Òàáë. 1. Äàííûå õåìîñîðáöèîííûõ èçìåðåíèé äëÿ îáðàçöîâ 0.5%Pt/γ-Al 2 O 3 , ïðèãîòîâëåííûõ èç 2-õ ïðåäøåñòâåííèêîâ è âîññòàíîâëåííûõ â æåñòêèõ óñëîâèÿõ. Èñõîäíûé êîìïëåêñ Pt Îáðàáîòêà â òîêå Í 2 ïðè 500 î Ñ Äèñïåðñíîñòü ïëàòèíû (%)* OC OT HT CO H 2 PtCl 6 1 ÷ - 71 67 91 “ 10 ÷ 46 62 67 80 (NMe 4 ) 2 [Pt(OH) 6 ] 1 ÷ - 68 67 79 “ 10 ÷ 50 63 67 79 *Ïî õåìîñîðáöèè Î 2 (ÎÑ) è ÑÎ è òèòðîâàíèþ êèñëîðîäîì (ÎÒ) è âîäîðîäîì (ÍÒ). 43
ÑÈÍÒÅÇ, ÈÑÑËÅÄÎÂÀÍÈÅ È ÏÐÈÌÅÍÅÍÈÅ Â ÊÀÒÀËÈÇÅ ÃÅÒÅÐÎÃÅÍÍÛÕ ÊÈÑËÎÒÍÛÕ ÊÀÒÀËÈÇÀÒÎÐΠWO 3 (MoO 3 )/MO 2 (M=Sn, Zr, Ti) Ìàêñèìîâ Ã.Ì., Ïàóêøòèñ Å.À., Ëèòâàê Ã.Ñ. Èíñòèòóò êàòàëèçà èì. Ã.Ê. Áîðåñêîâà ÑÎ ÐÀÍ, Íîâîñèáèðñê E-mail: maks@catalysis.nsk.su Ñèíòåçèðîâàíû è èçó÷åíû (ÈÊ-ñïåêòðîñêîïèÿ, ñêàíèðóþùàÿ ýëåêòðîííàÿ ìèêðîñêîïèÿ, ñîñòàâ âîäíûõ ñìûâîâ, êîëè÷åñòâî è ñèëà êèñëîòíûõ öåíòðîâ ïî òåðìîäåñîðáöèè ïèðèäèíà) ãåòåðîãåííûå êèñëîòíûå êàòàëèçàòîðû 5-40 % WO 3 (MoO 3 )/MO 2 (M=Zr, Ti, Sn). Âñå êàòàëèçàòîðû ÿâëÿþòñÿ ñèëüíûìè áðåíñòåäîâñêèìè êèñëîòàìè, ÷òî îáóñëîâëåíî íàëè÷èåì â èõ ñîñòàâå ñòðóêòóð, ïîõîæèõ íà ãåòåðîïîëèêèñëîòû. Îíè ýôôåêòèâíî êàòàëèçèðóþò æèäêîôàçíûå ðåàêöèè (â ÷àñòíîñòè, ðàçëîæåíèÿ ãèäðîïåðåêèñè êóìîëà è ñèíòåçà âèòàìèíà Å) è ñïîñîáíû çàìåíèòü â íèõ ìèíåðàëüíûå êèñëîòû (íàïðèìåð, H 2 SO 4 ). Ãåòåðîãåííûå êèñëîòíûå êàòàëèçàòîðû øèðîêî ïðèìåíÿþòñÿ â ïðîìûøëåííîñòè, ãëàâíûì îáðàçîì, â ãàçîôàçíûõ ïðîöåññàõ. Óæåñòî÷åíèå ýêîëîãè÷åñêèõ òðåáîâàíèé ïðèâåëî ê íåîáõîäèìîñòè ðàçðàáîòêè íîâûõ êàòàëèçàòîðîâ, ñïîñîáíûõ çàìåíèòü ìèíåðàëüíûå êèñëîòû (îñîáåííî H 2 SO 4 ) â æèäêîôàçíûõ ïðîöåññàõ. Ê ÷èñëó îòíîñèòåëüíî íåäàâíî íàéäåííûõ îòíîñÿòñÿ êèñëîòíûå êàòàëèçàòîðû WO 3 (MoO 3 )/MO 2 (M=Zr,Ti,Sn), îáëàäàþùèå ðÿäîì ïîëåçíûõ ñâîéñòâ: âûñîêàÿ êèñëîòíîñòü, ïðèìåíèìîñòü ê æèäêîôàçíûì è ãàçîôàçíûì ðåàêöèÿì, íå÷óâñòâèòåëüíîñòü ê ïðèìåñÿì â ñûðüå, ë¸ãêîñòü ðåãåíåðàöèè.  äàííîé ðàáîòå ñèíòåçèðîâàíû ñåðèè êàòàëèçàòîðîâ 5-40 % WO 3 (MoO 3 )/MO 2 (M=Zr,Ti,Sn). Îíè èññëåäîâàíû ìåòîäàìè ÈÊ-ñïåêòðîñêîïèè, ñêàíèðóþùåé ýëåêòðîííîé ìèêðîñêîïèè, èçó÷åíû èõ âîäíûå ñìûâû. Êèñëîòíîñòü îïðåäåëÿëàñü ìåòîäàìè ÄÒÀ è ÈÊÑ àäñîðáèðîâàííîãî ïèðèäèíà è ïî øêàëå ÐÀ (proton affinity). Âñå êàòàëèçàòîðû ïîêàçàëè íàëè÷èå áðåíñòåäîâñêèõ ñèëüíîêèñëûõ (óäàëåíèå ïèðèäèíà äî 490-520 î Ñ, çíà÷åíèå ÐÀ 1140 ÊÄæ/ìîëü – íà óðîâíå ãåòåðîïîëèêèñëîò) öåíòðîâ. Èõ êîëè÷åñòâî è ðàñïðåäåëåíèå ïî ñèëå çíà÷èòåëüíî çàâèñÿò îò Ì è óñëîâèé ñèíòåçà. Ïîêàçàíî, ÷òî âñå êàòàëèçàòîðû ÿâëÿþòñÿ îäíîòèïíûìè è ñîäåðæàò Mo èëè W â ñèëüíî- è 44
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ñèíäèîòàêòè÷åñêèé
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ÝËÅÊÒÐÎÕÈÌÈ×ÅÑÊÈÉ
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ÑÒÅÍÄÎÂÛÅ ÄÎÊËÀÄÛ
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Ðèñóíîê 2. Äèôôåðåí
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ÑÒÐÓÊÒÓÐÍÎ-ÎÐÃÀÍÈÇ
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Òàáëèöà 2. Ðàñïðåäå
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ÐÀÇÐÀÁÎÒÊÀ È ÈÑÑËÅ
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êèñëîðîäó øïèíåëè C
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èçîìåðèçàöèè í-ãåê
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ÃÅÍÅÇÈÑ ÔÀÇÎÂÎÃÎ Ñ
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Ïðèðîäà èñõîäíûõ ñ
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ÏÎËÈÌÅÐÍÛÅ ÐÎÄÈÉÑÎ
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Äàëüíåéøàÿ äåãèäðî
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ÌÅÒÎÄÛ ÐÅÃÓËÈÐÎÂÀÍ
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ÂËÈßÍÈÅ ÎÁÐÀÁÎÒÎÊ
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Íàðÿäó ñ óâåëè÷åíè
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îáîðîòîâ êàòàëèçàò
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Íàìè ðàçðàáîòàí ïð
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äî 0,5 ÌÏà. Ôîðìû çàâ
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Î ÏÐÎÖÅÑÑÀÕ ÏÐÅÄÎÒ
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ÐÀÇÐÀÁÎÒÊÀ ÊÀÒÀËÈÒ
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ÏÐÅÂÐÀÙÅÍÈß ÑÒÈÐÎË
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ÆÈÄÊÎÔÀÇÍÀß ÈÇÎÌÅÐ
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ÍÅÏÎËÍÎÅ ÎÊÈÑËÅÍÈÅ
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ÍÀÍÎÑÒÐÓÊÒÓÐÍÛÅ ÊÀ
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ÃÈÄÐÎÊÎÍÂÅÐÑÈß Í-Ã
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ðàñòåò ñ ïîâûøåíèå
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Èíäèâèäóàëüíàÿ àäñ
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â ÑÍÃ ñíèæàåò òåìïå
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Ïðîöåññ áèôîðìèíãà
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ÈÑÏÎËÜÇÎÂÀÍÈÅ ÊÀÒÀ
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Ïîâûøåíèå äàâëåíèÿ
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Èç ïðèðîäíîãî öåîë
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ÄÅÃÈÄÐÈÐÎÂÀÍÈÅ ËÅÃ
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ðîäèåâûå è ðóòåíèå
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Òàáëèöà 1. Âëèÿíèå ï
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ÈÑÑËÅÄÎÂÀÍÈÅ ÏÐÎÖÅ
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ÏÅÐÅÐÀÁÎÒÊÀ ÄÈÑÒÈË
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ÃÈÄÐÎÏÅÐÅÐÀÁÎÒÊÀ í
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ÊÐÅÊÈÍà ÒßÆÅËÎÃÎ Í
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óãëåðîäà â äèîêñèä
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ïîäà÷è ñûðüÿ 1,0-1,5 ÷
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CÓËÜÔÎÊÀÒÈÎÍÈÒÛ ÍÀ
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Ïðè íàëè÷èè â ñèñòå
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ãåêñàäåêàíîë-2 (ïðè
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óñëîâèÿ îêèñëåíèÿ
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ãàçîâ òåðìîäåñîðáö
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ÊÀÒÀËÈÇÈÐÓÅÌÎÅ ÏÀË
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ÈÑÑËÅÄÎÂÀÍÈÅ ÂËÈßÍ
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ÄÈÌÅÐÈÇÀÖÈß ÝÒÈËÅÍ
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ÈÇÓ×ÅÍÈÅ ÏÐÎÖÅÑÑÎÂ
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ÐÀÑÏÐÅÄÅËÅÍÈÅ ÂÍÓÒ
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ÃÎÌÎ - È ÑÎÏÎËÈÌÅÐÈ
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ÏÎËÈÌÅÐÈÇÀÖÈß ÝÒÈË
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Ñ ïðèìåíåíèåì ìåòî
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àìîðôíûìè è êðèñòà
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ÑÏÈÑÎÊ ÀÄÐÅÑΠÓ×À
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ÃÐÈÃÎÐÜÅÂÀ Íåëëè Ã
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ÊÀÐÛÌÎÂÀ Ðàøèäà Õà
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ÌÓÍØÈÅÂÀ Ìèíà Êåðè
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ÓÑÌÀÍÎÂÀ Ìàíçóðà Ì
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ÑÎÄÅÐÆÀÍÈÅ ÊËÞ×ÅÂÛ
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Ñåêöèÿ II Êàòàëèç â
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CÄ-I-3 CÄ-I-4 CÄ-I-5 CÄ-I-6 CÄ
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CÄ-II-10 Çàêèðîâà À.Ã.,
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CÄ-III-4 Ìèêåíàñ T.Á., Å
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