ʻO ka Methyl methacrylate (MMA) he mea koʻikoʻi ka mea hoʻokalakupua a me ka polymer monomer, i hoʻohana nui ʻia i ka hana ʻana i ke aniani organik, molding plastics, acrylics, coatings a me pharmaceutical functional polymer material, etc.

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 copolymerized 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) additives 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 o MMA ma ka home a ma waho: methacrylamide hydrolysis esterification ala (acetone cyanohydrin method and methacrylonitrile method), isobutylene oxidation route (Mitsubishi process and Asahi Kasei process) a me ethylene carbonyl synthesis route (BASF method and Lucite Alpha method).

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 (waipuna wai me ka sulfuric acid a me ka ammonium bisulfate ma ke ʻano he mea nui a loaʻa kahi mea liʻiliʻi o nā mea organik), ʻo ia ka nui o 2.5 ~ 3.5 mau manawa o MMA, a he kumu koʻikoʻi o ka pollution 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 e loaʻa ai ka MAN, ka mea e hoʻopili ai me ka sulfuric acid e hana i ka methacrylamide, a laila hana me ka sulfuric acid a me ka methanol e hana ai i ka 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 waiwai kanaka a me ke kālā, a ma hope o 15 mau makahiki o ka hoʻomau ʻana a me ka hoʻomau ʻole ʻana o nā hanauna ʻelua, ua hoʻomohala kūʻokoʻa ʻo ia i ʻelua mau ʻanuʻu oxidation a me ka esterification o ka isobutylene maʻemaʻe hana MMA ʻenehana, a ma Dekemaba 2017, ua hoʻopau a hoʻokomo i ka hana he 50,000-ton i kāna ʻoihana hui ʻo MMA ʻo Yuhuhu. Heze, ka mokuʻo Shandong, e uhaki ana i ka monopoly ʻenehana o Iapana a lilo i ʻoihana hoʻokahi 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 pane, 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 wai ma lalo o ka hana a Pd-Pb catalyst e hana pololei i ka MMA, kahi o kēia alahele 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 industrialization o Asahi Kasei enehana, mai 2003 a hiki i 2008, hale noiʻi hale hoʻomaka i ka noiʻi boom ma keia wahi, me kekahi mau wae e like me Hebei Normal University, Institute o ka hana 'enekinia, Chinese Academy o Sciences, Tianjin University a me Harbin 'enekinia University e kālele ana i ka hoʻomohala a me ka hoʻomaikaʻi o Pd-Pb catalysts, etc. ʻO Dalian Institute of Chemical Engineering, Chinese Academy of Sciences, ua holomua nui i ka noiʻi hoʻokele liʻiliʻi, ua hoʻopau i ka optimization o ke kaʻina hana hoʻomākaukau ʻana o ka nano-gold catalyst, ka nānā ʻana i ke kūlana a me ka hoʻonui ʻana i ka loiloi loiloi lōʻihi, a ke hana pū nei me nā ʻoihana e hoʻomohala i ka ʻenehana industrialization.

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)

ʻEhā mau ʻanuʻu ka hana: hydroformylated ka ethylene no ka loaʻa ʻana o propionaldehyde, hoʻopili ʻia ka propionaldehyde me ka formaldehyde e hana ai i ka MAL, ʻo MAL ka ea i hoʻoheheʻe ʻia i loko o kahi reactor moe paʻa tubular e hana i ka MAA, a ua hoʻokaʻawale ʻia a hoʻomaʻemaʻe ʻia ʻo MAA e hana i ka MMA e ka esterification me ka methanol. ʻO ka pane ke kaʻina nui. Pono ke kaʻina hana i ʻehā mau ʻanuʻu, he mea paʻakikī a koi ʻia nā mea hana kiʻekiʻe a me ke kumukūʻai hoʻolimalima kiʻekiʻe, ʻoiai ʻo ka pōmaikaʻi ke kumu kūʻai haʻahaʻa o nā mea maka.

Ua hana ʻia hoʻi 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 Tianjin University, 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 hoʻokō kūleʻa i ka hana paʻa ma 2018.

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

ʻO ke kaʻina hana ʻo Lucite Alpha he maʻalahi, kiʻekiʻe ka hua o ka huahana, ʻoi aku ka liʻiliʻi o ka hoʻopukapuka mea kanu a me nā kumu waiwai maka, a ʻo ka nui o kahi ʻāpana he maʻalahi ke hana nui, i kēia manawa ʻo Lucite wale nō ka mana o kēia ʻenehana i ka honua a ʻaʻole i hoʻoili ʻia i waho o ka honua.

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 ka lōʻihi o ka lawelawe ʻana, a ke hoʻokō ʻia nei ka hopena ma lalo o nā kūlana haʻahaʻa, ʻoi aku ka corrosive i ka hāmeʻa a hoʻemi 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 nā noi ʻoihana.