响应面法优化设计木质素基活性炭的制备

doi:10.3969/j.issn.0253-2417.2020.03.015

林产化学与工业 ›› 2020, Vol. 40 ›› Issue (3): 115-122.doi: 10.3969/j.issn.0253-2417.2020.03.015

响应面法优化设计木质素基活性炭的制备

侯兴隆^1,²,郭奇¹,建晓朋¹,吴迪超¹,许伟¹,刘军利^1,*()

1. 中国林业科学研究院林产化学工业研究所; 生物质化学利用国家工程实验室; 国家林业和草原局林产化学工程重点实验室; 江苏省生物质能源与材料重点实验室, 江苏南京 210042
2. 南京林业大学江苏省林业资源高效加工利用协同创新中心, 江苏南京 210037

收稿日期:2019-10-23 出版日期:2020-06-28 发布日期:2020-06-29
通讯作者: 刘军利 E-mail:liujunli1974@126.com
作者简介:侯兴隆(1995-),男,山东威海人,硕士生,研究方向为多孔质炭材料的制备及应用研究
基金资助:
国家重点研发计划资助项目(2019YFB1503804);中国林科院中央级公益性科研院所基本科研业务费专项资金(CAFYBB2018SZ011);江苏省333人才项目(BRA2019293)

Optimization of Design of Lignin-based Activated Carbon Based on Response Surface Methodology

Xinglong HOU^1,²,Qi GUO¹,Xiaopeng JIAN¹,Dichao WU¹,Wei XU¹,Junli LIU^1,*()

1. Institute of Chemical Industry of Forest Products, CAF; National Engineering Lab. for Biomass Chemical Utilization; Key Lab. of Chemical Engineering of Forest Products, National Forestry and Grassland Administration; Key Lab. of Biomass Energy and Material, Jiangsu Province, Nanjing 210042, China
2. Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources, Nanjing Forestry University, Nanjing 210037, China

Received:2019-10-23 Online:2020-06-28 Published:2020-06-29
Contact: Junli LIU E-mail:liujunli1974@126.com

摘要/Abstract

摘要：

以玉米芯木质素为原料，采用磷酸活化法制备木质素基活性炭；并以亚甲基蓝吸附值为考察指标，通过Plackett-Burman设计、最陡爬坡实验和中心复合设计方法，探究了不同工艺条件在活性炭制备过程中的交互作用及最优工艺参数。结果发现：Plackett-Burman设计筛选得到的3个最重要因素分别为浸渍比、活化温度和活化时间；通过最陡爬坡实验确定了其最佳中心点区域；中心复合设计（CCD）和响应面分析（RSM）得到的最佳工艺条件为浸渍比3：1（g：g）、活化温度563℃和活化时间2.75 h。通过验证实验表明：在上述优化工艺及磷酸质量分数60%、浸渍时间12 h、浸渍温度90℃条件下，木质素基活性炭的孔径主要集中在2~10 nm，BET比表面积为1 436 m²/g，总孔容为1.041 cm³/g，微孔孔容为0.385 6 cm³/g，亚甲基蓝吸附值为240 mg/g。

关键词: 磷酸活化, 木质素, 活性炭, 中孔

Abstract:

Lignin-based activated carbon was prepared from corn cob lignin by using phosphoric acid activation method.Taking methylene blue adsorption value (MB) as the index, the interaction during the preparation of activated carbon were explored by Plackett-Burman design, the steepest climbing test, and the center composite design method.The results showed that the three most important factors obtained by Plackett-Burman design were immersion ratio, activation temperature, and activation time.The best center region was determined through the steepest climbing test.The optimal process conditions obtained by the center composite design (CCD) and response surface analysis (RSM) were impregnation ratio 3:1(g:g), activation temperature 563℃, and activation time 2.75 h. The verification experiment was performed under the above optimized process of 60% phosphoric acid mass fraction, 12 h immersion time, 90℃ immersion temperature. The pore size of the lignin-based activated carbon was mainly concentrated at 2-10 nm, the BET specific surface area was 1 436 m²/g, total pore volume was 1.041 cm³/g, the micropore pore volume was 0.385 6 cm³/g and the methylene blue adsorption value (MB)was 240 mg/g.

Key words: phosphoric acid activation, lignin, activated carbon, mesopores

中图分类号:

TQ35

侯兴隆,郭奇,建晓朋,吴迪超,许伟,刘军利. 响应面法优化设计木质素基活性炭的制备[J]. 林产化学与工业, 2020, 40(3): 115-122.

Xinglong HOU,Qi GUO,Xiaopeng JIAN,Dichao WU,Wei XU,Junli LIU. Optimization of Design of Lignin-based Activated Carbon Based on Response Surface Methodology[J]. Chemistry and Industry of Forest Products, 2020, 40(3): 115-122.

图/表 8

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序号 No.	X₁(g:g)	X₂/%	X₃/h	X₄/℃	X₅/h	X₆/℃	X₇	X₈	亚甲基蓝吸附值MB/(mg·g^-1)
序号 No.	X₁(g:g)	X₂/%	X₃/h	X₄/℃	X₅/h	X₆/℃	X₇	X₈	实验值 experimental value	预测值 predicted value
1	1:1	60	12	90	1	700	0	0	82.5	103.13
2	4:1	30	6	90	1	350	0	0	112.5	111.87
3	1:1	30	6	140	7	700	0	0	82.5	63.13
4	4:1	30	12	140	1	700	0	0	150.0	148.13
5	1:1	30	6	90	1	350	0	0	60.0	60.61
6	1:1	60	6	90	7	700	0	0	82.5	80.61
7	4:1	60	6	140	1	700	0	0	157.5	143.13
8	1:1	30	12	140	7	350	0	0	45.0	49.39
9	4:1	60	12	90	7	350	0	0	105.0	114.41
10	4:1	60	6	140	7	350	0	0	112.5	103.15
11	4:1	30	12	90	7	700	0	0	120.0	136.87
12	1:1	60	12	140	1	350	0	0	82.5	78.13

因子 factors	效应 effect	系数 coefficient	标准误差 standard error	T值 T value	P值 P value	显著性 significance
常量constant	198.76	99.38	2.13	46.55	0.000
X₁	53.76	26.88	2.13	12.59	0.001	**
X₂	8.76	4.38	2.13	2.05	0.133
X₃	11.26	5.63	2.13	2.63	0.078
X₄	-3.74	-1.87	2.13	-0.88	0.444
X₅	-16.24	-8.12	2.13	-3.81	0.032	*
X₆	26.24	13.12	2.13	6.15	0.009	**
X₇	-3.74	-1.87	2.13	-0.88	0.444
X₈	1.24	0.62	2.13	0.29	0.789

来源 source	自由度 df	平方和 SS	均方 MS	F值 F value	P值 P value	显著性 significance
模型model	8	12225.0	1528.12	27.94	0.010	*
X₁	1	8667.2	8667.19	158.49	0.001	**
X₂	1	229.7	229.69	4.20	0.133
X₃	1	379.7	379.69	6.94	0.078
X₄	1	42.2	42.19	0.77	0.444
X₅	1	792.2	792.19	14.49	0.032	*
X₆	1	2067.2	2067.19	37.80	0.009	**
X₇	1	42.2	42.19	0.77	0.444
X₈	1	4.7	4.69	0.09	0.789
误差error	3	164.1	54.69
合计total	11	12389.1

序号 No.	X₁(g:g)	X₅/h	X₆/℃	亚甲基蓝吸附值/(mg·g^-1) methylene blue adsorption
1	0.5:1	5	350	105
2	1.5:1	4	450	160
3	2.5:1	3	550	202.5
4	3.5:1	2	650	180
5	4.5:1	1	700	150

运行序号 run order	X₁(g:g)	X₅/h	X₆/℃	亚甲基蓝吸附值MB/(mg·g^-1)
运行序号 run order	X₁(g:g)	X₅/h	X₆/℃	实验值 experimental value	预测值 predicted value
1	3.0:1	3.5	575	97.5	94.88
2	2.5:1	3.0	550	210.0	207.33
3	3.5:1	3.0	550	180.0	182.96
4	2.5:1	3.0	550	105.0	106.17
5	2.5:1	3.0	550	165.0	169.81
6	3.0:1	2.5	525	180.0	179.95
7	2.5:1	3.0	550	210.0	207.33
8	2.5:1	2.0	500	202.5	204.67
9	2.5:1	3.0	550	202.5	207.33
10	2.5:1	4.0	600	165.0	168.81
11	2.5:1	3.0	550	210.0	207.33
12	1.5:1	3.0	550	120.0	123.02
13	2.0:1	3.5	575	127.5	126.73
14	2.0:1	2.5	525	120.0	118.39
15	2.5:1	3.0	550	202.5	207.33
16	3.0:1	3.5	575	202.5	200.22
17	2.0:1	3.5	575	165.0	160.83
18	2.5:1	3.0	550	210.0	207.33
19	2.0:1	2.5	525	150.0	148.05
20	3.0:1	2.5	525	225.0	221.54

响应面法优化设计木质素基活性炭的制备

Optimization of Design of Lignin-based Activated Carbon Based on Response Surface Methodology

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来源 source	自由度 df	平方和 SS	均方 MS	F值 F value	P值 P value
模型model	9	30302.23	3366.91	181.73	< 0.0001
X₁	1	4338.28	4338.28	234.16	< 0.0001
X₅	1	1551.59	1551.59	83.75	< 0.0001
X₆	1	4889.45	4889.45	263.91	< 0.0001
X₁X₅	1	2032.03	2032.03	109.68	< 0.0001
X₁X₆	1	2538.28	2538.28	137.00	< 0.0001
X₅X₆	1	2032.03	2032.03	109.68	< 0.0001
X₁²	1	5319.04	5319.04	287.09	< 0.0001
X₅²	1	763.62	763.62	41.22	< 0.0001
X₆²	1	8660.95	8660.95	467.47	< 0.0001
残差residual	10	185.27	18.53
失拟项lack of fit	5	110.27	22.05	1.47	0.3413
纯误差pure error	5	75.00	15.00
总变异cor total	19	30487.50