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ÈÇÓ×ÅÍÈÅ ÔÎÐÌÈÐÎÂÀÍÈß ÍÀÍÎÐÀÇÌÅÐÍÛÕ ×ÀÒÈÖ ÏÀËËÀÄÈß ÍÀ ÓÃËÅÐÎÄÍÛÕ ÏÎÄËÎÆÊÀÕ ÈÇ ÏÐÈÐÎÄÍÛÕ ÃÐÀÔÈÒÎÂ È ÀÍÒÐÀÖÈÒÎÂ Êóçíåöîâ Á.Í., ×åñíîêîâ Í.Â., Ìèêîâà Í.Ì., Çàéêîâñêèé Â.È. 1 Èíñòèòóò õèìèè è õèìè÷åñêîé òåõíîëîãèè ÑÎ ÐÀÍ, Êðàñíîÿðñê 1 Èíñòèòóò êàòàëèçà èì. Ã.Ê. Áîðåñêîâà ÑÎ ÐÀÍ, Íîâîñèáèðñê E-mail: bnk@icct.ru, inm@icct.ru Äëÿ ïàëëàäèåâûõ êàòàëèçàòîðîâ, ïîëó÷åííûõ íàíåñåíèåì H 2 PdCl 4 íà óãëåðîäíûå ïîäëîæêè èç òåðìîðàñøèðåííîãî ïðèðîäíîãî ãðàôèòà è õèìè÷åñêè ìîäèôèöèðîâàííûõ àíòðàöèòîâ, õàðàêòåð ðàñïðåäåëåíèÿ è ðàçìåð ÷àñòèö íàíåñåííîãî ïàëëàäèÿ â çíà÷èòåëüíîé ñòåïåíè îïðåäåëÿåòñÿ ïðèðîäîé èñõîäíîãî ìàòåðèàëà è ïðèìåíÿåìûì ñïîñîáîì ôîðìèðîâàíèÿ ïîðèñòîé ñòðóêòóðû ïîäëîæêè. Â ïðîöåññå íàíåñåíèÿ H 2 PdCl 4 íà óãëåðîäíóþ ïîâåðõíîñòü ïðîèñõîäèò ÷àñòè÷íîå èëè ïðàêòè÷åñêè ïîëíîå âîññòàíîâëåíèå ïàëëàäèÿ, â çàâèñèìîñòè îò ñïîñîáà ïðèãîòîâëåíèÿ óãëåðîäíîé ïîäëîæêè. Íàèáîëåå ðàâíîìåðíîå ðàñïðåäåëåíèå íàíîðàçìåðíûõ ÷àñòèö ïàëëàäèÿ íàáëþäàåòñÿ íà íîñèòåëÿõ èç òåðìîðàñøèðåííîãî ãðàôèòà. Îñóùåñòâëåí ïîäáîð óñëîâèé ñèíòåçà óãëåðîäíûõ ïîäëîæåê èç ãðàôèòîâ è àíòðàöèòîâ, îáåñïå÷èâàþùèõ ïðåèìóùåñòâåííîå ôîðìèðîâàíèå â ïàëëàäèåâûõ êàòàëèçàòîðàõ ÷àñòèö ìåòàëëà ðàçìåðîì 1-2 íì èëè èõ àññîöèàòîâ, ëèáî ëîêàëèçàöèþ ìåòàëëà âíóòðè óçêèõ ìèêðîïîð. Îáíàðóæåíî ñóùåñòâåííîå ðàçëè÷èå â ãèäðèðóþùåé àêòèâíîñòè êàòàëèçàòîðîâ, îòëè÷àþùèõñÿ ñîñòîÿíèåì íàíåñåííîãî ïàëëàäèÿ. Íàèáîëåå âûñîêóþ àêòèâíîñòü â ãèäðèðîâàíèè ãåêñåíà-1 è öèêëîãåêñåíà ïðîÿâëÿþò êàòàëèçàòîðû, ñîäåðæàùèå àññîöèàòû íàíîðàçìåðíûõ ÷àñòèö ïàëëàäèÿ. Ïîíèæåííîé àêòèâíîñòüþ îòëè÷àþòñÿ êàòàëèçàòîðû, äëÿ êîòîðûõ õàðàêòåðíà ëîêàëèçàöèÿ ïàëëàäèÿ âíóòðè óçêèõ ìèêðîïîð óãëåðîäíîé ïîäëîæêè. Àêòèâíîñòü òàêèõ êàòàëèçàòîðîâ â ðåàêöèè ãèäðèðîâàíèÿ ãåêñåíà-1 ïðåâûøàåò îò íåñêîëüêèõ äî äåñÿòêîâ ðàç èõ àêòèâíîñòü â ãèäðèðîâàíèè öèêëîãåêñåíà. Íàáëþäàåìûå ýôôåêòû îáñóæäåíû ñ ïîçèöèé íàëè÷èÿ ñèëüíîãî âçàèìîäåéñòâèÿ ñ óãëåðîäíîé ïîäëîæêîé ëîêàëèçîâàííîãî â ìèêðîïîðàõ ìåòàëëà è çàòðóäíåííîé äèôôóçèè ìîëåêóë ðåàãåíòîâ è ïðîäóêòîâ â ìèêðîïîðàõ íîñèòåëÿ. 39
ÔÎÐÌÈÐÎÂÀÍÈÅ ÀÊÒÈÂÍÎÃÎ ÊÎÌÏÎÍÅÍÒÀ Â ÍÀÍÅÑÅÍÍÛÕ ÖÈÐÊÎÍÈÉÑÓËÜÔÀÒÍÛÕ ÊÀÒÀËÈÇÀÒÎÐÀÕ ÀËÊÈËÈÐÎÂÀÍÈß ÈÇÎÁÓÒÀÍÀ ÁÓÒÅÍÀÌÈ Ëàâðåíîâ À.Â., Ôèíåâè÷ Â.Ï., Äóïëÿêèí Â.Ê., Çàéêîâñêèé Â.È. 1 , Ïàóêøòèñ Å.À. 1 , Áàëüæèíèìàåâ Á.Ñ. 1 Èíñòèòóò ïðîáëåì ïåðåðàáîòêè óãëåâîäîðîäîâ ÑÎ ÐÀÍ, Îìñê 1 Èíñòèòóò êàòàëèçà èì. Ã.Ê. Áîðåñêîâà ÑÎ ÐÀÍ, Íîâîñèáèðñê E-mail: lavr@incat.okno.ru Ïðåäñòàâëåíû ðåçóëüòàòû îïòèìèçàöèè õèìè÷åñêîãî ñîñòàâà è èçó÷åíèÿ ôèçèêî-õèìè÷åñêèõ ñâîéñòâ íàíåñåííûõ öèðêîíèéñóëüôàòíûõ êàòàëèçàòîðîâ, àêòèâíûõ è ñåëåêòèâíûõ â æèäêîôàçíîì àëêèëèðîâàíèè èçîáóòàíà áóòåíàìè. Ïîêàçàíî, ÷òî äîñòèæåíèå âûñîêîé êàòàëèòè÷åñêîé àêòèâíîñòè ñóëüôàòèðîâàííîãî äèîêñèäà öèðêîíèÿ (SZ), äèñïåðãèðîâàííîãî íà ïîâåðõíîñòè ñèëèêàãåëÿ, ñâÿçàíî ñ ôîðìèðîâàíèåì äåôåêòíîãî êðèñòàëëè÷åñêîãî SZ c ðàçìåðîì ÷àñòèö ïîðÿäêà 1-3 íì. Ïðîãðåññ èíäóñòðèàëüíîãî àëêèëèðîâàíèÿ èçîáóòàíà áóòåíàìè â îñíîâíîì ñâÿçûâàåòñÿ ñ ïåðåõîäîì îò èñïîëüçîâàíèÿ æèäêèõ êèñëîò ê ïðèìåíåíèþ òâåðäûõ êàòàëèçàòîðîâ. Ñðåäè ïîñëåäíèõ îñîáûé èíòåðåñ âûçûâàþò ñèñòåìû íà îñíîâå ñóëüôàòèðîâàííîãî äèîêñèäà öèðêîíèÿ (SZ), ïîçâîëÿþùèå îñóùåñòâëÿòü ðåàêöèè èçîìåðèçàöèè è àëêèëèðîâàíèÿ óãëåâîäîðîäîâ â “ìÿãêèõ” òåìïåðàòóðíûõ óñëîâèÿõ. Ïðè ýòîì äî ñèõ ïîð ìàëî èçó÷åííîé îñîáåííîñòüþ êîíñòðóèðîâàíèÿ öèðêîíèéñóëüôàòíûõ êàòàëèçàòîðîâ îñòàåòñÿ ôîðìèðîâàíèå äèñïåðñíûõ ñîñòîÿíèé SZ, äîñòèãàåìîå â ðåçóëüòàòå íàíåñåíèÿ àêòèâíîãî êîìïîíåíòà íà ïîâåðõíîñòü ïîðèñòûõ ìàòðèö. Òàêèå ñîñòîÿíèÿ ìîãóò îïðåäåëÿòü áîëåå âûñîêèå ïîêàçàòåëè àêòèâíîñòè è ñåëåêòèâíîñòè íàíåñåííûõ öèðêîíèéñóëüôàòíûõ ñèñòåì ïî ñðàâíåíèþ ñ ìàññèâíûì SZ. Â íàñòîÿùåé ðàáîòå ïðåäñòàâëåíû ðåçóëüòàòû îïòèìèçàöèè õèìè÷åñêîãî ñîñòàâà è èçó÷åíèÿ ôèçèêî-õèìè÷åñêèõ ñâîéñòâ íàíåñåííûõ SZ-ñèñòåì ïðèìåíèòåëüíî ê ïðîöåññó æèäêîôàçíîãî àëêèëèðîâàíèÿ èçîáóòàíà áóòåíàìè. Â êà÷åñòâå íîñèòåëåé äëÿ SZ èñïîëüçîâàëèñü ñèëèêàãåëü è γ?-îêñèä àëþìèíèÿ. Äëÿ ñèíòåçà êàòàëèçàòîðîâ ïðèìåíÿëàñü êàê ìíîãîêðàòíàÿ, òàê è îäíîêðàòíàÿ ïðîïèòêà íîñèòåëåé ðàñòâîðîì íèòðàòà öèðêîíèëà ðàçëè÷íîé êîíöåíòðàöèè ñ ïîñëåäóþùåé îáðàáîòêîé â àììèà÷íîé ñðåäå ñóëüôàòîì àììîíèÿ è ïðîêàëèâàíèåì. 40
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 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 58 and 59: ÏÎËÓ×ÅÍÈÅ ÆÈÄÊÈÕ Ó
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
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âòîðîé ïî èíòåíñèâ
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êîëåáàíèÿ â ìîñòèê
Page 110 and 111:
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
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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
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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 162 and 163:
ÃÈÄÐÎÊÎÍÂÅÐÑÈß Í-Ã
Page 164 and 165:
ðàñòåò ñ ïîâûøåíèå
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Èíäèâèäóàëüíàÿ àäñ
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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
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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
Page 212 and 213:
ÈÑÑËÅÄÎÂÀÍÈÅ ÂËÈßÍ
Page 214 and 215:
ÄÈÌÅÐÈÇÀÖÈß ÝÒÈËÅÍ
Page 216 and 217:
ÈÇÓ×ÅÍÈÅ ÏÐÎÖÅÑÑÎÂ
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ÐÀÑÏÐÅÄÅËÅÍÈÅ ÂÍÓÒ
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ÃÎÌÎ - È ÑÎÏÎËÈÌÅÐÈ
Page 222 and 223:
ÏÎËÈÌÅÐÈÇÀÖÈß ÝÒÈË
Page 224 and 225:
Ñ ïðèìåíåíèåì ìåòî
Page 226 and 227:
àìîðôíûìè è êðèñòà
Page 228 and 229:
ÑÏÈÑÎÊ ÀÄÐÅÑÎÂ Ó×À
Page 230 and 231:
ÃÐÈÃÎÐÜÅÂÀ Íåëëè Ã
Page 232 and 233:
ÊÀÐÛÌÎÂÀ Ðàøèäà Õà
Page 234 and 235:
ÌÓÍØÈÅÂÀ Ìèíà Êåðè
Page 236 and 237:
ÓÑÌÀÍÎÂÀ Ìàíçóðà Ì
Page 238 and 239:
ÑÎÄÅÐÆÀÍÈÅ ÊËÞ×ÅÂÛ
Page 240 and 241:
Ñåêöèÿ II Êàòàëèç â
Page 242 and 243:
CÄ-I-3 CÄ-I-4 CÄ-I-5 CÄ-I-6 CÄ
Page 244 and 245:
CÄ-II-10 Çàêèðîâà À.Ã.,
Page 246 and 247:
CÄ-III-4 Ìèêåíàñ T.Á., Å
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ÐÐ¾Ð»ÐµÐºÑÐ»ÑÑÐ½ÑÐ¹ Ð´Ð¸Ð·Ð°Ð¹Ð½ ÐºÐ°ÑÐ°Ð»Ð¸Ð·Ð°ÑÐ¾ÑÐ¾Ð² Ð¸ ÐºÐ°ÑÐ°Ð»Ð¸Ð· Ð² Ð¿ÑÐ¾ÑÐµÑÑÐ°Ñ ...

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ÐÐ¾Ð»ÐµÐºÑÐ»ÑÑÐ½ÑÐ¹ Ð´Ð¸Ð·Ð°Ð¹Ð½ ÐºÐ°ÑÐ°Ð»Ð¸Ð·Ð°ÑÐ¾ÑÐ¾Ð² Ð¸ ÐºÐ°ÑÐ°Ð»Ð¸Ð· Ð² Ð¿ÑÐ¾ÑÐµÑÑÐ°Ñ...