Nyob rau thaum ntxov 50, lub teb chaws txawv teb chaws pib tsim epoxy soybean roj, yog lub tseem fwv Teb Chaws Asmeskas, Lub teb chaws As Mes Lis Kas, Lub teb chaws Yelemees, Nyij Pooj Teb thiab cov qub Soviet Union. Los ntawm 70's, cov txheej txheem ntawm cov roj epoxy soybean hloov tau los ntawm cov organic hnyav rau hnyav dawb txoj kev, los ntawm sib quas ntus ntau lawm mus ntxiv ntau lawm, ntawm tib catalyst rau compound hom. Nyob rau thaum ntxov 60's, zus tau cov roj epoxy soybean roj tsuas yog npaj los ntawm hnyav txoj kev thiab hnyav hom dawb. Ua ntej siv cov tshuaj ua kom hnyav, vim yog muaj teeb meem ntawm cov khoom hnyav, kev ua haujlwm ntev ntev, cov khoom lag luam tsis zoo, siab nqi, kev ua qias tuaj thiab lwm yam kev qaug, kev loj hlob qeeb. Txij li thaum lub 80's pib kawm txog cov txheej txheem ntawm cov khoom xyaw tsis haum, tus 90 tau tiav ib qho kev loj dua, nws kuj tau hloov qhov kev ua kom lub cev muaj zog ntau lawm. Cov txheej txheem hnyav yog ua raws li cov roj kua roj, thiab cov hluavtaws sib txawv txawv xaiv cov organic acid carboxylic acids (homic acid lossis acetic acid), oxidant, catalyst, stabilizer, etc. Cov roj siv roj yuav siv tau cov roj tseem ceeb thiab roj cov roj, thiab qhov tseem ceeb roj yog ncaj qha oxidized mus rau lub nplhaib, thiab cov coarse roj yuav tsum tau ua kom zoo ua ntej. Wen Jinping [2] thiab lwm yam kev hloov alkaline ntawm cov kev tshawb xyuas roj, cov txiaj ntsim tau zoo. Raws li kev siv cov organic carboxylic acid, cov txheej txheem hluavtaws ntawm cov tshuaj epoxy kua roj yuav muab faib ua peracetic acid oxidation txoj kev, tsis muaj carboxylic acid catalytic oxidation method (belongs rau cov qauv hnyav), thiab cov catalysts uas siv los ntawm cov tshuaj peroxide carboxylic acid oxidation yog cov concentrated , ion txauv resins, txhuas, theem hloov catalyst, heteropoly acid (ntsev), lwm yam.
Peracetic acid oxidation txoj kev
Cov txheej txheem no yog cov organic carboxylic acid thiab hydrogen peroxide nyob rau hauv qhov kev txiav txim ntawm cov catalyst, cov tshuaj tiv thaiv los tsim cov tshuaj epoxy acid ring oxidant, thiab kua tshuaj oxidation kua roj rau tsim epoxy kua roj. Hauv cov txheej txheem ntawm epoxidation, muaj ob txoj hauv kev npaj lub nplhaib oxidant:
Ua ntej, kev npaj ntawm Peracetic acid txoj kev: Cov organic carboxylic acid thiab hydrogen peroxide los tsim peroxide acid, thiab tom qab ntawd ntxiv cov tshuaj peroxide acid poob mus rau cov kua roj kua hauv cov tshuaj tua kab mob;
Qhov thib ob yog kev npaj ntawm Peracetic acid txoj kev: Ua ntej, kua roj thiab cov organic carboxylic acid rau hauv reactor, thiab ces poob thiab hydrogen peroxide rau qhov tshuaj tiv thaiv epoxidation. Tom qab cov tshuaj tiv thaiv ntawm cov khoom ntawm ib yam kub tiav lawm, cov khoom siv ntxig yog cov neutralized los ntawm dilute alkali, thiab ces cov khoom uas tau los ntawm cov dej ntxuav muag, nqus distillation thiab siab pom. Kev tsim cov txheej txheem yog ib qho yooj yim, qhov ntsuas kub tsis tshua zoo, cov voj voog yog qhov tsawg, qhov khoom siv yog tsawg, qhov kev kho mob tom qab yog qhov yooj yim, qhov khoom zoo yog qhov zoo, raws li qhov yuav tsum tau ua.
Vim hais tias cov nyhuv ntawm formic acid zoo dua li ntawm acetic acid, feem ntau cov tuam txhab siv formic acid ua nquag ua pa cov kab mob ntawm epoxidation. Yeej hloov ntau txoj kev nrog benzene li qhov hnyav, ua rau thaj chaw ua haujlwm ntawm cov neeg ua haujlwm, daws qhov teeb meem muaj kuab paug kua tshuaj lom cov khoom ua rau cov khoom, thiab ua ntau yam khoom siv, cov nqi qis thiab "pov tseg" ntawm cov qauv hnyav. Tus nqi loj ntawm kev ua, xws li kev ua tsis taus [4], yog li ntawd qhov zoo ntawm cov khoom ua tau zoo tuaj, xws li kev ruaj ntseg ntawm 60% -80% los ntawm qhov hnyav txoj kev nce mus rau ntau dua 95%. Txoj kev siv tsis muaj teeb meem tau ua kom tau zoo tshaj qhov sib piv nrog cov qauv hnyav, thiab ntau txoj kev catalyst muaj qhov zoo thiab qhov tsis zoo.
Concentrated Catalytic txoj kev
Txoj kev ua kom zoo tshaj plaws muaj lub keeb kwm yav dhau los ntawm kev lag luam, qhov feem ntau siv rau hauv kev lag luam, nws cov kev tsis txaus siab yog pom nyob rau hauv: ① tshaj tawm cov pa oxygen yooj yim rau decompose, cov tshuaj tiv thaiv ntau ntau exothermic, kub hloov amplitude, ua rau tsis ruaj ruaj epoxidation, txhawb epoxy lub nplhaib, by-products ntau zog, cov khoom ua rau cov khoom raug txo nqi; ② nplhaib oxidation cov tshuaj tiv thaiv hauv cov kua qaub (acid), ua rau muaj xim ntxaum dua qub, tom qab kev kho mob ntau dua, cov reactor thiab cov raj xa dej muaj zog heev, tsis hloov raws li txoj cai, kev tswj kev kub, yooj yim rau "punch" los yog kev tawg , kev nyab xeeb yog tsis siab tshaj plaws, kev tsim tawm kettle ntau yog me me. Yuav kom kov yeej kev tsis zoo ntawm txoj haujlwm no, vim yog lub neej ntawm carboxylic acid nyob rau hauv lub cev tiv thaiv kab mob, nws yog ib qho tsim nyog ntxiv rau stabilizer nrog urea raws li lub ntsiab ua khoom noj los tsim cov peracetic acid, uas muaj peev xwm muab tau zoo dua thiab tsis noj khoom.
Catalytic txoj kev ion txauv resins
Strong acidic cation txauv resins kuj feem ntau siv catalysts. Kev tsim cov tshuaj epoxy kua ntsev los ntawm cationic cob catalytic countercurrent txoj kev yog ib qho zoo rau cov kev tsis haum ntawm txoj kev ua kom tsis haum, qhov tsis muaj peev xwm ntawm cov khoom uas yuav tsum tau ua ncaj qha ua ntej, lub lag luam yog complex, epoxidation lub sijhawm ntev dua thiab tus nqi yog siab dua. Cationic resin yuav rov qab siv dua, thaum cov tshuaj ua hauj lwm tsawg dua, nrog 95% ethanol reflux washing 2h, ntxuav, kom qhuav, thiab tom qab muab cov tshuaj ua kom rov zoo, ua kom qhov kev ua kom rov zoo, rov ua dua thiab rov siv dua.
Txhuas Catalysis txoj kev
Kev siv cov txhuas ua ib qho khoom noj khoom haus, yuav txaus siab rau cov khoom, cov nqi ntawm 6.2%, cov kua qaub qis dua 0.5mgkoh / g. Cov txheej txheem muaj kev ua haujlwm siab dav dav, kev ua tau yooj yim, tawm los mus txog 96%, cov nqi ntawm tus nqi qis dua yog ion exchange resin. Lub deficiency yog cov ntsiab lus ntawm Fe2 hauv lub catalyst, lub catalysis ntawm cov decomposition ntawm hydrogen peroxide, ua rau cov khoom kub kom nce zuj zus, nws yuav yooj yim rau kev tswj cov kub, nws yog unfavorable rau cov tshuaj tiv thaiv epoxidation.
Qib Hloov Catalysis txoj kev
Ib qhov sib txawv ntawm cov khoom xa tuaj hloov mus rau cov pa tshuaj (uas tseem hu ua Oxygen hloov tus neeg saib xyuas) uas yog sib npaug li 1% ntawm cov roj nyhav ntxiv rau cov tshuaj tiv thaiv, cov pa oxygen hauv cov aqueous theem tau pauv mus rau cov kev tsis sib tua ntawm cov organic theem, tus nqi ntawm cov tshuaj epoxidation yog nce ntau tshaj ib zaug, thiab cov nqi ntawm epoxy yog qhov yooj yim dua, ob qho tib si iodine thiab cov acid ntau yog obviously tsawg.
Heteropoly acid (ntsev) Catalysis txoj kev
Los ntawm kev siv heteropoly acid (ntsev) raws li catalyst, peracetic acid uas ua los ntawm formic acid thiab hydrogen peroxide yog siv los ua epoxy kua ntsev roj ntawm nplhaib oxidizer. Txoj kev muaj qhov zoo ntawm cov txheej txheem yooj yim, lub sij hawm luv luv luv, siab tshaj epoxy nqi, ntiav xim thiab qis dua kua qis. Cov kev sim qhia tau hais tias lub sij hawm zoo tshaj ntawm cov roj kua roj yog 3.5h, qhov zoo tshaj plaws cov tshuaj tiv thaiv yog 45 ℃, epoxy roj yog 6.6%, iodine 4.4gl / 100g, acid nqi tsawg dua 0.2mg / g, xim tsawg dua Tsis muaj. 250, thiab qhov ceev nyiaj ntawm epoxy yog 99%. Heteropoly acid Catalyst CPW yog cov dej tsis haum thiab rov tuaj yeem hloov tau tom qab pom.
Non-carboxylic acid catalytic oxidation txoj kev
Raws li tsis muaj cov carboxylic acid, acetic acid ethyl ester tau siv ua kuab, phosphor-tungsten compound, methyl tri-octyl hydrogen ammonia li theem hloov catalyst, soybean roj tau synthesized los ntawm epoxidation los ntawm hydrogen peroxide ua oxidant. Cov txiaj ntsim tau pom tias cov tshuaj epoxy, tus nqi iodine thiab cov kua qaub qes tau yog 6.28%, 5.80gl / 100g, 0.3mgkoh / g thiab Xim (PT-CO) los ntawm kev siv lub phosphor-tungsten compound (WPC) raws li cov catalyst thiab ethyl acetate li hnyav, thiab cov tshuaj tiv thaiv yog 7h nyob rau hauv lub zwj ceeb ntawm lub cev daws phaus 2,60 ℃. Raws li tus xov tooj 250¯300, tag nrho mus txog lub teb chaws tus qauv zoo, txo kev tsim cov khoom ntawm by-products. Cov txheej txheem los tiv thaiv kev siv cov organic carboxylic acid thiab ua rau cov teeb meem tshwm sim los ntawm kev pab cuam ntawm peracetic acid. Txawm li cas los xij, kev siv cov kuab tshuaj nrog cov yam ntxwv nplaim taws thiab cov nplaum tawg, cov txheej txheem ntau lawm tau muaj kev phom sij, kev tsim cov khoom tsis yog mature.