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o o o F=- ZS00 2000 1800 1600 Wavenumber (cm -I } 1300 Figuye 22. FT-IR spectra of NO adsorbed at 25 °C on 25 ~ % Fe/SiO2 containing 5 ~rt % K that ]aacl been calcined for 16 hrs at 300 °C and subsequently treated in H2 for 16 ]xrs at 300 °C. The uppermost spectrum was obtained following exposure of the sample to 10 tort of NO for 15 ~ followed by e~cuation. The second spectrum was obtained immediately a~ter admission of 10 tort of 02 at 25 °C. ~e remaining spectra were then obtained at 15 rain int~ in the continuing presence of gaseous 02. 76 e- ¢_ r=, s._ v u c- o Z J 2500 2000 1800 1600 Wavenumber (cm "l) m t • 1300 Figure 23. FT-IR spectra of NO a~sorbed at 25 °C on 25 wt % Fe/SiOz that had been calcined fo~ 16 hrs at 300 °C and subsequent])- treated in H2 for 8 hrs at 730 °C. The uppermort spe~ruzn was obtained followin 8 exposure of the sample ~o 10 tort of NO for 15 rain, followed bs evacuadon. The second spectrum was obtained immediatdy after admission of 10 to~ of 0 at 25 °C. The remaining spectra were then obtah~ed at 15 ml~ interrals in the conr2nuing presence of gaseous, 0,. 77 I "I' "'1 ! • , '1 ! I , I I I. t' Ti ~'~" ' "r 't; 1-::-:.t: " I ~ ::: i ]~iI i~t:~]- =~!] -~, t I: I J ! I" ! -t:[ -___~ ____ /J =-_E .z ~-:-: ~- , . : ~ =-t ! 2500 2000 1800 1600 Wavenumber (¢m -1) t, ~-I- I 1300 Figure 24. FT-IR spectra of NO adsorbed at 25 °C on 25 wt % Fe/SiOm thst had bee~ ~ed for 16 hrs at 300 =C and subseque_nt]y treated ~ ]]2 for 16 ]~'s at 730 °C. Tb~e u~ermost spectrum was obtained followhlg exposure of the sample to 10 tor~ of :NO-; for~15 rain, foI]owed by evacuation. The second spectrum was obtained immedialely ~ffFe.~ ~dmissJon of 10 tort of 02 at 25 °C. The r~g spectrs vere then obtained ~t 15 rh~:inter~ls in the continuing presence of gaseous Oz. ?8 ~0 ; - " "'" " 1 " " •' |" " " " " I "" " " " ' I " " ' " I ' '' " ' I' I~'' ', '; ; 46 r- 0 m L O > C O O 40 O O + C~ 3: 8g 80 0 dt . Q q, in Q) 13 :1 o m JD CO m L- CO in In @ U 0 L 13. SA-99-0888 (Ruhrchemle LP 33181) 250 °C 1.48 MPa t (H2/CO) = 0.67 2.0 NI/g-Fe.h | • • , , | a i I a ,~ 100 200 300 400 500 Time on stream (h) i • | 800 700 FiB.re 2r,. Stnbilily plot, (lira+CO) converdon vemls t|me on Jtre~m, for .m 5A-09-0885. °E 4O 0 20.g 1£L0 13.0 I I C:'~ C4 C5-~11 Ci2~- I I = ! 4-3 ~5 15"7 254 ~ 61~ 8.g 7.g 5.0 4,g 3.0 20 • 1,,0 O J: = "m m 49 95 157 284 ~ • 819 1:;2 I,, I C4 C8 I C10 Figure 2~. F_~ecz of r~ae on .~reaan on R~hr~emie LP 33/81 se]ectis-it.v for run SA-99-08S$: 250 =('~ 1.48 MaPa, 2.7~'2/g-cat-t~, CH±/CO) = 0.67. 80 En .is 3: m ~5.0 - 25J3- 2~3- 15J3- ~,~,,~ - 5J3- 0J3 m 235 2S5 I c12+ I 2~ 253 2.0 1.0 Ni/g-cat.h Temperature (° C) 7°F .'~ m t D.0 "~ "~" ¢ 235 2~5 235 250 2.0 1.0 NI/g ~t-h Temperature ~ C) Fig~e 2T. EKect oftemperatuze on Ru.l~'chemie LP 33/81 se]ecti%'hy lot l-u~ $A-99-08SS: 1.48 MPa, (~ /CO) = 0.67. 81 35.~- 1DD - :.:, °=- I I~1 " 1 2 1 2 t. 235 °C 250 °C Space Velochy (N1/g-cat-h) E ~3 ,01 m 7.0- I~] It~ _ _=- I~ li~ ,- - 1 2 1 2 4 235 o C 250 o C Space Velocity (Nl/g-cat-h) CA¢ I I C5-~I FJg~'e 2S. Effect of space ve]ocit3" on ~h~che~ie LP 33/81 selectivity for ru~ SA-99-0888:1.48 MPa, (H~./CO) = 0.6T. Gg7 ID0 r- E E {3 m 3SD- 3aD- 25D- :2OD- ISD- ;r ID0 ~4 I I ~ CA CS C11 ~2÷ 1.48 MPa 2.96 MPa (H2/CO) Feed Ratio 7• ! ° r~- I I c3 cA C~ !9- i ~0 2.0- I_0- I nn 1.48 MPa 2.96 MPa (H:~/CO) Feed Ratio Figure 29. Effect of feed ratio and pressure on Ru~rc.hegfie LP 33/~ 1 selectivity for ru~ 5A-99-0888: 250 °C- 80 70 I:: O ~mm co L- >, O0 r" 0 0 0 0 + 60 40 • O0 • (I O O l(H2/~O) = 1.0 Q o '"I ,I i J i . = . I | IN nm [] FA-63-1308 (100 Fe/5 Cu/4.2 K/8 810 2) 235 eC , 1.48 MPa 2,0 NI/g-Fe.h ~0 , o , . I 0 100 N I • , I • , , l_ 200 800 400 Time on stream (h) (H2/CO) = 0.67 mm dmuu uu un mira, • ! 600 m 000 . Pigtzte ,10. Stability plot, {I!2-1-CO) conversion vers,s U,ne on streanl, for rim FA-fi,1-13ClS. 7QD 6QD 5QD i ° ZZD 1DD O m - t L J I ~7 nn 48 Time m St~rn ~) BO , . ~ 421 ~ l~l~l~+J~:i~i~~ ~DID ~ 48 144 240 ~ ~ ~ R~I Time c~ St~=m ~) Fi~n'e 31. Effect o[ t.~e o:~ stream on 100 Fe/5 Cu/4.2 K/8 SiO2 c~t.~.vst se.]ecti~tv for Tan FA- 63-1308:235 °C, 1.48 MPa, 2 Nl/g-cat.l%. (H2/CO) = 1.0 (48-240, 662 h) and 0.67 (s3;-528 h). 85 . c3 cA C~ !9- i ~0 2.0- I_0- I nn 1.48 MPa 2 .96 MPa (H:~/CO) Feed Ratio Figure 29. Effect of feed ratio and pressure on Ru~rc.hegfie LP 33/~ 1 selectivity for ru~ 5A -99 -0888: 250 °C-. 5A- 09- 0885. °E 4O 0 20.g 1£L0 13.0 I I C:'~ C4 C5-~11 Ci2~- I I = ! 4-3 ~5 15"7 254 ~ 61~ 8.g 7.g 5.0 4,g 3.0 20 • 1,,0 O J: = "m m 49 95 157 284 ~ • 8 19. selectivity for ru~ SA -99 -0888:1.48 MPa, (H~./CO) = 0.6T. Gg7 ID0 r- E E {3 m 3SD- 3aD- 25D- :2OD- ISD- ;r ID0 ~4 I I ~ CA CS C11 ~2÷ 1.48 MPa 2 .96 MPa (H2/CO) Feed Ratio