synthesis from laboratory to engineering scale up

Transcription

1 Fscher-Tropsch synthess from laboratory to engneerng scale up Hao Xu Insttute of Coal Chemstry, Chnese Academy of Scences State key laboratory of Coal chemstry Synfuels Chna 1

2 Introducton Government need Internatonal technology stuatons Sasol: hgh temperature FTS Shell: SMDS Low temperature FTS Technology development n Chna Synfuels Chna : HFPT ICC-IA LFPT ICC-IIA 2

3 CTL process: Coal gasfcaton Fxed-bed or movng bed gasfer Flud-bed gasfer Entraned flow gasfer shft reacton Acdc gas removal Slurry FTS Product upgradng 3

4 Coal gasfcaton Lurg Texaco Shell GSP Burner Fuel Gas to plot burner Oxygen Pressur. water outlet Coolng screen Pressur. water nlet GSP Quench water Coolng jacket Gas outlet Water overflow Granulated slag Cheap n constructon Methane rch syngas Coal adaptablty Tar recovery Water treatment Expensve n constructon Hgh qualty Syngas Coal adaptablty * Short tme on stream Hgh O 2 consumpton Expensve n constructon Hgh qualty Syngas Coal adaptablty** Hot stream quenchng Large boler sze Cheap n constructon Hgh qualty Syngas Coal adaptablty*** Quenchng type and heat recovery BDI SVP FUTURE ENERGY CHOREN 4

5 Laboratory research catalyst development and research ICC-IA catalyst Converson and selectvty,% C 5 + +C 2-4 = CO Converson CH Tme on stream, h Changes of conversons and selectvty wth tme-on-stream n slurry phase reactor ( , MPa, 2.0 NL/g-cat./h, H2/CO=0.67) 5

6 Laboratory research ICC-IIA catalyst Converson/Selectvty (%) CO con. H 2 con. CO+H 2 con. CH 4 sel. C + 5 sel. C 2 -C 4 = sel Tme on stream (h) Changes of conversons and selectvty wth tme-on-stream n slurry phase reactor ( , MPa, 2.0 NL/g-cat./h, H2/CO=0.67) 6

7 Catalyst characterstzaton XRD,SEM,MES (b) Converson (%) CO H 2 Catalyst composton (%) ron carbdes (ε'-fe 2.2 C + χ-fe 5 C 2 ) (a) spm phases (Fe 3+ +Fe 2+ ) Fe 3 O 4 ε'-fe 2.2 C χ-fe 5 C Tme on stream (h) Correlatve studes of phase transfer and actvtes of an ICC-IA model catalyst durng FTS reacton. ( , MPa, 2.0 NL/g-cat./h, H2/CO=0.67) 7

8 Quantum chemstry calculaton Schematc unt cell of Fe5C2. (Fe: lght gray; C: deep gray.) 1 CO adsorpton on the surface of Fe5C

9 Schematc top and front vews of Fe5C2(001) (a); top and sde vews of (110) (b); and top and front vews of (100) (c) n a p(1 1) unt cell. 9

10 Adsorpton energetcs (left) and C-O bond actvaton (rght) of CO adsorpton on Fe5C2 surfaces 10

11 Knetc and slurry reactor model research Develop user databank for FTS Enthalpy of vaporzaton kj/mol T = 250 o C T = 150 o C T = 50 o C Carbon number Enthalpy of vaporzaton at dfferent temperature for n-paraffns, C7 ~ C30 data are from Aspen Plus, C31 - C60 data are fromths work 11

12 FTS Knetc research : Knetc research for Fe-Cu Cu-K K catalyst Ma Wen-pn pn s s model Wang Y-nng nng s Model Zhang rong-le le s model 12

13 FTS Knetc research : Knetc research for Fe-Cu Cu-K K catalyst J Yuan-yuan yuan s model Yang Jun s Model Teng Bo-tao tao s model 13

14 Develop slurry bubble reactor Gas CSTR Lqud CSTR ε g d C dt g, = u g 0 C g 0, u h g C g, C g, ( k L, a)( CL, m ) ε L d C dt L, u = L0 C L0, u C h L L, Cg, Wcat + ( kl, a)( CL, ) α, jr m hs j j Gas CSTR Gas CSTR Lqud CSTR Lqud CSTR Molar selectvty (%) for paraffns exp. calc. T = 260 o C H2/CO = Carbon Number 14

15 Plot plant research Constructon began n 2001 Frst run n 2002, 25 days Modfcatons n wnter of 2002 Three runs n 2003, Two runs n 2004, 1500 hours Catalyst, knetc model and slurry bubble reactor were tested n the plot plant. 15

16 Develop product upgradng technology Cooperate wth ndustral partner to Develop hydrogenaton and hydrocrackng technology Developng hydrogenaton and hydrocrackng technology n laboratory 16

17 Indexes CTL desel propertes (Synfuels Chna ) Hydrogenated Fracton Refnery Co-MoS2 catalyst Hydrocracked Co-MoS2 catalyst Hydrogenated Fracton S-free catalyst Densty kg/l Vscosty /mm2/s, 20 o C Intal bolng pont / o C Fnal bolng pont / o C Dst. Range / o C 5% % % % % % % dred Flash pont / o C >70 Cetane number Total aromatcs % Olefn /% Sulfur / ppm < 4 <5 <0.5 CFPP / o C

18 Process ntegraton research Coal gasfcaton Water gas shft reacton Acdc gas removal Slurry FTS Product upgradng oxygen and stream Acd gas,co2 so on Intermedates refnery Naphtha desel Coal Gasfcaton water gas Shft reacton acdc gas removal slurry FTS product separaton H2 CO2 Tal gas Waste water dstllaton Oxygenates Water 18

19 Comparson between smulaton and ndustral results Coal slurry coal gasfcaton GSP coal gasfcaton Industral value smulaton Industral value smula ton Gasfcaton temperature Gasfcaton pressure Mpa Coal slurry concentraton(wt%) 63.96% Coal converson syngas %(dry base) H CO CO N NH H2S others

20 SHELL gasfcaton Illnos 6# coal SHELL gasfcaton Texas Lgnte lterature calculaton lterature calculaton Gasfcaton temperature Gasfcaton pressure Mpa Coal converson syngas %(dry base) CO H CO CH Ar N H2S COS

21 Poly-generaton generaton the future of CTL n Chna Poly-generaton based on coal gasfcaton s a promsng sustanable strategy Poly-generaton of CTL and co-produce electrcty by combned cycle s an effcent way. The optmzaton of the poly-generaton system should be carefully evaluated. 21

22 Summary CTL n chna can be a feasble way from vewpont of technology,resource,economcs, and envronment CTL technology developed n Synfuels Chna has been tested n plot plant, can be scaled up to demonstraton plant scale. The demonstraton plant s been desgn. Poly-generaton of ol and electrcty,and chemcals s the future of Large CTL 22

23 Thank you 23