Ama-Catalyst Asekelwe ku-Antimony

I-polyester (PET) fiber iyinhlobonhlobo enkulu yefayibha yokwenziwa. Izingubo ezenziwe nge-polyester fiber zikhululekile, zihlanzekile, ziwashwa kalula, futhi ziyashesha ukukoma. I-polyester iphinde isetshenziswe kabanzi njengempahla eluhlaza yokupakisha, izintambo zezimboni, namapulasitiki obunjiniyela. Ngenxa yalokho, i-polyester ithuthuke ngokushesha emhlabeni wonke, ikhula ngesilinganiso sonyaka se-7% kanye nomkhiqizo omkhulu.

Ukukhiqizwa kwe-polyester kungahlukaniswa ngomzila we-dimethyl terephthalate (DMT) kanye nomzila we-terephthalic acid (PTA) ngokomzila wenqubo futhi ingahlukaniswa ngenqubo yesikhashana kanye nenqubo eqhubekayo mayelana nokusebenza. Ngaphandle komzila wenqubo yokukhiqiza owamukelwe, ukusabela kwe-polycondensation kudinga ukusetshenziswa kwezinhlanganisela zensimbi njengama-catalyst. Ukusabela kwe-polycondensation kuyisinyathelo esibalulekile enqubweni yokukhiqiza i-polyester, futhi isikhathi se-polycondensation siyibhodlela lokuthuthukisa isivuno. Ukuthuthukiswa kwesistimu ye-catalyst kuyisici esibalulekile ekuthuthukiseni ikhwalithi ye-polyester kanye nokunciphisa isikhathi se-polycondensation.

I-UrbanMines Tech. I-Limited yinkampani yaseShayina ehamba phambili egxile ku-R&D, ukukhiqiza, kanye nokuhlinzekwa kwe-polyester catalyst-grade antimony trioxide, i-antimony acetate, ne-antimony glycol. Senze ucwaningo olunzulu ngale mikhiqizo—umnyango we-R&D we-UrbanMines manje ufingqa ucwaningo nokusebenzisa ama-antimony catalysts kulesi sihloko ukuze sisize amakhasimende ethu asebenzise kalula, athuthukise izinqubo zokukhiqiza, futhi anikeze ukuncintisana okuphelele kwemikhiqizo ye-polyester fiber.

Izazi zasekhaya nezakwamanye amazwe ngokuvamile zikholelwa ukuthi i-polyester polycondensation iyindlela yokusabela enwetshiwe, futhi indlela ye-catalytic ingeyokuxhumanisa i-chelation, okudinga ukuthi i-athomu yensimbi yecatalyst inikeze ama-orbitals angenalutho ukuze axhumanise ne-arc electron yama-electron e-carbonyl oxygen ukuze kuzuzwe inhloso i-catalysis. Nge-polycondensation, njengoba ukuminyana kwamafu we-electron we-carbonyl oxygen eqenjini le-hydroxyethyl ester iphansi ngokuqhathaniswa, i-electronegativity yama-ion ensimbi iphakeme uma kuqhathaniswa, ukuze kube lula ukusebenzisana nokwelulwa kweketango.

Okulandelayo kungasetshenziswa njengama-catalysts e-polyester: 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 namanye ama-oxide ensimbi, ama-alcohol, ama-carboxylates, ama-borates, ama-halides nama-amine, ama-urea, ama-guanidine, ama-organic compounds anesulfure. Kodwa-ke, ama-catalyst asetshenziswayo njengamanje futhi afundelwa ekukhiqizweni kwezimboni ikakhulukazi ama-Sb, Ge, kanye ne-Ti series compounds. Inombolo enkulu yocwaningo ibonise ukuthi: Ama-catalysts asekelwe ku-Ge anokusabela okuncane okuncane futhi akhiqiza i-PET yekhwalithi ephezulu, kodwa umsebenzi wabo awuphakeme, futhi unezinsiza ezimbalwa futhi uyabiza; Ama-catalyst asekelwe ku-Ti anomsebenzi ophezulu kanye nesivinini sokuphendula ngokushesha, kodwa ukusabela kwawo ohlangothini lwe-catalytic kubonakala kakhudlwana, okuholela ekuzinzeni okuncane kokushisa nombala ophuzi womkhiqizo, futhi ngokuvamile angasetshenziswa kuphela ukuhlanganiswa kwe-PBT, i-PTT, i-PCT, njll.; Ama-catalyst asekelwe ku-Sb awasebenzi nje kuphela. Ikhwalithi yomkhiqizo iphezulu ngoba ama-catalyst asuselwa ku-Sb asebenza kakhulu, anokusabela okuseceleni okumbalwa, futhi ashibhile. Ngakho-ke, ziye zasetshenziswa kabanzi. Phakathi kwazo, ama-catalysts asekelwe e-Sb asetshenziswa kakhulu yi-antimony trioxide (Sb2O3), i-antimony acetate (Sb(CH3COO)3), njll.

Uma sibheka umlando wokuthuthukiswa kwemboni ye-polyester, singathola ukuthi ngaphezu kwe-90% yezitshalo ze-polyester emhlabeni zisebenzisa ama-antimony compounds njengama-catalysts. Ngonyaka ka-2000, i-China yase yethule izitshalo eziningi ze-polyester, zonke ezazisebenzisa izinhlanganisela ze-antimony njenge-catalyst, ikakhulukazi i-Sb2O3 kanye ne-Sb(CH3COO)3. Ngemizamo ehlanganyelwe yocwaningo lwesayensi lwaseShayina, amanyuvesi, kanye neminyango yokukhiqiza, lezi zisusa ezimbili manje sezikhiqizwe ngokugcwele kuleli.

Kusukela ngo-1999, inkampani yamakhemikhali yaseFrance i-Elf yethule i-antimony glycol [Sb2 (OCH2CH2CO) 3] catalyst njengomkhiqizo othuthukisiwe wama-catalysts wendabuko. Ama-chips e-polyester akhiqizwayo anobumhlophe obuphezulu kanye nokuphonswa okuhle, okudonse ukunaka okukhulu okuvela ezikhungweni zokucwaninga zasekhaya, amabhizinisi, nabakhiqizi be-polyester e-China.

I. Ucwaningo nokusebenzisa i-antimony trioxide
I-United States ingelinye lamazwe okuqala kakhulu ukukhiqiza nokusebenzisa i-Sb2O3. Ngo-1961, ukusetshenziswa kwe-Sb2O3 e-United States kwafinyelela amathani angu-4,943. Ngawo-1970, izinkampani ezinhlanu eJapane zakhiqiza i-Sb2O3 enamandla okukhiqiza amathani angu-6,360 ngonyaka.

Amayunithi amakhulu ocwaningo nokuthuthukiswa kwe-Sb2O3 aseShayina agxile kakhulu emabhizinisini angaphambilini kahulumeni esifundazweni sase-Hunan nase-Shanghai. I-UrbanMines Tech. I-Limited iphinde yasungula ulayini wokukhiqiza ochwepheshe esifundazweni saseHunan.

(Mina). Indlela yokukhiqiza i-antimony trioxide
Ukwakhiwa kwe-Sb2O3 kuvame ukusebenzisa i-antimony sulfide ore njengempahla eluhlaza. I-antimony yensimbi ilungiswa kuqala, bese i-Sb2O3 ikhiqizwa kusetshenziswa i-antimony yensimbi njengempahla eluhlaza.
Kunezindlela ezimbili eziyinhloko zokukhiqiza i-Sb2O3 kusuka ku-antimony yensimbi: i-oxidation eqondile kanye nokubola kwe-nitrogen.

1. Indlela ye-oxidation eqondile
I-antimony yensimbi isabela nomoya-mpilo ngaphansi kokushisisa ukuze yakhe i-Sb2O3. Inqubo yokusabela imi kanje:
4Sb＋3O2＝＝2Sb2O3

2. Ammonolysis
I-Antimony metal isabela ne-chlorine ukuze ihlanganise i-antimony trichloride, ebese igaywa, i-hydrolyzed, i-ammonolyzed, igezwe, futhi yomiswe ukuze kutholwe umkhiqizo oqediwe we-Sb2O3. Izibalo zokusabela eziyisisekelo yilezi:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O

(II). Ukusetshenziswa kwe-antimony trioxide
Ukusetshenziswa okuyinhloko kwe-antimony trioxide kunjenge-catalyst ye-polymerase kanye ne-flame retardant yezinto zokwenziwa.
Embonini ye-polyester, i-Sb2O3 yaqala ukusetshenziswa njenge-catalyst. I-Sb2O3 isetshenziswa kakhulu njenge-polycondensation catalyst yomzila we-DMT kanye nomzila wokuqala we-PTA futhi ngokuvamile isetshenziswa ngokuhlanganiswa ne-H3PO4 noma ama-enzyme ayo.

(III). Izinkinga nge-antimony trioxide
I-Sb2O3 inokuncibilika okungekuhle ku-ethylene glycol, ne-solubility engu-4.04% kuphela ku-150°C. Ngakho-ke, lapho i-ethylene glycol isetshenziselwa ukulungisa i-catalyst, i-Sb2O3 ine-dispersibility embi, engabangela kalula i-catalyst ngokweqile ohlelweni lwe-polymerization, ikhiqize i-high-melting-point cyclic trimers, futhi ilethe ubunzima ekujikelezeni. Ukuze kuthuthukiswe ukunyibilika nokuhlakazeka kwe-Sb2O3 ku-ethylene glycol, ngokuvamile kwamukelwa ukusebenzisa i-ethylene glycol ngokweqile noma ukukhulisa izinga lokushisa lokuncibilika libe ngaphezu kuka-150°C. Nokho, ngaphezu kuka-120°C, i-Sb2O3 ne-ethylene glycol zingakhiqiza imvula ye-ethylene glycol antimony lapho zisebenza ndawonye isikhathi eside, futhi i-Sb2O3 ingase yehliswe ibe yi-antimony yensimbi ekuphenduleni kwe-polycondensation, engabangela "inkungu" kuma-chips e-polyester futhi ithinte. izinga lomkhiqizo.

II. Ucwaningo kanye nokusetshenziswa kwe-antimony acetate
Ukulungiselela indlela ye-antimony acetate
Ekuqaleni, i-antimony acetate yalungiswa ngokusabela kwe-antimony trioxide nge-acetic acid, futhi i-acetic anhydride yasetshenziswa njenge-agent eqeda amanzi ukuze imunce amanzi akhiqizwa ukusabela. Izinga lomkhiqizo oqediwe otholwe ngale ndlela lalingekho phezulu, futhi kwathatha amahora angaphezu kuka-30 ukuthi i-antimony trioxide incibilike ku-acetic acid. Kamuva, i-antimony acetate yalungiswa ngokusabela kwe-antimony yensimbi, i-antimony trichloride, noma i-antimony trioxide ene-acetic anhydride, ngaphandle kwesidingo se-ejenti eqeda amanzi emzimbeni.

1. Indlela ye-Antimony trichloride
Ngo-1947, u-H. Schmidt et al. eNtshonalanga Jalimane ilungiselele i-Sb(CH3COO)3 ngokusabela i-SbCl3 nge-acetic anhydride. Ifomula yokusabela imi kanje:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl

2. Indlela yensimbi ye-Antimony
Ngo-1954, i-TAPaybea ye-Soviet Union yangaphambili yalungisa i-Sb(CH3COO)3 ngokusabela i-antimony ye-metallic ne-peroxyacetyl kusixazululo se-benzene. Ifomula yokusabela ithi:
Sb＋(CH3COO)2==Sb(CH3COO)3

3. Indlela ye-Antimony trioxide
Ngo-1957, uF. Nerdel waseNtshonalanga Jalimane wasebenzisa i-Sb2O3 ukuze asabele nge-acetic anhydride ukukhiqiza i-Sb(CH3COO)3.
I-Sb2O3＋3(CH3CO)2O(2Sb)(CH3COO)3
Ububi bale ndlela ukuthi amakristalu ajwayele ukunqwabelana abe yizicucu ezinkulu futhi anamathele ngokuqinile odongeni lwangaphakathi lwe-reactor, okuholela ekhwalithi yomkhiqizo ompofu kanye nombala.

4. Indlela ye-Antimony trioxide solvent
Ukuze unqobe ukushiyeka kwendlela engenhla, i-solvent engathathi hlangothi ivame ukungezwa ngesikhathi sokusabela kwe-Sb2O3 ne-acetic anhydride. Indlela eqondile yokulungiselela imi kanje:
(1) Ngo-1968, u-R. Thoms we-American Mosun Chemical Company washicilela ilungelo lobunikazi ngokulungiswa kwe-acetate ye-antimony. Ilungelo lobunikazi lasebenzisa i-xylene (o-, m-, p-xylene, noma ingxube yayo) njengesinyibilikisi esingathathi hlangothi ukuze kukhiqizwe amakristalu amahle e-antimony acetate.
(2) Ngo-1973, iRiphabhulikhi yaseCzech yasungula indlela yokukhiqiza i-antimony acetate enhle isebenzisa i-toluene njengesincibilikisi.

 

III. Ukuqhathaniswa kwama-catalyst amathathu asekelwe ku-antimony