Polyester (PET) fiber shine mafi girman nau'in fiber na roba. Tufafin da aka yi da zaren polyester yana da daɗi, ƙwanƙwasa, sauƙin wankewa, da saurin bushewa. Hakanan ana amfani da polyester sosai azaman albarkatun ƙasa don marufi, yadudduka na masana'antu, da robobin injiniya. Sakamakon haka, polyester ya haɓaka cikin sauri a duk duniya, yana ƙaruwa a matsakaicin ƙimar shekara na 7% kuma tare da babban fitarwa.
Ana iya raba samar da polyester zuwa hanyar dimethyl terephthalate (DMT) da kuma hanyar terephthalic acid (PTA) dangane da hanyar tsari kuma za'a iya raba shi cikin tsari mai tsaka-tsaki da ci gaba da tsari cikin sharuddan aiki. Ko da kuwa hanyar tsarin samarwa da aka karɓa, yanayin daɗaɗɗen ƙwayar cuta yana buƙatar amfani da mahadi na ƙarfe azaman masu haɓakawa. Halin daɗaɗɗen ɗabi'a shine maɓalli mai mahimmanci a cikin tsarin samar da polyester, kuma lokacin daɗaɗɗen polycondensation shine ƙulli don haɓaka yawan amfanin ƙasa. Haɓaka tsarin haɓakawa shine muhimmin mahimmanci don haɓaka ingancin polyester da rage lokacin haɓakar polycondensation.
UrbanMines Tech. Limited babban kamfani ne na kasar Sin wanda ya kware a cikin R&D, samarwa, da samar da polyester mai kara kuzari-sa antimony trioxide, antimony acetate, da antimony glycol. Mun gudanar da bincike mai zurfi akan waɗannan samfurori-ma'aikatar R & D na UrbanMines yanzu ta taƙaita bincike da aikace-aikacen antimony catalysts a cikin wannan labarin don taimakawa abokan cinikinmu su yi amfani da su a hankali, inganta tsarin samarwa, da kuma samar da cikakkiyar gasa na samfuran fiber polyester.
Masana cikin gida da na kasashen waje gabaɗaya sun yi imanin cewa polyester polycondensation shine haɓakar sarkar sarkar, kuma tsarin catalytic yana cikin daidaitawar chelation, wanda ke buƙatar atom ɗin ƙarfe mai ƙara kuzari don samar da komai a cikin orbitals don daidaitawa tare da arc biyu na electrons na carbonyl oxygen don cimma manufar. catalysis. Don polycondensation, tun lokacin da ƙarfin lantarki na iskar oxygen na carbonyl oxygen a cikin ƙungiyar hydroxyethyl ester yana da ƙasa kaɗan, electronegativity na ions karfe yana da girma yayin daidaitawa, don sauƙaƙe daidaitawa da haɓaka sarkar.
Ana iya amfani da masu zuwa azaman masu haɓaka 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 da sauran karfe oxides, alcoholates, carboxylates, borates, halides da amines, ureas, guanidines, sulfur-dauke da kwayoyin mahadi. Duk da haka, abubuwan da ake amfani da su a halin yanzu da kuma nazarin su a cikin samar da masana'antu sun fi Sb, Ge, da Ti jerin mahadi. Yawancin karatu sun nuna cewa: Ge-based catalysts suna da ƙananan halayen gefe kuma suna samar da PET mai inganci, amma ayyukansu ba su da yawa, kuma suna da 'yan albarkatu kuma suna da tsada; Ti-based catalysts da high aiki da sauri dauki gudun, amma su catalytic gefen halayen sun fi bayyananne, sakamakon da matalauta thermal kwanciyar hankali da rawaya launi na samfurin, kuma su za a iya kullum kawai a yi amfani da kira na PBT, PTT, PCT, da dai sauransu; Sb-based catalysts ba kawai sun fi aiki ba. Ingancin samfurin yana da girma saboda masu haɓaka tushen Sb sun fi aiki, suna da ƙarancin halayen gefe, kuma suna da rahusa. Saboda haka, an yi amfani da su sosai. Daga cikin su, mafi yawan amfani da Sb-based catalysts sune antimony trioxide (Sb2O3), antimony acetate (Sb (CH3COO) 3), da dai sauransu.
Duban tarihin ci gaban masana'antar polyester, zamu iya gano cewa fiye da 90% na shuke-shuken polyester a duniya suna amfani da mahadi na antimony a matsayin masu haɓakawa. A shekara ta 2000, kasar Sin ta bullo da shuke-shuken polyester da dama, wadanda dukkansu sun yi amfani da sinadarin antimony a matsayin masu kara kuzari, musamman Sb2O3 da Sb(CH3COO)3. Ta hanyar hadin gwiwa na binciken kimiyya, jami'o'i, da sassan samar da kayayyaki na kasar Sin, yanzu an samar da wadannan abubuwa guda biyu gaba daya a cikin gida.
Tun daga 1999, kamfanin Faransa Elf ya ƙaddamar da glycol antimony glycol [Sb2 (OCH2CH2CO) 3] mai haɓakawa a matsayin ingantaccen samfuri na abubuwan haɓakawa na gargajiya. Chips ɗin polyester da aka samar yana da babban fari da kuma iya jurewa, wanda ya jawo hankali sosai daga cibiyoyin bincike na gida, masana'antu, da masana'antun polyester a China.
I. Bincike da aikace-aikacen antimony trioxide
Amurka tana ɗaya daga cikin ƙasashe na farko don samarwa da amfani da Sb2O3. A cikin 1961, amfani da Sb2O3 a Amurka ya kai ton 4,943. A cikin 1970s, kamfanoni biyar a Japan sun samar da Sb2O3 tare da jimlar samar da ton 6,360 a kowace shekara.
Babban sashin bincike da ci gaban Sb2O3 na kasar Sin ya fi mayar da hankali ne a tsoffin kamfanonin gwamnati a lardin Hunan da Shanghai. UrbanMines Tech. Limited kuma ya kafa ƙwararrun layin samarwa a lardin Hunan.
(I). Hanyar samar da antimony trioxide
Ƙirƙirar Sb2O3 yawanci yana amfani da sinadarin antimony sulfide a matsayin albarkatun ƙasa. Metal antimony aka fara shirya, sa'an nan kuma ana samar da Sb2O3 ta amfani da antimony karfe a matsayin albarkatun kasa.
Akwai manyan hanyoyi guda biyu don samar da Sb2O3 daga ƙarfe antimony: kai tsaye oxidation da bazuwar nitrogen.
1. Hanyar oxidation kai tsaye
Metal antimony yana amsawa tare da iskar oxygen a ƙarƙashin dumama don samar da Sb2O3. Tsarin dauki shine kamar haka:
4Sb＋3O2＝2Sb2O3
2. Ammonolysis
Antimony karfe yana amsawa tare da chlorine don haɗa antimony trichloride, wanda aka distilled, hydrolyzed, ammonolyzed, wanke, da bushe don samun samfurin Sb2O3 da aka gama. Ma'auni na asali shine:
2Sb＋3Cl2＝2SbCl3
SbCl3＋H2O＝SbOCl＋2HCl
4SbOCl ＋H2O＝ Sb2O3 · 2SbOCl＋2HCl
Sb2O3·2SbOCl —OH＝2Sb2O3＋2NH4Cl＋H2O
(II). Amfani da antimony trioxide
Babban amfani da antimony trioxide shine a matsayin mai kara kuzari ga polymerase da kuma mai hana wuta don kayan roba.
A cikin masana'antar polyester, an fara amfani da Sb2O3 azaman mai kara kuzari. Ana amfani da Sb2O3 galibi azaman mai haɓakawa na polycondensation don hanyar DMT da farkon PTA kuma ana amfani dashi gabaɗaya tare da H3PO4 ko enzymes.
(III). Matsaloli tare da antimony trioxide
Sb2O3 yana da ƙarancin solubility a cikin ethylene glycol, tare da solubility na kawai 4.04% a 150 ° C. Sabili da haka, lokacin da aka yi amfani da ethylene glycol don shirya mai kara kuzari, Sb2O3 yana da ƙarancin tarwatsewa, wanda zai iya haifar da haɓakar wuce gona da iri a cikin tsarin polymerization cikin sauƙi, yana haifar da manyan abubuwan hawan keke mai narkewa, kuma yana kawo matsaloli ga jujjuyawar. Don inganta solubility da dispersibility na Sb2O3 a cikin ethylene glycol, ana amfani da shi don amfani da ethylene glycol mai yawa ko ƙara yawan zafin jiki zuwa sama da 150 ° C. Duk da haka, sama da 120 ° C, Sb2O3 da ethylene glycol na iya haifar da hazo na ethylene glycol antimony lokacin da suka yi aiki tare na dogon lokaci, kuma Sb2O3 na iya ragewa zuwa antimony na ƙarfe a cikin maganin polycondensation, wanda zai iya haifar da "hazo" a cikin kwakwalwan polyester kuma yana tasiri. ingancin samfurin.
II. Bincike da aikace-aikacen antimony acetate
Hanyar shiri na antimony acetate
Da farko, an shirya maganin antimony acetate ta hanyar mayar da martani ga antimony trioxide tare da acetic acid, kuma an yi amfani da acetic anhydride a matsayin wakili na dehydrating don shafe ruwan da aka haifar da shi. Ingancin samfurin da aka gama samu ta wannan hanyar bai yi girma ba, kuma ya ɗauki fiye da sa'o'i 30 don antimony trioxide ya narke a cikin acetic acid. Daga baya, an shirya maganin antimony acetate ta hanyar amsa maganin antimony na ƙarfe, antimony trichloride, ko antimony trioxide tare da acetic anhydride, ba tare da buƙatar wani wakili na dehydrating ba.
1. Hanyar antimony trichloride
A cikin 1947, H. Schmidt et al. a Yammacin Jamus sun shirya Sb (CH3COO) 3 ta hanyar amsawa SbCl3 tare da acetic anhydride. Tsarin amsawa shine kamar haka:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Antimony karfe Hanyar
A cikin 1954, TAPaybea na tsohuwar Tarayyar Soviet ta shirya Sb (CH3COO) 3 ta hanyar amsa maganin antimony na ƙarfe da peroxyacetyl a cikin maganin benzene. Tsarin amsawa shine:
Sb＋(CH3COO)2==Sb(CH3COO)3
3. Hanyar antimony trioxide
A cikin 1957, F. Nerdel na Yammacin Jamus ya yi amfani da Sb2O3 don amsawa da acetic anhydride don samar da Sb (CH3COO) 3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
Rashin lahani na wannan hanya shine cewa lu'ulu'u suna taruwa zuwa manyan guda kuma su tsaya da ƙarfi ga bangon ciki na reactor, yana haifar da rashin ingancin samfur da launi.
4. Hanyar maganin antimony trioxide
Don shawo kan gazawar hanyar da ke sama, ana ƙara yawan ƙarfi mai tsaka tsaki yayin amsawar Sb2O3 da acetic anhydride. Takamammen hanyar shiri shine kamar haka:
(1) A cikin 1968, R. Thoms na Kamfanin Mosun Chemical na Amurka ya buga wani haƙƙin mallaka akan shirye-shiryen antimony acetate. Tabbacin ya yi amfani da xylene (o-, m-, p-xylene, ko cakuduwarta) a matsayin tsaka tsaki don samar da kyawawan lu'ulu'u na antimony acetate.
(2) A cikin 1973, Jamhuriyar Czech ta ƙirƙira wata hanya don samar da lafiya antimony acetate ta amfani da toluene a matsayin sauran ƙarfi.
III. Kwatanta abubuwan da ke haifar da antimony guda uku
| Antimony Trioxide | Antimony acetate | Antimony Glycolate | |
| Basic Properties | Wanda aka fi sani da antimony fari, dabarar kwayoyin Sb 2 O 3, nauyin kwayoyin halitta 291.51, farin foda, alamar narkewa 656 ℃. Abubuwan da ke cikin ka'idar antimony kusan 83.53%. Matsakaicin dangi 5.20g/ml . Mai narkewa a cikin mai daɗaɗɗen hydrochloric acid, sulfuric acid mai mai da hankali, nitric acid mai ƙarfi, tartaric acid da maganin alkali, wanda ba zai iya narkewa cikin ruwa, barasa, tsarma sulfuric acid. | Tsarin kwayoyin halitta Sb (AC) 3, nauyin kwayoyin 298.89, abun ciki na ka'idar antimony game da 40.74%, maki narkewa 126-131 ℃, yawa 1.22g / ml (25 ℃), fari ko kashe-fari foda, sauƙi mai narkewa a cikin ethylene glycol, to da xylene. | Tsarin kwayoyin halitta Sb 2 (EG) 3 , Nauyin kwayoyin yana kusan 423.68, ma'anar narkewa shine ＞ 100 ℃ ( Dec.) , Theoretical antimony abun ciki ne game da 57.47 %, bayyanar ne farin crystalline m, ba mai guba da m, sauki sha danshi. Yana da sauƙin narkewa a cikin ethylene glycol. |
| Hanyar Magana da Fasaha | An haɗa shi da hanyar stibnite: 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 3Lura: Stibnite / Iron Ore → Limestone Dumama da Fuming → Tari | Masana'antu galibi suna amfani da hanyar Sb 2 O 3-solvent don haɗawa:Sb2O3 da sauƙi hydrolyzed, don haka tsaka tsaki ƙarfi toluene ko xylene amfani dole ne m, Sb 2 O 3 ba zai iya zama a cikin rigar jihar, da kuma samar da kayan aiki dole ne a bushe. | Masana'antu galibi suna amfani da hanyar Sb 2 O 3 don haɗawa: Sb 2 O 3 + 3EG → Sb 2 (EG) 3 +3H 2 OProcess: Ciyarwa (Sb 2 O 3, ƙari da EG) → dumama da matsa lamba → cire slag , ƙazanta da ruwa → decolorization → zafi tacewa → sanyaya da crystallization → rabuwa da bushewa → ProductNote: Tsarin samarwa yana buƙatar ware shi daga ruwa don hana hydrolysis. Wannan martanin shine martani mai jujjuyawa, kuma gabaɗaya ana haɓaka halayen ta amfani da wuce haddi na ethylene glycol da cire ruwan samfurin. |
| Amfani | Farashin yana da ƙarancin arha, yana da sauƙin amfani, yana da matsakaicin aiki na catalytic da ɗan gajeren lokacin polycondensation. | Antimony acetate yana da solubility mai kyau a cikin ethylene glycol kuma an tarwatsa shi a ko'ina a cikin ethylene glycol, wanda zai iya inganta ingantaccen amfani da antimony; Antimony acetate yana da halaye na babban aikin catalytic, ƙarancin lalacewa, juriya mai kyau da kwanciyar hankali; A lokaci guda, yin amfani da antimony acetate a matsayin mai haɓakawa baya buƙatar ƙarin haɗin gwiwa da mai daidaitawa. Halin tsarin maganin antimony acetate catalytic yana da sauƙi, kuma samfurin samfurin yana da girma, musamman launi, wanda ya fi na tsarin antimony trioxide (Sb 2 O 3). | Mai kara kuzari yana da babban solubility a cikin ethylene glycol; An cire sifili-valent antimony, kuma ƙazanta irin su ƙwayoyin ƙarfe, chlorides da sulfates waɗanda ke shafar polycondensation an rage su zuwa mafi ƙasƙanci, kawar da matsalar lalata ion acetate akan kayan aiki; Sb 3+ a cikin Sb 2 (EG) 3 yana da inganci. , wanda zai iya zama saboda solubility a cikin ethylene glycol a yanayin zafin jiki ya fi na Sb 2 O 3 Idan aka kwatanta da Sb (AC) 3, adadin Sb 3+ wanda ke taka rawar catalytic ya fi girma. Launi na samfurin polyester da Sb 2 (EG) 3 ya samar ya fi na Sb 2 O 3 Dan kadan sama da na asali, yana sa samfurin ya yi haske da fari; |
| Hasara | Solubility a cikin ethylene glycol ba shi da kyau, kawai 4.04% a 150 ° C. A aikace, ethylene glycol ya wuce kima ko kuma an ƙara yawan zafin jiki zuwa sama da 150 ° C. Duk da haka, lokacin da Sb 2 O 3 ya amsa tare da ethylene glycol na dogon lokaci a sama da 120 ° C, ethylene glycol antimony hazo na iya faruwa, kuma Sb 2 O 3 na iya ragewa zuwa tsani na karfe a cikin halayen polycondensation, wanda zai iya haifar da "hazo mai launin toka. "a cikin kwakwalwan polyester kuma yana shafar ingancin samfur. Abubuwan da ke faruwa na polyvalent antimony oxides yana faruwa a lokacin shirye-shiryen Sb 2 O 3, kuma ana shafar ingantaccen tsabta na antimony. | Abin da ke cikin antimony na mai kara kuzari yana da ɗan ƙaramin ƙarfi; datti na acetic acid sun gabatar da kayan aiki masu lalata, suna gurɓata muhalli, kuma basu dace da maganin ruwa ba; tsarin samarwa yana da rikitarwa, yanayin yanayin aiki ba shi da kyau, akwai gurbataccen yanayi, kuma samfurin yana da sauƙin canza launi. Yana da sauƙi don bazuwa lokacin zafi, kuma samfuran hydrolysis sune Sb2O3 da CH3COOH. Lokacin zama na kayan yana da tsayi, musamman ma a matakin ƙarshe na polycondensation, wanda ya fi girma fiye da tsarin Sb2O3. | Yin amfani da Sb 2 (EG) 3 yana ƙara haɓakar farashin na'urar (ƙarar farashin za a iya kashe shi kawai idan an yi amfani da kashi 25% na PET don juyar da kai na filament). Bugu da ƙari, ƙimar b na launin samfurin yana ƙaruwa kaɗan. |