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êîòîðûõ èììîáèëèçîâàíû êëàñòåðû Pd(0)) çàâèñèò îò ñîîòíîøåíèÿ ñêîðîñòåé âîññòàíîâëåíèÿ Pd(II) è äåñòðóêöèè ôîñôîðîðãàíè÷åñêèõ ëèãàíäîâ, êîòîðûå â ñâîþ î÷åðåäü îïðåäåëÿþòñÿ íå òîëüêî ïðèðîäîé âîññòàíîâèòåëÿ, íî è àòìîñôåðîé ïðîöåññà (âîäîðîä èëè àðãîí), ñîîòíîøåíèåì âîññòàíîâèòåëü/ïàëëàäèé. Ïðèâîäÿòñÿ îáùèå ñõåìû ôîðìèðîâàíèÿ è ñâîéñòâà ìèêðîãåòåðîãåííûõ ïàëëàäèåâûõ êàòàëèçàòîðîâ ãèäðèðîâàíèÿ. 29
ÌÎËÅÊÓËßÐÍÛÉ ÄÈÇÀÉÍ È ÑÓÏÐÀÌÎËÅÊÓËßÐÍÎÅ ÑÒÐÎÅÍÈÅ ÊÀÒÀËÈÇÀÒÎÐÎÂ ÊÐÅÊÈÍÃÀ ÍÎÂÎÃÎ ÏÎÊÎËÅÍÈß Äðîçäîâ Â.À., Äîðîíèí Â.Ï., Ñîðîêèíà Ò.Ï., Ãóëÿåâà Ò.È. Èíñòèòóò ïðîáëåì ïåðåðàáîòêè óãëåâîäîðîäîâ ÑÎ ÐÀÍ, Îìñê E-mail: drozdov@incat.okno.ru Óñòàíîâëåíû íåêîòîðûå çàêîíîìåðíîñòè, îòðàæàþùèå âçàèìîñâÿçü ìîëåêóëÿðíîãî (êðèñòàëëîõèìè÷åñêîãî) ñòðîåíèÿ êîìïîíåíòîâ êàòàëèçàòîðà êðåêèíãà ñ åãî ñóïðàìîëåêóëÿðíûì (ïðîñòðàíñòâåííûì) ñòðîåíèåì. Ñôîðìóëèðîâàíû òðåáîâàíèÿ ê ïîðèñòîé ñòðóêòóðå (òåêñòóðå) êàòàëèçàòîðîâ êðåêèíãà äëÿ ïåðåðàáîòêè ðàçëè÷íîãî óãëåâîäîðîäíîãî ñûðüÿ â ðàçíûõ òåõíîëîãè÷åñêèõ ðåæèìàõ. Ðàññìîòðåíû ïðè÷èíû èçìåíåíèÿ ôðàãìåíòîâ ïîðèñòîé ñòðóêòóðû êàòàëèçàòîðîâ ïîä âîçäåéñòâèåì ðåàêöèîííîé ñðåäû è â óñëîâèÿõ ðåãåíåðàöèè. Ñîâðåìåííûé êàòàëèçàòîð êðåêèíãà èìååò ñëîæíîå ñòðîåíèå [1]. Îñíîâíîé àêòèâíûé êîìïîíåíò - ìîäèôèöèðîâàííûé öåîëèò òèïà Y – ðàñïðåäåëåí â ìíîãîêîìïîíåíòíîé ìàòðèöå. Ìàòðèöà, ÿâëÿþùàÿñÿ íàïîëíèòåëåì è ñâÿçóþùèì, â ñâîþ î÷åðåäü, ñîñòîèò èç ôàçû êîìïîçèòîâ îêñèä Al-ìîíòìîðèëëîíèò è ôàçû àëþìîñèëèêàòà. Íàðÿäó ñ ñîçäàíèåì îïòèìàëüíîãî õèìè÷åñêîãî, ôàçîâîãî ñîñòàâà è ïðèðîäû êàòàëèòè÷åñêè àêòèâíîé ïîâåðõíîñòè, ôîðìèðîâàíèå çàäàííîãî ñóïðàìîëåêóëÿðíîãî ñòðîåíèÿ (òåêñòóðû) ÿâëÿåòñÿ îäíîé èç ôóíäàìåíòàëüíûõ çàäà÷ íàó÷íîãî êîíñòðóèðîâàíèÿ êàòàëèçàòîðîâ êðåêèíãà [2]. Ðàçíîîáðàçèå èñõîäíîãî ïåðåðàáàòûâàåìîãî óãëåâîäîðîäíîãî ñûðüÿ, à òàêæå ðàçëè÷íûå òåõíîëîãè÷åñêèå óñëîâèÿ ïðîâåäåíèÿ ïðîöåññà òðåáóþò ñîçäàíèÿ àññîðòèìåíòà ñîâðåìåííûõ êàòàëèçàòîðîâ êðåêèíãà ðàçëè÷íîãî ñîñòàâà è ñòðîåíèÿ. Â äàííîé ðàáîòå óñòàíîâëåíû íåêîòîðûå ôèçèêî-õèìè÷åñêèå çàêîíîìåðíîñòè, îòðàæàþùèå âçàèìîñâÿçü ìîëåêóëÿðíîãî, êðèñòàëëîõèìè÷åñêîãî ñòðîåíèÿ êîìïîíåíòîâ êàòàëèçàòîðîâ ñ ïðîñòðàíñòâåííûì ñòðîåíèåì êàòàëèçàòîðîâ â öåëîì. Ïîêàçàíà ýâîëþöèÿ ìîëåêóëÿðíîãî è òåêñòóðíîãî äèçàéíà ïðîìûøëåííûõ êàòàëèçàòîðîâ, ðàçðàáîòàííûõ ñîâìåñòíî ÈÏÏÓ ÑÎ ÐÀÍ è ÎÀÎ «Ñèáíåôòü-ÎÍÏÇ», (ñåðèÿ «ÊÌÖ» è «Ëþêñ»), 30
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 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 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
Page 106 and 107:
âòîðîé ïî èíòåíñèâ
Page 108 and 109:
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
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 162 and 163:
ÃÈÄÐÎÊÎÍÂÅÐÑÈß Í-Ã
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
Page 212 and 213:
ÈÑÑËÅÄÎÂÀÍÈÅ ÂËÈßÍ
Page 214 and 215:
ÄÈÌÅÐÈÇÀÖÈß ÝÒÈËÅÍ
Page 216 and 217:
ÈÇÓ×ÅÍÈÅ ÏÐÎÖÅÑÑÎÂ
Page 218 and 219:
ÐÀÑÏÐÅÄÅËÅÍÈÅ ÂÍÓÒ
Page 220 and 221:
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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