Antimony-Based Catalysts

Ko te muka polyester (PET) te momo nui rawa atu o te muka waihanga. Ko nga kakahu he mea hanga ki te muka polyester he pai, he kirikiri, he ngawari ki te horoi, he tere ki te maroke. Ka whakamahia te polyester hei rauemi mata mo te takai, miro ahumahi, me nga kirihou miihini. Ko te mutunga, kua tere te tipu o te polyester puta noa i te ao, ka piki ake i te reeti toharite o te tau o te 7% me te hua nui.

Ka taea te wehewehe i te hanga polyester ki te ara dimethyl terephthalate (DMT) me te terephthalic acid (PTA) ara i runga i te huarahi tukanga, ka taea te wehewehea ki te tukanga mokowhiti me te tukanga tonu i runga i te mahi. Ahakoa te huarahi o te mahi whakaputa, me whakamahi te tauhohenga polycondensation ki te whakamahi i nga puhui whakarewa hei whakakorikori. Ko te tauhohenga polycondensation he taahiraa matua i roto i te tukanga whakaputa polyester, me te wa polycondensation ko te pounamu mo te whakapai ake i te hua. Ko te whakapai ake i te punaha whakakorikori he mea nui ki te whakapai ake i te kounga o te polyester me te whakapoto i te wa polycondensation.

UrbanMines Hangarau. He kamupene Hainamana nui a Limited e mahi ana i te R&D, te whakaputa, me te tuku i te polyester catalyst-grade antimony trioxide, antimony acetate, me te antimony glycol. Kua whakahaeretia e matou he rangahau hohonu mo enei hua—ko te tari R&D o UrbanMines inaianei kua whakarāpopotohia te rangahau me te tono o nga whakakorikori antimony i roto i tenei tuhinga hei awhina i o taatau kaihoko ki te tono ngawari, ki te arotau i nga tikanga whakaputa, me te whakarato whakataetae matawhānui o nga hua muka polyester.

Ko nga tohunga o te kainga me nga iwi ke e whakapono ana ko te polycondensation polyester he tauhohenga toronga mekameka, a ko te tikanga catalytic no te chelation coordination, e hiahia ana te ngota konganuku whakakōkī ki te whakarato orbitals kau ki te ruruku ki te rua arc o irahiko o carbonyl hāora ki te whakatutuki i te kaupapa o whakatiki. Mo te polycondensation, i te mea he iti te kiato kapua irahiko o te hauwao waro i roto i te roopu haukawa hydroxyethyl, he tino nui te electronegativity o nga katote whakarewa i te wa o te ruruku, hei whakahaere i te ruruku me te toronga mekameka.

Ka taea te whakamahi i enei e whai ake nei hei whakakorikori 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 me etahi atu waikura whakarewa, waipiro, carboxylates, borates, halides me amines, urea, guanidines, pūhui waro kei roto te whanariki. Heoi, ko nga whakakorikori e whakamahia ana, e akohia ana i roto i nga mahi ahumahi ko te nuinga o nga huinga raupapa Sb, Ge, me Ti. He maha nga rangahau i whakaatu ko: He iti ake nga tauhohenga taha o nga kaiwhakatuma Ge-based me te whakaputa i te PET kounga teitei, engari kaore i te teitei o raatau mahi, he iti nga rauemi, he utu nui; He nui te mahi me te tere tauhohenga tere o te whakakōkī Ti, engari he tino kitea o ratou tauhohenga taha catalytic, hua i roto i te rawakore pūmautanga waiariki me te tae kōwhai o te hua, a ka taea anake te whakamahi mo te kōtuitanga o PBT, PTT, PCT, aha atu; Ehara i te mea he kaha ake nga whakakorikori a-Sb. He teitei te kounga o te hua na te mea he kaha ake te kaha o te whakakorikori a Sb, he iti ake nga tauhohenga taha, he iti ake te utu. Nō reira, kua whakamahia whānuitia. I roto i a raatau, ko te nuinga o te whakamahi Sb-based catalysts he antimony trioxide (Sb2O3), antimony acetate (Sb(CH3COO)3), etc.

Ma te titiro ki te hitori o te whanaketanga o te umanga polyester, ka kitea e matou neke atu i te 90% o nga tipu polyester o te ao e whakamahi ana i nga pūhui antimony hei whakakorikori. No te tau 2000, he maha nga tipu polyester i whakauruhia e Haina, ka whakamahia katoatia nga pūhui antimony hei whakakorikori, ko te nuinga ko Sb2O3 me Sb(CH3COO)3. Na roto i nga mahi tahi a Hainamana rangahau pūtaiao, whare wananga, me nga tari whakangao, kua oti enei whakakorikori e rua kua oti katoa te whakaputa i te kainga.

Mai i te tau 1999, kua whakarewahia e te kamupene matū Wīwī a Elf he whakakōkī antimony glycol [Sb2 (OCH2CH2CO) 3] hei hua whakahou o ngā whakakōkī tuku iho. Ko nga maramara polyester i hangaia he maamaa nui me te pai o te hurihuri, i aro nui mai i nga whare rangahau whakakorikori whare, hinonga, me nga kaihanga polyester i Haina.

I. Te rangahau me te tono o te antimony trioxide
Ko Amerika tetahi o nga whenua tuatahi ki te whakaputa me te tono Sb2O3. I te tau 1961, ko te kai o te Sb2O3 i te United States i eke ki te 4,943 tone. I te tekau tau atu i 1970, e rima nga kamupene i Hapani i whakaputa i te Sb2O3 me te katoa o te kaha whakaputa 6,360 tone ia tau.

Ko nga waahanga rangahau me te whanaketanga Sb2O3 matua o Haina kei te aro nui ki nga umanga a- kawanatanga o mua i te Porowini o Hunan me Shanghai. UrbanMines Hangarau. Kua whakapumautia ano e Limited he raina whakaputa ngaio ki te Porowini o Hunan.

(I). Tikanga mo te whakaputa antimony trioxide
Ko te hanga o te Sb2O3 te nuinga o te waa ka whakamahi i te ore antimony sulfide hei rauemi mata. Ko te antimony konganuku ka taka tuatahi, katahi ka hangaia te Sb2O3 ma te whakamahi i te antimony whakarewa hei rauemi mata.
E rua nga tikanga matua mo te whakaputa i te Sb2O3 mai i te antimony konganuku: te waiora tika me te hauota pirau.

1. Tikanga hāora tika
Ka tauhohe te antimony konganuku ki te hāora i raro i te whakamahana kia puta ko Sb2O3. Ko te tukanga tauhohenga e whai ake nei:
4Sb＋3O2＝＝2Sb2O3

2. Ammonolysis
Ka tauhohe te konganuku Antimony ki te chlorine ki te whakahiato i te antimony trichloride, katahi ka whakamarohia, ka whakamarohia, ka whakamarohia, ka horoi, ka whakamaroke kia whiwhi ai i te hua Sb2O3 kua oti. Ko te whārite tauhohenga taketake ko:
2Sb＋3Cl2＝＝2SbCl3
SbCl3＋H2O＝＝SbOCl＋2HCl
4SbOCl＋H2O＝＝Sb2O3·2SbOCl＋2HCl
Sb2O3·2SbOCl＋OH＝＝2Sb2O3＋2NH4Cl＋H2O

(II). Nga whakamahinga o te antimony trioxide
Ko te whakamahinga matua o te antimony trioxide hei whakakorikori mo te polymerase me te mura ahi mo nga rawa waihanga.
I roto i te ahumahi polyester, i whakamahia tuatahi a Sb2O3 hei whakakorikori. Ko te Sb2O3 te nuinga o te whakamahi hei whakakorikori polycondensation mo te ara DMT me te huarahi PTA moata, a ka whakamahia i te nuinga o te waa me te H3PO4 me ona enzymes.

(III). He raruraru ki te antimony trioxide
He kino te whakarewatanga o te Sb2O3 i roto i te ethylene glycol, me te 4.04% anake i te 150°C. No reira, ka whakamahia te ethylene glycol ki te whakarite i te whakakorikori, he kino te mararatanga a Sb2O3, ka ngawari te whakakorikori i te taikaha i roto i te punaha polymerization, te whakaputa i nga trimers porohita-whakarewa teitei, me te raru ki te hurihuri. Hei whakapai ake i te wairewa me te mararatanga o Sb2O3 i roto i te ethylene glycol, ka whakamahia te nui o te ethylene glycol, te whakanui ake ranei i te pāmahana rewa ki runga ake i te 150°C. Engari, i runga ake i te 120°C, ka taea e Sb2O3 me te ethylene glycol te whakaputa i te rerenga antimony ethylene glycol ina mahi tahi ana mo te wa roa, a ka heke te Sb2O3 ki te antimony konganuku i roto i te tauhohenga polycondensation, ka puta he "kohu" i roto i nga maramara polyester ka pa kounga hua.

II. Te rangahau me te tono o te antimony acetate
Te tikanga whakarite o te antimony acetate
I te tuatahi, i whakaritea te antimony acetate ma te tauhohe i te antimony trioxide ki te waikawa acetic, a ka whakamahia te anhydride acetic hei kaihoko whakamaroke ki te tango i te wai i hangaia e te tauhohenga. Ko te kounga o te hua kua oti i riro mai i tenei tikanga kaore i teitei, a ka neke atu i te 30 haora mo te antimony trioxide ki te memeha i roto i te waikawa acetic. I muri mai, i takahia te antimony acetate ma te whakahoki i te antimony whakarewa, te antimony trichloride, te antimony trioxide ranei me te acetic anhydride, me te kore e hiahiatia he kaihoko whakamaori.

1. Tikanga antimony trichloride
I te tau 1947, H. Schmidt et al. i te Hauauru o Tiamana i whakarite te Sb(CH3COO)3 ma te tauhohe i te SbCl3 me te anhydride acetic. Ko te tauira tauhohenga e whai ake nei:
SbCl3+3(CH3CO)2O==Sb(CH3COO)3+3CH3COCl

2. Tikanga whakarewa Antimony
I te tau 1954, i whakarite a TAPaybea o te Soviet Union o mua i te Sb(CH3COO)3 ma te tauhohe i te antimony konganuku me te peroxyacetyl i roto i te otinga benzene. Ko te tauira tauhohenga ko:
Sb＋(CH3COO)2==Sb(CH3COO)3

3. Tikanga antimony trioxide
I te tau 1957, ka whakamahia e F. Nerdel o Tiamana ki te Hauauru a Sb2O3 ki te tauhohe me te anhydride acetic hei whakaputa i te Sb(CH3COO)3.
Sb2O3＋3（CH3CO）2O＝＝2Sb（CH3COO）3
Ko te kino o tenei tikanga ko nga tioata ka whakahiato ki roto ki nga waahanga nui ka piri ki te pakitara o roto o te reactor, na reira ka kino te kounga o te hua me te tae.

4. Antimony trioxide tikanga whakarewa
Hei whakakore i nga ngoikoretanga o te tikanga i runga ake nei, ka taapirihia he whakarewa kore i te wa o te tauhohenga o te Sb2O3 me te anhydride acetic. Ko te tikanga whakarite motuhake e whai ake nei:
(1) I te 1968, R. Thoms o te American Mosun Chemical Company i whakaputa he patent mo te whakarite i te acetate antimony. I whakamahia e te patent te xylene (o-, m-, p-xylene, he ranunga ranei) hei whakarewa korekore hei whakaputa i nga tioata pai o te acetate antimony.
(2) I te tau 1973, i hangaia e te Czech Republic tetahi tikanga mo te hanga acetate antimony pai ma te whakamahi i te toluene hei whakarewa.

 

III. Whakatauritenga o nga whakakorikori-a-antimony e toru