Methyl methacrylate (MMA) yog ib qho tseem ceeb organic chemical raw khoom thiab polymer monomer, tsuas yog siv nyob rau hauv zus tau tej cov organic iav, molding plastics, acrylics, coatings thiab tshuaj haumxeeb ntaub ntawv polymer, thiab lwm yam. Nws yog ib tug high-end khoom rau aerospace, hluav taws xob. cov ntaub ntawv, kho qhov muag fiber ntau, robotics thiab lwm yam.

Raws li cov khoom siv monomer, MMA feem ntau yog siv los tsim cov polymethyl methacrylate (feem ntau hu ua plexiglass, PMMA), thiab tseem tuaj yeem ua copolymerized nrog lwm cov vinyl tebchaw kom tau cov khoom sib txawv, xws li kev tsim cov polyvinyl chloride (PVC). ) additives ACR, MBS thiab raws li ib tug thib ob monomer nyob rau hauv zus tau tej cov acrylics.

Tam sim no, muaj peb hom kev paub tab rau kev tsim MMA hauv tsev thiab txawv teb chaws: methacrylamide hydrolysis esterification txoj kev (acetone cyanohydrin method thiab methacrylonitrile method), isobutylene oxidation route (Mitsubishi process thiab Asahi Kasei process) thiab ethylene carbonyl synthesis route ( Txoj kev BASF thiab Lucite Alpha txoj kev).

1, Methacrylamide hydrolysis esterification txoj kev
Txoj kev no yog txoj kev tsim MMA ib txwm muaj, suav nrog acetone cyanohydrin txoj kev thiab methacrylonitrile txoj kev, ob qho tib si tom qab methacrylamide intermediate hydrolysis, esterification synthesis ntawm MMA.

(1) Acetone cyanohydrin method (ACH method)

ACH txoj kev, thawj zaug tsim los ntawm Asmeskas Lucite, yog txoj kev tsim khoom lag luam ntxov tshaj plaws ntawm MMA, thiab tseem yog cov txheej txheem MMA tseem ceeb hauv ntiaj teb tam sim no. Txoj kev no siv acetone, hydrocyanic acid, sulfuric acid thiab methanol ua raw cov ntaub ntawv, thiab cov kauj ruam cov tshuaj tiv thaiv muaj xws li: cyanohydrinization cov tshuaj tiv thaiv, amidation cov tshuaj tiv thaiv thiab hydrolysis esterification cov tshuaj tiv thaiv.

Cov txheej txheem ACH yog technically paub tab, tab sis muaj qhov tsis zoo hauv qab no:

○ Kev siv cov tshuaj lom hydrocyanic acid, uas yuav tsum tau muaj kev tiv thaiv nruj heev thaum lub sijhawm khaws cia, kev thauj mus los thiab siv;

○ Los ntawm kev tsim cov kua qaub ntau ntau (aqueous tov nrog sulfuric acid thiab ammonium bisulfate ua cov khoom tseem ceeb thiab muaj me me ntawm cov organic teeb meem), tus nqi uas yog 2.5 ~ 3.5 npaug ntawm MMA, thiab yog ib qho loj heev. qhov chaw ntawm ib puag ncig muaj kuab paug;

o Vim yog siv cov sulfuric acid, cov khoom siv los tiv thaiv corrosion yuav tsum tau, thiab kev tsim kho ntawm cov cuab yeej yog kim.

(2) Methacrylonitrile method (MAN method)

Asahi Kasei tau tsim cov txheej txheem methacrylonitrile (MAN) raws li txoj hauv kev ACH, piv txwv li, isobutylene lossis tert-butanol yog oxidized los ntawm ammonia kom tau txais MAN, uas ua rau cov tshuaj sulfuric acid los tsim methacrylamide, uas tom qab ntawd cov tshuaj sulfuric acid thiab methanol los tsim. MMA. MAN txoj kev suav nrog ammonia oxidation cov tshuaj tiv thaiv, cov tshuaj tiv thaiv amidation thiab hydrolysis esterification cov tshuaj tiv thaiv, thiab tuaj yeem siv feem ntau ntawm cov cuab yeej ntawm ACH cog. Cov tshuaj tiv thaiv hydrolysis siv ntau tshaj sulfuric acid, thiab cov txiaj ntsig ntawm nruab nrab methacrylamide yog yuav luag 100%. Txawm li cas los xij, cov txheej txheem muaj cov tshuaj lom hydrocyanic acid los ntawm cov khoom lag luam, hydrocyanic acid thiab sulfuric acid yog corrosive heev, cov khoom siv tshuaj tiv thaiv yuav tsum siab heev, thaum muaj kev phom sij ib puag ncig siab heev.

2, Isobutylene oxidation txoj kev
Isobutylene oxidation tau yog txoj kev siv thev naus laus zis rau cov tuam txhab loj hauv ntiaj teb vim tias nws cov kev ua haujlwm siab thiab kev tiv thaiv ib puag ncig, tab sis nws cov txheej txheem kev ua haujlwm siab, thiab tsuas yog Nyiv ib zaug muaj cov thev naus laus zis hauv ntiaj teb thiab thaiv cov thev naus laus zis rau Tuam Tshoj. Cov txheej txheem suav nrog ob hom txheej txheem Mitsubishi thiab Asahi Kasei txheej txheem.

(1) Mitsubishi txheej txheem (isobutylene peb-kauj ruam txoj kev)

Nyiv lub Mitsubishi Rayon tau tsim cov txheej txheem tshiab los tsim MMA los ntawm isobutylene los yog tert-butanol ua raw khoom, ob-kauj ruam xaiv oxidation los ntawm huab cua kom tau methacrylic acid (MAA), thiab ces esterified nrog methanol. Tom qab kev lag luam ntawm Mitsubishi Rayon, Nyiv Asahi Kasei Tuam Txhab, Nyiv Kyoto Monomer Tuam Txhab, Kaus Lim Kauslim Tuam Txhab, thiab lwm yam tau paub txog kev lag luam ib tom qab. Lub tuam txhab Shanghai Huayi Group tuam txhab tau nqis peev ntau ntawm tib neeg thiab nyiaj txiag, thiab tom qab 15 xyoo ntawm kev ua haujlwm tas mus li thiab tsis muaj zog ntawm ob tiam neeg, nws tau ua tiav ntawm nws tus kheej ob-kauj ruam oxidation thiab esterification ntawm isobutylene huv si MMA technology, thiab nyob rau lub Kaum Ob Hlis 2017. , nws ua tiav thiab muab tso rau hauv kev ua haujlwm 50,000-tuj MMA kev lag luam cog hauv nws lub tuam txhab sib koom ua lag luam Dongming Huayi Yuhuang nyob hauv Heze, Shandong Xeev, rhuav tshem cov thev naus laus zis monopoly ntawm Nyiv thiab dhau los ua tib lub tuam txhab nrog cov thev naus laus zis no hauv Suav teb. thev naus laus zis, tseem ua rau Tuam Tshoj yog lub teb chaws thib ob kom muaj kev lag luam thev naus laus zis rau kev tsim MAA thiab MMA los ntawm oxidation ntawm isobutylene.

(2) Asahi Kasei txheej txheem (isobutylene ob kauj ruam txheej txheem)

Nyiv lub Asahi Kasei Corporation tau ntev tau cog lus rau txoj kev loj hlob ncaj qha esterification txoj kev rau zus tau tej cov MMA, uas tau ntse tsim thiab muab tso rau hauv lub lag luam nyob rau hauv 1999 nrog ib tug 60,000-ton industrial cog nyob rau hauv Kawasaki, Nyiv, thiab tom qab ntawd nthuav mus rau 100,000 tons. Cov txheej txheem kev muaj ob-kauj ruam cov tshuaj tiv thaiv, piv txwv li oxidation ntawm isobutylene los yog tert-butanol nyob rau hauv cov roj theem nyob rau hauv qhov kev txiav txim ntawm Mo-Bi composite oxide catalyst los tsim methacrolein (MAL), ua raws li oxidative esterification ntawm MAL nyob rau hauv lub Ua kua theem nyob rau hauv qhov kev txiav txim ntawm Pd-Pb catalyst los tsim MMA ncaj qha, qhov twg oxidative esterification ntawm MAL yog cov kauj ruam tseem ceeb hauv txoj kev no los tsim MMA. Asahi Kasei txheej txheem txheej txheem yog yooj yim, tsuas yog ob kauj ruam ntawm cov tshuaj tiv thaiv thiab tsuas yog dej raws li ib tug by-product, uas yog ntsuab thiab ib puag ncig tus phooj ywg, tab sis tus tsim thiab kev npaj ntawm catalyst yog heev xav tau. Nws tau tshaj tawm tias Asahi Kasei's oxidative esterification catalyst tau hloov kho los ntawm thawj tiam ntawm Pd-Pb mus rau tiam tshiab ntawm Au-Ni catalyst.

Tom qab kev lag luam ntawm Asahi Kasei thev naus laus zis, los ntawm 2003 txog 2008, cov tsev tshawb fawb hauv tsev tau pib tshawb fawb hauv cheeb tsam no, nrog ntau lub koom haum xws li Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University thiab Harbin Engineering University tsom. ntawm kev txhim kho thiab txhim kho Pd-Pb catalysts, thiab lwm yam. Tom qab xyoo 2015, kev tshawb fawb hauv tsev ntawm Au-Ni catalysts pib Lwm qhov ntawm boom, tus neeg sawv cev ntawm uas yog Dalian Institute of Chemical Engineering, Suav Academy ntawm Kev Tshawb Fawb, tau ua tiav zoo hauv kev kawm me me, ua tiav qhov kev ua kom zoo ntawm nano-kub catalyst txheej txheem, tshuaj tiv thaiv kab mob tshuaj ntsuam xyuas thiab ntsug nce mus ntev-khiav kev ntsuas kev ntsuas , thiab tam sim no nquag koom tes nrog cov lag luam los tsim kev lag luam thev naus laus zis.

3, Ethylene carbonyl synthesis txoj kev
Lub tshuab ntawm ethylene carbonyl synthesis txoj kev industrialization muaj xws li BASF txheej txheem thiab ethylene-propionic acid methyl ester txheej txheem.

(1) ethylene-propionic acid txoj kev (BASF txheej txheem)

Cov txheej txheem muaj plaub kauj ruam: ethylene yog hydroformylated kom tau propionaldehyde, propionaldehyde yog condensed nrog formaldehyde los tsim MAL, MAL yog cua oxidized nyob rau hauv tubular tsau-txaj reactor los tsim MAA, thiab MAA yog sib cais thiab purified los tsim MMA los ntawm esterification nrog methanol. Cov tshuaj tiv thaiv yog cov kauj ruam tseem ceeb. Cov txheej txheem yuav tsum muaj plaub kauj ruam, uas yog qhov tseem ceeb thiab xav tau cov cuab yeej siv siab thiab cov peev txheej siab, thaum qhov kom zoo dua yog tus nqi qis ntawm cov khoom siv raw.

Cov kev sib tw hauv tsev kuj tau ua hauv kev tsim kho tshuab ntawm ethylene-propylene-formaldehyde synthesis ntawm MMA. 2017, Shanghai Huayi Group Company, koom tes nrog Nanjing NOAO Cov Khoom Siv Tshiab thiab Tianjin University, ua tiav kev sim ntawm 1,000 tons ntawm propylene-formaldehyde condensation nrog formaldehyde rau methacrolein thiab kev txhim kho cov txheej txheem pob rau 90,000-tuj kev lag luam cog. Tsis tas li ntawd, lub koom haum ntawm Txheej Txheem Engineering ntawm Tuam Tshoj Academy ntawm Sciences, koom tes nrog Henan Zog thiab Chemical Group, ua tiav ib tug 1,000-tuj industrial pilot cog thiab ua tiav kev ua haujlwm ruaj khov hauv 2018.

(2) Ethylene-methyl propionate txheej txheem (Lucite Alpha txheej txheem)

Lucite Alpha txheej txheem kev khiav hauj lwm yog me me, cov khoom yield yog siab, cog kev nqis peev thiab cov khoom siv raw cov nqi qis, thiab cov nplai ntawm ib chav tsev yog ib qho yooj yim los ua loj, tam sim no tsuas yog Lucite muaj kev tswj hwm ntawm cov cuab yeej no hauv ntiaj teb thiab tsis yog. pauv mus rau lub ntiaj teb sab nraud.

Cov txheej txheem Alpha tau muab faib ua ob kauj ruam:

Thawj kauj ruam yog cov tshuaj tiv thaiv ntawm ethylene nrog CO thiab methanol los tsim methyl propionate

siv palladium-raws li homogeneous carbonylation catalyst, uas muaj cov yam ntxwv ntawm kev ua haujlwm siab, kev xaiv siab (99.9%) thiab lub neej ua haujlwm ntev, thiab cov tshuaj tiv thaiv yog nqa tawm hauv cov xwm txheej me me, uas tsis tshua muaj corrosive rau cov cuab yeej thiab txo cov peev txheej tsim kho. ;

Cov kauj ruam thib ob yog cov tshuaj tiv thaiv ntawm methyl propionate nrog formaldehyde los ua MMA

Ib tug tswv cuab ntawm ntau theem catalyst yog siv, uas muaj siab MMA xaiv. Nyob rau hauv xyoo tas los no, cov tuam txhab lag luam hauv tsev tau nqis peev zoo txaus siab rau hauv kev tsim kho thev naus laus zis ntawm methyl propionate thiab formaldehyde condensation rau MMA, thiab tau ua tiav zoo hauv cov txheej txheem catalyst thiab kho cov txheej txheem kev txhim kho hauv txaj, tab sis lub neej catalyst tseem tsis tau mus txog qhov yuav tsum tau muaj rau kev lag luam. daim ntawv thov.