Recent Advances in the Synthesis of Zeolites from Solid Wastes

doi:10.1007/s40242-024-4122-5

高等学校化学研究 ›› 2024, Vol. 40 ›› Issue (4): 646-656.doi: 10.1007/s40242-024-4122-5

Recent Advances in the Synthesis of Zeolites from Solid Wastes

LIU Pei¹, WU Qinming^1,2, CHEN Zhenghai³, XIAO Feng-Shou^1,2

1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education and College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, P. R. China;
2. Zhejiang Provincial Innovation Center of Green Petrochemical Technology, Ningbo 315048, P. R. China;
3. Kente Catalysts Inc., Xianju 317300, P. R. China

收稿日期:2024-05-14 出版日期:2024-08-01 发布日期:2024-07-24
通讯作者: WU Qinming,qinmingwu@zju.edu.cn;XIAO Feng-Shou,fsxiao@zju.edu.cn E-mail:qinmingwu@zju.edu.cn;fsxiao@zju.edu.cn
基金资助:
This work was supported by the National Natural Science Foundation of China (Nos. 22288101, U21B20101, 22172141) and the Zhejiang Provincial Natural Science Foundation, China (No. LR24B030001).

Recent Advances in the Synthesis of Zeolites from Solid Wastes

LIU Pei¹, WU Qinming^1,2, CHEN Zhenghai³, XIAO Feng-Shou^1,2

1. Key Laboratory of Biomass Chemical Engineering of Ministry of Education and College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, P. R. China;
2. Zhejiang Provincial Innovation Center of Green Petrochemical Technology, Ningbo 315048, P. R. China;
3. Kente Catalysts Inc., Xianju 317300, P. R. China

Received:2024-05-14 Online:2024-08-01 Published:2024-07-24
Contact: WU Qinming,qinmingwu@zju.edu.cn;XIAO Feng-Shou,fsxiao@zju.edu.cn E-mail:qinmingwu@zju.edu.cn;fsxiao@zju.edu.cn
Supported by:
This work was supported by the National Natural Science Foundation of China (Nos. 22288101, U21B20101, 22172141) and the Zhejiang Provincial Natural Science Foundation, China (No. LR24B030001).

摘要/Abstract

摘要： With the rapid development of industrialization, it is inevitable to produce solid wastes in the fields of energy petrochemical industry. However, the storage and utilization of these solid wastes have become a considerable challenge. Due to the main element composition of these solid wastes including silicon and aluminum, it has attracted extensive attention for synthesizing zeolites. This review summarized the properties of major solid wastes including coal fly ash, coal gangue, spent fluid catalytic cracking (FCC) catalyst, lithium slag, bauxite residue, and waste glass. Then, the preparation of LTA, FAU, ZSM-5, SSZ-13, Beta, and MOR zeolites from these solid wastes were introduced. Finally, the current challenges and perspectives were discussed.

关键词: Solid waste, Zeolite, Utilization, Sustainable route, Application

Abstract: With the rapid development of industrialization, it is inevitable to produce solid wastes in the fields of energy petrochemical industry. However, the storage and utilization of these solid wastes have become a considerable challenge. Due to the main element composition of these solid wastes including silicon and aluminum, it has attracted extensive attention for synthesizing zeolites. This review summarized the properties of major solid wastes including coal fly ash, coal gangue, spent fluid catalytic cracking (FCC) catalyst, lithium slag, bauxite residue, and waste glass. Then, the preparation of LTA, FAU, ZSM-5, SSZ-13, Beta, and MOR zeolites from these solid wastes were introduced. Finally, the current challenges and perspectives were discussed.

Key words: Solid waste, Zeolite, Utilization, Sustainable route, Application

LIU Pei, WU Qinming, CHEN Zhenghai, XIAO Feng-Shou. Recent Advances in the Synthesis of Zeolites from Solid Wastes[J]. 高等学校化学研究, 2024, 40(4): 646-656.

LIU Pei, WU Qinming, CHEN Zhenghai, XIAO Feng-Shou. Recent Advances in the Synthesis of Zeolites from Solid Wastes[J]. Chemical Research in Chinese Universities, 2024, 40(4): 646-656.

参考文献

[1] Wang Z. P., Yu J. H., Xu R. R., Chem. Soc. Rev., 2012, 41, 1729.
[2] Garces L. J., Makwana V. D., Hincapie B., Sacco A., Suib S. L., J. Catal., 2003, 217, 107.
[3] Higuchi Y., Tanaka S., Microporous Mesoporous Mater., 2023, 354, 112550.
[4] Shi D. D., Haw K.-G., Kouvatas C., Tang L. X., Zhang Y. Y., Fang Q. R., Qiu S. L., Valtchev V., Angew. Chem. Int. Ed., 2020, 59, 19576.
[5] Tang L. X., Haw K.-G., Zhang Y. Y, Fang Q. R., Qiu S. L., Valtchev V., Microporous Mesoporous Mater., 2019, 280, 306.
[6] Wu Q. M., Zhu L. F., Chu Y. Y., Liu X. L., Zhang C. S., Zhang J., Xu H., Xu J., Deng F., Feng Z. C., Meng X. J., Xiao F.-S., Angew. Chem. Int. Ed., 2019, 58, 12138.
[7] Cao C. Y., Xuan W. W., Yan S. Y., Wang Q., J. Environ. Chem. Eng., 2023, 11, 110898.
[8] Chang H. L., Shih W. H., Ind. Eng. Chem. Res., 2000, 39, 4185.
[9] Coronas J., Chem. Eng. J., 2010, 156, 236.
[10] Xu H., Wu P., Natl. Sci. Rev., 2022, 9, nwac045.
[11] Belviso C., Prog. Energy Combust. Sci., 2018, 65, 109.
[12] Collins F., Rozhkovskaya A., Outram J. G., Millar G. J., Microporous Mesoporous Mater., 2020, 291, 109667.
[13] Fan X. H., Yuan R. R., Gan M. J., Ji Z. Y., Sun Z. Q., Sci. Total Environ., 2023, 865, 160745.
[14] Lee Y.-R., Soe J. T., Zhang S. Q., Ahn J.-W., Park M. B., Ahn W.-S., Chem. Eng. J., 2017, 317, 821.
[15] Chen X. Y., Zhang P., Wang Y., Peng W., Ren Z. F., Li Y. H., Chu B. S., Zhu Q., Front. Environ. Sci. Eng., 2023, 17, 149.
[16] Kaithwas A., Prasad M., Kulshreshtha A., Verma S., Chem. Eng. Res. Des., 2012, 90, 1632.
[17] Elidrissi Z. C., Idrissi D. E. M., Kouzi Y., Achiou B., Tahiri S., Ouammou M., Younssi S. A., Inorg. Chem. Commun., 2023, 156, 111192.
[18] Fan Y., Zhang F.-S.; Zhu, J. X., Liu Z. G., J. Hazard. Mater., 2008, 153, 382.
[19] Mamaghani F. A. A., Salem A., Salem S., Process Saf. Environ. Prot., 2022, 159, 500.
[20] Silva B., Martins M., Rosca M., Rocha V., Lago A., Neves I. C., Tavares T., Sep. Purif. Technol., 2020, 235, 116139.
[21] Mlonka-Medrala A., Energies., 2023, 16, 6593.
[22] Montalvo S., Huilinir C., Borja R., Sanchez E., Herrmann C., Bioresource Technol., 2020, 301, 122808.
[23] Zhang X. Y., Li C. Q., Zheng S. L., Di Y. H., Sun Z. M., Int. J. Min. Met. Mater., 2022, 29, 1.
[24] Bukhari S. S., Behin J., Kazemian H., Rohani S., Fuel, 2015, 140, 250.
[25] Wang R. Y., Song Y., Yang X., Zhou J. H., Jiang Q. Q., Wang Z. B., Wang L., Peng B., Song H. T., Lin W., ACS Sustainable Chem. Eng., 2022, 10, 11376.
[26] Li H., Zheng F., Wang J., Zhou J. M., Huang X. H., Chen L., Hu P. F., Gao J.-M., Zhen Q., Bashir S., Liu J. B. L., Chem. Eng. J., 2020, 390, 124513.
[27] Xue Y. J., Wei X. T., Zhao H., Wang T., Xiao Y., J. Cleaner Prod., 2020, 259, 120830.
[28] Basaldella E. I., Paladino J. C., Solari M., Valle G. M., Appl. Catal. B: Environ., 2006, 66, 186.
[29] Huang S. Z., Wang Y., Zhang L., Zhu S. J., Ma Z. F., Cui Q., Wang H. Y., New J. Chem., 2023, 47, 14335.
[30] Wang B. Y., Li J., Zhou X., Hao W. F., Zhang S. Q., Lan C., Wang X. M., Wang Z. Y., Xu J., Zhang J.-N., Yan W. F., Inorg. Chem. Front., 2022, 9, 468.
[31] Qiang Z. Q., Li R., Yang Z. Q., Guo M., Cheng F. Q., Zhang M., Energy Fuels, 2019, 33, 6641.
[32] Hernandez-Tamargo C., Kwakye-Awuah B., O'Malley A. J., de Leeuw N. H., Microporous Mesoporous Mater., 2021, 315, 110903.
[33] Kang Y. B., Swain B., Im B., Yoon J.-H., Park K. H., Lee C. G., Kim D. G., Metals, 2019, 9, 1240.
[34] Ojumu T. V., Du Plessis P. W., Petrik L. F., Ultrason. Sonochem., 2016, 31, 342.
[35] Liu P., Wu Q. M., Yan K. P., Wang L., Xiao F. -S., Dalton Trans., 2022, 52, 24.
[36] Rodríguez E. D., Bernal S. A., Provis J. L., Gehman J. D., Monzó J. M., Payá J., Borrachero M. V., Fuel, 2013, 109, 493.
[37] Rozhkovskaya A., Rajapakse J., Millar G. J., Adv. Powder Technol., 2021, 32, 3248.
[38] Qiang Z. Q., Shen X. J., Guo M., Cheng F. Q., Zhang M. A., Microporous Mesoporous Mater., 2019, 287, 77.
[39] Liu L. Y., Du T., Li G., Yang F., Che S., J. Hazard. Mater., 2014, 278, 551.
[40] Kim J.-C., Choi M., Song H. J., Park J. E., Yoon J.-H., Park K.-S., Lee C. G., Kim D.-W., Mater. Chem. Phys., 2015, 166, 20.
[41] Sayehi M., Delahay G., Tounsi H., J. Environ. Chem. Eng., 2022, 10, 108561.
[42] Breck D. W., Eversole W. G., Milton R. M., J. Am. Chem. Soc., 1956, 78, 2338.
[43] Escamilla-Perez A. M., Barre Y., Grandjean A., Hertz A., J. Supercrit. Fluid., 2023, 199, 105940.
[44] Mouna S., Hajji S., Tounsi H., J. Cleaner Prod., 2024, 434, 139946.
[45] Lee K. M., Jo Y. M., J. Mater. Cycles. Waste. Manage., 2010, 12, 212.
[46] Qian T. T., Li J. H., Adv. Powder Technol., 2015, 26, 98.
[47] Jin Y. X., Li L., Liu Z., Zhu S. Y., Wang D. M., Adv. Powder Technol., 2021, 32, 791.
[48] Escardino A., Barba A., Sánchez E., Cantavella V., Br. Ceram. Trans., 1999, 98, 172.
[49] Basaldella E. I., Torres Sanchez R. M., Conconi M. S., Appl. Clay Sci., 2009, 42, 611.
[50] Ferella F., Leone S., Innocenzi V., De Michelis I., Taglieri G., Gallucci K., J. Cleaner Prod., 2019, 230, 910.
[51] Li L., Xu S. C., Liu Z., Wang D. M., Materials, 2024, 17, 568.
[52] Ma D. Y., Wang Z. D., Guo M., Zhang M., Liu J. B., Waste Manage., 2014, 34, 2365.
[53] Lei P.-C., Shen X.-J., Li Y., Guo M., Zhang M., Int. J. Min. Met. Mater., 2016, 23, 850.
[54] Tsujiguchi M., Kobashi T., Utsumi Y., Kakimori N., Nakahira A., J. Am. Ceram. Soc., 2014, 97,114.
[55] Tae L. C., Appl. Chem. Eng., 2017, 28, 521.
[56] Li W. J, Chai Y. C., Wu G. J., Li L. D., J. Phys. Chem. Lett., 2022, 13, 11419.
[57] Nazir L. S. M., Yeong Y. F., Chew T. L., J. Asian Ceram. Soc., 2020, 8, 553.
[58] Yu Q., Zhang W. N., Li J. J., Liu W., Wang Y. N., Chu W. F., Zhang X. B., Xu L. Y., Zhu X. X., Li X. J., Microporous Mesoporous Mater., 2023, 355, 112570.
[59] Holler H., Wirsching U., Fortschr. Mineral., 1985, 63, 21.
[60] Molina A., Poole, C. A., Miner. Eng., 2004, 17, 167.
[61] Belviso C., Cavalcante F., Javier Huertas F., Lettino A., Ragone P., Fiore S., Microporous Mesoporous Mater., 2012, 162, 115.
[62] Murukutti M. K., Jena H., J. Hazard. Mater., 2022, 423, 127085.
[63] Ren L. M., Wu Q. M., Yang C. G., Zhu L. F., Li C. J, Zhang P. L., Zhang H. Y., Meng X. J., Xiao F.-S. J. Am. Chem. Soc., 2012, 134, 15173.
[64] Wu Q. M., Meng X. J, Gao X. H., Xiao F.-S., Acc. Chem. Res., 2018, 51, 1396.
[65] Sivalingam S., Sen S., Environ. Sci. Pollut. Res., 2019, 26, 34693.
[66] Belviso C., Ultrason. Sonochem., 2018, 43, 9.
[67] Liu X. M., Li L., Yang T. T., Yan Z. F., J. Porous Mater., 2012, 19, 133.
[68] Yang N. N., Gou L. Z., Bai Z. T., Cheng F. Q., Guo M., Zhang M., J. Inorg. Organomet. Poly. Mater., 2022, 32, 3496.
[69] Chen G. R., Li J. Y., Wang S., Han J., Wang X. X., She P. H., Fan W. B., Guan B. Y., Tian P., Yu J. H., Angew. Chem. Int. Ed., 2022, 61, e202200677.
[70] Bensafi B., Chouat N., Djafri F., Coord. Chem. Rev., 2023, 496, 215397.
[71] Rahimi N., Karimzadeh R., Appl. Catal. A: Gen., 2011, 398, 1.
[72] Rajakrishnamoorthy P., Saravanan C. G., Natarajan R., Karthikeyan D., Sasikala J., Femilda Josephin J. S., Vikneswaran M., Sonthalia A., Varuvel E. G., Fuel, 2023, 340, 127380.
[73] Zhao Y. F., Gu S. Y., Li L., Wang M., Environ. Pollut., 2024, 345, 1.
[74] Li H. P., Cheng R. Q., Liu Z. L., Du C. F., Sci. Total Environ., 2019, 683, 638.
[75] Tehubijuluw H., Subagyo R., Yulita M. F., Nugraha R. E., Kusumawati Y., Bahruji H., Jalil A. A., Hartati H., Prasetyoko D., Environ. Sci. Pollut. Res., 2021, 28, 37354.
[76] Timoshev V., Haufe L. A., Busse O., Hamedi H., Seifert M., Weigand J. J., ChemSusChem, 2024, e202301642.
[77] Wu Q. M., Luan H. M., Xiao F.-S., Sci. China Chem., 2022, 65, 1683.
[78] Liu L. J., Ji W. X., Li K. N., Yu W. H., Lan L. P., Ye J. J., Gao X., Li Y. Y., Ma Y. L., Sun Y. G., Silicon, 2022, 14, 8855.
[79] Gao J. D., Lin Q. J., Yang T. Z., Bao Y. C., Liu J., Chemosphere, 2023, 341, 139741.
[80] Wu Y. F., Liang G. B., Zhao X. N., Wang H., Qu Z. P., J. Environ. Chem. Eng., 2023, 11, 109589.
[81] Beale A. M., Gao F., Lezcano-Gonzalez I., Peden C. H. F., Szanyi J., Chem. Soc. Rev., 2015, 44, 7371.
[82] Fickel D. W., D'Addio E., Lauterbach J. A., Lobo R. F., Appl. Catal. B-Environ., 2011, 102, 441.
[83] Deimund M. A., Harrison L., Lunn J. D., Liu Y., Malek A., Shayib R., Davis M. E., ACS Catal., 2016, 6, 542.
[84] Hudson M. R., Queen W. L., Mason J. A., Fickel D. W., Lobo R. F., Brown C. M., J. Am. Chem. Soc., 2012, 134, 1970.
[85] Han J. F., Ha Y., Guo M. Y., Zhao P. P., Liu Q. L., Liu C. X., Song C. F., Ji N, Lu X. B., Ma D. G., Li Z. G., Ultrason. Sonochem., 2019, 59, 104703.
[86] Han J. F., Jin X. T., Song C. F., Bi Y. L., Liu Q. L., Liu C. X., Ji N., Lu X. B., Ma D. G., Li Z. G., Green Chem., 2020, 22, 219.
[87] Gollakota A. R. K., Munagapati V. S., Volli V., Gautam S., Wen J.-C., Shu C.-M., J. Hazard. Mater., 2021, 416, 125925.
[88] Liao X., Wang B., Yin R., Ren W. G., Li J., Gan H. T., Lv P. B., Bao W. R., Wang J. C., Chang, L. P., Huang Z. G., Han L. N., J. Solid. State Chem., 2023, 323, 124024.
[89] Lv W. T., Sun F. M., Zhang R. H., Jiao W. Y., Qin Z. F., Dong M., Fan W. B., Wang J. G., Microporous Mesoporous Mater., 2024, 370, 113073.
[90] Ren L. M., Zhang Y. B., Zeng S. J., Zhu L. F., Sun Q., Zhang H. Y., Yang C. G., Meng X. J., Yang X. G., Xiao F.-S., Chin. J. Catal., 2012, 33, 92.
[91] Liu P., Wu Q. M., Yan K. P., Wang L., Xiao F.-S., J. Catal., 2024, 432, 115442.
[92] Jiang J. X., Xu Y., Cheng P., Sun Q. M., Yu J. H., Corma A., Xu R. R., Chem. Mater., 2011, 23, 4709.
[93] Lu T. T., Yan W. F., Xu R. R., Inorg. Chem. Front., 2019, 6, 1938.
[94] Meng X. J., Xie B., Xiao F.-S., Chin. J. Catal., 2009, 30, 965.
[95] Muñiz J. G. R., Ramirez A. M., Robles J. M. A., Melo P. G., Bocard J. C. E., Martine A. M. M., Lat. Am. Appl. Res., 2010, 4, 323.
[96] Ameh A. E., Musyoka N. M., Oyekola O., Louis B., Petrik L. F., Front. Chem., 2021, 9, 683125.
[97] Gao W. Z., Amoo C. C., Zhang G. H., Javed M., Mazonde B., Lu C. X., Yang R. Q., Xing C., Tsubaki N., Microporous Mesoporous Mater., 2019, 280, 187.
[98] Fischer J. W. A., Brenig A., Klose D., van Bokhoven J. A., Sushkevich V. L., Jeschke G., Angew. Chem. Int. Ed., 2023, 62, e2023035.
[99] Lu K., Huang J., Ren L., Li C., Guan Y., Hu B. W., Xu H., Jiang J. G., Ma Y. H., Wu P., Angew. Chem. Int. Ed., 2020, 59, 6258.
[100] Zhou T., Wang B., Dai Z. D., Jiang X., Wang Y., Microporous Mesoporous Mater., 2021, 314, 110872.
[101] Liu X. C., Lu P., Jiang W. L., Shan Y. L., Li S., Wang X. S., Liu S. W., Han L., Liu Y. X., Chem. Eng. Sci., 2023, 281, 118967.

Recent Advances in the Synthesis of Zeolites from Solid Wastes

Recent Advances in the Synthesis of Zeolites from Solid Wastes

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	ZHENG Mingdan, CHEN Ya, LIU Zhan, LYU Jiamin, YE Bo, SUN Ming-Hui, CHEN Li-Hua, SU Bao-Lian. Hierarchically Macroporous Zeolite ZSM-5 Microspheres for Efficient Catalysis[J]. 高等学校化学研究, 2024, 40(4): 704-711.
[2]	HAN Xiaoyang, XIA Huicong, TU Weifeng, WEI Yifan, XUE Dongping, LI Minhan, YAN Wenfu, ZHANG Jia-Nan, HAN Yi-Fan. Zeolite-confined Fe-site Catalysts for the Hydrogenation of CO₂ to Produce High-value Chemicals[J]. 高等学校化学研究, 2024, 40(1): 78-95.
[3]	QU Ziqiang, ZHANG Tianjun, YIN Xichen, ZHANG Junyi, XIONG Xiaoyun, and SUN Qiming. Zeolite-encaged Ultrasmall Pt-Zn Species with Trace Amount of Pt for Efficient Propane Dehydrogenation[J]. 高等学校化学研究, 2023, 39(6): 870-876.
[4]	HE Huan, ZOU Zhengxi, HUA Weiming, YUE Yinghong, and GAO Zi. Promoting Effect of ZnO on the Catalytic Performance of CoZSM-5 for CO₂-Assisted Dehydrogenation of Ethane[J]. 高等学校化学研究, 2023, 39(6): 1064-1069.
[5]	LUO Yichen, ZHU Canhong, ZHANG Tianlong, YAN Tengfei, LIU Junqiu. Self-assembled Supramolecular Artificial Transmembrane Ion Channels: Recent Progress and Application[J]. 高等学校化学研究, 2023, 39(1): 3-12.
[6]	LIU Zailun, SUN Like, ZHANG Qitao, TENG Zhenyuan, SUN Hongli, SU Chenliang. TiO₂-supported Single-atom Catalysts: Synthesis, Structure, and Application[J]. 高等学校化学研究, 2022, 38(5): 1123-1138.
[7]	TU Tingting, HUAN Shuangyan, KE Guoliang, ZHANG Xiaobing. Functional Xeno Nucleic Acids for Biomedical Application[J]. 高等学校化学研究, 2022, 38(4): 912-918.
[8]	XIAO Peiwen, LI Hui, WANG Pingmei, LIU Bolun, JING Wendan, HE Lipeng, WANG Runwei, HAN Xue, ZHANG Zongtao, QIU Shilun, LUO Jianhui. Functionalized Hierarchical ZSM-5 Zeolites for the Viscosity Reduction of Heavy Oil at Low Temperature[J]. 高等学校化学研究, 2022, 38(4): 1083-1088.
[9]	LIAN Xiaodong, SONG Chenhao and WANG Yapei. Regulating the Oil-Water Interface to Construct Double Emulsions: Current Understanding and Their Biomedical Applications[J]. 高等学校化学研究, 2022, 38(3): 698-715.
[10]	LIU Yifeng, WANG Liang, and XIAO Feng-Shou. Selective Oxidation of Methane into Methanol Under Mild Conditions[J]. 高等学校化学研究, 2022, 38(3): 671-676.
[11]	CHENG Dajun, and MENG Xiangju. Recent Advances of Beta Zeolite in the Volatile Organic Compounds(VOCs) Elimination by the Catalytic Oxidations[J]. 高等学校化学研究, 2022, 38(3): 716-722.
[12]	FU Yu, LI Yinhui, ZHANG Wenxiang, LUO Chen, JIANG Lingchang, MA Heping. Ionic Covalent Organic Framework: What Does the Unique Ionic Site Bring to Us?[J]. 高等学校化学研究, 2022, 38(2): 296-309.
[13]	MI Zhenrui, LU Tingting, ZHANG Jia-Nan, XU Ruren, YAN Wenfu. Synthesis of Pure Silica Zeolites[J]. 高等学校化学研究, 2022, 38(1): 9-17.
[14]	LI Jun, RONG Huazhen, CHEN Cong, LI Ziyi, ZUO Jiayu, WANG Wenjian, LIU Xinjian, GUAN Yixing, YANG Xiong, LIU Yingshu, ZOU Xiaoqin, ZHU Guangshan. Synthesis Optimization of SSZ-13 Zeolite Membranes by Dual Templates for N₂/NO₂ Separation[J]. 高等学校化学研究, 2022, 38(1): 250-256.
[15]	LUAN Huimin, WU Qinming, ZHANG Jian, WANG Yeqing, MENG Xiangju, XIAO Feng-Shou. Sustainable Synthesis of Core-Shell Structured ZSM-5@Silicalite-1 Zeolite[J]. 高等学校化学研究, 2022, 38(1): 136-140.