Methyl methacrylate (MMA) ndi yofunika organic mankhwala zopangira ndi polima monomer, makamaka ntchito kupanga organic galasi, akamaumba mapulasitiki, acrylics, zokutira ndi mankhwala zinchito polima zipangizo, etc. Ndi mkulu-mapeto zinthu zakuthambo, zamagetsi zambiri, kuwala kwa fiber, robotics ndi zina.

Monga monomer zakuthupi, MMA imagwiritsidwa ntchito makamaka popanga polymethyl methacrylate (yomwe imadziwika kuti plexiglass, PMMA), komanso imatha kupangidwanso ndi zinthu zina za viniya kuti ipeze zinthu zamitundu yosiyanasiyana, monga kupanga polyvinyl kolorayidi (PVC). ) zowonjezera ACR, MBS komanso ngati monomer yachiwiri pakupanga ma acrylics.

Pakali pano, pali mitundu itatu ya njira okhwima kupanga MMA kunyumba ndi kunja: methacrylamide hydrolysis esterification njira (acetone cyanohydrin njira ndi methacrylonitrile njira), isobutylene makutidwe ndi okosijeni njira (Mitsubishi ndondomeko ndi Asahi Kasei ndondomeko) ndi ethylene carbonyl kaphatikizidwe njira ( Njira ya BASF ndi njira ya Lucite Alpha).

1, Methacrylamide hydrolysis esterification njira
Njira imeneyi ndi chikhalidwe MMA kupanga njira, kuphatikizapo acetone cyanohydrin njira ndi methacrylonitrile njira, onse pambuyo methacrylamide wapakatikati hydrolysis, esterification kaphatikizidwe wa MMA.

(1) Acetone cyanohydrin njira (ACH njira)

Njira ya ACH, yomwe idapangidwa koyamba ndi US Lucite, ndiyo njira yoyamba yopangira mafakitale ya MMA, komanso ndiyo njira yayikulu yopanga MMA padziko lonse lapansi pano.Njirayi imagwiritsa ntchito acetone, hydrocyanic acid, sulfuric acid ndi methanol ngati zopangira, ndipo masitepe omwe amachitira akuphatikizapo: cyanohydrinization reaction, amidation reaction ndi hydrolysis esterification reaction.

Njira ya ACH ndi yokhwima mwaukadaulo, koma ili ndi zovuta zotsatirazi:

○ Kugwiritsa ntchito poizoni wa hydrocyanic acid, komwe kumafunikira njira zodzitchinjiriza posungira, poyendetsa ndi kugwiritsidwa ntchito;

○ Popanga zotsalira zambiri za asidi (muyeyu wamadzi wokhala ndi sulfuric acid ndi ammonium bisulfate monga zigawo zikuluzikulu zomwe zimakhala ndi zinthu zochepa), kuchuluka kwake ndi 2.5~3.5 kuposa MMA, ndipo ndizovuta kwambiri. gwero la kuipitsa chilengedwe;

o Chifukwa cha kugwiritsa ntchito sulfuric acid, zida zothana ndi dzimbiri zimafunikira, ndipo kupanga chipangizocho ndi kokwera mtengo.

(2) Njira ya Methacrylonitrile (MAN njira)

Asahi Kasei wapanga njira ya methacrylonitrile (MAN) yotengera njira ya ACH, mwachitsanzo, isobutylene kapena tert-butanol ndi oxidized ndi ammonia kuti ipeze MAN, yomwe imakhudzidwa ndi sulfuric acid kuti ipange methacrylamide, yomwe imakhudzidwa ndi sulfuric acid ndi methanol kupanga. MMA.Njira ya MAN imaphatikizapo ammonia oxidation reaction, amidation reaction ndi hydrolysis esterification reaction, ndipo imatha kugwiritsa ntchito zida zambiri za chomera cha ACH.The hydrolysis anachita ntchito owonjezera sulfuric acid, ndi zokolola za wapakatikati methacrylamide ndi pafupifupi 100%.Komabe, njira ali kwambiri poizoni hydrocyanic asidi ndi mankhwala, asidi hydrocyanic ndi asidi sulfuric ndi dzimbiri, anachita zida zofunika kwambiri, pamene zoopsa zachilengedwe ndi mkulu kwambiri.

2, Isobutylene oxidation njira
Isobutylene oxidation yakhala njira yabwino kwambiri yaukadaulo yamakampani akuluakulu padziko lonse lapansi chifukwa chakuchita bwino kwambiri komanso kuteteza chilengedwe, koma luso lake ndilokwera, ndipo Japan yokha inali ndi ukadaulo padziko lonse lapansi ndikuletsa ukadaulo ku China.Njirayi imaphatikizapo mitundu iwiri ya njira ya Mitsubishi ndi njira ya Asahi Kasei.

(1) Mitsubishi ndondomeko (isobutylene njira zitatu)

Mitsubishi Rayon yaku Japan idapanga njira yatsopano yopangira MMA kuchokera ku isobutylene kapena tert-butanol ngati zopangira, masitepe awiri osankha oxidation ndi mpweya kuti apeze methacrylic acid (MAA), kenako ndi esterified ndi methanol.Pambuyo pakukula kwamakampani a Mitsubishi Rayon, Japan Asahi Kasei Company, Japan Kyoto Monomer Company, Korea Lucky Company, ndi zina zambiri.The zoweta Shanghai Huayi Gulu Company padera kwambiri anthu ndi ndalama, ndipo patapita zaka 15 mosalekeza ndi unremitting khama mibadwo iwiri, bwinobwino anayamba paokha masitepe awiri makutidwe ndi okosijeni ndi esterification wa isobutylene woyera kupanga MMA luso, ndipo mu December 2017. , idamaliza ndikuyika ntchito yamakampani opanga matani 50,000 a MMA mu kampani yake yogwirizana ya Dongming Huayi Yuhuang yomwe ili ku Heze, m'chigawo cha Shandong, ndikuphwanya ulamuliro waukadaulo wa Japan ndikukhala kampani yokhayo yokhala ndiukadaulo ku China.ukadaulo, zomwe zimapangitsanso China kukhala dziko lachiwiri kukhala ndiukadaulo wamakampani opanga MAA ndi MMA pogwiritsa ntchito oxidation ya isobutylene.

(2) Asahi Kasei process (isobutylene masitepe awiri)

Asahi Kasei Corporation waku Japan wakhala akudzipereka pakupanga njira yachindunji ya esterification yopanga MMA, yomwe idapangidwa bwino ndikuyamba kugwira ntchito mu 1999 ndi fakitale yamatani 60,000 ku Kawasaki, Japan, ndipo kenako idakulitsidwa mpaka matani 100,000.Njira yaukadaulo imakhala ndi njira ziwiri, mwachitsanzo, makutidwe ndi okosijeni a isobutylene kapena tert-butanol mu gawo la mpweya pansi pa zochita za Mo-Bi composite oxide catalyst kupanga methacrolein (MAL), kutsatiridwa ndi oxidative esterification ya MAL mu madzi gawo pansi zochita za Pd-Pb chothandizira kubala MMA mwachindunji, kumene oxidative esterification wa MAL ndi sitepe yaikulu panjira iyi kubala MMA.Njira ya Asahi Kasei ndi yosavuta, yokhala ndi masitepe awiri okha ochitapo kanthu ndi madzi okha monga mankhwala, omwe ali obiriwira komanso okonda zachilengedwe, koma mapangidwe ndi kukonzekera kwa chothandizira ndizovuta kwambiri.Zimanenedwa kuti chothandizira cha Asahi Kasei cha oxidative esterification chasinthidwa kuchokera ku mbadwo woyamba wa Pd-Pb kupita ku mbadwo watsopano wa Au-Ni chothandizira.

Pambuyo pakukula kwaukadaulo wa Asahi Kasei, kuyambira 2003 mpaka 2008, mabungwe ofufuza zoweta adayambitsa kafukufuku m'derali, ndi mayunitsi angapo monga Hebei Normal University, Institute of Process Engineering, Chinese Academy of Sciences, Tianjin University ndi Harbin Engineering University ikuyang'ana kwambiri. pa chitukuko ndi kusintha Pd-Pb chothandizira, etc. Pambuyo 2015, kafukufuku zoweta pa Au-Ni zothandizira anayamba wozungulira Wina wa boom, woimira amene Dalian Institute of Chemical Engineering, Chinese Academy of Sciences, wapita patsogolo kwambiri mu maphunziro ang'onoang'ono oyendetsa ndege, anamaliza kukhathamiritsa kwa nano-golide chothandizira kukonzekera ndondomeko, mmene zinthu zounikira ndi ofukula kukweza mokweza yaitali mkombero kuwunika ntchito mayeso, ndipo tsopano mwachangu kugwirizana ndi mabizinezi kuti apange ukadaulo wa mafakitale.

3, Ethylene carbonyl synthesis njira
Ukadaulo wa ethylene carbonyl synthesis route industrialization imaphatikizapo njira ya BASF ndi ethylene-propionic acid methyl ester process.

(1) njira ya ethylene-propionic acid (njira ya BASF)

Njirayi imakhala ndi masitepe anayi: ethylene ndi hydroformylated kuti ipeze propionaldehyde, propionaldehyde imafupikitsidwa ndi formaldehyde kuti ipange MAL, MAL imapangidwa ndi mpweya wotsekemera mu tubular fixed bed reactor kuti ipange MAA, ndipo MAA imalekanitsidwa ndikuyeretsedwa kuti ipange MMA ndi esterification ndi methanoli.Zomwe zimachitika ndiye gawo lofunikira.Njirayi imafuna masitepe anayi, omwe ndi ovuta kwambiri ndipo amafuna zida zapamwamba komanso mtengo wapamwamba wa ndalama, pamene ubwino wake ndi wotsika mtengo wa zipangizo.

Kupambana kwapakhomo kwapangidwanso pakukula kwaukadaulo wa ethylene-propylene-formaldehyde synthesis ya MMA.2017, Shanghai Huayi Group Company, mogwirizana ndi Nanjing NOAO New Materials Company ndi Tianjin University, anamaliza mayeso woyendetsa matani 1,000 propylene-formaldehyde condensation ndi formaldehyde kuti methacrolein ndi chitukuko cha ndondomeko phukusi kwa 90,000 tani mafakitale mafakitale.Komanso, Institute of Process Engineering ya Chinese Academy of Sciences, mogwirizana ndi Henan Energy ndi Chemical Gulu, anamaliza 1,000 tani mafakitale woyendetsa zomera ndi bwino akwaniritsa ntchito khola mu 2018.

(2) Njira ya Ethylene-methyl propionate (njira ya Lucite Alpha)

Njira zogwirira ntchito za Lucite Alpha ndizochepa, zokolola zamakampani ndizokwera, ndalama zogulira mbewu komanso mtengo wazinthu zopangira ndizotsika, ndipo kukula kwa gawo limodzi ndikosavuta kuchita zazikulu, pakali pano ndi Lucite yekha amene amalamulira ukadaulo uwu padziko lapansi ndipo sali. kusamutsidwira kudziko lakunja.

Njira ya Alpha imagawidwa m'magawo awiri:

Gawo loyamba ndikuchita kwa ethylene ndi CO ndi methanol kupanga methyl propionate

ntchito palladium ofotokoza homogeneous carbonylation chothandizira, amene ali makhalidwe a ntchito mkulu, selectivity mkulu (99,9%) ndi moyo wautali utumiki, ndi zimene ikuchitika pansi pa zinthu wofatsa, amene ndi zochepa dzimbiri kwa chipangizo ndi kuchepetsa yomanga likulu ndalama. ;

Gawo lachiwiri ndikuchita kwa methyl propionate yokhala ndi formaldehyde kupanga MMA

Chothandizira chamagulu ambiri chimagwiritsidwa ntchito, chomwe chili ndi kusankha kwakukulu kwa MMA.M'zaka zaposachedwa, mabizinesi apakhomo adayika chidwi chachikulu pakukula kwaukadaulo wa methyl propionate ndi formaldehyde condensation kupita ku MMA, ndipo apita patsogolo kwambiri pakupanga njira zolimbikitsira komanso zokhazikika, koma moyo wothandizira sunafikebe zofunikira zamakampani. mapulogalamu.