Kinetic Modeling of Quinoline Hydrodenitrogenation over a

Transcription

1 Kinetic Modelin of Quinoline Hydrodenitroenation over a NiMo(P)/Al 2 O 3 catalyst in a batch reactor Minh-Tuan Nuyen 1,2, Melaz Tayakout-Fayolle 1, Gerhard D Pirnruber 2, Fabien Chainet 2, Christophe Geantet 1 1 Institut de recherches sur la catalyse et l environnement de Lyon, IRCELYON, UMR CNRS, 2 avenue Albert Einstein, F illeurbanne, France 2 IFP-Eneries nouvelles, Rond-point de l échaneur de Solaize, BP 3, Solaize, France Correspondin author: melaztayakout@ircelyonuniv-lyon1fr S1

2 Supportin Information Liquid-apor equilibrium The comparison between the experimental composition of uid samples taken at operatin conditions (350 C, 7 MPa) and after coolin down (25 C, 3 MPa) for the same reaction time revealed a considerable evaporation of compounds (especially the liht compounds such as PCH, PCHE, PB) (Table S1) By accountin for LE, the mass balance at hih conversions improves sinificantly Table S1: Concentration of components in uid sample at reaction condition ( hot ) and after coolin down reactor to ambient temperature ( cold ), at different reaction times At 30 min At 2h At 3h30 At 5h Concentration (mmol/l) Hot Cold Hot Cold Hot Cold Hot Cold HDN products HYD products +Q PCHA + OPA SUM Balance error (%) The simulation by Prosim 33 has iven equilibrium constants of all components at reaction conditions These values remain constants durin reaction The correction of the S2

3 concentration in uid phase at operatin conditions by the suitable ratio has iven ood mass balance durin reaction, and to evaluate the conversion and the yield of every component Table S2: Equilibrium constants of all components at different temperatures, 7 MPa (Simulation by ProSim 33) PCH PB Quinoline H 2 H 2 S NH 3 m-xylene squalane 340 C C C S3

4 Table S3: Textural characterizations and carbon content of used and fresh NiMo(P)/Al 2 O 3 catalyst Reaction conditions BET Total pore Averae Carbon Temperature Initial Reaction surface volume pore content concentration time (h) area (ml/) diameter (wt %) of quinoline (m 2 /) (nm) 340 C 1 wt % 8h x C 15 wt % 10h x C 2 wt % 10h x C 1 wt % 6h x C 15 wt % 8h x C 2 wt % 8h x C 1 wt % 4h x C 15 wt % 6h x C 2 wt % 8h x Fresh NiMo(P)/Al 2 O 3 catalyst x Used NiMo(P)/Al 2 O 3 after white test x (350 C, 6h, without quinoline) S4

5 Table S4: Standard deviations of 4 experiments at 350 C, 1 wt% of quinoline and after 15 hours of reaction time Compound Concentration of component in uid phase (mmol/l) Averae Standard deviation Test 1 Test 2 Test 3 Test 4 (mmol/l) (mmol/l) PCH PB PCHE PCHA DHQ THQ Quinoline OPA THQ S5

6 Table S5: Comparison between experimental data and estimated data (concentration of components in uid phase) of the catalytic test at 360 C and 1 wt% of quinoline Experimental results (table S5a) Concentration (mmol/l) 0h 025h 05h 075h 1h 15h 2h 3h 4h Q THQ THQ DHQ OPA PCHA PB PCHE PCH Estimated data (table S5b) Concentration (mmol/l) 0h 025h 05h 075h 1h 15h 2h 3h 4h Q THQ THQ DHQ OPA PCHA PB PCHE PCH Table S6: alues of k L a at different temperatures estimated from the kinetic modelin 340 o C 350 o C 360 o C k L a (s -1 ) Accuracy, % S6

7 Fiure S1: Comparison of the product yield of DHQ, OPA (fiure S1a) and PCH, PB (fiure S1b) as function of HYD conversion, of 3 catalytic tests: 1; 15 and 2 wt% of quinoline Product yield, % mol (a) DHQ Test 1 wt% quinoline DHQ Test 15 wt% quinoline DHQ Test 2 wt% quinoline OPA Test 1 wt% quinoline OPA Test 15 wt% quinoline OPA Test 2 wt% quinoline HYD Conversion, % 100 (b) Product Yield, ol PCH Test 1 wt% quinoline PCH Test 15 wt% quinoline PCH Test 2 wt% quinoline PB Test 1 wt% quinoline PB Test 15 wt% quinoline PB Test 2 wt% quinoline HYD Conversion, % S7

8 Fiure S2: The estimated concentration of components in as phase of the catalytic test at 350 C, 7 MPa and 1 wt% of quinoline Product concentration, mmol/l (a) Q 14THQ 58THQ DHQ OPA PCHA Reaction time (h) Product concentration, mmol/l (b) PB PCHE PCH NH Reaction time (h) S8

9 20 equations correspondin to the mass balance of all components in the kinetic model: In the uid phase: Q, solid ( r + r r ) + k a L Q, Q, (1) 14THQ, 58THQ, solid ( r r r r ) + k a L 14THQ, 14THQ, (2) solid ( r r + r ) + k a L 58THQ, 58THQ, (3) DHQ, OPA, PCHA, solid ( r r + r r ) + k a L DHQ, DHQ, (4) solid ( r r + r r ) + k a L OPA, OPA, (5) solid ( r + r r r r ) + k a L PCHA, PCHA, (6) PB, ( C C ) r (7) solid 11 + kla PB, PB, PCHE, PCH, NH 3, solid ( r r ) + k a L PCHE, PCHE, (8) solid ( r + r ) + k a L PCH, PCH, (9) solid ( r + r + r ) + k a L NH 3, NH 3, (10) In the as phase: Q, kla ( CQ, CQ, ) (11) S9

10 14THQ, 58THQ, DHQ, kla ( C14THQ, C14THQ, ) (12) kla ( C58 THQ, C58 THQ, ) (13) kla ( CDHQ, CDHQ, ) (14) OPA, PCHA, kla ( COPA, COPA, ) (15) k La ( CPCHA, CPCHA, ) (16) PB, r kla ( CPB, CPB, ) (17) PCHE, PCH, NH 3, kla ( CPCHE, CPCHE, ) (18) kla ( CPCH, CPCH, ) (19) kla ( CNH 3, CNH 3, ) (20) Q 14THQ OPA r 1 r 7 CH 3 r 11 CH 3 N r 2 N H NH 2 PB r 3 r 6 r 10 r 9 CH 3 r 4 r 8 CH 3 r 12 PCHE N 58THQ r 5 N H DHQ PCHA NH 2 r 14 CH 3 r 13 PCH r i is the reaction rate of the conversion of component i (mmoll -1 s -1 ) S10

11 solid kikici v, i 2 i a / i ads / n 1 + K jc j j 1 k i is the apparent rate constant of reaction i, calculated with Arrhenius equation K i is the adsorption constant of compound i, calculated with an t Hoff equation r ; k A exp( E RT) ; K B exp( H RT) This material is available free of chare via the Internet at S11