Citation: GUO Hai-jun, LI Qing-lin, ZHANG Hai-rong, XIONG Lian, PENG Fen, YAO Shi-miao, CHEN Xin-de. Attapulgite supported Cu-Fe-Co based catalyst combination system for CO hydrogenation to lower alcohols[J]. Journal of Fuel Chemistry and Technology, ;2019, 47(11): 1346-1356. shu

Attapulgite supported Cu-Fe-Co based catalyst combination system for CO hydrogenation to lower alcohols

GUO Hai-jun ^1,2,3,4 ,
LI Qing-lin ^1,5 ,
ZHANG Hai-rong ^1,2,3,4 ,
XIONG Lian ^1,2,3,4 ,
PENG Fen ^1,2,3,4 ,
YAO Shi-miao ^1,2,3,4 ,
CHEN Xin-de ^1,2,3,4,,

1.
Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou 510640, China
2.
Key Laboratory of Renewable Energy, Chinese Academy of Sciences, Guangzhou 510640, China
3.
Guangdong Key Laboratory of New and Renewable Energy Research and Development, Guangzhou 510640, China
4.
R & D Center of Xuyi Attapulgite Applied Technology, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Xuyi 211700, China
5.
Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215123, China

Corresponding author: CHEN Xin-de, cxd_cxd@hotmail.com
Received Date: 12 August 2019
Revised Date: 28 September 2019

Fund Project: the Project of Jiangsu Province Science and Technology BE2018342the Science and Technology Program of Guangzhou 201707010240the Project of Guangdong Provincial Natural Science Foundation 2018A030313150The project was supported by the Science and Technology Program of Guangzhou (201707010240), the Project of Guangdong Provincial Natural Science Foundation (2018A030310126, 2018A030313150), the Project of Jiangsu Province Science and Technology (BE2018342) and the Project of Key Laboratory Foundation of Renewable Energy, Chinese Academy of Sciences (CAS) (Y807jc1001)the Project of Guangdong Provincial Natural Science Foundation 2018A030310126the Project of Key Laboratory Foundation of Renewable Energy, Chinese Academy of Sciences (CAS) Y807jc1001

Figures(7)

Attapulgite (ATP) and ATP mixed with SiO₂ microspheres (ATPS) supported Cu-Fe-Co modified Fischer-Tropsch (F-T) catalysts were prepared by impregnation method (IM) and impregnation-solution combustion method (IMSC). The catalysts were characterized by N₂ adsorption-desorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), hydrogen temperature-programmed reduction (H₂-TPR) and CO₂-temperature programmed desorption (CO₂-TPD). The catalysts were also applied to lower alcohols synthesis from CO hydrogenation. Results show that the IMSC method is much beneficial for the loading, dispersion and reduction of CuO on the prepared catalyst than IM method, which promots the touch of H₂ and CO with Cu active site. The optimum reaction temperature for lower alcohols synthesis is 280℃ for the catalysts prepared by both methods. Through the optimization of catalyst combination system between ATP and ATPS supported Cu-Fe-Co based catalysts (CFCK/ATP, CFCK/ATPS) and Cu/ZnO/Al₂O₃ catalyst (CZA) for methanol synthesis, the ideal catalyst combination system, CZA‖CFCK/ATPS-IMSC, is obtained for lower alcohols synthesis. For the dual-bed configuration, a lower alcohols selectivity of 39.6% with the fraction of C₂₊ alcohols of 22.7% in oxygenates is achieved at CO conversion of 46.3% via the product conversion coupling effect.
- attapulgite,
- CO hydrogenation,
- lower alcohols,
- catalyst combination system,
- product conversion coupling effect
1. [1]
  ZHOU W, CHENG K, KANG J C, ZHOU C, SUBRAMANIAN V, ZHANG Q H, WANG Y. New horizon in C1 chemistry:Breaking the selectivity limitation in transformation of syngas and hydrogenation of CO₂ into hydrocarbon chemicals and fuels[J]. Chem Soc Rev, 2019,48(12):3193-3228. doi: 10.1039/C8CS00502H
2. [2]
  LUK H T, MONDELLI C, FERRE D C, STEWART J A, PEREZ-RAMIREZ J. Status and prospects in higher alcohols synthesis from syngas[J]. Chem Soc Rev, 2017,46(5):1358-1426. doi: 10.1039/C6CS00324A
3. [3]
  AO M, PHAM G H, SUNARSO J, TADE M O, LIU S M. Active centers of catalysts for higher alcohol synthesis from syngas:A review[J]. ACS Catal, 2018,8(8):7025-7050. doi: 10.1021/acscatal.8b01391
4. [4]
  ZAMAN S, SMITH K J. A review of molybdenum catalysts for synthesis gas conversion to alcohols:Catalysts, mechanisms and kinetics[J]. Catal Rev, 2012,54(1):41-132. doi: 10.1080/01614940.2012.627224
5. [5]
  AN Y L, LIN T J, YU F, YANG Y Z, ZHONG L S, WU M H, SUN Y H. Advances in direct production of value-added chemicals via syngas conversion[J]. Sci China Chem, 2017,60(7):887-903. doi: 10.1007/s11426-016-0464-1
6. [6]
  XIAO Kang, BAO Zheng-hong, QI Xing-zhen, WANG Xin-xing, ZHONG Liang-shu, FANG Ke-gong, LIN Ming-gui, SUN Yu-han. Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J]. Chin J Catal, 2013,34(1):116-129.
7. [7]
  DING M Y, TU J L, LIU J G, TSUBAKI N, WANG T J, MA L L. Copper-iron supported bimodal pore catalyst and its application for higher alcohols synthesis[J]. Catal Today, 2014,234:278-284. doi: 10.1016/j.cattod.2014.01.039
8. [8]
  LIU Jian-guo, DING Ming-yue, WANG Tie-jun, MA Long-long. Structure and performance of Cu-Fe bimodal support for higher alcohol syntheses[J]. Acta Phys-Chim Sin, 2012,28(8):1964-1970. doi: 10.3866/PKU.WHXB201205213
9. [9]
  HOU Bin, HAN Xin-you, LIN Ming-gui, FANG Ke-gong. Preparation of SiO₂-coated CuFe catalysts for synthesis of higher alcohols from CO hydrogenation[J]. J Fuel Chem Technol, 2016,44(2):217-224. doi: 10.3969/j.issn.0253-2409.2016.02.012
10. [10]
  GUO Hai-jun, XIONG Lian, LUO Cai-rong, DING Fei, CHEN Xin-de, CHEN Yong. Effect of Fe/Co mass ratio on catalytic performances of Cu-Fe-Co based catalysts for mixed alcohols synthesis[J]. Acta Phys-Chim Sin, 2011,27(11):2632-2638. doi: 10.3866/PKU.WHXB20111114
11. [11]
  XIANG Y Z, CHITRY V, LIDDICOAT P, FELFER P, CAIRNEY J, RINGER S, KRUSE N. Long-chain terminal alcohols through catalytic CO hydrogenation[J]. J Am Chem Soc, 2013,135(19):7114-7117. doi: 10.1021/ja402512r
12. [12]
  GAO W, ZHAO Y F, CHEN H R, CHEN H, LI Y W, HE S, ZHANG Y K, WEI M, EVANS D G, DUAN X. Core-shell Cu@(CuCo-alloy)/Al₂O₃ catalysts for the synthesis of higher alcohols from syngas[J]. Green Chem, 2015,17(3):1525-1534. doi: 10.1039/C4GC01633E
13. [13]
  GUO H J, LI S G, ZHANG H R, PENG F, XIONG L, YANG J, WANG C, CHEN X D, CHEN Y. Reaction condition optimization and lumped kinetics study for lower alcohols synthesis from syngas using a two-stage bed catalyst combination system[J]. Ind Eng Chem Res, 2014,53(1):123-131. doi: 10.1021/ie402422p
14. [14]
  LIN T J, QI X Z, WANG X X, XIA L, WANG C Q, YU F, WANG H, LI S G, ZHONG L S, SUN Y H. Direct production of higher oxygenates by syngas conversion over amultifunctional catalyst[J]. Angew Chem Int Ed, 2019,58(14):4627-4631. doi: 10.1002/anie.201814611
15. [15]
  DAS S K, MAJHI S, MOHANTY P, PANT K K. CO-hydrogenation of syngas to fuel using silica supported Fe-Cu-K catalysts:Effects of active components[J]. Fuel Process Technol, 2014,118:82-89. doi: 10.1016/j.fuproc.2013.08.014
16. [16]
  MAO Dong-sen, GUO Qiang-sheng, YU Jun, HAN Lu-peng, LU Guan-zhong. Effect of Cerium addition on the catalytic performance of Cu-Fe/SiO₂ for the synthesis of lower alcohols from syngas[J]. Acta Phys-Chim Sin, 2011,27(11):2639-2645. doi: 10.3866/PKU.WHXB20111125
17. [17]
  LU R L, MAO D S, YU J, GUO Q S. Enhanced activity of Cu-Fe/SiO₂ catalyst for CO hydrogenation to higher alcohols by pretreating the support with ammonia[J]. J Ind Eng Chem, 2015,25:338-343. doi: 10.1016/j.jiec.2014.11.013
18. [18]
  GUO Qiang-sheng, MAO Dong-sen, YU Jun, HAN Lu-peng. Effects of different supports on the catalytic performance of supported Cu-Fe catalyst for CO hydrogenation[J]. J Fuel Chem Technol, 2012,40(9):1103-1109. doi: 10.3969/j.issn.0253-2409.2012.09.013
19. [19]
  SHI X P, YU H B, GAO S, LI X Y, FANG H H, LI R J, LI Y Y, ZHANG L J, LIANG X L, YUAN Y Z. Synergistic effect of nitrogen-doped carbon-nanotube-supported Cu-Fe catalyst for the synthesis of higher alcohols from syngas[J]. Fuel, 2017,210:241-248. doi: 10.1016/j.fuel.2017.08.064
20. [20]
  LI Zhi-wen, CHEN Cong-biao, WANG Jun-gang, LIN Ming-gui, HOU Bo, JIA Li-tao, LI De-bao. Nitrogen-doped mesoporous carbon supported FeCu bimetallic catalyst and its CO hydrogenation performance[J]. J Fuel Chem Technol, 2019,47(6):709-717. doi: 10.3969/j.issn.0253-2409.2019.06.008
21. [21]
  LUK H T, MONDELLI C, MITCHELL S, SIOL S, STEWART J A, CURULLA FERRÉ D, PÉREZ-RAMÍREZ J. Role of carbonaceous supports and Potassium promoter on higher alcohols synthesis over copper-iron catalysts[J]. ACS Catal, 2018,8(10):9604-9618. doi: 10.1021/acscatal.8b02714
22. [22]
  LUK H T, MONDELLI C, MITCHELL S, FERRE D C, STEWART J A, PEREZ-RAMIREZ J. Impact of carrier acidity on the conversion of syngas to higher alcohols over zeolite-supported copper-iron catalysts[J]. J Catal, 2019,371:116-125. doi: 10.1016/j.jcat.2019.01.021
23. [23]
  JIANG J L, XU Y, DUANMU C S, GU X, CHEN J. Preparation and catalytic properties of sulfonated carbon-palygorskite solid acid catalyst[J]. Appl Clay Sci, 2014,95:260-264. doi: 10.1016/j.clay.2014.04.020
24. [24]
  LI X Z, SHI H Y, ZHU W, ZUO S X, LU X W, LUO S P, LI Z Y, YAO C, CHEN Y S. Nanocomposite LaFe_1-xNi_xO₃/Palygorskite catalyst for photo-assisted reduction of NO_x:Effect of Ni doping[J]. Appl Catal B:Environ, 2018,231:92-100. doi: 10.1016/j.apcatb.2018.03.008
25. [25]
  OUYANG J, ZHAO Z, SUIB S L, YANG H M. Degradation of Congo Red dye by a Fe₂O₃@CeO₂-ZrO₂/Palygorskite composite catalyst:Synergetic effects of Fe₂O₃[J]. J Colloid Interf Sci, 2019,539:135-145. doi: 10.1016/j.jcis.2018.12.052
26. [26]
  WANG Y Z, WANG Y N, LI X, LIU Z T, ZHAO Y X. Effect of ultrasonic treatment of palygorskite on the catalytic performance of Pd-Cu/palygorskite catalyst for room temperature CO oxidation in humid circumstances[J]. Environ Technol, 2018,39(6):780-786. doi: 10.1080/09593330.2017.1311944
27. [27]
  GUO H J, ZHANG H R, PENG F, YANG H J, XIONG L, HUANG C, WANG C, CHEN X D, MA L L. Mixed alcohols synthesis from syngas over activated palygorskite supported Cu-Fe-Co based catalysts[J]. Appl Clay Sci, 2015,111:83-89. doi: 10.1016/j.clay.2015.03.009
28. [28]
  GUO X M, MAO D S, LU G Z, WANG S, WU G S. Glycine-nitrate combustion synthesis of CuO-ZnO-ZrO₂ catalysts for methanol synthesis from CO₂ hydrogenation[J]. J Catal, 2010,271(2):178-185. doi: 10.1016/j.jcat.2010.01.009
29. [29]
  CHU Z, CHEN H B, YU Y, WANG Q, FANG D Y. Surfactant-assisted preparation of Cu/ZnO/Al₂O₃ catalyst for methanol synthesis from syngas[J]. J Mol Catal A:Chem, 2013,366:48-53. doi: 10.1016/j.molcata.2012.09.007
30. [30]
  LEI H, HOU Z Y, XIE J W. Hydrogenation of CO₂ to CH₃OH over CuO/ZnO/Al₂O₃ catalysts prepared via a solvent-free routine[J]. Fuel, 2016,164:191-198. doi: 10.1016/j.fuel.2015.09.082
31. [31]
  GRUNWALDT J D, MOLENBROEK A M, TOPSØE N Y, TOPSØE H, CLAUSEN B S. In situ investigations of structural changes in Cu/ZnO catalysts[J]. J Catal, 2000,194(2):452-460. doi: 10.1006/jcat.2000.2930
32. [32]
  XU R, YANG C, WEI W, LI W H, SUN Y H, HU T D. Fe-modified CuMnZrO₂ catalysts for higher alcohols synthesis from syngas[J]. J Mol Catal A:Chem, 2004,221(1/2):51-58.
33. [33]
  XU R, WEI W, LI W H, HU T D, SUN Y H. Fe modified CuMnZrO₂ catalysts for higher alcohols synthesis from syngas:Effect of calcination temperature[J]. J Mol Catal A:Chem, 2005,234(1/2):75-83. doi: 10.1016/j.molcata.2005.01.048
34. [34]
  DING M Y, QIU M H, LIU J G, LI Y P, WANG T J, MA L L, WU C Z. Influence of manganese promoter on co-precipitated Fe-Cu based catalysts for higher alcohols synthesis[J]. Fuel, 2013,109:21-27. doi: 10.1016/j.fuel.2012.06.034
35. [35]
  TIEN-THAO N, ZAHEDI-NIAKI M H, ALAMDARI H, KALIAGUINE S. Conversion of syngas to higher alcohols over nanosized LaCo_0.7Cu_0.3O₃ perovskite precursors[J]. Appl Catal A:Gen, 2007,326(2):152-163. doi: 10.1016/j.apcata.2007.04.009
36. [36]
  GUPTA M, SMITH M L, SPIVEY J J. Heterogeneous catalytic conversion of dry syngas to ethanol and higher alcohols on Cu-based catalysts[J]. ACS Catal, 2011,1(6):641-656. doi: 10.1021/cs2001048
37. [37]
  GUO H J, ZHANG H R, PENG F, YANG H J, XIONG L, WANG C, HUANG C, CHEN X D, MA L L. Effects of Cu/Fe ratio on structure and performance of attapulgite supported CuFeCo-based catalyst for mixed alcohols synthesis from syngas[J]. Appl Catal A:Gen, 2015,503:51-61. doi: 10.1016/j.apcata.2015.07.008
1. [1]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
2. [2]
  Xue Dong , Xiaofu Sun , Shuaiqiang Jia , Shitao Han , Dawei Zhou , Ting Yao , Min Wang , Minghui Fang , Haihong Wu , Buxing Han . Electrochemical CO₂ Reduction to C₂₊ Products with Ampere-Level Current on Carbon-Modified Copper Catalysts. Acta Physico-Chimica Sinica, 2025, 41(3): 2404012-0. doi: 10.3866/PKU.WHXB202404012
3. [3]
  Feifei Yang , Wei Zhou , Chaoran Yang , Tianyu Zhang , Yanqiang Huang . Enhanced Methanol Selectivity in CO₂ Hydrogenation by Decoration of K on MoS₂ Catalyst. Acta Physico-Chimica Sinica, 2024, 40(7): 2308017-0. doi: 10.3866/PKU.WHXB202308017
4. [4]
  Xudong Lv , Tao Shao , Junyan Liu , Meng Ye , Shengwei Liu . Paired Electrochemical CO₂ Reduction and HCHO Oxidation for the Cost-Effective Production of Value-Added Chemicals. Acta Physico-Chimica Sinica, 2024, 40(5): 2305028-0. doi: 10.3866/PKU.WHXB202305028
5. [5]
  Yajin Li , Huimin Liu , Lan Ma , Jiaxiong Liu , Dehua He . Photothermal Synthesis of Glycerol Carbonate via Glycerol Carbonylation with CO₂ over Au/Co₃O₄-ZnO Catalyst. Acta Physico-Chimica Sinica, 2024, 40(9): 2308005-0. doi: 10.3866/PKU.WHXB202308005
6. [6]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Liu Fei . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 2408004-0. doi: 10.3866/PKU.WHXB202408004
7. [7]
  Haoyu Sun , Dun Li , Yuanyuan Min , Yingying Wang , Yanyun Ma , Yiqun Zheng , Hongwen Huang . Hierarchical Palladium-Copper-Silver Porous Nanoflowers as Efficient Electrocatalysts for CO₂ Reduction to C₂₊ Products. Acta Physico-Chimica Sinica, 2024, 40(6): 2307007-0. doi: 10.3866/PKU.WHXB202307007
8. [8]
  Yixuan Wang , Canhui Zhang , Xingkun Wang , Jiarui Duan , Kecheng Tong , Shuixing Dai , Lei Chu , Minghua Huang . Engineering Carbon-Chainmail-Shell Coated Co₉Se₈ Nanoparticles as Efficient and Durable Catalysts in Seawater-Based Zn-Air Batteries. Acta Physico-Chimica Sinica, 2024, 40(6): 2305004-0. doi: 10.3866/PKU.WHXB202305004
9. [9]
  Liuyun Chen , Wenju Wang , Tairong Lu , Xuan Luo , Xinling Xie , Kelin Huang , Shanli Qin , Tongming Su , Zuzeng Qin , Hongbing Ji . Soft template-induced deep pore structure of Cu/Al₂O₃ for promoting plasma-catalyzed CO₂ hydrogenation to DME. Acta Physico-Chimica Sinica, 2025, 41(6): 100054-0. doi: 10.1016/j.actphy.2025.100054
10. [10]
  Yongqing Xu , Yuyao Yang , Mengna Wu , Xiaoxiao Yang , Xuan Bie , Shiyu Zhang , Qinghai Li , Yanguo Zhang , Chenwei Zhang , Robert E. Przekop , Bogna Sztorch , Dariusz Brzakalski , Hui Zhou . Review on Using Molybdenum Carbides for the Thermal Catalysis of CO₂ Hydrogenation to Produce High-Value-Added Chemicals and Fuels. Acta Physico-Chimica Sinica, 2024, 40(4): 2304003-0. doi: 10.3866/PKU.WHXB202304003
11. [11]
  Dong Xiang , Kunzhen Li , Kanghua Miao , Ran Long , Yujie Xiong , Xiongwu Kang . Amine-Functionalized Copper Catalysts: Hydrogen Bonding Mediated Electrochemical CO₂ Reduction to C₂ Products and Superior Rechargeable Zn-CO₂ Battery Performance. Acta Physico-Chimica Sinica, 2024, 40(8): 2308027-0. doi: 10.3866/PKU.WHXB202308027
12. [12]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . Designing thermodynamically stable noble metal single-atom photocatalysts for highly efficient non-oxidative conversion of ethanol into high-purity hydrogen and value-added acetaldehyde. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-0. doi: 10.1016/j.actphy.2025.100067
13. [13]
  Xuejie Wang , Guoqing Cui , Congkai Wang , Yang Yang , Guiyuan Jiang , Chunming Xu . Research Progress on Carbon-based Catalysts for Catalytic Dehydrogenation of Liquid Organic Hydrogen Carriers. Acta Physico-Chimica Sinica, 2025, 41(5): 100044-0. doi: 10.1016/j.actphy.2024.100044
14. [14]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
15. [15]
  Kun WANG , Wenrui LIU , Peng JIANG , Yuhang SONG , Lihua CHEN , Zhao DENG . Hierarchical hollow structured BiOBr-Pt catalysts for photocatalytic CO₂ reduction. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1270-1278. doi: 10.11862/CJIC.20240037
16. [16]
  Xueting Feng , Ziang Shang , Rong Qin , Yunhu Han . Advances in Single-Atom Catalysts for Electrocatalytic CO₂ Reduction. Acta Physico-Chimica Sinica, 2024, 40(4): 2305005-0. doi: 10.3866/PKU.WHXB202305005
17. [17]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
18. [18]
  Shuang Cao , Bo Zhong , Chuanbiao Bie , Bei Cheng , Feiyan Xu . Insights into Photocatalytic Mechanism of H₂ Production Integrated with Organic Transformation over WO₃/Zn_0.5Cd_0.5S S-Scheme Heterojunction. Acta Physico-Chimica Sinica, 2024, 40(5): 2307016-0. doi: 10.3866/PKU.WHXB202307016
19. [19]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-Based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-0. doi: 10.3866/PKU.WHXB202406029
20. [20]
  Wen YANG , Didi WANG , Ziyi HUANG , Yaping ZHOU , Yanyan FENG . La promoted hydrotalcite derived Ni-based catalysts: In situ preparation and CO₂ methanation performance. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 561-570. doi: 10.11862/CJIC.20230276

Get Citation

PDF

XML

Metrics

PDF Downloads(3)
Abstract views(1190)
HTML views(191)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142