Polyester (PET) fiber ntau yog ntau hom hluavtaws fiber ntau. Cov khaub ncaws ua los ntawm polyester fiber yog xis nyob, nkig, yooj yim los ntxuav, thiab ceev kom qhuav. Polyester kuj yog siv los ua cov khoom siv raw rau kev ntim khoom, cov xov paj, thiab cov yas engineering. Raws li qhov tshwm sim, polyester tau tsim sai heev thoob ntiaj teb, nce ntawm qhov nruab nrab txhua xyoo tus nqi ntawm 7% thiab nrog cov khoom siv loj.
Polyester ntau lawm tuaj yeem muab faib ua dimethyl terephthalate (DMT) txoj kev thiab terephthalic acid (PTA) txoj hauv kev ntawm txoj kev txheej txheem thiab tuaj yeem muab faib ua cov txheej txheem sib tshuam thiab cov txheej txheem txuas ntxiv ntawm kev ua haujlwm. Txawm hais tias cov txheej txheem ntau lawm tau txais, cov tshuaj tiv thaiv polycondensation yuav tsum tau siv cov hlau sib txuas ua cov catalysts. Cov tshuaj tiv thaiv polycondensation yog ib kauj ruam tseem ceeb hauv cov txheej txheem polyester ntau lawm, thiab lub sij hawm polycondensation yog lub hauv paus rau kev txhim kho cov txiaj ntsig. Kev txhim kho cov txheej txheem catalyst yog ib qho tseem ceeb hauv kev txhim kho cov polyester zoo thiab ua kom lub sijhawm polycondensation luv.
UrbanMines Tech. Limited yog ib lub tuam txhab ua lag luam hauv Suav teb tshwj xeeb hauv R & D, ntau lawm, thiab muab khoom ntawm polyester catalyst-qib antimony trioxide, antimony acetate, thiab antimony glycol. Peb tau tshawb xyuas qhov tob ntawm cov khoom no - R & D department ntawm UrbanMines tam sim no sau cov kev tshawb fawb thiab kev siv cov antimony catalysts hauv tsab xov xwm no los pab peb cov neeg siv khoom yooj yim siv, txhim kho cov txheej txheem ntau lawm, thiab muab kev sib tw ntawm cov khoom siv polyester fiber ntau.
Cov kws tshawb fawb hauv tsev thiab txawv teb chaws feem ntau ntseeg tias polyester polycondensation yog cov tshuaj tiv thaiv txuas ntxiv, thiab cov txheej txheem catalytic belongs rau chelation kev sib koom tes, uas yuav tsum muaj cov catalyst hlau atom muab cov khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob khoob. catalysis. Rau polycondensation, txij li thaum lub electron huab ceev ntawm carbonyl oxygen nyob rau hauv cov hydroxyethyl ester pawg yog kuj tsawg, lub electronegativity ntawm hlau ions yog kuj siab thaum lub sij hawm sib koom ua ke, los pab txhawb kev sib koom tes thiab cov saw txuas ntxiv.
Cov nram qab no tuaj yeem siv los ua polyester catalysts: Li, Na, K, Be, Mg, Ca, Sr, B, Al, Ga, Ge, Sn, Pb, Sb, Bi, Ti, Nb, Cr, Mo, Mn, Fe , Co, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Hg thiab lwm yam hlau oxides, alcoholates, carboxylates, borates, halides thiab amines, ureas, guanidines, sulfur-muaj organic tebchaw. Txawm li cas los xij, cov catalysts uas tam sim no siv thiab kawm hauv kev tsim khoom yog tsuas yog Sb, Ge, thiab Ti series compounds. Ntau cov kev tshawb fawb tau pom tias: Ge-based catalysts muaj tsawg dua kev cuam tshuam sab nraud thiab tsim cov PET zoo, tab sis lawv cov dej num tsis siab, thiab lawv muaj peev txheej tsawg thiab kim; Ti-raws li catalysts muaj kev ua haujlwm siab thiab ceev cov tshuaj tiv thaiv ceev, tab sis lawv cov catalytic sab kev xav tau pom tseeb dua, ua rau tsis zoo thermal stability thiab xim daj ntawm cov khoom, thiab lawv feem ntau tsuas yog siv rau kev sib txuas ntawm PBT, PTT, PCT, lwm.; Sb-raws li catalysts tsis tsuas yog muaj zog dua. Cov khoom lag luam zoo siab vim tias Sb-based catalysts muaj zog dua, muaj kev cuam tshuam sab qis dua, thiab pheej yig dua. Yog li ntawd, lawv tau siv dav. Ntawm lawv, feem ntau siv Sb-raws li catalysts yog antimony trioxide (Sb2O3), antimony acetate (Sb (CH3COO) 3), thiab lwm yam.
Saib ntawm kev txhim kho keeb kwm ntawm kev lag luam polyester, peb tuaj yeem pom tias ntau dua 90% ntawm cov nroj tsuag polyester hauv ntiaj teb siv cov tshuaj tiv thaiv antimony ua catalysts. Los ntawm 2000, Tuam Tshoj tau qhia ntau yam polyester nroj tsuag, tag nrho cov uas siv antimony compounds raws li catalysts, feem ntau yog Sb2O3 thiab Sb (CH3COO)3. Los ntawm kev sib koom tes ntawm Suav kev tshawb fawb tshawb fawb, tsev kawm qib siab, thiab chaw tsim khoom, ob lub catalysts tam sim no tau ua tiav hauv tsev.
Txij li thaum xyoo 1999, Fabkis lub tuam txhab tshuaj lom neeg Elf tau tsim cov tshuaj antimony glycol [Sb2 (OCH2CH2CO) 3] catalyst raws li cov khoom hloov kho ntawm cov tshuaj catalysts. Polyester chips uas tsim muaj siab dawb thiab zoo spinnability, uas tau nyiam heev los ntawm domestic catalyst kev tshawb fawb cov koom haum, qhauj, thiab polyester manufacturers nyob rau hauv Suav teb.
I. Kev tshawb fawb thiab kev siv tshuaj antimony trioxide
Tebchaws Asmeskas yog ib lub tebchaws ntxov tshaj plaws los tsim thiab siv Sb2O3. Xyoo 1961, kev noj ntawm Sb2O3 hauv Tebchaws Meskas tau mus txog 4,943 tons. Hauv xyoo 1970, tsib lub tuam txhab hauv Nyij Pooj tau tsim Sb2O3 nrog tag nrho cov peev txheej ntawm 6,360 tons hauv ib xyoos.
Tuam Tshoj lub ntsiab Sb2O3 kev tshawb fawb thiab kev loj hlob units yog mas concentrated nyob rau hauv lub qub xeev cov lag luam nyob rau hauv Hunan xeev thiab Shanghai. UrbanMines Tech. Limited kuj tau tsim ib txoj kab ntau lawm hauv Hunan Province.
(Kuv). Txoj kev tsim cov tshuaj antimony trioxide
Kev tsim khoom ntawm Sb2O3 feem ntau yog siv antimony sulfide ore ua raw khoom. Hlau antimony yog thawj zaug npaj, thiab tom qab ntawd Sb2O3 yog tsim siv hlau antimony ua raw khoom.
Muaj ob txoj hauv kev tseem ceeb rau kev tsim Sb2O3 los ntawm hlau antimony: ncaj qha oxidation thiab nitrogen decomposition.
1. Direct oxidation txoj kev
Hlau antimony reacts nrog oxygen nyob rau hauv cua sov rau daim ntawv Sb2O3. Cov txheej txheem tshuaj tiv thaiv yog raws li nram no:
4Sb+3O2 ＝2Sb2O3
2. Ammonolysis
Antimony hlau reacts nrog chlorine rau synthesize antimony trichloride, uas tom qab ntawd distilled, hydrolyzed, ammonolyzed, ntxuav, thiab qhuav kom tau cov khoom tiav Sb2O3. Qhov sib npaug ntawm cov tshuaj tiv thaiv yog:
2Sb+3Cl2＝2SbCl3
SbCl3+H2O＝SbOCl+2HCl
4SbOCl + H2O 2HCl
Sb2O3·2SbOCl+OH＝＝2Sb2O3＋2NH4Cl＋H2O
(II). Kev siv cov tshuaj antimony trioxide
Lub ntsiab siv ntawm antimony trioxide yog raws li ib tug catalyst rau polymerase thiab ib tug nplaim retardant rau cov khoom hluavtaws.
Hauv kev lag luam polyester, Sb2O3 yog thawj zaug siv los ua catalyst. Sb2O3 feem ntau yog siv los ua polycondensation catalyst rau txoj kev DMT thiab txoj kev PTA thaum ntxov thiab feem ntau yog siv ua ke nrog H3PO4 lossis nws cov enzymes.
(III). Teeb meem nrog antimony trioxide
Sb2O3 muaj cov dej tsis zoo hauv ethylene glycol, nrog rau solubility ntawm 4.04% ntawm 150 ° C. Yog li ntawd, thaum ethylene glycol yog siv los npaj cov catalyst, Sb2O3 muaj cov dispersibility tsis zoo, uas tuaj yeem ua rau cov catalyst ntau dhau hauv cov txheej txheem polymerization, tsim cov high-melting-point cyclic trimers, thiab ua rau muaj teeb meem rau spinning. Txhawm rau txhim kho cov solubility thiab dispersibility ntawm Sb2O3 nyob rau hauv ethylene glycol, nws yog feem ntau saws los siv ntau tshaj ethylene glycol los yog ua kom lub dissolution kub kom siab tshaj 150 ° C. Txawm li cas los xij, siab dua 120 ° C, Sb2O3 thiab ethylene glycol tuaj yeem tsim ethylene glycol antimony nag lossis daus thaum lawv ua ke rau lub sijhawm ntev, thiab Sb2O3 tuaj yeem txo qis rau cov xim hlau antimony hauv cov tshuaj tiv thaiv polycondensation, uas tuaj yeem ua rau "fog" hauv polyester chips thiab cuam tshuam. khoom zoo.
II. Kev tshawb nrhiav thiab kev siv tshuaj antimony acetate
Txoj kev npaj ntawm antimony acetate
Thaum xub thawj, antimony acetate tau npaj los ntawm reacting antimony trioxide nrog acetic acid, thiab acetic anhydride tau siv los ua tus neeg ua kom lub cev qhuav dej kom nqus cov dej los ntawm cov tshuaj tiv thaiv. Qhov zoo ntawm cov khoom tiav tau los ntawm txoj kev no tsis siab, thiab nws siv sijhawm ntau dua 30 teev rau antimony trioxide kom yaj hauv acetic acid. Tom qab ntawd, antimony acetate tau npaj los ntawm reacting hlau antimony, antimony trichloride, los yog antimony trioxide nrog acetic anhydride, tsis tas yuav muaj tus neeg sawv cev lub cev qhuav dej.
1. Antimony trichloride txoj kev
Xyoo 1947, H. Schmidt et al. nyob rau sab hnub poob lub teb chaws Yelemees npaj Sb (CH3COO) 3 los ntawm reacting SbCl3 nrog acetic anhydride. Cov tshuaj tiv thaiv mis yog raws li nram no:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Antimony hlau txoj kev
Nyob rau hauv 1954, TAPaybea ntawm lub qub Soviet Union tau npaj Sb (CH3COO) 3 los ntawm reacting metallic antimony thiab peroxyacetyl nyob rau hauv ib tug benzene tov. Cov tshuaj tiv thaiv formula yog:
Sb(CH3COO)2==Sb(CH3COO)3
3. Antimony trioxide txoj kev
Xyoo 1957, F. Nerdel ntawm West Lub Tebchaws Yelemees siv Sb2O3 los ua haujlwm nrog acetic anhydride los tsim Sb(CH3COO)3.
Sb2O3＋3(CH3CO)2O＝＝2Sb(CH3COO)3
Qhov tsis zoo ntawm txoj kev no yog tias cov crystals zoo li sib sau ua ke rau hauv cov khoom loj thiab lo khov kho rau sab hauv phab ntsa ntawm lub reactor, ua rau cov khoom tsis zoo thiab xim.
4. Antimony trioxide hnyav txoj kev
Txhawm rau kov yeej qhov tsis txaus ntawm cov txheej txheem saum toj no, cov kuab tshuaj nruab nrab feem ntau yog ntxiv thaum lub sij hawm cov tshuaj tiv thaiv ntawm Sb2O3 thiab acetic anhydride. Txoj kev npaj tshwj xeeb yog raws li hauv qab no:
(1) Xyoo 1968, R. Thoms ntawm American Mosun Chemical Company tau luam tawm patent ntawm kev npaj antimony acetate. Cov patent siv xylene (o-, m-, p-xylene, los yog sib tov ntawm) ua ib qho hnyav nruab nrab los tsim cov muaju zoo ntawm antimony acetate.
(2) Xyoo 1973, Czech koom pheej tau tsim ib txoj hauv kev los tsim cov khoom zoo antimony acetate siv toluene ua cov kuab tshuaj.
III. Kev sib piv ntawm peb cov antimony-based catalysts
| Antimony Trioxide | Antimony Acetate | Antimony Glycolate | |
| Cov cuab yeej yooj yim | Feem ntau hu ua antimony dawb, molecular mis Sb 2 O 3, molecular hnyav 291.51, dawb hmoov, melting point 656 ℃. Theoretical antimony cov ntsiab lus yog hais txog 83.53%. Relative ntom ntom 5.20g / ml Soluble nyob rau hauv concentrated hydrochloric acid, concentrated sulfuric acid, concentrated nitric acid, tartaric acid thiab alkali tov, insoluble nyob rau hauv dej, cawv, dilute sulfuric acid. | Molecular formula Sb(AC) 3, molecular hnyav 298.89, theoretical antimony cov ntsiab lus txog 40.74%, melting point 126-131 ℃, ntom 1.22g / ml (25 ℃), dawb los yog dawb hmoov, yooj yim soluble hauv ethylene glycol, toluene thiab xylene. | Cov mis mos molecular Sb 2 (EG) 3, Lub cev hnyav yog li 423.68, lub ntsiab lus melting yog ＞ 100 ℃ (dec.), cov ntsiab lus theoretical antimony yog li 57.47%, qhov tsos yog dawb crystalline khoom, tsis muaj tshuaj lom thiab saj, yooj yim nqus dej noo. Nws yooj yim soluble hauv ethylene glycol. |
| Synthesis Method thiab Technology | Feem ntau ua los ntawm stibnite txoj kev: 2Sb 2 S 3 + 9O 2 → 2Sb 2 O 3 + 6SO 2 ↑Sb 2 O 3 + 3C → 2Sb + 3CO↑ 4Sb + O 2 → 2Sb 2 O 3Note: Stibnite / Iron Ore / Lime Cua sov thiab Fuming → Sau | Kev lag luam feem ntau yog siv Sb 2 O 3 -solvent method for synthesis: Sb2O3 ＋ 3 (CH3CO) 2O → 2Sb (AC) 3Process: cua sov reflux → kub filtration → crystallization → nqus tsev ziab → productNote: Sb (AC) 3 yog yooj yim hydrolyzed, yog li qhov nruab nrab hnyav toluene lossis xylene siv yuav tsum tsis muaj dej, Sb 2 O 3 tsis tuaj yeem nyob hauv lub xeev ntub dej, thiab cov khoom siv yuav tsum tau qhuav. | Kev lag luam feem ntau siv Sb 2 O 3 txoj kev los ua ke: Sb 2 O 3 + 3EG → Sb 2 (EG) 3 + 3H 2 OProcess: Pub (Sb 2 O 3, additives thiab EG) → cua sov thiab cov tshuaj tiv thaiv → tshem tawm slag , impurities thiab dej → decolorization → kub filtration → txias thiab crystallization → sib cais thiab ziab → productNote: Cov txheej txheem ntau lawm yuav tsum tau muab cais tawm ntawm dej los tiv thaiv hydrolysis. Cov tshuaj tiv thaiv no yog cov tshuaj tiv thaiv rov qab, thiab feem ntau cov tshuaj tiv thaiv yog txhawb nqa los ntawm kev siv ntau tshaj ethylene glycol thiab tshem tawm cov khoom siv dej. |
| Qhov zoo | Tus nqi kuj pheej yig, nws yog ib qho yooj yim mus use, muaj me ntsis catalytic kev ua si thiab lub sij hawm luv luv polycondensation. | Antimony acetate muaj zoo solubility nyob rau hauv ethylene glycol thiab yog tusyees dispersed nyob rau hauv ethylene glycol, uas yuav txhim khu kev siv efficiency ntawm antimony; Antimony acetate muaj cov yam ntxwv ntawm high catalytic kev ua si, tsawg degradation cov tshuaj tiv thaiv, zoo tshav kub kuj thiab ua stability; Nyob rau tib lub sijhawm, siv antimony acetate raws li cov khoom siv catalyst tsis tas yuav tsum tau ntxiv cov co-catalyst thiab stabilizer. Cov tshuaj tiv thaiv ntawm antimony acetate catalytic system yog qhov me me, thiab cov khoom zoo yog siab, tshwj xeeb tshaj yog cov xim, uas yog zoo dua li ntawm antimony trioxide (Sb 2 O 3) system. | Cov catalyst muaj cov solubility siab hauv ethylene glycol; xoom-valent antimony raug tshem tawm, thiab impurities xws li hlau molecules, chlorides thiab sulfates uas cuam tshuam rau polycondensation raug txo kom qis qis, tshem tawm cov teeb meem ntawm acetate ion corrosion ntawm cov cuab yeej; Sb 3+ hauv Sb 2 (EG) 3 yog qhov siab. , uas tej zaum yuav yog vim hais tias nws solubility nyob rau hauv ethylene glycol ntawm cov tshuaj tiv thaiv kub yog ntau dua li ntawm Sb 2 O 3 Piv nrog rau Sb (AC) 3, tus nqi ntawm Sb 3 + uas plays lub luag hauj lwm catalytic ntau dua. Cov xim ntawm cov khoom polyester uas ua los ntawm Sb 2 (EG) 3 yog zoo dua li ntawm Sb 2 O 3 me ntsis siab dua qhov qub, ua rau cov khoom zoo dua qub thiab zoo dua qub; |
| Qhov tsis zoo | Lub solubility hauv ethylene glycol tsis zoo, tsuas yog 4.04% ntawm 150 ° C. Hauv kev xyaum, ethylene glycol yog ntau dhau los yog qhov kub ntawm qhov sib tov yog nce mus rau saum 150 ° C. Txawm li cas los xij, thaum Sb 2 O 3 reacts nrog ethylene glycol rau lub sijhawm ntev ntawm qhov kub siab tshaj 120 ° C, ethylene glycol antimony nag lossis daus tuaj yeem tshwm sim, thiab Sb 2 O 3 tuaj yeem txo qis rau hlau ntaiv hauv cov tshuaj tiv thaiv polycondensation, uas tuaj yeem ua rau "grey pos huab. "nyob rau hauv polyester chips thiab cuam tshuam cov khoom zoo. Qhov tshwm sim ntawm polyvalent antimony oxides tshwm sim thaum lub sij hawm kev npaj ntawm Sb 2 O 3, thiab qhov zoo purity ntawm antimony yog cuam tshuam. | Cov ntsiab lus antimony ntawm cov catalyst yog qhov tsawg; acetic acid impurities qhia cov khoom siv corrode, ua paug rau ib puag ncig, thiab tsis tsim nyog rau kev kho dej khib nyiab; cov txheej txheem ntau lawm yog complex, kev khiav hauj lwm ib puag ncig tej yam kev mob tsis zoo, muaj kuab paug, thiab cov khoom yog yooj yim hloov xim. Nws yooj yim rau decompose thaum rhuab, thiab cov khoom siv hydrolysis yog Sb2O3 thiab CH3COOH. Cov khoom siv nyob rau lub sijhawm ntev, tshwj xeeb tshaj yog nyob rau theem kawg polycondensation, uas yog qhov siab dua li Sb2O3 system. | Kev siv Sb 2 (EG) 3 tsub kom tus nqi catalyst ntawm cov cuab yeej (tus nqi nce tsuas yog offset yog tias 25% ntawm PET yog siv rau tus kheej spinning ntawm filaments). Tsis tas li ntawd, b tus nqi ntawm cov khoom hue nce me ntsis. |