ʻO ka fiber Polyester (PET) ka ʻano nui loa o ke fiber synthetic. ʻO nā lole i hana ʻia me ke fiber polyester he ʻoluʻolu, ʻōlinolino, maʻalahi e holoi, a wikiwiki e maloʻo. Hoʻohana nui ʻia ka polyester ma ke ʻano he mea maka no ka hoʻopili ʻana, nā olonā ʻoihana, a me nā plastics ʻenekinia. ʻO ka hopena, ua ulu wikiwiki ka polyester ma ka honua holoʻokoʻa, e piʻi ana ma ka awelika makahiki o 7% a me ka hana nui.
Hiki ke hoʻokaʻawale ʻia ka hana polyester i ke ala dimethyl terephthalate (DMT) a me ke ala terephthalic acid (PTA) ma ke ʻano o ke ala hana a hiki ke hoʻokaʻawale ʻia i ke kaʻina hana intermittent a me ke kaʻina hana hoʻomau ma ke ʻano o ka hana. Me ka nānā ʻole i ke ala hana i lawe ʻia, pono ka hana polycondensation i ka hoʻohana ʻana i nā hui metala e like me nā catalysts. ʻO ka hana polycondensation kahi hana koʻikoʻi i ke kaʻina hana polyester, a ʻo ka manawa polycondensation ka bottleneck no ka hoʻomaikaʻi ʻana i ka hua. ʻO ka hoʻomaikaʻi ʻana o ka ʻōnaehana catalyst he mea nui ia i ka hoʻomaikaʻi ʻana i ka maikaʻi o ka polyester a me ka hoʻopōkole ʻana i ka manawa polycondensation.
He hui Kina alakaʻi ʻo UrbanMines Tech. Limited i loea i ka R&D, ka hana ʻana, a me ka hoʻolako ʻana i ka polyester catalyst-grade antimony trioxide, antimony acetate, a me ka antimony glycol. Ua hana mākou i kahi noiʻi hohonu e pili ana i kēia mau huahana—ke hōʻuluʻulu nei ka ʻoihana R&D o UrbanMines i ka noiʻi a me ka hoʻohana ʻana i nā catalysts antimony ma kēia ʻatikala e kōkua i kā mākou mea kūʻai aku e hoʻopili maʻalahi, hoʻomaikaʻi i nā kaʻina hana, a hāʻawi i ka hoʻokūkū piha o nā huahana polyester fiber.
Manaʻo nui nā kānaka loea kūloko a me nā haole he hopena hoʻonui kaulahao ka polyester polycondensation, a no ke ʻano catalytic ka chelation coordination, e koi ana i ka atom metala catalyst e hāʻawi i nā orbitals hakahaka e hoʻonohonoho me ka arc pair o nā electrons o ka carbonyl oxygen e hoʻokō i ke kumu o ka catalysis. No ka polycondensation, ʻoiai ʻo ka nui o ke ao electron o ka carbonyl oxygen i loko o ka hui hydroxyethyl ester he haʻahaʻa loa, ʻoi aku ka kiʻekiʻe o ka electronegativity o nā ion metala i ka wā o ka hoʻonohonoho ʻana, e hoʻomaʻamaʻa i ka hoʻonohonoho ʻana a me ka hoʻonui ʻana i ke kaulahao.
Hiki ke hoʻohana ʻia kēia mau mea ma ke ʻano he mau mea hoʻouluulu 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 a me nā ʻokikene metala ʻē aʻe, alcoholates, carboxylates, borates, halides a me amines, ureas, guanidines, nā hui organik i loaʻa ka sulfur. Eia nō naʻe, ʻo nā mea hoʻouluulu i hoʻohana ʻia a aʻo ʻia i kēia manawa ma ka hana ʻoihana, ʻo ia nā hui Sb, Ge, a me Ti. Ua hōʻike ʻia he nui nā haʻawina: ʻOi aku ka liʻiliʻi o nā hopena ʻaoʻao o nā mea hoʻouluulu Ge a hana i ka PET kiʻekiʻe, akā ʻaʻole kiʻekiʻe kā lākou hana, a he kakaikahi kā lākou kumuwaiwai a he pipiʻi; Loaʻa i nā mea hoʻouluulu Ti ka hana kiʻekiʻe a me ka wikiwiki o ka hopena, akā ʻoi aku ka maopopo o kā lākou mau hopena ʻaoʻao catalytic, e hopena ana i ka paʻa wela maikaʻi ʻole a me ke kala melemele o ka huahana, a hiki ke hoʻohana wale ʻia no ka synthesis o PBT, PTT, PCT, etc.; ʻAʻole wale nā mea hoʻouluulu Sb-based i ʻoi aku ka ikaika. Kiʻekiʻe ke ʻano o ka huahana no ka mea ʻoi aku ka ikaika o nā mea hoʻouluulu Sb-based, ʻoi aku ka liʻiliʻi o nā hopena ʻaoʻao, a ʻoi aku ke kumu kūʻai. No laila, ua hoʻohana nui ʻia lākou. I waena o lākou, ʻo nā mea hoʻouluulu Sb-based i hoʻohana pinepine ʻia ʻo ia ka antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), etc.
Ke nānā nei i ka mōʻaukala hoʻomohala o ka ʻoihana polyester, hiki iā mākou ke ʻike he ʻoi aku ma mua o 90% o nā hale hana polyester ma ka honua e hoʻohana ana i nā hui antimony ma ke ʻano he catalysts. I ka makahiki 2000, ua hoʻolauna ʻo Kina i kekahi mau hale hana polyester, kahi i hoʻohana ai i nā hui antimony ma ke ʻano he catalysts, ʻo ia hoʻi ʻo Sb2O3 a me Sb(CH3COO)3. Ma o nā hana like ʻana o ka noiʻi ʻepekema Kina, nā kulanui, a me nā keʻena hana, ua hana piha ʻia kēia mau catalysts ʻelua ma ka home.
Mai ka makahiki 1999, ua hoʻokuʻu ka hui kemika Farani ʻo Elf i kahi mea hoʻouluulu antimony glycol [Sb2 (OCH2CH2CO) 3] ma ke ʻano he huahana i hoʻomaikaʻi ʻia o nā mea hoʻouluulu kuʻuna. Loaʻa i nā ʻāpana polyester i hana ʻia ke keʻokeʻo kiʻekiʻe a me ka spinnability maikaʻi, kahi i huki nui ʻia ai ka manaʻo mai nā ʻoihana noiʻi mea hoʻouluulu kūloko, nā ʻoihana, a me nā mea hana polyester ma Kina.
I. Noiʻi a me ka hoʻohana ʻana o ka antimony trioxide
ʻO ʻAmelika Hui Pū ʻIa kekahi o nā ʻāina mua loa e hana a hoʻopili iā Sb2O3. I ka makahiki 1961, ua hōʻea ka hoʻohana ʻana o Sb2O3 ma ʻAmelika Hui Pū ʻIa i 4,943 tons. I nā makahiki 1970, ʻelima mau ʻoihana ma Iapana i hana iā Sb2O3 me ka huina o ka hiki ke hana he 6,360 tons i kēlā me kēia makahiki.
ʻO nā ʻāpana noiʻi a me ka hoʻomohala ʻana o Sb2O3 nui o Kina e kau nui ʻia ana ma nā ʻoihana aupuni mua ma ka Panalāʻau ʻo Hunan a me Shanghai. Ua hoʻokumu pū ʻo UrbanMines Tech. Limited i kahi laina hana ʻoihana ma ka Panalāʻau ʻo Hunan.
(I). Ke ʻano hana no ka hana ʻana i ka antimony trioxide
ʻO ka hana ʻana o Sb2O3 e hoʻohana pinepine i ka antimony sulfide ore ma ke ʻano he mea maka. Hoʻomākaukau mua ʻia ka metala antimony, a laila hana ʻia ʻo Sb2O3 me ka hoʻohana ʻana i ka metala antimony ma ke ʻano he mea maka.
ʻElua mau ʻano nui no ka hana ʻana iā Sb2O3 mai ka antimony metala: ka oxidation pololei a me ka decomposition nitrogen.
1. Ke ʻano hana hoʻomake pololei
Hoʻopili ka antimony metala me ka oxygen ma lalo o ka hoʻomehana ʻana e hana iā Sb2O3. Penei ke kaʻina hana:
4Sb + 3O2 = = 2Sb2O3
2. ʻAmōnolisis
Hoʻopili ka metala antimony me ka chlorine e hana i ka antimony trichloride, a laila hoʻoheheʻe ʻia, hydrolyzed, ammonolyzed, holoi ʻia, a hoʻomaloʻo ʻia e loaʻa ai ka huahana Sb2O3 i hoʻopau ʻia. ʻO ke kaulike hopena kumu:
2Sb + 3Cl2 = = 2SbCl3
SbCl3 + H2O = = SbOCl + 2HCl
4SbOCl + H2O = = Sb2O3 · 2SbOCl + 2HCl
Sb2O3·2SbOCl+OH==2Sb2O3+2NH4Cl+H2O
(II). Nā hoʻohana ʻana o ka antimony trioxide
ʻO ka hoʻohana nui ʻana o ka antimony trioxide ma ke ʻano he mea hoʻoulu no ka polymerase a me kahi mea pale ahi no nā mea synthetic.
I ka ʻoihana polyester, ua hoʻohana mua ʻia ʻo Sb2O3 ma ke ʻano he mea hoʻoulu. Hoʻohana nui ʻia ʻo Sb2O3 ma ke ʻano he mea hoʻoulu polycondensation no ke ala DMT a me ke ala PTA mua a hoʻohana nui ʻia me ka hui pū ʻana me H3PO4 a i ʻole kāna mau enzymes.
(III). Nā pilikia me ka antimony trioxide
ʻAʻole maikaʻi ka solubility o Sb2O3 i loko o ka ethylene glycol, me ka solubility o 4.04% wale nō ma 150°C. No laila, i ka wā e hoʻohana ʻia ai ka ethylene glycol e hoʻomākaukau i ka catalyst, ʻaʻole maikaʻi ka dispersibility o Sb2O3, hiki ke hoʻoulu maʻalahi i ka catalyst nui i loko o ka ʻōnaehana polymerization, hoʻoulu i nā trimers cyclic melting-point kiʻekiʻe, a lawe mai i nā pilikia i ka milo. No ka hoʻomaikaʻi ʻana i ka solubility a me ka dispersibility o Sb2O3 i loko o ka ethylene glycol, ua hoʻohana pinepine ʻia e hoʻohana i ka ethylene glycol nui a hoʻonui paha i ka mahana hoʻoheheʻe ma luna o 150°C. Eia nō naʻe, ma luna o 120°C, hiki i ka Sb2O3 a me ka ethylene glycol ke hoʻoulu i ka ethylene glycol antimony precipitation ke hana pū lākou no ka manawa lōʻihi, a hiki ke hoʻemi ʻia ʻo Sb2O3 i ka metallic antimony i loko o ka polycondensation reaction, hiki ke hana i ka "noe" i loko o nā ʻāpana polyester a hoʻopilikia i ka maikaʻi o ka huahana.
II. Noiʻi a me ka hoʻohana ʻana o ka antimony acetate
ʻAno hoʻomākaukau o ka antimony acetate
I ka wā mua, ua hoʻomākaukau ʻia ka antimony acetate ma ka hoʻohui ʻana i ka antimony trioxide me ka waikawa acetic, a ua hoʻohana ʻia ka acetic anhydride ma ke ʻano he mea hoʻomaloʻo e omo i ka wai i hana ʻia e ka hopena. ʻAʻole kiʻekiʻe ke ʻano o ka huahana i hoʻopau ʻia i loaʻa ma o kēia ʻano hana, a ua hala ma mua o 30 mau hola no ka hoʻoheheʻe ʻana o ka antimony trioxide i loko o ka waikawa acetic. Ma hope mai, ua hoʻomākaukau ʻia ka antimony acetate ma ka hoʻohui ʻana i ka metala antimony, antimony trichloride, a i ʻole antimony trioxide me ka acetic anhydride, me ka ʻole o ka pono no kahi mea hoʻomaloʻo.
1. Ke ʻano hana antimony trichloride
I ka makahiki 1947, ua hoʻomākaukau ʻo H. Schmidt et al. ma Kelemania Komohana iā Sb(CH3COO)3 ma ka hoʻohui ʻana iā SbCl3 me ka acetic anhydride. Penei ke ʻano o ka hopena:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl
2. Ke ʻano hana metala antimony
I ka makahiki 1954, ua hoʻomākaukau ʻo TAPaybea o ka Soviet Union mua iā Sb(CH3COO)3 ma ka hoʻopili ʻana i ka antimony metala a me ka peroxyacetyl i loko o kahi hopena benzene. ʻO ke ʻano hana:
Sb+(CH3COO)2==Sb(CH3COO)3
3. Ke ʻano hana trioxide antimony
I ka makahiki 1957, ua hoʻohana ʻo F. Nerdel o Kelemānia Komohana iā Sb2O3 e hana me ka acetic anhydride e hana iā Sb(CH3COO)3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
ʻO ka hemahema o kēia ʻano hana, ʻo ia ka hōʻuluʻulu ʻana o nā kristal i nā ʻāpana nui a pipili paʻa i ka paia o loko o ka reactor, e hopena ana i ka maikaʻi ʻole o ka huahana a me ke kala.
4. Ke ʻano hana hoʻoheheʻe antimony trioxide
No ka lanakila ʻana i nā hemahema o ke ʻano hana i luna, hoʻohui pinepine ʻia kahi mea hoʻoheheʻe kūlike ʻole i ka wā o ka hopena o Sb2O3 a me ka acetic anhydride. ʻO ke ʻano hoʻomākaukau kikoʻī penei:
(1) I ka makahiki 1968, ua paʻi ʻo R. Thoms o ka American Mosun Chemical Company i kahi palapala Sila Nui no ka hoʻomākaukau ʻana o ka antimony acetate. Ua hoʻohana ka palapala Sila Nui i ka xylene (o-, m-, p-xylene, a i ʻole ka hui ʻana o ia mea) ma ke ʻano he mea hoʻoheheʻe kūlike ʻole e hana i nā kristal maikaʻi o ka antimony acetate.
(2) I ka makahiki 1973, ua hana ka Czech Republic i kahi ʻano hana no ka hana ʻana i ka antimony acetate maikaʻi me ka hoʻohana ʻana i ka toluene ma ke ʻano he mea hoʻoheheʻe.
III. Hoʻohālikelike ʻana o ʻekolu mau mea hoʻouluulu antimony
| ʻAntimony Trioxide | ʻAntimony Acetate | ʻAntimony Glycolate | |
| Nā Waiwai Kumu | ʻIke nui ʻia ʻo antimony keʻokeʻo, ʻo ke ʻano molekala Sb2O3, ke kaumaha molekala 291.51, pauka keʻokeʻo, kiko heheʻe 656 ℃. ʻO ka nui o ka antimony kumumanaʻo ma kahi o 83.53%. ʻO ka nui pili 5.20g/ml. Hoʻoheheʻe ʻia i loko o ka waikawa hydrochloric i hoʻohuihui ʻia, ka waikawa sulfuric i hoʻohuihui ʻia, ka waikawa nitric i hoʻohuihui ʻia, ka waikawa tartaric a me ka hopena alkali, ʻaʻole hoʻoheheʻe ʻia i ka wai, ka waiʻona, ka waikawa sulfuric dilute. | ʻO ke ʻano molekala Sb(AC)3, ke kaumaha molekala 298.89, ka nui o ka antimony kumumanaʻo ma kahi o 40.74%, ka helu heheʻe 126-131℃, ka nui o ka 1.22g/ml (25℃), pauka keʻokeʻo a keʻokeʻo paha, maʻalahi ke hoʻoheheʻe ʻia i loko o ka ethylene glycol, toluene a me ka xylene. | ʻO ke ʻano molekala Sb 2 (EG) 3, ʻO ke kaumaha molekala ma kahi o 423.68, ʻo ke kiko heheʻe he ＞ 100 ℃ (dec.), ʻo ka nui o ka antimony theoretical ma kahi o 57.47%, he keʻokeʻo ke ʻano o ka kristal paʻa, ʻaʻohe mea ʻawahia a ʻono ʻole, maʻalahi ke omo i ka makū. He maʻalahi ke hoʻoheheʻe ʻia i loko o ka ethylene glycol. |
| ʻAno Hana a me ka ʻenehana | Hoʻohui nui ʻia e ke ʻano stibnite: 2Sb 2S 3 +9O 2 →2Sb 2O 3 +6SO 2 ↑Sb 2O 3 +3C→2Sb+3CO↑ 4Sb+O 2 →2Sb 2O 3 Nānā: Stibnite / Iron Ore / Limestone → Hoʻomehana a me ka Fuming → Hōʻiliʻili | Hoʻohana nui ka ʻoihana i ke ʻano hana hoʻoheheʻe Sb2O3 no ka synthesis: Sb2O3 + 3 (CH3CO) 2O→ 2Sb(AC) 3Kaʻina hana: hoʻomehana reflux → kānana wela → crystallization → hoʻomaloʻo vacuum → huahanaNānā: Maʻalahi ka hydrolyzed ʻana o Sb(AC) 3, no laila pono e anhydrous ka toluene solvent neutral a i ʻole xylene i hoʻohana ʻia, ʻaʻole hiki iā Sb2O3 ke noho i kahi ʻano pulu, a pono hoʻi e maloʻo nā lako hana. | Hoʻohana nui ka ʻoihana i ke ʻano hana Sb2O3 e synthesize:Sb2O3 +3EG→Sb2(EG)3 +3H2OKaʻina Hana: Ka hānai ʻana (Sb2O3, nā mea hoʻohui a me EG) → ka hoʻomehana ʻana a me ka hopena kaomi → ka wehe ʻana i ka slag, nā haumia a me ka wai → decolorization → kānana wela → hoʻoluʻu a me ka crystallization → ka hoʻokaʻawale ʻana a me ka hoʻomaloʻo ʻana → huahanaNānā: Pono e hoʻokaʻawale ʻia ke kaʻina hana mai ka wai e pale aku i ka hydrolysis. He hopena hoʻohuli kēia hopena, a ma ke ʻano laulā e hoʻolaha ʻia ka hopena ma ka hoʻohana ʻana i ka ethylene glycol keu a me ka wehe ʻana i ka wai o ka huahana. |
| Pōmaikaʻi | He haʻahaʻa ke kumukūʻai, maʻalahi ka hoʻohana ʻana, he hana catalytic maʻamau a me ka manawa polycondensation pōkole. | He maikaʻi ka solubility o ka Antimony acetate i loko o ka ethylene glycol a ua hoʻopuehu like ʻia i loko o ka ethylene glycol, hiki ke hoʻomaikaʻi i ka hoʻohana pono ʻana o ka antimony; Loaʻa i ka Antimony acetate nā ʻano o ka hana catalytic kiʻekiʻe, ka emi ʻana o ka hopena degradation, ke kūpaʻa wela maikaʻi a me ke kūpaʻa hana; I ka manawa like, ʻo ka hoʻohana ʻana i ka antimony acetate ma ke ʻano he catalyst ʻaʻole ia e koi i ka hoʻohui ʻana o kahi co-catalyst a me kahi stabilizer. He ʻoluʻolu iki ka hopena o ka ʻōnaehana catalytic antimony acetate, a kiʻekiʻe ke ʻano o ka huahana, ʻoi aku ka waihoʻoluʻu, ʻoi aku ka maikaʻi ma mua o ka ʻōnaehana antimony trioxide (Sb2O3). | He kiʻekiʻe ka solubility o ka mea hoʻouluulu i loko o ka ethylene glycol; wehe ʻia ka antimony zero-valent, a hoʻemi ʻia nā haumia e like me nā molekala hao, nā chlorides a me nā sulfates e hoʻopilikia ana i ka polycondensation i ka haʻahaʻa loa, e hoʻopau ana i ka pilikia o ka acetate ion corrosion ma nā lako; ʻOi aku ka kiʻekiʻe o Sb 3+ ma Sb 2 (EG) 3, ʻo ia paha no ka mea ʻoi aku ka nui o kona solubility i loko o ka ethylene glycol ma ka mahana o ka hopena ma mua o Sb 2 O 3. Ke hoʻohālikelike ʻia me Sb (AC) 3, ʻoi aku ka nui o Sb 3+ e pāʻani ana i kahi hana catalytic. ʻOi aku ka maikaʻi o ke kala o ka huahana polyester i hana ʻia e Sb 2 (EG) 3 ma mua o Sb 2 O 3. ʻOi iki aʻe ke kiʻekiʻe ma mua o ka mea mua, e ʻoi aku ka mālamalama a me ke keʻokeʻo o ka huahana; |
| Ka hemahema | ʻAʻole maikaʻi ka solubility i loko o ka ethylene glycol, 4.04% wale nō ma 150°C. I ka hana maoli, nui loa ka ethylene glycol a i ʻole hoʻonui ʻia ka mahana hoʻoheheʻe ma luna o 150°C. Eia nō naʻe, i ka wā e hana ai ʻo Sb2O3 me ka ethylene glycol no ka manawa lōʻihi ma luna o 120°C, hiki ke loaʻa ka ethylene glycol antimony precipitation, a hiki ke hoʻemi ʻia ʻo Sb2O3 i ke alapiʻi metala i ka hopena polycondensation, hiki ke hana i ka "noe hina" i loko o nā ʻāpana polyester a hoʻopilikia i ka maikaʻi o ka huahana. Hana ʻia ka hanana o nā polyvalent antimony oxides i ka wā o ka hoʻomākaukau ʻana o Sb2O3, a ua hoʻopilikia ʻia ka maʻemaʻe o ka antimony. | He haʻahaʻa iki ka nui o ka antimony o ka mea hoʻouluulu; ʻo nā mea haumia o ka waikawa acetic i hoʻokomo ʻia e hōʻino i nā lako hana, hoʻohaumia i ke kaiapuni, a ʻaʻole kūpono i ka mālama ʻana i ka wai hoʻoneoneo; he paʻakikī ke kaʻina hana, ʻaʻole maikaʻi nā kūlana o ke kaiapuni hana, aia ka haumia, a maʻalahi ka hoʻololi ʻana i ke kala o ka huahana. He maʻalahi ke palaho i ka wā e hoʻomehana ʻia ai, a ʻo nā huahana hydrolysis he Sb2O3 a me CH3COOH. He lōʻihi ka manawa noho o ka mea, ʻoi aku hoʻi i ka pae polycondensation hope loa, ʻoi aku ka kiʻekiʻe ma mua o ka ʻōnaehana Sb2O3. | ʻO ka hoʻohana ʻana o Sb 2 (EG) 3 e hoʻonui i ke kumukūʻai catalyst o ka hāmeʻa (hiki ke hoʻopau ʻia ka piʻi ʻana o ke kumukūʻai inā hoʻohana ʻia he 25% o PET no ka milo ponoʻī ʻana o nā filaments). Eia kekahi, piʻi iki ka waiwai b o ka hue huahana. |