Antimony-Based Catalysts

Ifiber yepolyester (PET) lolona didi lukhulu lwefayibha zokwenziwa. Impahla eyenziwe ngefiber yepolyester ikhululekile, ikhrisimesi, kulula ukuyihlamba, kwaye iyakhawuleza ukoma. Ipolyester ikwasetyenziswa ngokubanzi njengemathiriyeli ekrwada yokupakisha, imisonto yamashishini, kunye neeplastiki zobunjineli. Ngenxa yoko, i-polyester iphuhliswe ngokukhawuleza kwihlabathi jikelele, inyuka kumyinge wonyaka we-7% kunye nemveliso enkulu.

Imveliso yePolyester inokwahlulwa ibe yi-dimethyl terephthalate (DMT) indlela kunye ne-terephthalic acid (PTA) indlela ngokwendlela yenkqubo kwaye inokwahlulwa ibe yinkqubo ephakathi kunye nenkqubo eqhubekayo ngokwemigaqo yokusebenza. Kungakhathaliseki ukuba yeyiphi indlela yenkqubo yokuvelisa eyamkelweyo, i-polycondensation reaction ifuna ukusetyenziswa kweekhompawundi zetsimbi njenge-catalysts. Impendulo ye-polycondensation linyathelo eliphambili kwinkqubo yokuvelisa i-polyester, kwaye ixesha le-polycondensation liyi-bottleneck yokuphucula isivuno. Ukuphuculwa kwenkqubo ye-catalyst yinto ebalulekileyo ekuphuculeni umgangatho we-polyester kunye nokunciphisa ixesha le-polycondensation.

UrbanMines Tech. I-Limited yinkampani ekhokelayo yaseTshayina egxile kwi-R&D, imveliso, kunye nonikezelo lwe-polyester catalyst-grade antimony trioxide, i-acetate ye-antimony, kunye ne-antimony glycol. Senze uphando olunzulu kwezi mveliso-isebe le-R & D le-UrbanMines ngoku lishwankathela uphando kunye nokusetyenziswa kwe-antimony catalysts kweli nqaku ukunceda abathengi bethu basebenzise ngokuguquguqukayo, basebenzise iinkqubo zokuvelisa, kunye nokubonelela ngokukhuphisana okubanzi kweemveliso zefiber polyester.

Abaphengululi basekhaya nabangaphandle ngokubanzi bakholelwa ukuba i-polyester polycondensation yindlela yokusabela okwandisiweyo, kwaye indlela yokwenza i-catalytic ye-chelation coordination, efuna i-athomu yensimbi yecatalyst ibonelele nge-orbitals engenanto yokulungelelanisa kunye ne-arc pair of electrons of carbonyl oxygen ukufezekisa injongo i-catalysis. Kwi-polycondensation, ekubeni i-electron cloud cloud of carbonyl oxygen kwiqela le-hydroxyethyl ester iphantsi, i-electronegativity ye-ion yensimbi iphezulu kakhulu ngexesha lokulungelelaniswa, ukuququzelela ulungelelwaniso kunye nokwandiswa kwekhonkco.

Oku kulandelayo kunokusetyenziswa njengezixhobo zepolyester: Li, Na, K, Be, Mg, Ca, Sr, B, Al, Ga, Ge, Sn, Pb, Sb, Bi, Ti, Nb, Cr, Mo, Mn, Fe , I-Co, i-Ni, i-Pd, i-Pt, i-Cu, i-Ag, i-Zn, i-Cd, i-Hg kunye nezinye i-oxides zetsimbi, i-alcoholates, i-carboxylates, i-borates, i-halides kunye ne-amines, i-ureas, i-guanidines, i-sulfur equkethe i-organic compounds. Nangona kunjalo, ii-catalysts ezisetyenziswayo ngoku kwaye zifundwe kwimveliso yemizi-mveliso ubukhulu becala yi-Sb, Ge, kunye ne-Ti series compounds. Inani elikhulu lezifundo libonise ukuba: I-Ge-based catalysts ineempendulo ezimbalwa zecala kwaye ivelise i-PET ephezulu, kodwa umsebenzi wabo awuphezulu, kwaye banezixhobo ezimbalwa kwaye zibiza; Ii-catalysts ezisekelwe kwi-Ti zinomsebenzi ophezulu kunye nesantya sokuphendula ngokukhawuleza, kodwa iimpendulo zabo zecala zicacile, zikhokelela ekuzinzeni kakubi kwe-thermal kunye nombala otyheli wemveliso, kwaye ngokubanzi zinokusetyenziswa kuphela ukudibanisa i-PBT, i-PTT, i-PCT, njl. I-catalysts esekelwe kwi-Sb ayisebenzi nje kuphela. Umgangatho wemveliso uphezulu ngenxa yokuba ii-catalysts ezise-Sb zisebenza kakhulu, zineempendulo ezisecaleni ezimbalwa, kwaye zinexabiso eliphantsi. Ngoko ke, ziye zasetyenziswa ngokubanzi. Phakathi kwazo, i-catalysts esetyenziswa ngokuqhelekileyo ye-Sb-based antimony trioxide (Sb2O3), i-antimony acetate (Sb (CH3COO) 3), njl.

Ukujonga kwimbali yophuhliso lweshishini le-polyester, sinokufumanisa ukuba ngaphezu kwe-90% yezityalo ze-polyester kwihlabathi zisebenzisa i-antimony compounds njenge-catalysts. Ngo-2000, i-China yazisa izityalo ezininzi ze-polyester, zonke ezazisebenzisa i-antimony compounds njenge-catalysts, ikakhulukazi i-Sb2O3 kunye ne-Sb(CH3COO)3. Ngeenzame ezidibeneyo zophando lwezenzululwazi zaseTshayina, iidyunivesithi, kunye namasebe emveliso, ezi zintlupheko zimbini ngoku ziveliswe ngokupheleleyo ngaphakathi.

Ukususela ngo-1999, inkampani yeekhemikhali zaseFransi i-Elf iqalise i-antimony glycol [Sb2 (OCH2CH2CO) 3] i-catalyst njengemveliso ephuculweyo ye-catalysts yendabuko. Iitshiphusi zepolyester eziveliswe zinobumhlophe obuphezulu kunye nokujikeleza okuhle, okuthe kwatsala umdla omkhulu kumaziko ophando asekhaya, amashishini, kunye nabavelisi bepolyester eTshayina.

I. Uphando kunye nokusetyenziswa kwe-antimony trioxide
I-United States lelinye lamazwe okuqala ukuvelisa nokusebenzisa i-Sb2O3. Kwi-1961, ukusetyenziswa kwe-Sb2O3 e-United States kwafikelela kwiitoni ze-4,943. Ngama-1970, iinkampani ezintlanu zaseJapan zavelisa i-Sb2O3 kunye nomthamo opheleleyo wemveliso yeetoni ezingama-6,360 ngonyaka.

Uphando oluphambili lwaseTshayina lwe-Sb2O3 kunye neeyunithi zophuhliso zigxile ikakhulu kumashishini angaphambili aphantsi kolawulo lukarhulumente kwiPhondo laseHunan naseShanghai. UrbanMines Tech. Limited kwakhona useke umgca imveliso yobungcali kwiPhondo Hunan.

(Mna). Indlela yokuvelisa i-antimony trioxide
Ukwenziwa kwe-Sb2O3 ngokuqhelekileyo kusebenzisa i-antimony sulfide ore njengento ekrwada. I-antimony yensimbi ilungiswa kuqala, kwaye emva koko i-Sb2O3 iveliswa kusetyenziswa i-antimony yensimbi njengento ekrwada.
Kukho iindlela ezimbini eziphambili zokuvelisa i-Sb2O3 kwi-antimony yensimbi: i-oxidation ngqo kunye nokubola kwe-nitrogen.

1. Indlela ye-oxidation ngokuthe ngqo
I-antimony yensimbi isabela ngeoksijini phantsi kokufudumeza ukwenza i-Sb2O3. Inkqubo yokusabela imi ngolu hlobo lulandelayo:
4Sb＋3O2＝＝2Sb2O3

2. Ammonolysis
Isinyithi se-Antimony sisabela kunye neklorini ukudibanisa i-antimony trichloride, ethi emva koko i-distilled, i-hydrolyzed, i-ammonolyzed, ihlanjwe, kwaye yomiswe ukufumana imveliso ye-Sb2O3 egqityiweyo. Eyona equation yokusabela yile:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O

(II). Ukusetyenziswa kwe-antimony trioxide
Ukusetyenziswa okuphambili kwe-antimony trioxide kufana ne-catalyst ye-polymerase kunye ne-flame retardant kwizinto zokwenziwa.
Kwishishini le-polyester, i-Sb2O3 yaqala ukusetyenziswa njenge-catalyst. I-Sb2O3 isetyenziswa kakhulu njenge-polycondensation catalyst yendlela ye-DMT kunye nendlela yokuqala ye-PTA kwaye isetyenziswa ngokubanzi kunye ne-H3PO4 okanye i-enzymes yayo.

(III). Iingxaki nge-antimony trioxide
I-Sb2O3 ine-solubility embi kwi-ethylene glycol, kunye ne-solubility ye-4.04% kuphela kwi-150 ° C. Ngoko ke, xa i-ethylene glycol isetyenziselwa ukulungisa i-catalyst, i-Sb2O3 ine-dispersibility embi, enokuthi ibangele i-catalyst egqithisileyo kwi-polymerization system, ivelise i-high-melting-point cyclic trimers, kwaye izise ubunzima ekujikelezeni. Ukuphucula ukunyibilika kunye ne-dispersibility ye-Sb2O3 kwi-ethylene glycol, ngokuqhelekileyo yamkelwa ukusebenzisa i-ethylene glycol eninzi okanye ukwandisa ubushushu bokutshatyalaliswa ukuya ngaphezu kwe-150 ° C. Nangona kunjalo, ngaphezu kwe-120 ° C, i-Sb2O3 kunye ne-ethylene glycol inokuvelisa i-ethylene glycol antimony precipitation xa isebenza kunye ixesha elide, kwaye i-Sb2O3 ingancitshiswa ibe yi-antimony ye-metallic kwi-polycondensation reaction, enokubangela "inkungu" kwi-polyester chips kwaye ichaphazele. umgangatho wemveliso.

II. Uphando kunye nokusetyenziswa kwe-acetate ye-antimony
Ukulungiselela indlela ye-antimony acetate
Ekuqaleni, i-acetate ye-antimony yalungiswa ngokuphendula i-antimony trioxide nge-acetic acid, kwaye i-acetic anhydride yayisetyenziswe njenge-agent ye-dehydrating ukuze ithathe amanzi awenziwe yi-reaction. Umgangatho wemveliso egqityiweyo efunyenwe yile ndlela yayingekho phezulu, kwaye kuthatha iiyure ezingaphezu kwe-30 ukuba i-antimony trioxide inyibilike kwi-acetic acid. Kamva, i-antimony acetate yalungiswa ngokusabela kwe-antimony yensimbi, i-antimony trichloride, okanye i-antimony trioxide ene-acetic anhydride, ngaphandle kwemfuneko ye-agent ekhupha amanzi.

1. Indlela ye-Antimony trichloride
Ngowe-1947, uH. Schmidt et al. eNtshona Jamani ilungiselele i-Sb(CH3COO)3 ngokusabela i-SbCl3 nge-acetic anhydride. Ifomula yokusabela imi ngolu hlobo lulandelayo:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl

2. Indlela yensimbi ye-Antimony
Ngo-1954, i-TAPaybea yendawo eyayisakuba yiSoviet Union yalungisa i-Sb(CH3COO)3 ngokusabela i-antimony yensimbi kunye ne-peroxyacetyl kwisisombululo se-benzene. Indlela yokusabela yile:
Sb＋(CH3COO)2==Sb(CH3COO)3

3. Indlela ye-Antimony trioxide
Kwi-1957, uF. Nerdel waseNtshona Jamani wasebenzisa i-Sb2O3 ukusabela nge-acetic anhydride ukuvelisa i-Sb (CH3COO)3.
Sb2O3＋3(CH3CO)2O(2Sb)(CH3COO)3
Ukungalungi kwale ndlela kukuba iikristale zivame ukuhlanganisana zibe ngamaqhekeza amakhulu kwaye zinamathele ngokuqinileyo kudonga lwangaphakathi lwe-reactor, okubangela umgangatho ombi wemveliso kunye nombala.

4. Indlela yokunyibilikisa i-Antimony trioxide
Ukunqoba iintsilelo zendlela engentla, i-solvent engathathi hlangothi idla ngokudityaniswa ngexesha lokuphendula kwe-Sb2O3 kunye ne-acetic anhydride. Indlela ethile yokulungiselela yile ilandelayo:
(1) Kwi-1968, uR. Thoms we-American Mosun Chemical Company wapapasha ilungelo lomenzi malunga nokulungiswa kwe-acetate ye-antimony. I-patent isetyenziswe i-xylene (o-, m-, p-xylene, okanye umxube wayo) njenge-solvent engathathi hlangothi ukuvelisa iikristale ezintle ze-antimony acetate.
(2) Ngowe-1973, iRiphabliki yaseCzech yavelisa indlela yokuvelisa i<em>antimony acetate entle kusetyenziswa i<em>toluene njengesinyibilikisi.

 

III. Ukuthelekiswa kwe-antimony-based catalysts ezintathu