Ama-Catalyst Asekelwe ku-Antimony

I-fiber ye-Polyester (PET) iyinhlobo enkulu kunazo zonke ye-fiber yokwenziwa. Izingubo ezenziwe nge-fiber ye-polyester zikhululekile, ziqinile, kulula ukuzigeza, futhi zomile ngokushesha. I-Polyester isetshenziswa kabanzi njengezinto zokusetshenziswa zokupakisha, izindwangu zezimboni, kanye nepulasitiki yobunjiniyela. Ngenxa yalokho, i-polyester ithuthuke ngokushesha emhlabeni wonke, ikhula ngesilinganiso sonyaka esingu-7% futhi ikhiqiza umkhiqizo omkhulu.

Ukukhiqizwa kwe-polyester kungahlukaniswa ngomzila we-dimethyl terephthalate (DMT) kanye nomzila we-terephthalic acid (PTA) ngokwenqubo futhi kungahlukaniswa ngenqubo eqhubekayo kanye nenqubo eqhubekayo ngokwenqubo yokusebenza. Kungakhathaliseki ukuthi inqubo yokukhiqiza isetshenziswa kanjani, ukusabela kwe-polycondensation kudinga ukusetshenziswa kwamakhemikhali ensimbi njengezinto ezibangela ukucindezeleka. Ukusabela kwe-polycondensation kuyisinyathelo esibalulekile enkambisweni yokukhiqiza i-polyester, futhi isikhathi se-polycondensation siyisithiyo sokuthuthukisa isivuno. Ukuthuthukiswa kohlelo lwe-catalyst kuyisici esibalulekile ekuthuthukiseni ikhwalithi ye-polyester kanye nokunciphisa isikhathi se-polycondensation.

I-UrbanMines Tech. Limited iyinkampani ehamba phambili yaseShayina egxile ku-R&D, ukukhiqizwa, kanye nokuhlinzekwa kwe-antimony trioxide ye-polyester catalyst-grade, i-antimony acetate, kanye ne-antimony glycol. Senze ucwaningo olujulile ngale mikhiqizo—umnyango we-R&D we-UrbanMines manje ufingqa ucwaningo kanye nokusetshenziswa kwe-antimony catalysts kulesi sihloko ukusiza amakhasimende ethu ukuthi asebenzise kalula, athuthukise izinqubo zokukhiqiza, futhi ahlinzeke ngokuncintisana okuphelele kwemikhiqizo ye-polyester fiber.

Izazi zasekhaya nezakwamanye amazwe ngokuvamile zikholelwa ukuthi i-polyester polycondensation iyindlela yokwandisa uchungechunge, futhi indlela yokulungisa i-catalytic ingeye-chelation coordination, edinga i-athomu yensimbi ye-catalyst ukuthi inikeze ama-orbitals angenalutho ukuze ahambisane ne-arc pair yama-electron e-carbonyl oxygen ukuze kufezwe injongo ye-catalysis. Nge-polycondensation, njengoba i-electron cloud density ye-carbonyl oxygen eqenjini le-hydroxyethyl ester iphansi kakhulu, i-electronegativity yama-ion ensimbi iphezulu kakhulu ngesikhathi sokuxhumanisa, ukuze kube lula ukuxhumanisa kanye nokwandiswa kochungechunge.

Lokhu okulandelayo kungasetshenziswa njengezinto zokuthuthukisa i-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 kanye nezinye izinto zokuthuthukisa i-metal oxides, ama-alcoholates, ama-carboxylates, ama-borates, ama-halides nama-amine, ama-ureas, ama-guanidine, izinto zokuthuthukisa i-organic eziqukethe i-sulfur. Kodwa-ke, izinto zokuthuthukisa i-catalysts ezisetshenziswa futhi ezifundwayo ekukhiqizweni kwezimboni ikakhulukazi yizinto zokuthuthukisa i-Sb, Ge, kanye ne-Ti. Ucwaningo oluningi luye lwabonisa ukuthi: Izinto zokuthuthukisa i-Ge-based zinemiphumela emibi embalwa futhi zikhiqiza i-PET esezingeni eliphezulu, kodwa umsebenzi wazo awuphezulu, futhi zinezinsiza ezimbalwa futhi ziyabiza; Ama-catalyst asekelwe ku-Ti anomsebenzi ophezulu kanye nesivinini sokuphendula okusheshayo, kodwa ukusabela kwawo okubangelwa yi-catalytic kusobala kakhulu, okuholela ekuzinzeni okungekuhle kokushisa kanye nombala ophuzi womkhiqizo, futhi ngokuvamile angasetshenziswa kuphela ekuhlanganiseni i-PBT, i-PTT, i-PCT, njll.; Ama-catalyst asekelwe ku-Sb awagcini nje ngokusebenza kakhulu. Ikhwalithi yomkhiqizo iphezulu ngoba ama-catalyst asekelwe ku-Sb asebenza kakhulu, anemiphumela embalwa ebangelwa yi-side, futhi ashibhile. Ngakho-ke, asetshenziswe kabanzi. Phakathi kwawo, ama-catalyst asekelwe ku-Sb asetshenziswa kakhulu yi-antimony trioxide (Sb2O3), i-antimony acetate (Sb(CH3COO)3), njll.

Uma sibheka umlando wentuthuko yemboni ye-polyester, singathola ukuthi izitshalo ze-polyester ezingaphezu kuka-90% emhlabeni zisebenzisa ama-antimony compounds njengezinto zokuthuthukisa. Ngo-2000, iShayina yayisiqalise izitshalo eziningana ze-polyester, zonke ezazisebenzisa ama-antimony compounds njengezinto zokuthuthukisa, ikakhulukazi i-Sb2O3 kanye ne-Sb(CH3COO)3. Ngemizamo ehlangene yocwaningo lwesayensi lwaseShayina, amanyuvesi, kanye neminyango yokukhiqiza, lezi zinto zokuthuthukisa ezimbili sezikhiqizwe ngokugcwele ngaphakathi ezweni.

Kusukela ngo-1999, inkampani yamakhemikhali yaseFrance i-Elf yethule i-catalyst ye-antimony glycol [Sb2 (OCH2CH2CO) 3] njengomkhiqizo othuthukisiwe wama-catalyst endabuko. Ama-chip e-polyester akhiqizwayo anobumhlophe obukhulu kanye nokuguquguquka okuhle, okudonsele ukunaka okukhulu ezikhungweni zocwaningo lwe-catalyst zasekhaya, amabhizinisi, kanye nabakhiqizi be-polyester eShayina.

I. Ucwaningo kanye nokusetshenziswa kwe-antimony trioxide
I-United States ingenye yamazwe okuqala 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 enekhono lokukhiqiza eliphelele lamathani angu-6,360 ngonyaka.

Amayunithi ocwaningo nentuthuko amakhulu aseShayina i-Sb2O3 agxile kakhulu emabhizinisini kahulumeni angaphambilini eSifundazweni saseHunan naseShanghai. I-UrbanMines Tech. Limited iphinde yasungula umugqa wokukhiqiza ochwepheshe eSifundazweni saseHunan.

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

1. Indlela yokuxova ngqo
I-antimony yensimbi isabela nomoya-mpilo oshiswayo ukuze yakhe i-Sb2O3. Inqubo yokusabela imi kanje:
4Sb＋3O2＝＝2Sb2O3

2. I-Ammolysis
I-Antimony metal iphendula ne-chlorine ukuze kwakhiwe i-antimony trichloride, bese ihluzwa, i-hydrolyzed, i-ammonolyzed, igezwe, bese yomiswa ukuze kutholakale umkhiqizo we-Sb2O3 oqediwe. I-equation eyisisekelo yokusabela yile:
2Sb＋3Cl2＝＝2SbCl3
I-SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
I-Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O

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

(III). Izinkinga nge-antimony trioxide
I-Sb2O3 ayinakho ukuncibilika okuhle ku-ethylene glycol, kanti ukuncibilika kwayo kungu-4.04% kuphela ku-150°C. Ngakho-ke, uma i-ethylene glycol isetshenziswa ukulungiselela i-catalyst, i-Sb2O3 ayinakho ukuncibilika okuhle, okungadala kalula i-catalyst eningi ohlelweni lwe-polymerization, kukhiqize ama-cyclic trimers asezingeni eliphezulu lokuncibilika, futhi kulethe ubunzima ekuphotheni. Ukuze kuthuthukiswe ukuncibilika kanye nokuncibilika kwe-Sb2O3 ku-ethylene glycol, ngokuvamile kusetshenziswa ukusebenzisa i-ethylene glycol eningi noma ukwandisa izinga lokushisa lokuncibilika libe ngaphezu kuka-150°C. Kodwa-ke, ngaphezu kuka-120°C, i-Sb2O3 kanye ne-ethylene glycol zingakhiqiza i-ethylene glycol antimony precipitation uma zisebenza ndawonye isikhathi eside, kanti i-Sb2O3 ingancishiswa ibe yi-metallic antimony ekusabeleni kwe-polycondensation, okungabangela "inkungu" kuma-polyester chips futhi kuthinte ikhwalithi yomkhiqizo.

II. Ucwaningo kanye nokusetshenziswa kwe-antimony acetate
Indlela yokulungiselela i-antimony acetate
Ekuqaleni, i-antimony acetate yayilungiswa ngokuphendula i-antimony trioxide ne-acetic acid, kanti i-acetic anhydride yayisetshenziswa njenge-ejenti yokumunca amanzi akhiqizwa yi-reaction. Ikhwalithi yomkhiqizo oqediwe otholwe ngale ndlela yayingephezulu, futhi kwathatha amahora angaphezu kwama-30 ukuthi i-antimony trioxide incibilike ku-acetic acid. Kamuva, i-antimony acetate yalungiswa ngokuphendula i-metal antimony, i-antimony trichloride, noma i-antimony trioxide ne-acetic anhydride, ngaphandle kwesidingo se-ejenti yokumunca amanzi.

1. Indlela ye-antimony trichloride
Ngo-1947, u-H. Schmidt nabanye eNtshonalanga Jalimane balungisa i-Sb(CH3COO)3 ngokuphendula 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 ngokuphendula i-antimony yensimbi kanye ne-peroxyacetyl esixazululweni se-benzene. Ifomula yokusabela yile:
I-Sb＋(CH3COO)2==Sb(CH3COO)3

3. Indlela ye-antimony trioxide
Ngo-1957, u-F. Nerdel waseNtshonalanga Jalimane wasebenzisa i-Sb2O3 ukuze asabelane ne-acetic anhydride ukuze akhiqize i-Sb(CH3COO)3.
Sb2O3＋3(CH3CO)2O(2Sb)(CH3COO)3
Ububi bale ndlela ukuthi amakristalu avame ukuhlangana abe yizicucu ezinkulu futhi anamathele ngokuqinile odongeni lwangaphakathi lwe-reactor, okuholela ekhwalithini yomkhiqizo nombala ongemuhle.

4. Indlela ye-antimony trioxide solvent
Ukuze kunqotshwe ukushiyeka kwendlela engenhla, i-solvent engathathi hlangothi ivame ukungezwa ngesikhathi sokusabela kwe-Sb2O3 kanye ne-acetic anhydride. Indlela ethile yokulungiselela yile elandelayo:
(1) Ngo-1968, u-R. Thoms we-American Mosun Chemical Company washicilela ilungelo lobunikazi lokulungiselela i-acetate ye-antimony. Leli lungelo lobunikazi lasebenzisa i-xylene (o-, m-, p-xylene, noma ingxube yayo) njengesinyibilikisi esingathathi hlangothi ukukhiqiza amakristalu amahle e-acetate ye-antimony.
(2) Ngo-1973, iCzech Republic yasungula indlela yokukhiqiza i-acetate ye-antimony encane isebenzisa i-toluene njengesinyibilikisi.

 

III. Ukuqhathaniswa kwama-catalyst amathathu asekelwe ku-antimony