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ÃÈÄÐÎÊÎÍÂÅÐÑÈß Í-ÃÅÊÑÀÍÀ ÍÀ Ni²-ZSM-5/ÍÀÐÛÍÊÎËÜÑÊÀß ÃËÈÍÀ ÊÀÒÀËÈÇÀÒÎÐÀÕ, ÌÎÄÈÔÈÖÈÐÎÂÀÍÍÛÕ ÃÅÒÅÐÎÏÎËÈÊÈÑËÎÒÀÌÈ Çàêàðèíà Í.À., Êîðíàóõîâà Í.À. Èíñòèòóò îðãàíè÷åñêîãî êàòàëèçà è ýëåêòðîõèìèè èì. Ä.Â. Ñîêîëüñêîãî ÌÎÍ ÐÊ, Àëìàòû, Êàçàõñòàí E-mail: nelly_zakarina@rambler.ru Ââåäåíèå ÃÏÊ ïîâûøàåò êîíâåðñèþ í-ãåêñàíà íà Ni-ZSM-5êàòàëèçàòîðàõ â èíòåðâàëå òåìïåðàòóð 250-450 î Ñ. Íàéäåíî îïòèìàëüíîå ñîîòíîøåíèå ãëèíà : öåîëèò â Ni-ñîäåðæàùèõ êàòàëèçàòîðàõ, ìîäèôèöèðîâàííûõ âûñîêîêðåìíåçåìíûì öåîëèòîì. Ïîêàçàíî, ÷òî ïðè îïòèìàëüíîì ñîäåðæàíèè Íàðûíêîëüñêîé ãëèíû è öåîëèòà ïðè 250-300 î Ñ íà Ni-êàòàëèçàòîðå èäåò ïðîöåññ èçîìåðèçàöèè í-ãåêñàíà ñ îáðàçîâàíèåì 2- è 3-ìåòèëïåíòàíîâ, â òî âðåìÿ êàê ïðè 350-400 î íà÷èíàþò ïðåîáëàäàòü ïðîöåññû ãèäðîêðåêèíãà ñ îáðàçîâàíèåì Ñ 1 -Ñ 3 - óãëåâîäîðîäîâ. Ìåòîäîì ÒÏÄ NH 3 íàéäåíî, ÷òî ïðè ââåäåíèè ÃÏÊ ðàñòåò êîëè÷åñòâî êèñëîòíûõ öåíòðîâ, ÷òî âëèÿåò íà íàïðàâëåíèå ïðåâðàùåíèÿ í-ãåêñàíà. Ïðè ïåðåðàáîòêå ðàçëè÷íûõ âèäîâ óãëåâîäîðîäíîãî ñûðüÿ øèðîêî èñïîëüçóþò ìåòàëëöåîëèòíûå êàòàëèçàòîðû. Íàïðàâëåíèå ïðåâðàùåíèÿ óãëåâîäîðîäîâ îïðåäåëÿåòñÿ ñîîòíîøåíèåì êèñëîòíîé è ãèäðî-äåãèäðèðóþùåé ôóíêöèé êàòàëèçàòîðîâ. Â íàñòîÿùåé ðàáîòå èññëåäîâàíî âëèÿíèå äîáàâîê ãåòåðîïîëèêèñëîò íà ãèäðîêîíâåðñèþ í-ãåêñàíà íà Ni-êàòàëèçàòîðàõ ñ ZSM-5, íàíåñåííûõ íà àêòèâèðîâàííóþ Íàðûíêîëüñêóþ ãëèíó (Í. Ê.) [1]. Ýêñïåðèìåíòû áûëè ïðîâåäåíû â ïðîòî÷íîé óñòàíîâêå â èíòåðâàëå òåìïåðàòóð 250-450 î Ñ, ïðè àòìîñôåðíîì äàâëåíèè Í 2 , ìîëüíîì ñîîòíîøåíèè Í 2 :Ñ 6 Í 14 = 3,5 è îáúåìíîé ñêîðîñòè ïîäà÷è í-ãåêñàíà 0,82 ÷àñ -1 . Àíàëèç ïðîäóêòîâ îñóùåñòâëÿëè õðîìàòîãðàôè÷åñêè. Ôèçèêî-õèìè÷åñêèå ñâîéñòâà êàòàëèçàòîðîâ áûëè èçó÷åíû ìåòîäàìè ýëåêòðîííîé ìèêðîñêîïèè, ÐÔÀ, ÁÝÒ è òåðìîïðîãðàììèðîâàííîé äåñîðáöèè (ÒÏÄ) NH 3 . Â ðåçóëüòàòå èññëåäîâàíèé áûëî íàéäåíî îïòèìàëüíîå ñîäåðæàíèå íèêåëÿ è öåîëèòà ZSM-5 â êàòàëèçàòîðàõ ãèäðîêîíâåðñèè í-ãåêñàíà. Óñòàíîâëåíî ðàçëè÷èå âî âëèÿíèè ÃÏÊ íà ïðîöåññû ãèäðîêðåêèíãà è ãèäðîèçîìåðèçàöèè í-ãåêñàíà íà Ni-ZSM-êàòàëèçàòîðàõ (òàáëèöà). Äëÿ âñåõ êàòàëèçàòîðîâ õàðàêòåðíî ñíà÷àëà ðåçêîå óâåëè÷åíèå êîíâåðñèè ñ ðîñòîì òåìïåðàòóðû îò 250 äî 300-350 î Ñ, çàòåì äîñòèæåíèå ïîñòîÿííîé 161
âåëè÷èíû êîíâåðñèè ïðè ïîâûøåíèè òåìïåðàòóðû äî 400 î Ñ. Ââåäåíèå ÃÏÊ â ñîñòàâ Ni-ZSM-5-êàòàëèçàîðîâ ïîâûøàåò êîíâåðñèþ í-ãåêñàíà äëÿ âñåõ èçó÷åííûõ ÃÏÊ â èíòåðâàëå òåìïåðàòóð 250-400 î Ñ. Ïî âëèÿíèþ íà êîíâåðñèþ í-ãåêñàíà ïðè 300-350 î Ñ ÃÏÊ ìîæíî ðàñïîëîæèòü â ðÿä: SiMo 12 > PW 12 > PV 3 Mo 9 > SiW 12 . Òàáëèöà. Ñîñòàâ ïðîäóêòîâ ðåàêöèè èçîìåðèçàöèè í-ãåêñàíà íà (5% Ni, 1% ÃÏÊ)/ ZSM-5 /HÊ- êàòàëèçàòîðàõ, ìîäèôèöèðîâàííûõ ðàçëè÷íûìè ÃÏÊ ¹ ÃÏÊ 1 SiW 12 2 SiMo 12 3 PV 3 Mo 9 Ò, î Ñ ?α, % S Ñ4+ S Ñ6 Âûõîä ïðîäóêòîâ ðåàêöèè, % ?Ñ 1 -Ñ 3 ?Ñ 4 ?Ñ 5 2ÌÏ 3ÌÏ 250 13,2 24,4 7,6 4,2 1,2 4,7 0,1 1,0 300 58,7 13,0 7,4 28,2 10,5 15,9 3,0 1,3 350 73,3 28,0 16,8 37,8 9,5 29,4 8,4 4,0 400 72,3 28,0 20,8 44,3 6,2 6,7 9,6 5,5 250 43,7 54,3 46,8 10,7 3,2 9,4 3,1 16,9 300 82,0 25,0 3,4 48,6 13,8 16,7 2,2 0,7 350 86,0 24,0 7,4 56,2 9,1 14,3 4,5 1,9 400 87,7 19,6 10,6 65,3 4,2 8,8 6,4 2,9 250 59,2 46,5 34,3 17,0 4,9 17,0 14,6 5,7 300 76,7 29,2 9,4 48,5 9,4 11,5 5,0 2,2 350 83,0 31,3 15,9 52,3 6,9 22,1 8,7 4,5 400 83,6 17,7 11,2 67,4 3,8 3,0 5,7 3,7 4 PW 12 250 31,4 80,3 48,7 6,2 1,9 8,0 10,7 4,6 300 64,8 34,7 14,7 33,5 7,8 14,0 6,5 2,9 350 84,0 29,7 13,3 54,0 7,5 11,4 7,3 3,8 400 88,4 11,3 7,4 77,3 2,2 2,4 4,0 2,5 Õðîìàòîãðàôè÷åñêèé àíàëèç ïðîäóêòîâ ðåàêöèè ïîêàçàë, ÷òî íà èçó÷åííûõ êàòàëèçàòîðàõ â îñíîâíîì ïðîõîäÿò ðåàêöèè ãèäðîêðåêèíãà ñ îáðàçîâàíèåì áîëüøîãî êîëè÷åñòâà Ñ 1 -Ñ 5 -óãëåâîäîðîäîâ íîðìàëüíîãî è èçîñòðîåíèÿ (òàáëèöà). Ðÿä ÃÏÊ ïî âëèÿíèþ íà ñåëåêòèâíîñòü ïî èçîìåðàì ïðè 250 î Ñ èìååò âèä: PW 12 > SiMo 12 > PV 3 Mo 9 > SiW 12 . Ñ ïîâûøåíèåì òåìïåðàòóðû ñåëåêòèâíîñòü ïî èçîìåðàì ñíèæàåòñÿ äëÿ âñåõ ÃÏÊ êðîìå SiW 12 , êîòîðàÿ îòëè÷àåòñÿ òåðìè÷åñêîé óñòîé÷èâîñòüþ è îêàçûâàåò ìîäèôèöèðóþùåå äåéñòâèå â áîëåå øèðîêîì èíòåðâàëå òåìïåðàòóð. Äëÿ âñåõ èçó÷åííûõ êàòàëèçàòîðîâ õàðàêòåðíî îáðàçîâàíèå áîëüøîãî êîëè÷åñòâà ãàçîîáðàçíûõ óãëåâîäîðîäîâ, âûõîä ãàçîâ 162
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Èíñòèòóò êàòàëèçà
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Îðãàíèçàòîðû êîíôå
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SINGLE SITE CATALYSTS - IDEAL MODEL
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ÑÒÀÁÈËÈÇÈÐÎÂÀÍÍÛÅ
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ÈÇÓ×ÅÍÈÅ ÌÅÕÀÍÈÇÌÎ
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Ñðàâíåíèå äèíàìèêè
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ÐÎËÜ ÍÎÑÈÒÅËÅÉ Â ÔÎ
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ÒÐÈÈÇÎÁÓÒÈËÀËÞÌÈÍ
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ÏÐÎÃÐÅÑÑ Â ÎÁËÀÑÒÈ
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MOLECULAR DESIGN OF NEW TYPE OF CAT
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PALLADIUM AND COBALT CATALYZED OXID
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ÍÎÂÛÉ ÏÎÄÕÎÄ Ê ÔÎÐÌ
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Èîííûé îáìåí Al 2O 3 2+
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êîòîðûõ èììîáèëèçî
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ïðèâåäøàÿ ê ñîçäàí
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ÐÀÇÐÀÁÎÒÊÀ ÊÀÒÀËÈÇ
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ðàñïðåäåëåíèÿ ÷àñò
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÷òî äåôåêòû ýòîãî â
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ÈÇÓ×ÅÍÈÅ ÔÎÐÌÈÐÎÂÀ
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Ñîäåðæàíèå äèîêñèä
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Òàáë. 1. Äàííûå õåìî
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ñëàáîñâÿçàííîì ñîñ
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ãèäðîãåíèçàöèè, âå
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ÑÅËÅÊÒÈÂÍÀß ÎÊÈÑËÈ
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ÌÎÄÈÔÈÖÈÐÎÂÀÍÈÅ ÀË
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ãèäðîîêèñüþ àëþìèí
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ïðîìûñëîâûõ ìèíè-Í
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ÏÎËÓ×ÅÍÈÅ ÆÈÄÊÈÕ Ó
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ÈÇÎÌÅÐÈÇÀÖÈß ÓÃËÅÂ
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ÊÀÒÀËÈÒÈ×ÅÑÊÈÅ ÏÐÅ
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îáðàçîâàíèÿ öèêëîï
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ïðåèìóùåñòâåííîå ï
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ÈÍÒÅÐÊÀËÈÐÎÂÀÍÍÛÅ
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ÊÐÅÊÈÍÃ Ñ 10 -Ñ 15 - ÀË
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Â ÈÊ- ñïåêòðàõ àäñî
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Ïî âëèÿíèþ íà êàòàë
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Ïðåîáëàäàþùèìè ïðè
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ÃÈÄÐÎÏÅÐÅÐÀÁÎÒÊÀ Í
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Ïîñëå ãèäðîïåðåðàá
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óñëîâèé ïðîöåññà î
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åå ðåàêöèè. Èìåííî
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í-C 4 H 8 + Pd II + Í 2 Î ⎯⎯
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ïðîäóêòîâ. Íàïðèìå
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×ÈÑËÎ È ÐÅÀÊÖÈÎÍÍÀ
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Äëÿ âñåõ ñèñòåì îïð
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ñèíäèîòàêòè÷åñêèé
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ñâÿçåé è ýêâèâàëåí
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ÝËÅÊÒÐÎÕÈÌÈ×ÅÑÊÈÉ
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ÑÒÅÍÄÎÂÛÅ ÄÎÊËÀÄÛ
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ÈÇÓ×ÅÍÈÅ ÌÅÕÀÍÈÇÌÀ
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Ðèñóíîê 2. Äèôôåðåí
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âòîðîé ïî èíòåíñèâ
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êîëåáàíèÿ â ìîñòèê
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ÑÒÐÓÊÒÓÐÍÎ-ÎÐÃÀÍÈÇ
Page 112 and 113: Òàáëèöà 2. Ðàñïðåäå
Page 114 and 115: 50 Rate/10 -8 mol g -1 s -1 40 30 2
Page 116 and 117: ÐÀÇÐÀÁÎÒÊÀ È ÈÑÑËÅ
Page 118 and 119: êèñëîðîäó øïèíåëè C
Page 120 and 121: èçîìåðèçàöèè í-ãåê
Page 122 and 123: ÃÅÍÅÇÈÑ ÔÀÇÎÂÎÃÎ Ñ
Page 124 and 125: óïëîòíåíèÿ çàïîëíÿ
Page 126 and 127: Ïðèðîäà èñõîäíûõ ñ
Page 128 and 129: ÏÎËÈÌÅÐÍÛÅ ÐÎÄÈÉÑÎ
Page 130 and 131: ïðîìîòîðîâ. Â ðàáîò
Page 132 and 133: ôîðìàëüäåãèä, äè- è
Page 134 and 135: Äàëüíåéøàÿ äåãèäðî
Page 136 and 137: ÌÅÒÎÄÛ ÐÅÃÓËÈÐÎÂÀÍ
Page 138 and 139: ÑÈÍÒÅÇ È ÈÑÑËÅÄÎÂÀ
Page 140 and 141: ÂËÈßÍÈÅ ÎÁÐÀÁÎÒÎÊ
Page 142 and 143: Íàðÿäó ñ óâåëè÷åíè
Page 144 and 145: îáîðîòîâ êàòàëèçàò
Page 146 and 147: Íàìè ðàçðàáîòàí ïð
Page 148 and 149: äî 0,5 ÌÏà. Ôîðìû çàâ
Page 150 and 151: Î ÏÐÎÖÅÑÑÀÕ ÏÐÅÄÎÒ
Page 152 and 153: ÐÀÇÐÀÁÎÒÊÀ ÊÀÒÀËÈÒ
Page 154 and 155: ÏÐÅÂÐÀÙÅÍÈß ÑÒÈÐÎË
Page 156 and 157: ÆÈÄÊÎÔÀÇÍÀß ÈÇÎÌÅÐ
Page 158 and 159: ÍÅÏÎËÍÎÅ ÎÊÈÑËÅÍÈÅ
Page 160 and 161: ÍÀÍÎÑÒÐÓÊÒÓÐÍÛÅ ÊÀ
Page 164 and 165: ðàñòåò ñ ïîâûøåíèå
Page 166 and 167: Èíäèâèäóàëüíàÿ àäñ
Page 168 and 169: â ÑÍÃ ñíèæàåò òåìïå
Page 170 and 171: Ïðîöåññ áèôîðìèíãà
Page 172 and 173: ÈÑÏÎËÜÇÎÂÀÍÈÅ ÊÀÒÀ
Page 174 and 175: Ïîâûøåíèå äàâëåíèÿ
Page 176 and 177: Èç ïðèðîäíîãî öåîë
Page 178 and 179: ÄÅÃÈÄÐÈÐÎÂÀÍÈÅ ËÅÃ
Page 180 and 181: ðîäèåâûå è ðóòåíèå
Page 182 and 183: Òàáëèöà 1. Âëèÿíèå ï
Page 184 and 185: ÈÑÑËÅÄÎÂÀÍÈÅ ÏÐÎÖÅ
Page 186 and 187: ÏÅÐÅÐÀÁÎÒÊÀ ÄÈÑÒÈË
Page 188 and 189: ÃÈÄÐÎÏÅÐÅÐÀÁÎÒÊÀ í
Page 190 and 191: ÊÐÅÊÈÍÃ ÒßÆÅËÎÃÎ Í
Page 192 and 193: óãëåðîäà â äèîêñèä
Page 194 and 195: ïîäà÷è ñûðüÿ 1,0-1,5 ÷
Page 196 and 197: ëîêàëèçîâàííûå íà
Page 198 and 199: CÓËÜÔÎÊÀÒÈÎÍÈÒÛ ÍÀ
Page 200 and 201: Ïðè íàëè÷èè â ñèñòå
Page 202 and 203: ãåêñàäåêàíîë-2 (ïðè
Page 204 and 205: óñëîâèÿ îêèñëåíèÿ
Page 206 and 207: ãàçîâ òåðìîäåñîðáö
Page 208 and 209: ïîëèìåðèçàöèè ýòèë
Page 210 and 211: 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.,
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CÄ-III-4 Ìèêåíàñ T.Á., Å
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