钴基费托合成复合集总宏观动力学模型及工业单管模拟

doi:10.11949/0438-1157.20250514

化工学报

• •

钴基费托合成复合集总宏观动力学模型及工业单管模拟

夏铭¹(), 黄帅², 石慧³, 牛丛丛⁴, 李德宝⁵, 乔旭¹^,⁶

^1.南京工业大学化工学院材料化学工程全国重点实验室，江苏南京 211816
^2.天华化工机械及自动化研究设计院有限公司，甘肃兰州 730060
^3.南京工业大学化学与分子工程学院，江苏南京 211816
^4.中石化石油化工科学研究院有限公司，北京 10083
^5.中国科学院山西煤炭化学研究所，山西太原 030001
^6.国家“江苏先进生物与化学制造协同创新中心”，江苏南京 211816

收稿日期:2025-05-09 修回日期:2025-06-13 出版日期:2025-07-08
通讯作者: 夏铭
基金资助:
国家自然科学基金项目(22202225);国家自然科学基金项目(22208361);国家自然科学基金项目(22208154);南京工业大学新进人才启动项目(39801177)

The Hybrid Lumping Macroscopic Kinetic Model for Cobalt-Based Fischer-Tropsch Synthesis and its Application in Industrial Single-Tube Simulation

Ming XIA¹(), Shuai HUANG², Hui SHI³, Congcong NIU⁴, Debao LI⁵, Xu QIAO¹^,⁶

^1.College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^2.Tianhua Institute of Chemical Machinery and Automation Co. , Ltd, Lanzhou 730060, Gansu, China
^3.School of Chemistry and Molecular Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^4.Sinopec Research Institute of Petroleum Processing CO. , LTD, Beijing 100083, China
^5.Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China
^6.Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing 211816, Jiangsu, China

Received:2025-05-09 Revised:2025-06-13 Online:2025-07-08
Contact: Ming XIA

摘要/Abstract

摘要：

采用集总动力学思想与链增长概率模型，结合工业单管试验数据，建立了钴基费托合成包含合成气消耗速率和集总组分选择性模型的复合集总宏观动力学模型。研究结果表明，建立的宏观集总动力学模型计算的单管CO单程转化率与试验值吻合良好，计算的集总组分CH₄、C₃H₈、C₁₂H₂₆和C₂₉H₆₀的时空收率与对应工况的试验值亦符合良好，绝大多数相对偏差在15%以内；将该复合集总宏观动力学模型应用于工业单管装置的全流程建模与模拟，结果表明该模型较好地计算不同工况下蜡油、水的流率以及CO的转化率。本文提出的钴基费托合成复合集总宏观动力学模型及其全流程模型方法，具有待定参数数量适中，能够同时模拟合成气转化率和集总组分生成速率的优点，表现出较好的应用与学术价值，有望拓展应用至其它类似的反应体系。

关键词: 费托合成, 宏观动力学, 集总动力学, 钴基催化剂

Abstract:

A hybrid lumping macroscopic kinetic model for cobalt-based Fischer-Tropsch synthesis was established, encompassing models for syngas-consumption rate and lumping fraction selectivity by adopting the lumping kinetics concept and the chain growth probability model on the basis of industrial single-tube experimental data. Research results indicate that the CO single-pass conversion calculated by the established macroscopic lumping kinetic model aligns well with experimental values, and the calculated space-time yields of lump components such as methane, C3 hydrocarbons, C12 hydrocarbons, and C29 hydrocarbons also show good agreement with experimental values under corresponding operating conditions, with maximum relative deviations usually <15%. Furthermore, the hybrid lumping macroscopic kinetic model was applied to modeling and simulation of the entire industrial single-tube unit process, it is demonstrated good performance in calculating the flow rates of wax oil and water, as well as the single-pass and overall CO conversion rates under different operating conditions. The hybrid lumping macroscopic kinetic model and its full-process modeling method for the cobalt-based Fischer-Tropsch synthesis proposed in this paper have the advantages of a moderate number of undetermined parameters and the ability to simultaneously simulate syngas conversion rate and lump component generation rates, showing good application value and academic significance. The presented hybrid lumping model could be extended to other similar reaction systems.

Key words: Fischer-Tropsch Synthesis, Macrokinetics, Lumped kinetics, Cobalt-based catalyst

中图分类号:

TQ 021

夏铭, 黄帅, 石慧, 牛丛丛, 李德宝, 乔旭. 钴基费托合成复合集总宏观动力学模型及工业单管模拟[J]. 化工学报, DOI: 10.11949/0438-1157.20250514.

Ming XIA, Shuai HUANG, Hui SHI, Congcong NIU, Debao LI, Xu QIAO. The Hybrid Lumping Macroscopic Kinetic Model for Cobalt-Based Fischer-Tropsch Synthesis and its Application in Industrial Single-Tube Simulation[J]. CIESC Journal, DOI: 10.11949/0438-1157.20250514.

图/表 9

参考文献 30

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	反应条件					产物生成质量，8小时					放料间隔	CO 总转化率	CO单程转化率，实验值Xsexp	CO单程转化率，计算值Xscalc	进料中各组分与CO的摩尔比				M0=1+R1+R2+R3+R4	单程转化的 CO物质的量	系数						实验数据计算的各段平均分子量
时间	T	P	U	V	V0	CH₄	C₃H₈	C₁₂H₂₆	C₂₉H₆₀	H₂O	t	X	Xsexp	Xscalc	R1, H2/CO	R2, CO2/CO	R3, CH4/CO	R4, N2/CO	M0	m_COs	A, CH4	B, C3	C, C12	D, C29	E, H2O	MCH4	MC3	MC12	MC29	MH2O
	K	MPa			L	g	g	g	g	g		%	%	%	/	/	/	/	/	mol						g/mol	g/mol	g/mol	g/mol	g/mol
2019.06.02	464.05	6.07	2.121	141.346	141346	1771.64	601.57	2948.62	2964.91	9924	8	79.18	31.378	30.97	2.414	0	0.295	0.205	3.914	1276.53	0.087	3.821	4.761	1.707	140.862	16	40.22	158.24	443.8	18
2019.06.05	467.85	6.08	2.009	137.583	137583	2026.62	773.86	3573.76	2482.79	10898	8	75.69	36.038	36.46	2.431	0	0.444	0.212	4.087	1137.498	0.111	4.616	5.335	1.443	148.139	16	41.02	163.9	420.89	18
2019.06.09	473.35	6.07	1.994	136.235	136235	1871.86	684.61	4503.84	2803.50	11687	8	77.48	34.439	33.94	1.921	0	0.421	0.192	3.534	1333.259	0.088	4.799	7.632	1.963	183.702	16	40.36	166.96	404.16	18
2019.06.10	473.45	6.06	2.102	139.371	139371	1735.6	658.86	3798.21	3561.24	11469	8	74.36	30.922	30.48	1.804	0	0.312	0.187	3.303	1400.732	0.077	4.977	7.082	2.418	192.905	16	40.08	162.37	445.87	18
2019.06.12	473.65	6.08	1.971	139.147	139147	1241.75	545.73	3890.46	3719.36	11437	8	74.07	29.439	29.98	1.675	0	0.244	0.231	3.150	1460.689	0.053	4.422	7.346	2.580	201.711	16	39.18	168.13	457.73	18
2019.06.13	473.65	6.08	1.996	142.245	142245	1273.47	561.31	3882.04	3647.42	11252	8	73.37	28.011	27.96	1.598	0	0.207	0.196	3.001	1552.535	0.051	4.893	7.859	2.824	208.301	16	38.23	164.6	430.31	18
2019.06.21	484.05	6.07	2.076	140.504	140504	1226.43	503.67	4221.75	4793.27	12939	8	83.38	30.848	32.24	1.520	0	0.307	0.258	3.085	1695.303	0.045	4.044	7.531	3.497	233.009	16	40.37	181.72	444.36	18
2019.06.24	488.95	6.07	2.005	132.947	132947	1314.00	374.07	5383.6	4094.02	13514	8	88.25	33.178	33.63	1.380	0	0.503	0.397	3.280	1596.877	0.051	2.873	9.407	3.000	228.896	16	39.69	174.48	415.99	18
2019.07.01	493.55	6.04	2.063	139.369	139369	1167.82	620.68	5413.03	5152.76	15192	8	87.66	35.540	33.23	1.310	0	0.35	0.349	3.009	1812.581	0.040	5.290	10.832	3.837	280.492	16	38.99	166.08	446.34	18
2019.07.08	493.85	6.05	1.97	145.156	145156	1479.35	708.24	4875.58	5282.83	15253	8	85.89	35.684	37.09	1.440	0	0.372	0.25	3.062	1817.709	0.051	6.122	9.904	3.915	276.744	16	37.78	160.77	440.72	18
2019.07.12	498.95	6.05	2.044	148.188	148188	1626.57	724.48	5405.9	6390.77	17146	8	86.10	37.749	37.66	1.400	0	0.362	0.287	3.049	1868.146	0.054	6.196	11.422	4.466	312.416	16	38.35	155.22	469.36	18

	反应条件					产物生成质量，8小时					放料间隔	CO 总转化率	CO单程转化率，实验值Xsexp	CO单程转化率，计算值Xscalc	进料中各组分与CO的摩尔比				M0=1+R1+R2+R3+R4	单程转化的 CO物质的量	系数						实验数据计算的各段平均分子量
时间	T	P	U	V	V0	CH₄	C₃H₈	C₁₂H₂₆	C₂₉H₆₀	H₂O	t	X	Xsexp	Xscalc	R1, H2/CO	R2, CO2/CO	R3, CH4/CO	R4, N2/CO	M0	m_COs	A, CH4	B, C3	C, C12	D, C29	E, H2O	MCH4	MC3	MC12	MC29	MH2O
	K	MPa			L	g	g	g	g	g		%	%	%	/	/	/	/	/	mol						g/mol	g/mol	g/mol	g/mol	g/mol
2019.06.02	464.05	6.07	2.121	141.346	141346	1771.64	601.57	2948.62	2964.91	9924	8	79.18	31.378	30.97	2.414	0	0.295	0.205	3.914	1276.53	0.087	3.821	4.761	1.707	140.862	16	40.22	158.24	443.8	18
2019.06.05	467.85	6.08	2.009	137.583	137583	2026.62	773.86	3573.76	2482.79	10898	8	75.69	36.038	36.46	2.431	0	0.444	0.212	4.087	1137.498	0.111	4.616	5.335	1.443	148.139	16	41.02	163.9	420.89	18
2019.06.09	473.35	6.07	1.994	136.235	136235	1871.86	684.61	4503.84	2803.50	11687	8	77.48	34.439	33.94	1.921	0	0.421	0.192	3.534	1333.259	0.088	4.799	7.632	1.963	183.702	16	40.36	166.96	404.16	18
2019.06.10	473.45	6.06	2.102	139.371	139371	1735.6	658.86	3798.21	3561.24	11469	8	74.36	30.922	30.48	1.804	0	0.312	0.187	3.303	1400.732	0.077	4.977	7.082	2.418	192.905	16	40.08	162.37	445.87	18
2019.06.12	473.65	6.08	1.971	139.147	139147	1241.75	545.73	3890.46	3719.36	11437	8	74.07	29.439	29.98	1.675	0	0.244	0.231	3.150	1460.689	0.053	4.422	7.346	2.580	201.711	16	39.18	168.13	457.73	18
2019.06.13	473.65	6.08	1.996	142.245	142245	1273.47	561.31	3882.04	3647.42	11252	8	73.37	28.011	27.96	1.598	0	0.207	0.196	3.001	1552.535	0.051	4.893	7.859	2.824	208.301	16	38.23	164.6	430.31	18
2019.06.21	484.05	6.07	2.076	140.504	140504	1226.43	503.67	4221.75	4793.27	12939	8	83.38	30.848	32.24	1.520	0	0.307	0.258	3.085	1695.303	0.045	4.044	7.531	3.497	233.009	16	40.37	181.72	444.36	18
2019.06.24	488.95	6.07	2.005	132.947	132947	1314.00	374.07	5383.6	4094.02	13514	8	88.25	33.178	33.63	1.380	0	0.503	0.397	3.280	1596.877	0.051	2.873	9.407	3.000	228.896	16	39.69	174.48	415.99	18
2019.07.01	493.55	6.04	2.063	139.369	139369	1167.82	620.68	5413.03	5152.76	15192	8	87.66	35.540	33.23	1.310	0	0.35	0.349	3.009	1812.581	0.040	5.290	10.832	3.837	280.492	16	38.99	166.08	446.34	18
2019.07.08	493.85	6.05	1.97	145.156	145156	1479.35	708.24	4875.58	5282.83	15253	8	85.89	35.684	37.09	1.440	0	0.372	0.25	3.062	1817.709	0.051	6.122	9.904	3.915	276.744	16	37.78	160.77	440.72	18
2019.07.12	498.95	6.05	2.044	148.188	148188	1626.57	724.48	5405.9	6390.77	17146	8	86.10	37.749	37.66	1.400	0	0.362	0.287	3.049	1868.146	0.054	6.196	11.422	4.466	312.416	16	38.35	155.22	469.36	18

T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{1, exp}	α _{1, calc}	W_{1, exp}	W_{1, calc}	RD %
464.05	6.07	3715.27	2.414	0.5419	0.5262	0.2138	0.2245	-5.01
467.85	6.08	3728.25	2.431	0.5269	0.5260	0.2288	0.2246	1.82
473.35	6.07	3789.95	1.921	0.5604	0.5803	0.1898	0.1762	7.17
473.45	6.06	3786.64	1.804	0.5737	0.5954	0.1779	0.1637	7.99
473.65	6.08	3764.47	1.675	0.6309	0.6153	0.1321	0.1480	-12.02
473.65	6.08	3774.52	1.598	0.6260	0.6271	0.1360	0.1391	-2.25
484.05	6.07	3961.53	1.52	0.6574	0.6395	0.1141	0.1300	-13.88
488.95	6.07	4209.79	1.38	0.6525	0.6613	0.1177	0.1147	2.54
493.55	6.04	4193.09	1.31	0.6885	0.6772	0.0945	0.1042	-10.26
493.85	6.05	4204.55	1.44	0.6495	0.6513	0.1198	0.1216	-1.46
498.95	6.05	4336.51	1.4	0.6563	0.6579	0.1150	0.1170	-1.78

T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{1, exp}	α _{1, calc}	W_{1, exp}	W_{1, calc}	RD %
464.05	6.07	3715.27	2.414	0.5419	0.5262	0.2138	0.2245	-5.01
467.85	6.08	3728.25	2.431	0.5269	0.5260	0.2288	0.2246	1.82
473.35	6.07	3789.95	1.921	0.5604	0.5803	0.1898	0.1762	7.17
473.45	6.06	3786.64	1.804	0.5737	0.5954	0.1779	0.1637	7.99
473.65	6.08	3764.47	1.675	0.6309	0.6153	0.1321	0.1480	-12.02
473.65	6.08	3774.52	1.598	0.6260	0.6271	0.1360	0.1391	-2.25
484.05	6.07	3961.53	1.52	0.6574	0.6395	0.1141	0.1300	-13.88
488.95	6.07	4209.79	1.38	0.6525	0.6613	0.1177	0.1147	2.54
493.55	6.04	4193.09	1.31	0.6885	0.6772	0.0945	0.1042	-10.26
493.85	6.05	4204.55	1.44	0.6495	0.6513	0.1198	0.1216	-1.46
498.95	6.05	4336.51	1.4	0.6563	0.6579	0.1150	0.1170	-1.78

T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{3, exp}	α _{3, calc}	W_{3, exp}	W_{3, calc}	RD %
464.05	6.07	3715.27	2.414	0.8120	0.8052	0.0726	0.0738	-1.65
467.85	6.08	3728.25	2.431	0.7868	0.7931	0.0874	0.0808	7.56
473.35	6.07	3789.95	1.921	0.8120	0.8103	0.0694	0.0709	-2.13
473.45	6.06	3786.64	1.804	0.8120	0.8141	0.0675	0.0687	-1.72
473.65	6.08	3764.47	1.675	0.8281	0.8274	0.0581	0.0612	-5.38
473.65	6.08	3774.52	1.598	0.8259	0.8366	0.0599	0.0561	6.48
484.05	6.07	3961.53	1.52	0.8492	0.8309	0.0469	0.0592	-26.35
488.95	6.07	4209.79	1.38	0.8754	0.8745	0.0335	0.0361	-7.80
493.55	6.04	4193.09	1.31	0.8436	0.8439	0.0502	0.0521	-3.63
493.85	6.05	4204.55	1.44	0.8289	0.8349	0.0574	0.0570	0.64
498.95	6.05	4336.51	1.4	0.8400	0.8417	0.0512	0.0533	-4.02

钴基费托合成复合集总宏观动力学模型及工业单管模拟

The Hybrid Lumping Macroscopic Kinetic Model for Cobalt-Based Fischer-Tropsch Synthesis and its Application in Industrial Single-Tube Simulation

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流股		新鲜气	循环气	入器气	费托蜡1	费托油2	费托油3	费托水1	费托水2	弛放气
		FF1	REC-S	FRIN	FT-WAX1	FT-OIL2	FT-OIL3	FT-WAT1	FT-WAT2	PURGE
模拟值	流量, kg/h	4.052	5.507	9.558	0.763	0.067	0.003	1.077	0.273	1.868
	流量, kg/h	4.052	5.507	9.558	SUM = 0.833			SUM=1.350		1.868
	质量或摩尔分数	mol/mol	mol/mol	mol/mol	wt/wt	wt/wt	wt/wt	wt/wt	wt/wt	mol/mol
	H₂	0.6703	0.5636	0.6138	0.0005	0.0004	0.0004	0	0.0000	0.5636
	CO	0.2886	0.2245	0.2547	0.0044	0.0050	0.0061	0	0.0000	0.2245
	N₂	0.0281	0.0723	0.0515	0.0086	0.0214	0.0418	0.0010	0.0006	0.0723
	CH₄	0.0129	0.1269	0.0732	0.0026	0.0039	0.0055	0	0.0000	0.1269
	C₃H₈	0	0.0114	0.0060	0.0038	0.0131	0.0308	0	0	0.0114
	C₁₂H₂₆	0	0	0	0.4719	0.9530	0.9047	0	0	0
	C₂₉H₆₀	0	0	0	0.4991	0.0001	0	0	0	0
	H₂O	0	0.0014	0.0007	0.0092	0.0031	0.0108	0.9989	0.9993	0.0014
试验值	流量, kg/h	3.814			SUM = 0.713, 各组分已全分析，不便列出			SUM = 1.241, 不便列出		1.822
	质量分数，wt/wt	mol/mol	mol/mol	mol/mol						mol/mol
	H₂	0.6728	0.5875	0.6114						0.5875
	CO	0.2990	0.2334	0.2533						0.2334
	N₂	0.018	0.0460	0.0518						0.0460
	CH₄	0.0023	0.1060	0.0747						0.1060
	C₂H₆+	/
	H₂O	/
相对误差	(模拟值-试验值)/试验值100	+6.24			+16.8			+8.87		+2.52

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T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{12, exp}	α _{12, calc}	W_{12, exp}	W_{12, calc}	RD %
464.05	6.07	3715.27	2.414	0.9143	0.9155	0.3558	0.3840	-7.91
467.85	6.08	3728.25	2.431	0.9182	0.9177	0.4035	0.3840	4.84
473.35	6.07	3789.95	1.921	0.9232	0.9187	0.4566	0.3839	15.93
473.45	6.06	3786.64	1.804	0.9171	0.9170	0.3894	0.3840	1.39
473.65	6.08	3764.47	1.675	0.9232	0.9236	0.4140	0.3825	7.61
473.65	6.08	3774.52	1.598	0.9232	0.9244	0.4146	0.3821	7.84
484.05	6.07	3961.53	1.52	0.9174	0.9223	0.3929	0.3830	2.52
488.95	6.07	4209.79	1.38	0.9236	0.9248	0.4822	0.3819	20.80
493.55	6.04	4193.09	1.31	0.9232	0.9168	0.4381	0.3840	12.36
493.85	6.05	4204.55	1.44	0.9175	0.9179	0.3949	0.3839	2.78
498.95	6.05	4336.51	1.4	0.9165	0.9185	0.3821	0.3839	-0.47

T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{12, exp}	α _{12, calc}	W_{12, exp}	W_{12, calc}	RD %
464.05	6.07	3715.27	2.414	0.9143	0.9155	0.3558	0.3840	-7.91
467.85	6.08	3728.25	2.431	0.9182	0.9177	0.4035	0.3840	4.84
473.35	6.07	3789.95	1.921	0.9232	0.9187	0.4566	0.3839	15.93
473.45	6.06	3786.64	1.804	0.9171	0.9170	0.3894	0.3840	1.39
473.65	6.08	3764.47	1.675	0.9232	0.9236	0.4140	0.3825	7.61
473.65	6.08	3774.52	1.598	0.9232	0.9244	0.4146	0.3821	7.84
484.05	6.07	3961.53	1.52	0.9174	0.9223	0.3929	0.3830	2.52
488.95	6.07	4209.79	1.38	0.9236	0.9248	0.4822	0.3819	20.80
493.55	6.04	4193.09	1.31	0.9232	0.9168	0.4381	0.3840	12.36
493.85	6.05	4204.55	1.44	0.9175	0.9179	0.3949	0.3839	2.78
498.95	6.05	4336.51	1.4	0.9165	0.9185	0.3821	0.3839	-0.47

T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{29, exp}	α _{29, calc}	W_{29, exp}	W_{29, exp}	RD %
464.05	6.07	3715.27	2.414	0.9698	0.9650	0.3578	0.3743	-4.62
467.85	6.08	3728.25	2.431	0.9676	0.9678	0.2803	0.3734	-33.22
473.35	6.07	3789.95	1.921	0.9601	0.9681	0.2842	0.3732	-31.30
473.45	6.06	3786.64	1.804	0.9649	0.9673	0.3651	0.3738	-2.39
473.65	6.08	3764.47	1.675	0.9707	0.9687	0.3958	0.3726	5.86
473.65	6.08	3774.52	1.598	0.9705	0.9683	0.3895	0.3730	4.23
484.05	6.07	3961.53	1.52	0.9716	0.9703	0.4461	0.3704	16.98
488.95	6.07	4209.79	1.38	0.9649	0.9684	0.3667	0.3729	-1.71
493.55	6.04	4193.09	1.31	0.9711	0.9691	0.4171	0.3721	10.79
493.85	6.05	4204.55	1.44	0.9713	0.9703	0.4279	0.3703	13.46
498.95	6.05	4336.51	1.4	0.9717	0.9709	0.4517	0.3690	18.31

T, K	P, MPag	GHSV, h^-1	R1, H₂/CO	α _{29, exp}	α _{29, calc}	W_{29, exp}	W_{29, exp}	RD %
464.05	6.07	3715.27	2.414	0.9698	0.9650	0.3578	0.3743	-4.62
467.85	6.08	3728.25	2.431	0.9676	0.9678	0.2803	0.3734	-33.22
473.35	6.07	3789.95	1.921	0.9601	0.9681	0.2842	0.3732	-31.30
473.45	6.06	3786.64	1.804	0.9649	0.9673	0.3651	0.3738	-2.39
473.65	6.08	3764.47	1.675	0.9707	0.9687	0.3958	0.3726	5.86
473.65	6.08	3774.52	1.598	0.9705	0.9683	0.3895	0.3730	4.23
484.05	6.07	3961.53	1.52	0.9716	0.9703	0.4461	0.3704	16.98
488.95	6.07	4209.79	1.38	0.9649	0.9684	0.3667	0.3729	-1.71
493.55	6.04	4193.09	1.31	0.9711	0.9691	0.4171	0.3721	10.79
493.85	6.05	4204.55	1.44	0.9713	0.9703	0.4279	0.3703	13.46
498.95	6.05	4336.51	1.4	0.9717	0.9709	0.4517	0.3690	18.31