Methyl methacrylate (MMA) bụ ihe dị mkpa organic chemical akụrụngwa na polymer monomer, tumadi na-eji na mmepụta nke organic iko, ịkpụzi plastik, acrylics, coatings na ọgwụ ọtọ polymer ihe, wdg Ọ bụ a elu-ọgwụgwụ ihe maka aerospace, electronics ozi, eriri anya, robotics na ubi ndị ọzọ.

Dịka monomer ihe onwunwe, a na-ejikarị MMA eme ihe na mmepụta nke polymethyl methacrylate (nke a na-akpọkarị plexiglass, PMMA), a pụkwara ijikọta ya na ogige vinyl ndị ọzọ iji nweta ngwaahịa nwere ihe dị iche iche, dị ka maka mmepụta nke polyvinyl chloride (PVC). ) ihe mgbakwunye ACR, MBS na dị ka monomer nke abụọ na mmepụta nke acrylics.

Ka ọ dị ugbu a, e nwere ụdị atọ nke usoro tozuru okè maka mmepụta nke MMA n'ụlọ na ná mba ọzọ: methacrylamide hydrolysis esterification ụzọ (acetone cyanohydrin usoro na methacrylonitrile usoro), isobutylene oxidation ụzọ (Mitsubishi usoro na Asahi Kasei usoro) na ethylene carbonyl njikọ ụzọ (usoro). Usoro BASF na usoro Lucite Alpha).

1. Methacrylamide hydrolysis esterification ụzọ
Ụzọ a bụ usoro mmepụta MMA ọdịnala, gụnyere acetone usoro cyanohydrin na usoro methacrylonitrile, ma mgbe methacrylamide intermediate hydrolysis, esterification synthesis of MMA.

(1) Usoro cyanohydrin acetone (usoro ACH)

Usoro ACH, nke US Lucite buru ụzọ mepụta, bụ usoro mmepụta ụlọ ọrụ izizi nke MMA, ma bụrụkwa usoro mmepụta MMA bụ isi n'ụwa ugbu a.Usoro a na-eji acetone, hydrocyanic acid, sulfuric acid na methanol dị ka akụrụngwa, usoro mmeghachi omume gụnyere: mmeghachi omume cyanohydrinization, mmeghachi omume amidation na mmeghachi omume esterification hydrolysis.

Usoro ACH tozuru oke na teknụzụ, mana ọ nwere nnukwu ọghọm ndị a:

○ Iji hydrocyanic acid na-egbu egbu nke ukwuu, nke chọrọ usoro nchebe siri ike n'oge nchekwa, njem na ojiji;

○ Site-mmepụta nke nnukwu ego nke acid residue (aqueous ngwọta na sulfuric acid na ammonium bisulfate dị ka isi components na nwere obere ego nke organic okwu), ego nke bụ 2.5 ~ 3.5 ugboro nke MMA, na dị oké njọ. isi iyi nke mmetọ gburugburu ebe obibi;

o N'ihi iji sulfuric acid, a chọrọ akụrụngwa mgbochi corrosion, na owuwu nke ngwaọrụ dị oke ọnụ.

(2) Usoro Methacrylonitrile (usoro MAN)

Asahi Kasei ewepụtala usoro methacrylonitrile (MAN) dabere na ụzọ ACH, ya bụ, isobutylene ma ọ bụ tert-butanol bụ oxidized site na amonia iji nweta MAN, nke na-emeghachi na sulfuric acid iji mepụta methacrylamide, nke na-emeghachi ya na sulfuric acid na methanol iji mepụta. MMA.ụzọ MAN na-agụnye mmeghachi omume oxidation amonia, mmeghachi omume amidation na mmeghachi omume esterification hydrolysis, ma nwee ike iji ọtụtụ ngwa nke ụlọ ọrụ ACH.Mmeghachi omume hydrolysis na-eji sulfuric acid ngafe, na mkpụrụ nke methacrylamide etiti bụ ihe fọrọ nke nta ka ọ bụrụ 100%.Otú ọ dị, usoro ahụ nwere ihe ndị na-emepụta hydrocyanic acid na-egbu egbu nke ukwuu, hydrocyanic acid na sulfuric acid na-emebi emebi, ihe ndị chọrọ mmeghachi omume chọrọ dị oke elu, ebe ihe egwu gburugburu ebe obibi dị oke elu.

2. isobutylene oxidation ụzọ
Isobutylene oxidation bụ ụzọ teknụzụ kachasị amasị maka ndị isi ụlọ ọrụ dị n'ụwa n'ihi arụmọrụ ya dị elu na nchekwa gburugburu ebe obibi, mana ọnụ ụzọ teknụzụ ya dị elu, na naanị Japan nwere teknụzụ n'ụwa ma gbochie teknụzụ China.Usoro ahụ gụnyere ụdị abụọ nke usoro Mitsubishi na usoro Asahi Kasei.

(1) Usoro Mitsubishi (isobutylene usoro nzọụkwụ atọ)

Mitsubishi Rayon nke Japan mepụtara usoro ọhụrụ iji mepụta MMA sitere na isobutylene ma ọ bụ tert-butanol dị ka akụrụngwa, oxidation nke nzọụkwụ abụọ na-ahọrọ site na ikuku iji nweta methacrylic acid (MAA), wee mechaa ya na methanol.Mgbe mmepụta nke Mitsubishi Rayon gasịrị, Japan Asahi Kasei Company, Japan Kyoto Monomer Company, Korea Lucky Company, wdg achọpụtala mmepụta ihe n'otu n'otu.The anụ ụlọ Shanghai Huayi Group Company nyekwara a otutu nke mmadụ na ego ego, na mgbe 15 afọ nke na-aga n'ihu na unremitting mgbalị nke ọgbọ abụọ, ọ gara nke ọma mepụtara onwe ha abụọ-nzọụkwụ oxidation na esterification nke isobutylene dị ọcha mmepụta MMA technology, na December 2017. , ọ dechara ma tinye n'ọrụ a 50,000-ton MMA ulo oru osisi na ya nkwonkwo venture ụlọ ọrụ Dongming Huayi Yuhuang emi odude ke Heze, Shandong Province, na-agbaji na nkà na ụzụ monopoly nke Japan na-aghọ nanị ụlọ ọrụ na a technology na China.teknụzụ, na-emekwa ka China bụrụ mba nke abụọ nwere teknụzụ mmepụta ihe maka imepụta MAA na MMA site na oxidation nke isobutylene.

(2) Usoro Asahi Kasei (usoro nzọụkwụ abụọ isobutylene)

Ụlọ ọrụ Asahi Kasei nke Japan anọwo na-etinye aka na mmepe nke usoro esterification kpọmkwem maka mmepụta nke MMA, bụ nke e mepụtara nke ọma ma tinye n'ọrụ na 1999 na ụlọ ọrụ mmepụta ihe dị 60,000 na Kawasaki, Japan, ma mesịa gbasaa ruo 100,000 tọn.Ụzọ teknuzu mejupụtara mmeghachi omume nzọụkwụ abụọ, ntụgharị oxidation nke isobutylene ma ọ bụ tert-butanol na usoro gas n'okpuru ọrụ nke Mo-Bi composite oxide catalyst iji mepụta methacrolein (MAL), sochiri oxidative esterification nke MAL na mmiri mmiri n'okpuru omume nke Pd-Pb catalyst na-emepụta MMA ozugbo, ebe oxidative esterification nke MAL bụ isi nzọụkwụ na ụzọ a iji mepụta MMA.Usoro usoro Asahi Kasei dị mfe, na-enwe nanị nzọụkwụ abụọ nke mmeghachi omume na naanị mmiri dị ka ihe na-emepụta ihe, nke na-acha akwụkwọ ndụ akwụkwọ ndụ na gburugburu ebe obibi, ma nhazi na nkwadebe nke ihe na-eme ka ọ na-achọsi ike.A na-akọ na Asahi Kasei's oxidative esterification catalyst ka emelitere site na ọgbọ mbụ nke Pd-Pb ruo ọgbọ ọhụrụ nke Au-Ni catalyst.

Mgbe mmepụta nke teknụzụ Asahi Kasei gasịrị, site na 2003 ruo 2008, ụlọ ọrụ nyocha ụlọ malitere ọganihu nyocha na mpaghara a, na ọtụtụ nkeji dị ka Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University na Harbin Engineering University na-elekwasị anya. na mmepe na nkwalite nke Pd-Pb catalysts, wdg Mgbe 2015, ụlọ nnyocha na Au-Ni catalysts malitere ọzọ gburugburu ọganihu, onye nnọchiteanya nke Dalian Institute of Chemical Engineering, Chinese Academy of Sciences, enweela ọganihu dị ukwuu na obere pilot ọmụmụ, dechara njikarịcha nke nano-gold catalyst usoro nkwadebe, mmeghachi omume ọnọdụ screening na vetikal kwalite ogologo okirikiri ọrụ nwale ule, na ugbu a ifịk ifịk na-arụkọ ọrụ na ụlọ ọrụ ịzụlite ulo oru technology.

3. Ethylene carbonyl njikọ ụzọ
Nkà na ụzụ nke ethylene carbonyl njikọ ụzọ mmepụta ihe gụnyere usoro BASF na usoro ethylene-propionic acid methyl ester.

(1) usoro ethylene-propionic acid (usoro BASF)

Usoro ahụ nwere usoro anọ: ethylene bụ hydroformylated iji nweta propionaldehyde, propionaldehyde bụ condensed na formaldehyde na-emepụta MAL, MAL bụ ikuku oxidized na tubular edozi-bed reactor na-emepụta MAA, na MAA kewapụrụ na ọcha iji mepụta MMA site esterification na. methanol.Mmeghachi omume bụ isi nzọụkwụ.Usoro a chọrọ nzọụkwụ anọ, nke dị ntakịrị ma na-achọ ngwá ọrụ dị elu na ọnụ ahịa ego dị elu, ebe uru bụ ọnụ ala nke akụrụngwa.

Emeela ihe ịga nke ọma n'ụlọ na mmepe teknụzụ nke njikọ ethylene-propylene-formaldehyde nke MMA.2017, Shanghai Huayi Group Company, na imekọ ihe ọnụ na Nanjing NOAO New Materials Company na Tianjin University, dechara a pilot ule nke 1,000 tọn propylene-formaldehyde condensation na formaldehyde ka methacrolein na mmepe nke a ngwugwu ngwugwu maka 90,000-ton ulo oru osisi.Na mgbakwunye, Institute of Process Engineering of the Chinese Academy of Sciences, na mmekorita ya na Henan Energy and Chemical Group, rụchara ụlọ ọrụ pilot ụlọ ọrụ 1,000-ton wee nweta ọrụ kwụsiri ike na 2018 nke ọma.

(2) Usoro Ethylene-methyl propionate (usoro Lucite Alpha)

Lucite Alpha usoro ọrụ ọnọdụ ndị dị nwayọọ, ngwaahịa mkpụrụ dị elu, osisi ego na akụrụngwa na-akwụ ụgwọ dị ala, na ọnụ ọgụgụ nke otu unit dị mfe ime nnukwu, ugbu a naanị Lucite nwere nanị akara nke nkà na ụzụ na ụwa na ọ bụghị. bufere na mpụga ụwa.

E kewara usoro Alfa ụzọ abụọ:

Nzọụkwụ mbụ bụ mmeghachi omume nke ethylene na CO na methanol iji mepụta methyl propionate

na-eji palladium dabeere homogeneous carbonylation catalyst, nke nwere àgwà nke elu ọrụ, elu selectivity (99.9%) na ogologo ndụ ndụ, na mmeghachi omume na-rụrụ n'okpuru nwayọọ ọnọdụ, nke bụ obere corrosive na ngwaọrụ ma na-ebelata-ewu isi obodo itinye ego. ;

Nzọụkwụ nke abụọ bụ mmeghachi omume nke methyl propionate na formaldehyde iji mepụta MMA

A na-eji ihe na-eme ka ọ bụrụ onye nwe ya, nke nwere nhọrọ MMA dị elu.N'ime afọ ndị na-adịbeghị anya, ụlọ ọrụ ụlọ etinyewo oke ịnụ ọkụ n'obi na mmepe teknụzụ nke methyl propionate na formaldehyde condensation na MMA, ma nwee ọganihu dị ukwuu na mmepe usoro mmeghachi omume na-eme ka ihe na-edozi ahụ na ihe ndina na-edozi ahụ, ma ndụ ndụ na-eme ka ahụ erubeghị ihe ndị a chọrọ maka ụlọ ọrụ mmepụta ihe. ngwa.