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ÏÎËÓ×ÅÍÈÅ ÆÈÄÊÈÕ ÓÃËÅÂÎÄÎÐÎÄÍÛÕ ÌÎÒÎÐÍÛÕ ÒÎÏËÈÂ ÈÇ ÝÒÀÍÎËÀ ÍÀ ÖÅÎËÈÒÍÛÕ ÊÀÒÀËÈÇÀÒÎÐÀÕ Òðåòüÿêîâ Â.Ô., Ëåðìîíòîâ À.Ñ., Ìàñòþíèíà Ò.Í., Áóðäåéíàÿ Ò.Í. Èíñòèòóò íåôòåõèìè÷åñêîãî ñèíòåçà èì. À.Â. Òîï÷èåâà ÐÀÍ, Ìîñêâà E-mail: tretjakov@ips.ac.ru Ïðîâåäåíû èññëåäîâàíèÿ öåîëèòíûõ êàòàëèçàòîðîâ â ïðîöåññå ïðåâðàùåíèÿ ýòèëîâîãî ñïèðòà. Áûëî ïîêàçàíî, ÷òî â çàâèñèìîñòè îò óñëîâèé ïðîâåäåíèÿ ðåàêöèè âîçìîæíî ïîëó÷åíèå ðÿäà öåííûõ îðãàíè÷åñêèõ ïðîäóêòîâ, îò ýòèëåíà è ë¸ãêèõ îëåôèíîâ äî óãëåâîäîðîäîâ, âõîäÿùèõ â ñîñòàâ ìîòîðíîãî òîïëèâà. Íàèáîëüøóþ àêòèâíîñòü â ïðåâðàùåíèè ýòàíîëà â óãëåâîäîðîäû áåíçèíîâîãî ðÿäà ïðîÿâèë êàòàëèçàòîð H-ZSM-5 ñ ìîäóëåì Si/Al=30. Ñîêðàùåíèå ìèðîâûõ çàïàñîâ íåôòè â ïîñëåäíåå âðåìÿ ïðîâîöèðóåò ðåçêèé ðîñò öåí íà òðàäèöèîííîå ìîòîðíîå òîïëèâî. Â ñâÿçè ñ ýòèì âî âñ¸ì ìèðå âîçîáíîâèëèñü çàêðûòûå â êîíöå 70-õ ãîäîâ ðàáîòû ïî ïîèñêó èñòî÷íèêîâ àëüòåðíàòèâíîãî òîïëèâà. Ýòàíîë ÿâëÿåòñÿ îäíèì èç íàèáîëåå ïåðñïåêòèâíûõ ñûðüåâûõ èñòî÷íèêîâ äëÿ ïîëó÷åíèÿ ìîòîðíîãî òîïëèâà êàê ñ ýêîëîãè÷åñêîé òî÷êè çðåíèÿ – ýòàíîë ìîæíî ïîëó÷àòü ñáðàæèâàíèåì áèîìàññû, òàê è ñ ïðàêòè÷åñêîé òî÷êè çðåíèÿ, ïîñêîëüêó ñòîèìîñòü ýòàíîëà ïàäàåò äî ñòîèìîñòè áåíçèíà. Êàòàëèòè÷åñêîé äåãèäðàòàöèåé ýòàíîëà ìîæíî ïîëó÷èòü øèðîêèé ðÿä îðãàíè÷åñêèõ ïðîäóêòîâ, ñîñòàâ êîòîðûõ çàâèñèò îò òèïà êàòàëèçàòîðà è óñëîâèé ïðîòåêàíèÿ ðåàêöèè. Òàê, íà öåîëèòíûõ êàòàëèçàòîðàõ, îáëàäàþùèõ îäíîâðåìåííî ñïîñîáíîñòüþ äåãèäðèðîâàòü ýòàíîë è îñóùåñòâëÿòü îëèãîìåðèçàöèþ ýòèëåíà, èç ýòèëîâîãî ñïèðòà îáðàçóåòñÿ ñïåêòð óãëåâîäîðîäîâ áåíçèíîâîãî ðÿäà. Â ïðîöåññå ïðåâðàùåíèÿ ýòàíîëà íà óñòàíîâêå ïðîòî÷íîãî òèïà íàìè áûëà èçó÷åíà ñåðèÿ öåîëèòíûõ êàòàëèçàòîðîâ: NaX, HX, H-ZSM-5. Óñòàíîâëåíî, ÷òî íà âñåõ èññëåäîâàííûõ îáðàçöàõ ïðè àòìîñôåðíîì äàâëåíèè è òåìïåðàòóðå îò 300 äî 450 o Ñ äîñòèãàåòñÿ ïðàêòè÷åñêè ïîëíàÿ êîíâåðñèÿ ýòèëîâîãî ñïèðòà. Íàèáîëåå àêòèâíûì îêàçàëñÿ êàòàëèçàòîð H-ZSM-5 ñ ìîäóëåì Si/Al=30. Ñîñòàâ è âûõîä ãàçîîáðàçíûõ ïðîäóêòîâ, ïîëó÷åííûõ ïðè àòìîñôåðíîì äàâëåíèè íà ýòîì êàòàëèçàòîðå, ïðåäñòàâëåí â òàáëèöå 1. 57
Ñîñòàâ ãàçîâîãî ïðîäóêòà ïðè ðàçëè÷íîé òåìïåðàòóðå m êàò =1ã.,V N2 =0,24 ë/÷àñ, V Ñ2 Í 5 ÎÍ=5 ë/÷àñ, ð=1 àòì. Òàáëèöà 1 Ñîñòàâ ãàçà, % Òåìïåðàòóðà, o Ñ Ñ 2 Ñ 3 Ñ 4 Ñ 4= 350 58 22 6 13 450 91 3 2 3 Ïðè àòìîñôåðíîì äàâëåíèè è òåìïåðàòóðàõ íèæå 300 o Ñ îñíîâíûì ïðîäóêòîì ïðåâðàùåíèÿ ýòàíîëà ÿâëÿåòñÿ äèýòèëîâûé ýôèð. Ìàêñèìàëüíûé âûõîä æèäêîé óãëåâîäîðîäíîé ôðàêöèè áûë ïîëó÷åí íà êàòàëèçàòîðå H-ZSM-5 ïðè òåìïåðàòóðå 350 o Ñ è ðàñõîäå ãàçîîáðàçíîãî ýòàíîëà 5 ë/÷àñ (òàáë. 2). Àíàëèç ñîñòàâà æèäêîé ôðàêöèè ïîêàçàë, ÷òî îñíîâíûìè åå êîìïîíåíòàìè ÿâëÿþòñÿ íåïðåäåëüíûå, à òàêæå ðàçëè÷íûå àëêèëàðîìàòè÷åñêèå óãëåâîäîðîäû. Òàáëèöà 2 Ðåçóëüòàòû ïðåâðàùåíèÿ ýòàíîëà íà êàòàëèçàòîðå ÍZSM-5 (Si/Al=30) m êàò =1ã., V Ñ2 Í 5 ÎÍ=5ë/÷àñ, ð=1 àòì. Ðàñõîä àçîòà, ë/÷àñ 0,24 0,36 Ò, o Ñ Ïðîèçâîäèòåëüíîñòü Ïðîèçâîäèòåëüíîñòü Âûõîä æèäêîé ïî ãàçó, ïî æèäêîé ôðàêöèè, ôðàêöèè, ë/ë êàò·÷àñ ìë/ã êàò·÷àñ % 350 3,4 1 7,5 450 2,5 0,7 5,2 350 1,4 0,8 6 450 3,3 0,5 3,7 Ïîâûøåíèå äàâëåíèÿ äî 10 àòì. ïðèâîäèò ê óâåëè÷åíèþ âûõîäà æèäêîé ôðàêöèè. Íà íà÷àëüíîì ýòàïå ðåàêöèè â äèàïàçîíå òåìïåðàòóð îò 250 äî 350 o Ñ âûõîä æèäêèõ óãëåâîäîðîäîâ áåíçèíîâîãî ðÿäà áëèçîê ê 50 % îò ïðåâðàùåííîãî ýòàíîëà. Ïðè ïîâûøåíèè òåìïåðàòóðû êàòàëèçàòîð äåçàêòèâèðóåòñÿ, âñëåäñòâèå çàêîêñîâûâàíèÿ ïîâåðõíîñòè. 58
Page 1 and 2:
Èíñòèòóò êàòàëèçà
Page 3 and 4:
Îðãàíèçàòîðû êîíôå
Page 6 and 7:
SINGLE SITE CATALYSTS - IDEAL MODEL
Page 8 and 9: ÑÒÀÁÈËÈÇÈÐÎÂÀÍÍÛÅ
Page 10 and 11: ÈÇÓ×ÅÍÈÅ ÌÅÕÀÍÈÇÌÎ
Page 12 and 13: Ñðàâíåíèå äèíàìèêè
Page 14 and 15: ÐÎËÜ ÍÎÑÈÒÅËÅÉ Â ÔÎ
Page 16 and 17: ÒÐÈÈÇÎÁÓÒÈËÀËÞÌÈÍ
Page 18: ÏÐÎÃÐÅÑÑ Â ÎÁËÀÑÒÈ
Page 22 and 23: MOLECULAR DESIGN OF NEW TYPE OF CAT
Page 24 and 25: PALLADIUM AND COBALT CATALYZED OXID
Page 26 and 27: ÍÎÂÛÉ ÏÎÄÕÎÄ Ê ÔÎÐÌ
Page 28 and 29: Èîííûé îáìåí Al 2O 3 2+
Page 30 and 31: êîòîðûõ èììîáèëèçî
Page 32 and 33: ïðèâåäøàÿ ê ñîçäàí
Page 34 and 35: ÐÀÇÐÀÁÎÒÊÀ ÊÀÒÀËÈÇ
Page 36 and 37: ðàñïðåäåëåíèÿ ÷àñò
Page 38 and 39: ÷òî äåôåêòû ýòîãî â
Page 40 and 41: ÈÇÓ×ÅÍÈÅ ÔÎÐÌÈÐÎÂÀ
Page 42 and 43: Ñîäåðæàíèå äèîêñèä
Page 44 and 45: Òàáë. 1. Äàííûå õåìî
Page 46 and 47: ñëàáîñâÿçàííîì ñîñ
Page 48 and 49: ãèäðîãåíèçàöèè, âå
Page 50 and 51: ÑÅËÅÊÒÈÂÍÀß ÎÊÈÑËÈ
Page 52 and 53: ÌÎÄÈÔÈÖÈÐÎÂÀÍÈÅ ÀË
Page 54 and 55: ãèäðîîêèñüþ àëþìèí
Page 56 and 57: ïðîìûñëîâûõ ìèíè-Í
Page 60 and 61: ÈÇÎÌÅÐÈÇÀÖÈß ÓÃËÅÂ
Page 62 and 63: ÊÀÒÀËÈÒÈ×ÅÑÊÈÅ ÏÐÅ
Page 64 and 65: îáðàçîâàíèÿ öèêëîï
Page 66 and 67: ïðåèìóùåñòâåííîå ï
Page 68 and 69: ÈÍÒÅÐÊÀËÈÐÎÂÀÍÍÛÅ
Page 70 and 71: ÊÐÅÊÈÍÃ Ñ 10 -Ñ 15 - ÀË
Page 72 and 73: Â ÈÊ- ñïåêòðàõ àäñî
Page 74 and 75: Ïî âëèÿíèþ íà êàòàë
Page 76 and 77: Ïðåîáëàäàþùèìè ïðè
Page 78 and 79: ÃÈÄÐÎÏÅÐÅÐÀÁÎÒÊÀ Í
Page 80 and 81: Ïîñëå ãèäðîïåðåðàá
Page 82 and 83: óñëîâèé ïðîöåññà î
Page 84 and 85: åå ðåàêöèè. Èìåííî
Page 86 and 87: í-C 4 H 8 + Pd II + Í 2 Î ⎯⎯
Page 88 and 89: ïðîäóêòîâ. Íàïðèìå
Page 90 and 91: ×ÈÑËÎ È ÐÅÀÊÖÈÎÍÍÀ
Page 92 and 93: Äëÿ âñåõ ñèñòåì îïð
Page 94 and 95: ñèíäèîòàêòè÷åñêèé
Page 96 and 97: ñâÿçåé è ýêâèâàëåí
Page 98 and 99: ÝËÅÊÒÐÎÕÈÌÈ×ÅÑÊÈÉ
Page 100 and 101: ÑÒÅÍÄÎÂÛÅ ÄÎÊËÀÄÛ
Page 102 and 103: ÈÇÓ×ÅÍÈÅ ÌÅÕÀÍÈÇÌÀ
Page 104 and 105: Ðèñóíîê 2. Äèôôåðåí
Page 106 and 107: âòîðîé ïî èíòåíñèâ
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êîëåáàíèÿ â ìîñòèê
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ÑÒÐÓÊÒÓÐÍÎ-ÎÐÃÀÍÈÇ
Page 112 and 113:
Òàáëèöà 2. Ðàñïðåäå
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50 Rate/10 -8 mol g -1 s -1 40 30 2
Page 116 and 117:
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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óïëîòíåíèÿ çàïîëíÿ
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Ïðèðîäà èñõîäíûõ ñ
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ÏÎËÈÌÅÐÍÛÅ ÐÎÄÈÉÑÎ
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ïðîìîòîðîâ. Â ðàáîò
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ôîðìàëüäåãèä, äè- è
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Äàëüíåéøàÿ äåãèäðî
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ÌÅÒÎÄÛ ÐÅÃÓËÈÐÎÂÀÍ
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ÑÈÍÒÅÇ È ÈÑÑËÅÄÎÂÀ
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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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ÊÐÅÊÈÍÃ ÒßÆÅËÎÃÎ Í
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óãëåðîäà â äèîêñèä
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ïîäà÷è ñûðüÿ 1,0-1,5 ÷
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ëîêàëèçîâàííûå íà
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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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ïîëèìåðèçàöèè ýòèë
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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 ÀÄÐÅÑÎÂ Ó×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.,
Page 246 and 247:
CÄ-III-4 Ìèêåíàñ T.Á., Å
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