kasei (isobutylene ʻelua ʻanuʻu kaʻina)

Ua paʻa lōʻihi ka hui ʻo Asahi Kasei o Iapana i ka hoʻomohala ʻana i ke ʻano esterification pololei no ka hana ʻana o MMA, i hoʻomohala maikaʻi ʻia a hoʻokomo ʻia i ka makahiki 1999 me kahi mea kanu ʻoihana 60,000-ton ma Kawasaki, Iapana, a ma hope ua hoʻonui ʻia i 100,000 tons.ʻO ke ala ʻenehana he ʻelua ʻanuʻu ka hopena, ʻo ia hoʻi ka oxidation o isobutylene a i ʻole tert-butanol i loko o ka māhele kinoea ma lalo o ka hana a Mo-Bi composite oxide catalyst e hana i ka methacrolein (MAL), a ukali ʻia e ka oxidative esterification o MAL i ka wai ma lalo o ka hana a Pd-Pb catalyst e hana pololei i ka MMA, kahi o ka oxidative esterification o MAL ka mea nui i kēia ala e hana ai i ka MMA.He mea maʻalahi ke kaʻina hana ʻo Asahi Kasei, ʻelua wale nō ʻanuʻu o ka hopena a me ka wai wale nō ma ke ʻano he huahana, ʻo ia ka ʻōmaʻomaʻo a me ke kaiapuni, akā koi nui ka hoʻolālā a me ka hoʻomākaukau ʻana o ka catalyst.Ua hōʻike ʻia ua hoʻomaikaʻi ʻia ka catalyst oxidative esterification o Asahi Kasei mai ka hanauna mua o Pd-Pb i ka hanauna hou o Au-Ni catalyst.

Ma hope o ka hana ʻenehana o Asahi Kasei ʻenehana, mai 2003 a 2008, ua hoʻomaka nā hale noiʻi kūloko i kahi boom noiʻi ma kēia wahi, me kekahi mau ʻāpana e like me Hebei Normal University, Institute of Process Engineering, Chinese Academy of Science, Tianjin University a me Harbin Engineering University e kālele ana. ma ka hooulu ana a me ka hooikaika ana o Pd-Pb catalysts, etc. Ma hope o 2015, hoʻomaka ka noiʻi kūloko ma Au-Ni catalysts Kekahi puni o ka boom, 'elele o ka Dalian Institute o Chemical 'enekinia, Chinese Academy o Sciences, ua hana nui holomua ma ka liʻiliʻi pilot study, hoʻopau i ka optimization o nano-gula catalyst kaʻina hoʻomākaukau, reaction condition screening a vertical upgrade long-cycle hana loiloi ho'āʻo, a i keia manawa ikaika cooperating me nā 'oihana e hoʻomohala industrialization 'enehana.

3、Ethylene carbonyl synthesis ala
ʻO ka ʻenehana o ka ethylene carbonyl synthesis route industryalization e pili ana i ka kaʻina BASF a me ka ethylene-propionic acid methyl ester process.

(1) ethylene-propionic acid method (BASF process)

ʻO ke kaʻina hana he ʻehā mau ʻanuʻu: ethylene hydroformylated e loaʻa ai ka propionaldehyde, propionaldehyde i condensed me formaldehyde e hana ai MAL, MAL ka ea oxidized i loko o ka tubular paʻa-moe reactor e hana MAA, a ua hoʻokaʻawale ʻia a hoʻomaʻemaʻe ʻia ʻo MAA e hana i ka MMA e ka esterification me methanol.ʻO ka pane ke kaʻina nui.Pono ke kaʻina hana i ʻehā mau ʻanuʻu, he mea paʻakikī a koi i nā mea hana kiʻekiʻe a me ke kumukūʻai hoʻolimalima kiʻekiʻe, ʻoiai ʻo ka pōmaikaʻi ʻo ia ke kumu kūʻai haʻahaʻa o nā mea maka.

Ua hana pū ʻia nā hanana kūloko i ka hoʻomohala ʻenehana o ka ethylene-propylene-formaldehyde synthesis o MMA.2017, Shanghai Huayi Group Company, me ka hui pū ʻana me Nanjing NOAO New Materials Company a me ke Kulanui ʻo Tianjin, ua hoʻopau i kahi hoʻokolohua hoʻokele o 1,000 tons o propylene-formaldehyde condensation me formaldehyde i ka methacrolein a me ka hoʻomohala ʻana i kahi pūʻolo kaʻina no kahi mea kanu ʻoihana 90,000-ton.Eia kekahi, ua hoʻopau ka Institute of Process Engineering o ka Chinese Academy of Science, me ka hui pū ʻana me Henan Energy and Chemical Group, i kahi mea kanu pilote 1,000-ton a ua hoʻokō kūleʻa i ka hana paʻa ma 2018.

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

ʻO ke kaʻina hana ʻo Lucite Alpha he haʻahaʻa, he kiʻekiʻe ka hua o ka huahana, ʻoi aku ka haʻahaʻa o ka hoʻopukapuka ʻana o nā mea kanu a me nā kumukūʻai maka, a ʻoi aku ka maʻalahi o ka nui o kahi ʻāpana hoʻokahi, i kēia manawa ʻo Lucite wale nō ka mana o kēia ʻenehana i ka honua a ʻaʻole ia. hoʻoneʻe ʻia i ka honua waho.

Ua māhele ʻia ke kaʻina hana Alpha i ʻelua mau ʻanuʻu:

ʻO ka hana mua ka hopena o ka ethylene me CO a me ka methanol e hana i ka methyl propionate

me ka hoʻohana ʻana i ka palladium homogeneous carbonylation catalyst, nona nā hiʻohiʻona o ka hana kiʻekiʻe, ke koho kiʻekiʻe (99.9%) a me ke ola lōʻihi o ka lawelawe ʻana, a lawe ʻia ka hopena ma lalo o nā kūlana haʻahaʻa, ʻoi aku ka liʻiliʻi o ka corrosive i ka hāmeʻa a hōʻemi i ka hoʻopukapuka kālā kūkulu. ;

ʻO ka ʻanuʻu ʻelua ka hopena o ka methyl propionate me ka formaldehyde e hana ai i ka MMA

Hoʻohana ʻia kahi catalyst multi-phase proprietary, nona ka koho MMA kiʻekiʻe.I nā makahiki i hala iho nei, ua hoʻokomo nā ʻoihana kūloko i ka hoihoi nui i ka hoʻomohala ʻenehana o ka methyl propionate a me ka condensation formaldehyde i MMA, a ua holomua nui i ka catalyst a me ka hoʻomohala ʻana i ke kaʻina hana, akā ʻaʻole i hiki ke ola catalyst i nā koi no ka ʻoihana. nā noi.