CIESC Journal ›› 2019, Vol. 70 ›› Issue (S1): 99-109.doi: 10.11949/j.issn.0438-1157.20181224

• Catalysis, kinetics and reactors • Previous Articles     Next Articles

Catalysis effects of K2CO3 for gasification of semi-coke

Fanrui MENG1(),Boyang LI1,Xianchun LI1,2(),Shuang QIU2   

  1. 1. Engineering Research Center of Advanced Coal & Coking Technology and Efficient Utilization of Coal Resources, the Education Department of Liaoning Province, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China
    2. School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, Liaoning, China
  • Received:2018-10-18 Revised:2018-11-23 Online:2019-03-31 Published:2019-04-26
  • Contact: Xianchun LI E-mail:mengfanrui1025@163.com;askd1972@163.com

Abstract:

Steam gasification of potassium-loaded semi-coke has been carried out with a fixed-bed laboratory gasifier at atmospheric pressure. With the K2CO3 loading increased the micropore area decreased. At a loading of 5% (mass), the K2CO3 mainly plays the role of filling pores. Above the loading of 10% (mass), the accumulation of catalyst will lead to more pores on the surface and interior of the particles. Increasing the gasification temperature could increase the carbon conversion rate, but above 750℃ the carbon conversion rate increased indistinctively. The loading values above which the effect was negligible were 10% (mass). High concentration of C(O) on the surface of particles and in open pores has a higher desorption rate and led to the generation rate of CO increase. Under non-catalytic conditions, CO/CO2 decreased as gasification time increasing, while H2/(2CO2+CO) increased first and then decreased. Under catalytic conditions, H2/(2CO2+CO) was stable at 1.5-1.7. The active components, such as K2Ca(CO3)2, K2O, and KO2, appeared in the catalyst semi-coke samples and increased with the catalyst loading increasing. Catalyst deactivation phenomenon was aggravated due to the loading increasing, but it was not completely inactivation under the condition of gasification 1 h at 750℃.

Key words: fixed-bed, catalyst, semi-coke, hydrogen production, gasification

CLC Number: 

  • TQ 536.1

Table 1

Proximate and ultimate analysis of semi-coke coal"

SampleProximate analysis/%Ultimate analysis /%
MadVadAadFCadCdHdNdSd
semi-coke3.6418.665.6372.0779.781.440.850.11

Fig.1

Schematic diagram of experimental set-up"

Fig.2

SEM images of K2CO3/semi-coke particles"

Table 2

Specific surface area and pore volume of K2CO3/semi-coke at different loading and residual coke"

Sample, K2CO3/%Surface area /(m2/g)Micropore area /(m2/g)External surface area /(m2/g)Pore volume/(ml/g)
017.765.7112.050.004
51.5701.570.002
102.510.132.380.002
155.951.554.400.002
0-ash598.13398.44199.700.148
5-ash338.97269.8969.080.035
10-ash189.57163.3926.180.009
15-ash52.6043.109.500.004

Fig.3

Gas yield distribution at different gasification temperature(10%K2CO3/semi-coke,steam flow 0.6 ml/min)"

Fig.4

Gas yield distribution at different catalyst loading(gasification temperature750℃,steam flow 0.6 ml/min)"

Table 3

Changes of CO/CO2 and H2/(2CO2+CO) at different catalyst loading during gasification"

Sample,

K2CO3/%

10 min20 min30 min40 min50 min
CO/CO2H2/(2CO2+CO)CO/CO2H2/(2CO2+CO)CO/CO2H2/(2CO2+CO)CO/CO2H2/(2CO2+CO)CO/CO2H2/(2CO2+CO)
02.131.061.221.861.202.360.662.230.462.05
50.630.901.382.021.001.400.951.571.611.56
104.181.950.950.910.841.651.111.560.581.52
156.021.661.541.580.561.510.711.520.651.63

Fig.5

FTIR spectrum of samples at different catalyst loading (gasification temperature750℃,steam flow 0.6 ml/min)"

Fig.6

XRD patterns of samples at different catalyst loading(gasification temperature750℃,steam flow 0.6 ml/min"

1 汪寿建. 兰炭固定床连续气化制备清洁燃料气的应用与实践[J]. 化肥设计, 2017, 55(5): 5-10.
WangS J. Application and practice of continous preparation of clean fuel gas though coal gasification in semi-coke fixed bed[J]. Chemical Fertilizer Design, 2017, 55(5): 5-10.
2 SharmaA, TakanohashiT, SaitoI, et al. Effect of catalyst addition on gasification reactivity of HyperCoal and coal with steam at 775—700℃[J]. Fuel, 2008, 87(12): 2686-2690.
3 ZhangF, XuD, WangY, et al. Catalytic CO2 gasification of a Powder River Basin coal[J]. Fuel, 2013, 103(130): 161-170.
4 McKeeD W, SpiroC L, KoskyP G, et al. Catalysis of coal char gasification by alkali metal salts [J]. Fuel, 1983, 62(2): 217-220.
5 AkyurtluJ F, AkyurtluA. Catalytic gasification of Pittsburgh coal char by potassium sulphate and ferrous sulphate mixtures[J]. Fuel Processing Technology, 1988, 43(1): 71-86.
6 SongB H, YongW J, YunS B, et al. Steam gasification of a bituminous char catalyzed by a salt mixture of potassium sulfate and nikel nitrate[J]. Korean Chemical Engineering Research, 2003, 41(3): 349-356.
7 MurakamiK, SatoM, TsubouchiN, et al. Steam gasification of Indonesian subbituminous coal with calcium carbonate as a catalyst raw material[J]. Fuel Processing Technology, 2015, 129(129): 91-97.
8 WoodB , SancierK. The mechanism of the catalytic gasification of coal char: a critical review[J]. Catalysis Reviews, 1984, 26(2): 233-279.
9 KapteijnF, MoulijnJ A. Kinetics of the CO2 gasification of activated carbon[J]. Fuel, 1983, 62(2): 221-225.
10 陈彦, 张济宇.福建无烟煤Na2CO3催化气化过程的比表面变化特性[J].化工学报, 2012, 63(8): 2443-2452.
ChenY, ZhangJ Y. Variation of specific surface area in catalytic gasification process of Fujian anthracite with Na2CO3 catalyst[J]. CIESC Journal, 2012, 63(8): 2443-2452.
11 KarimiA, GrayM R. Effectiveness and mobility of catalysts for gasification of bitumen coke[J]. Fuel, 2011, 90(1): 120-125.
12 陈彦, 张济宇. Na2CO3催化剂对福建高变质无烟煤比表面及气化反应特性的影响[J]. 化工学报,2011, 62(10): 2768-2775.
ChenY, ZhangJ Y. Effects of catalyst loading of Na2CO3 on specific surface area and gasification characteristics of Fujian high-metamorphous anthracite[J]. CIESC Journal, 2011, 62(10): 2768-2775.
13 HurtR H, SarofimA F, LongwellJ P. The role of microporous surface area in the gasification of chars from a sub-bituminous coal[J]. Fuel, 1991, 70(9): 1079-1082.
14 YokoyamaS Y, TanakaK I, ToyoshimaI, et al. X-ray photoelectron spectroscopic study of the surface of carbon doped with potassium carbonate[J]. Chemistry Letters, 1980, 16(5): 599-602.
15 KopyscinskiJ, RahmanM, GuptaR, et al. K2CO3 catalyzed CO2 gasification of ash-free coal. Interactions of the catalyst with carbon in N2 and CO2 atmosphere[J]. Fuel, 2014, 117(1): 1181-1189.
16 WangY, WangZ, HuangJ, et al. Catalytic gasification activity of Na2CO3 and comparison with K2CO3 for a high-aluminum coal char[J]. Energy & Fuels, 2015, 29(11): 6988-6998.
17 WangJ, JiangM, YaoY, et al. Steam gasification of coal char catalyzed by K2CO3 for enhanced production of hydrogen without formation of methane[J]. Fuel, 2009, 88(9): 1572-1579.
18 ChenS G, YangR T. Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O[J]. Energy & Fuels, 1997, 11(2): 421-427.
19 XuK, HuS, SuS, et al. Study on char surface active sites and their relationship to gasification reactivity[J]. Energy & Fuels, 2013, 27(1): 118-125.
20 CerfontainM B, MoulijnJ A. Alkali-catalysed gasification reactions studied by in situ FTIR spectroscopy[J]. Fuel, 1983, 62(2): 256-258.
21 ZhangF, XuD, WangY, et al. CO2 gasification of Powder River Basin coal catalyzed by a cost-effective and environmentally friendly iron catalyst[J]. Applied Energy, 2015, 145: 295-305.
22 SamsD A, ShadmanF. Catalytic effect of potassium on the rate of char-CO2 gasification[J]. Fuel, 1983, 62(8): 880-882.
23 SaberJ M, KesterK B, FalconerJ L, et al. A mechanism for sodium oxide catalyzed CO2 gasification of carbon[J]. Journal of Catalysis, 1988, 109(2): 329-346.
24 WigmansT, ElfringM, MoulijnJ A, et al. On the mechanism of the potassium catalysed gasification of activated carbon: differences in physical behaviour of sodium- and potassium-carbonate[J]. Carbon, 1982, 20(2): 140.
25 MoulijnJ A, KapteijnF. Towards a unified theory of reactions of carbon with oxygen-containing molecules[J]. Carbon, 1995, 33(8): 1155-1165.
26 TahmasebiA, YuJ, HanY, et al. A study of chemical structure changes of Chinese lignite during fluidized-bed drying in nitrogen and air[J]. Fuel Process. Technol., 2012, 101: 85-93.
27 IbarraJ, MuñozE, MolinerR, et al. FTIR study of the evolution of coal structure during the coalification process[J]. Org. Geochem., 1996, 24(6/7): 725-735.
28 ShangJ Y, WolfE E. FTIR studies of potassium catalyst-treated gasified coal chars and carbons[J]. Fuel, 1983, 62(2): 252-255.
29 XieA J, ShenY H, LiX Y, et al. The role of Mg2+ and Mg2+ /amino acid in controlling polymorph and morphology of calcium carbonate crystal[J]. Materials Chemistry & Physics, 2007, 101(1): 87-92.
30 RamasamyV, RajkumarP, PonnusamyV, et al. Depth wise analysis of recently excavated Vellar river sediments through FTIR and XRD studies[J]. Indian Journal of Physics, 2009, 83(9): 1295-1308.
31 MakreskiP, JovanovskiG, DimitrovskaS, et al. Minerals from Macedonia (): Identification of some sulfate minerals by vibrational (infrared and Raman) spectroscopy[J]. Vibrational Spectroscopy, 2005, 39(2): 229-239.
32 WangJ, DuJ, ChangL, et al. Study on the structure and pyrolysis characteristics of Chinese western coals[J]. Fuel Process. Technol., 2010, 91(4): 430-433.
33 PereiraP, CsencsitsR, SomorjaiG A, et al. Steam gasification of graphite and chars at temperatures <1000 K over potassium-calcium-oxide catalysts[J]. Journal of Catalysis, 1989, 123(2): 463-476.
34 PereiraP, SomorjaiG A, HeinemannH, et al. Catalytic steam gasification of coals[J]. Energy & Fuels, 1992, 6(4): 407-410.
35 JiangM Q, ZhouR, HuJ, et al. Calcium-promoted catalytic activity of potassium carbonate for steam gasification of coal char: influences of calcium species[J]. Fuel, 2012, 99(9): 64-71.
36 BrunoG, BuroniM, CarvaniL, et al. Water-insoluble compounds formed by reaction between potassium and mineral matter in catalytic coal gasification[J]. Fuel, 1988, 67(1): 67-72.
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