Recent advances in coal to chemicals technology developed by SINOPEC

Transcript

1 2013 Chinese Journal of Catalysis Vol. 34 No. 1 DOI: /SP.J : *,,, : : S-MTO ; ;. : ; ; ; ; ; : : : *. : (021) ; : (021) ; : 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 , 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 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 Accepted 3 December Published 20 January *Corresponding author Tel: ; Fax: ; chenql.sshy@sinopec.com This work was supported by the National Basic Research Program of China (973 Program, 2009CB523504). 1.., , 14 ; 1145, 3.,, , 56.5%.,,,.,. PVC., IGCC ( ).,

2 218 Chin. J. Catal., 2013, 34: ,,,. 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 Si NMR., A B = 91, Si(4Al). Si P. A = 95, , Si(3Al), Si(2Al) Si(4Si)..

3 : 219, MTO., , 3.6,, B,,.,,, [5]. ( 3),,.,,. Molecules/(Time*Cell) Sample B Sample A SAPO Si MAS NMR Fig Si MAS NMR spectra of SAPO-34. A: three silicon island; B: no silicon island 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 , S-MTO 60 /,, 7 h. S-MTO, S-MTO C4 C5,., 85%~86%, (79%~80%). S-MTO 254, 77, S-MTP S-MTP. 2001, Lurgi 15 kg/h MTP ; , 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),

4 220 Chin. J. Catal., 2013, 34: (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 h,.,,, MTP / MTP, , CO H 2,,. (dv/dd)/(cm 3 /(g nm)) S3 S2 S 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 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.

5 : 221,,,,,.,,, 20 /, ,, (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 (%) SAPO-11 ZSM-5 (SAR = 136) SAPO-5 MCM-22 ZSM-5 (SAR = 48) 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 o C. SAR: molar ratio of SiO 2 to Al 2 O 3. HZSM-5,,, ; La 2 O 3 -MgO, 93%.,, /. 20 / MTX, 2012, SNG,,.,., NCJ-1 NCJ h, ; -, 1.5~2.2, CO CO 2,,. SNG,,., 100 Nm 3 /h SNG, 100 Nm 3 /h

6 222 Chin. J. Catal., 2013, 34: ,. 13 Nm 3 /a SNG, SNG, 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 (%) BTX selectivity Aromatic yield BTX yield 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 (%) Aromatics yield BTX selectivity 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 -,,,

7 : 223 SiO 2. Fe Mn K Fe,,, CO. - Fe,, 70 μm, SEM 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 (%) Conversion of CO Selectivity for C 2 = C 4 = Selectivity for C TOS (h) Fig Stability of Fe-based catalyst for GTO. 4.3.,,, ;,,.,.,,,.,.,,,,, o C 2.5 MPa 0.3 h 1., 1000 h 90%, 95%. Conversion or selectivity (%) 100 Fig Conversion of acetic acid Selectivity for ethanol 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

8 224 Chin. J. Catal., 2013, 34: ; MTA, GTO.,,., S-MTO,,, ; S-MTP, ; MTX.,. MTO, MTP, MTA. 1,,,. (Liu H X, Xie Z K, Zhang Ch F, Chen Q L. Chin J Catal), 2004, 25:702 2,,,. (Liu H X, Xie Z K, Zhang Ch F, Chen Q L. Chin J Catal), 2004, 25: 707 3,,,. (Liu H X, Xie Z K, Zhang Ch F, Chen Q L. Chin J Catal), 2003, 24: 279 4,,,,. (Liu H X, Xie Z K, Zhang Ch F, Chen Q L, Zhang Y X. Chin J Catal), 2003, 24: 849 5,,,, (Guan H B, Xie Z K, Liu H X, Zhang H M, Fang J D). CN A ,,,,, (Liu H X, Xie Z K, Lu X, Qian K, Zhang Y X, Zhao Y). CN ,,, (Ren L P, Xu J J, He W R, Teng J W). CN A ,,, (Ren L P, He W R, Xu J J, Teng J W). CN A Mei Ch S, Wen P Y, Liu Zh Ch, Liu H X, Wang Y D, Yang W M, Xie Z K, Hua W M, Gao Z. J Catal, 2008, 258: ,. (Teng J W, Yang W M. Progr Chem), 2008, 27(suppl): Zhu Zh R, Chen Q L, Xie Z K, Yang W M, Li C. Microporous Mesoporous Mater, 2006, 88: 16 12,,, (Cao J S, Zhang J M, Xu L, Liu Zh M. Techno-Economics Petrochem), 2010, 26(1): 8 13,,,,,. (Zou W, Yang D Q, Zhu Zh R, Kong D J, Chen Q L, Gao Z. Chin J Catal), 2005, 26: Stöcker M. Microporous Mesoporous Mater, 1999, 29: 3 15,,,,. (Li J F, Tao Y W, Zhou X F, Chen Q L, Yuan W K. Chem Reac Eng Technol), 2010, 26: ,. (Pang Y C, Tao Y W. Petrochem Technol), 2012, 41(suppl): ,,,,,. (Wang H, Wang D J, Huang Q Q, Guo Y D, Zhang Q, Liu Zh N. Petrochem Technol), 2012, 41(suppl): 320 Graphical Abstract Chin. J. Catal. Recent advances in coal to chemicals technology developed by SINOPEC Shanghai Research Institute of Petrochemical Technology, SINOPEC Coal Gasification Syngas Natural gas MTG MEG MTA MTO/MTP Olefins Methanol Acetic acid Ethanol