2013 Chinese Journal of Catalysis Vol. 34 No. 1 DOI: 10.3724/SP.J.1088.2013.21056 : 217 224 *,,, 201208 : : S-MTO ; ;. : ; ; ; ; ; : 2012-10-31. : 2012-12-03. : 2013-01-20. *. : (021)68463382; : (021)68462283; : chenql.sshy@sinopec.com : (973, 2009CB523504). Recent advances in coal to chemicals technology developed by SINOPEC CHEN Qingling *, YANG Weimin, TENG Jiawei Shanghai Research Institute of Petrochemical Technology, SINOPEC, Shanghai 201208, China Abstract: Coal to chemicals technology has made a breakthrough in recent years in China, mainly driven by high crude oil price and strong market demand for chemicals. The latest advances in coal to chemicals technology developed by SINOPEC were reviewed. SINOPEC methanol to olefins (S-MTO) technology has been commercialized successfully in 2011. Industrial demo tests of SINOPEC methanol to propylene (S-MTP), syngas to ethylene glycol, methanol to xylene (MTX) and SNG processes are being carried out. A great progress has been made in the research area of methanol to aromatics (MTA), syngas to olefins (GTO) and acetic acid hydrogenation technology etc. in laboratory scale. Key words: coal to chemical; methanol; olefin; aromatic; ethylene glycol; acetic acid hydrogenation Received 31 October 2012. Accepted 3 December 2012. Published 20 January 2013. *Corresponding author Tel: +86-21-68463382; Fax: +86-21-68462283; E-mail: chenql.sshy@sinopec.com This work was supported by the National Basic Research Program of China (973 Program, 2009CB523504). 1.., 2011 27.76 3.03, 14 ; 1145, 3.,,. 2011 2.54, 56.5%.,,,.,. PVC., IGCC ( ).,
218 Chin. J. Catal., 2013, 34: 217 224,,,. 1.,. 1 Fig. 1. Scheme of coal to chemicals. : ( ) (S-MTO); ( ), (S-MTP) (MTX); (SNG); ( ), (MTA)., (GTL) (GTE). 2. S-MTO MTO,. 2006, 1.67 / DMTO ;, 2010, 180 / DMTO,, MTO., SAPO-34 -., SAPO-34. SAPO-34 [1~4]. 2 SAPO-34 29 Si NMR., A B = 91, Si(4Al). Si P. A = 95, 100 110, Si(3Al), Si(2Al) Si(4Si)..
www.chxb.cn : 219, MTO., 2007 10, 3.6,, B,,.,,, [5]. ( 3),,.,,. Molecules/(Time*Cell) 0.004 0.002 Sample B Sample A -60-70 -80-90 -100-110 -120-130 2 SAPO-34 29 Si MAS NMR Fig. 2. 29 Si MAS NMR spectra of SAPO-34. A: three silicon island; B: no silicon island. 0.000 0 10 20 30 40 50 60 70 80 Width (a.u.) 3 Fig. 3. Number of reactant diffusion out of zeolite as a function of size of cubic model..,, /, SAPO-34, MTO, [6]., MTO MTO,, / S-MTO., S-MTO, 100%, 80%, MTO. 2011 10, S-MTO 60 /,, 7 h. S-MTO, S-MTO C4 C5,., 85%~86%, (79%~80%). S-MTO 254, 77,. 3. 3.1. S-MTP S-MTP. 2001, Lurgi 15 kg/h MTP ; 2010 8, Lurgi 47 MTP ; 2011, Lurgi 47 MTP., ZSM-5. S-MTP ZSM-5 [7,8], MTP 2. (1).,,, ;,,., ZSM-5, ZSM-5. ( Ca, Mg, Sr, Ba),
220 Chin. J. Catal., 2013, 34: 217 224. (2).,.,, MTP., ZSM-5,,,. 4 ZSM-5., ZSM-5 S1 ; S2, ; S3, (SEM) ( 5). S3 MTP, P/E( ) 10/1 [9]. S-MTP 2008,, 99%, 45.6%;, 70%, [10]., S-MTP,, S-MTP SMAP-100 2000h,.,,, MTP. 5000 / MTP, 2012. 3.2., CO H 2,,. (dv/dd)/(cm 3 /(g nm)) 0.06 0.04 0.02 S3 S2 S1 0.00 10 20 30 40 50 60 70 80 Pore diameter (nm) 4 ZSM-5 Fig. 4. Pore size distributions of unmodified and mesopore-modified ZSM-5 samples. S1: untreated HZSM-5; S2: soft template synthesized HZSM-5; S3: alkaline treated HZSM-5., 20 /,..,, CO ;, ;,., 1000 /., CO., CO, 0~0.5 MPa 120~160 o C 1000~3000 h 1 600 g/(l h), 3. ; 200~240 o C, 2.8~3.5 MPa, 0.3~0.5 h 1, 80~120, 98%, 90%, 1. 5 S1, S2 S3 SEM Fig. 5. SEM images of S1, S2, and S3 samples.
www.chxb.cn : 221,,,,,.,,, 20 /, 2013. 200,,. 3.3. (MTX) [11].,,,. [12]. 40, MTX.,. MOR, MCM-22, SAPO-34, SAPO-11, SAPO-5 ZSM-5, ( 6) [11]., ZSM-5, SAPO-11 MCM-22 10,. La 2 O 3, MgO La 2 O 3 -MgO HZSM-5, [13]., HZSM-5,,. La 2 O 3 HZSM-5,,, ; MgO, MgO Toluene conversion for alkylation (%) 6 38 36 34 32 30 28 26 24 22 SAPO-11 ZSM-5 (SAR = 136) SAPO-5 MCM-22 ZSM-5 (SAR = 48) 20 0.2 0.3 0.4 0.5 0.6 0.7 0.8 Amount of mid-strong acid (mmol/g) Fig. 6. The reactivity for the toluene alkylation and the amount of medium acid of zeolites calculated by ammonia desorbed in 300 450 o C. SAR: molar ratio of SiO 2 to Al 2 O 3. HZSM-5,,, ; La 2 O 3 -MgO, 93%.,,. 2011 20 /. 20 / MTX, 2012,. 3.4. SNG,,.,., NCJ-1 NCJ-2 2000 h, ; -, 1.5~2.2, CO CO 2,,. SNG,,., 100 Nm 3 /h SNG, 100 Nm 3 /h
222 Chin. J. Catal., 2013, 34: 217 224,. 13 Nm 3 /a SNG, SNG,. 4. 4.1. MTA, (BTX).,, 85%.,,,,,.. 3 [14] : (1) ; (2) (CH 2 ) n ; (3)(CH 2 ) n. MTA, 3 : (1) ; (2) ; (3), MTA,,, ;,,. MTA, BTX, -., BTX, -. 7, MTA, ZSM-5,. ZSM-5,, 8., 23, BTX Selectivity or yield (%) 7 80 70 60 50 40 30 BTX selectivity Aromatic yield BTX yield 20 0 50 100 150 200 250 300 SiO 2/Al 2O 3 ZSM-5 Fig. 7. Aromatization performance of ZSM-5 catalysts with different SiO 2 /Al 2 O 3 ratios. Selectivity or yield (%) 100 90 80 70 60 50 40 30 Aromatics yield BTX selectivity 0 5 10 15 20 25 Recycle regeneration times 8 ZSM-5 Fig. 8. Regeneration performance of ZSM-5 catalyst for MTA. MTA methanol to aromatics.,., 400~450 o C, 0.5~2.0 h 1,, 50%, BTX 80%. MTA. MTA 15,. 4.2.,.,. Fe [15]., Al 2 O 3 Fe Fe -,,,
www.chxb.cn : 223 SiO 2. Fe Mn K Fe,,, CO. - Fe,, 70 μm, SEM 9. 3.8 cm. 350 o C, 1.0 MPa, H 2 /CO = 2 ( ), 6000 h 1, 2000 h, CO 90%, C 2+ ( C 2 ~C 4 ), 10 [16]. 9 Fe SEM Fig. 9. SEM image of Fe-based catalyst for GTO. GTO syngas to olefins. Conversion or selectivity (%) 100 90 80 70 60 50 40 30 20 10 0 Conversion of CO Selectivity for C 2 = C 4 = Selectivity for C 2+ 0 200 400 600 800 1000 1200 1400 1600 1800 2000 TOS (h) Fig. 10. 10 Stability of Fe-based catalyst for GTO. 4.3.,,, 2015 1000 ;,,.,.,,,.,.,,,,,. 11 245 o C 2.5 MPa 0.3 h 1., 1000 h 90%, 95%. Conversion or selectivity (%) 100 Fig. 11. 90 80 70 Conversion of acetic acid Selectivity for ethanol 60 0 120 240 360 480 600 720 840 960 1080 1200 Reaction time (h) 11 Cu Stability of Cu-based catalyst for acetic acid hydrogenation. 12 TEM.,, [17]. (a) (b) 50 nm 20 nm 12 Cu TEM Fig. 12. TEM images of Cu-based catalyst before (a) and after (b) reaction. 5.,,. S-MTO ; S-MTP MTX SNG
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