基于不同发泡剂的木质素基泡沫炭的制备及性能研究

doi:10.3969/j.issn.0253-2417.2020.04.009

摘要/Abstract

摘要：

采用玉米秸秆碱木质素部分替代苯酚与甲醛反应合成木质素基酚醛树脂，并利用正戊烷、正己烷、活性炭负载正己烷3种发泡剂，经过物理发泡、高温炭化分别制备得到木质素基泡沫炭CF-P、CF-H和CF-ACH。研究结果表明：不同发泡剂发泡制备得到的木质素基酚醛泡沫均具有良好的热稳定性，经800℃热分解后的最终炭收率依然为47.95%；木质素基酚醛树脂泡沫炭为非石墨化无定型炭，孔形呈球形或椭球形，孔径分布在20~300 μm之间；3种泡沫炭表观密度在0.15~0.55 g/cm³之间，最高压缩强度可达13.13 MPa；CF-P、CF-ACH、CF-H比表面积分别为471.22、186.72和42.08 m²/g，开孔率都大于64%，微孔面积百分比均在77%以上。

关键词: 木质素, 发泡剂, 泡沫炭

Abstract:

The lignin-based phenolic resin was synthesized by condensation reaction of phenol and formaldehyde, in which part of phenol was replaced with alkaline cornstalk lignin. To evaluate the effect of foaming agents on the structure property of the carbon foams, n-hexane, n-pentane and activated carbon loaded n-hexane were chosen as the foaming agents, and the prepared carbon foams were signed as CF-H, CF-P, and CF-ACH, respectively. The results indicated that the lignin-based phenolic foams prepared by different foaming agents exhibited excellent thermal stability, evidenced by the higher residual carbon recovery rate of 47.95% after thermal decomposition at 800 ℃. All of the prepared carbon foams belonged to amorphous carbon, in which non-graphitized carbonaceous structure was detected. The pore shape of CF-H, CF-P, and CF-ACH was spherical or ellipsoid with the pore size distribution of 20-300 μm, and their apparent densities ranged from 0.15 to 0.55 g/cm³. Compared with the normal carbon foams, the prepared lignin-based carbon foams had considerable compressive strength and the maximum compressive strength reached 13.13 MPa. In addition, the specific surface areas of CF-P, CF-ACH, and CF-H were 471.22 m²/g, 186.72 m²/g, and 42.08 m²/g, respectively. The pore opening rates of the carbon foams were all above 64%, and the area percentages of micropore were above 77%.

Key words: lignin, foaming agent, carbon foam

中图分类号:

TQ35

朱恩清,史正军,刘守庆,杨静,王大伟,杨海艳. 基于不同发泡剂的木质素基泡沫炭的制备及性能研究[J]. 林产化学与工业, 2020, 40(4): 63-70.

Enqing ZHU,Zhengjun SHI,Shouqing LIU,Jing YANG,Dawei WANG,Haiyan YANG. Preparation and Properties Evaluation of Lignin-based Carbon Foams with Different Foaming Agent[J]. Chemistry and Industry of Forest Products, 2020, 40(4): 63-70.

图/表 9

图1

图2

表1

图3

表2

图4

图5

图6

图7

参考文献 23

1	FARHAN S , WANG R M , LI K Z . Physical and electromagnetic shielding properties of green carbon foam prepared from biomaterials[J]. Transactions of Nonferrous Metals Society of China, 2018, 28 (1): 103- 113. doi: 10.1016/S1003-6326(18)64643-6
2	WANG C, PENG L, SHI Z H, et al.Preparation, thermal stability and deflection of a density gradient thermally-conductive carbon foam material derived from phenolic resin[J/OL]. Results in Physics, 2019, 14: 1-12[2019-10-30].http://doi.org/10.1016/j.rinp.2019.102448.
3	AGRAWAL P R , KUMAR R , TEOTIA S , et al. Lightweight, high electrical and thermal conducting carbon-rGO composites foam for superior electromagnetic interference shielding[J]. Composites Part B:Engineering, 2019, 160, 131- 139. doi: 10.1016/j.compositesb.2018.10.033
4	INAGAKI M , QIU J , GUO Q . Carbon foam:Preparation and application[J]. Carbon, 2015, 87, 128- 152. doi: 10.1016/j.carbon.2015.02.021
5	JANA P , BARRIO E P D , FIERRO V , et al. Design of carbon foams for seasonal solar thermal energy storage[J]. Carbon, 2016, 109, 771- 787. doi: 10.1016/j.carbon.2016.08.048
6	LI Q , CHEN L , DING J , et al. Open-cell phenolic carbon foam and electromagnetic interference shielding properties[J]. Carbon, 2016, 104, 90- 105. doi: 10.1016/j.carbon.2016.03.055
7	周方浪, 郑志锋, 杨静, 等. 木质素基酚醛树脂泡沫的制备及性能研究[J]. 林产化学与工业, 2018, 38 (6): 107- 113.
	ZHOU F L , ZHENG Z F , YANG J , et al. Preparation and characterization of lignin based phenolic foam[J]. Chemistry and Industry of Forest Products, 2018, 38 (6): 107- 113.
8	KLETT J , HARDY R , ROMINE E , et al. High-thermal-conductivity, mesophase-pitch-derived carbon foams:Effect of precursor on structure and properties[J]. Carbon, 2000, 38 (7): 953- 973. doi: 10.1016/S0008-6223(99)00190-6
9	SEO J , PARK H , SHIN K , et al. Lignin-derived macroporous carbon foams prepared by using poly(methyl methacrylate) particles as the template[J]. Carbon, 2014, 76, 357- 367. doi: 10.1016/j.carbon.2014.04.087
10	陈然.酚醛树脂基泡沫炭的制备及其结构控制[D].广州:华南理工大学, 2015.
	CHEN R.Preparation and structure control of phenlic resin based carbon foams[D]. Guangzhou: South China University of Technology, 2015.
11	黄普林.增韧阻燃酚醛泡沫的制备及性能研究[D].武汉:武汉工程大学, 2016.
	HUANG P L.Study on preparation and properties of toughened and flame retardant phenolic foam[D]. Wuhan: Wuhan Institute of Technology, 2016.
12	周方浪, 杨静, 杨海艳, 等. KOH原位活化对木质素基泡沫炭的结构性能调控[J]. 林业工程学报, 2019, 4 (2): 105- 111.
	ZHOU F L , YANG J , YANG H Y , et al. The in situ regulation of structural properties of lignin-based carbon foam by KOH[J]. Journal of Forestry Engineering, 2019, 4 (2): 105- 111.
13	MOUGEL C , GARNIER T , CASSAGNAU P . Phenolic foams:A review of mechanical properties, fire resistance and new trends in phenol substitution[J]. Polymer, 2019, 164, 86- 117. doi: 10.1016/j.polymer.2018.12.050
14	LI X M , LIU S Q , HUANG Y B , et al. Preparation and foaming mechanism of pyrocarbon foams controlled by activated carbon as the transplantation Core[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (3): 3515- 3524.
15	BAI J , CHEN X , SHAO J , et al. Study of breakage of main covalent bonds during co-pyrolysis of oil shale and alkaline lignin by TG-FTIR integrated analysis[J]. Journal of the Energy Institute, 2019, 92 (3): 512- 522. doi: 10.1016/j.joei.2018.04.007
16	李雪梅, 刘守庆, 黄元波, 等. 高强度酚醛树脂泡沫炭的制备研究[J]. 林产化学与工业, 2016, 36 (5): 53- 60. doi: 10.3969/j.issn.0253-2417.2016.05.008
	LI X M , LIU S Q , HUANG Y B , et al. Preparation of carbon foams with high compressive strength derived from phenolic resin[J]. Chemistry and Industry of Forest Products, 2016, 36 (5): 53- 60. doi: 10.3969/j.issn.0253-2417.2016.05.008
17	NARASIMMAN R , PRABHAKARAN K . Preparation of carbon foams with enhanced oxidation resistance by foaming molten sucrose using a boric acid blowing agent[J]. Carbon, 2013, 55, 305- 312. doi: 10.1016/j.carbon.2012.12.068
18	LI X , LIU S , HUANG Y , et al. Preparation and foaming mechanism of pyrocarbon foams controlled by activated carbon as the transplantation core[J]. ACS Sustainable Chemistry & Engineering, 2018, 6 (3): 3515- 3524.
19	KEARSLEY E P , WAINWRIGHT P J . The effect of porosity on the strength of foamed concrete[J]. Cement & Concrete Research, 2002, 32 (2): 233- 239.
20	QI L L , XU T , WANG Z F , et al. Pore characterization of different types of coal from coal and gas outburst disaster sites using low temperature nitrogen adsorption approach[J]. International Journal of Mining Science and Technology, 2017, 2 (27): 371- 377.
21	INAGAKI M . Carbon Materials Science and Engineering:From Fundament-Alsto Applications[M]. Beijing: Tsinghua University Press, 2006: 92- 120.
22	万永坤, 刘守庆, 赵建蓉, 等. 核桃壳粉液化产物大孔泡沫炭的制备研究[J]. 西南林业大学学报, 2017, 37 (3): 192- 198.
	WAN Y K , LIU S Q , ZHAO J R , et al. The preparation of carbon foam with macropores structure from the phenolated walnut shell powder[J]. Journal of Southwest Forestry University, 2017, 37 (3): 192- 198.
23	赵鑫, 李伟, 刘守新, 等. 泡沫炭的制备及应用[J]. 林产化学与工业, 2012, 32 (3): 117- 125.
	ZHAO X , LI W , LIU S H , et al. Preparation and apllication of carbon foams[J]. Chemistry and Industry of Forest Products, 2012, 32 (3): 117- 125.

样品 sample	发泡剂 foaming agent	真密度/(g·cm^-3) true density	开孔率/% open porosity	闭孔率/% close porosity
CF-H	正己烷n-hexane	1.56	64.37	35.63
CF-ACH	活性炭负载正己烷activated carbon loaded by n-hexane	1.31	70.87	29.13
CF-P	正戊烷n-pentane	1.30	87.63	12.37

样品 sample	S_BET/ (m²·g^-1)	S_mi/ (m²·g^-1)	P_mi/%	S_ex/ (m²·g^-1)	P_ex/%	V_mi/ (cm³·g^-1)	V_me/ (cm³·g^-1)	V_to/ (cm³·g^-1)	A/nm
CF-H	42.08	38.47	91.42	3.60	8.60	0.016	0.011	0.027	7.04
CF-ACH	186.72	144.57	77.43	42.16	22.58	0.059	1.05	1.11	2.38
CF-P	471.22	421.17	89.38	50.05	10.62	0.16	1.96	2.12	1.80

[1]	钟磊,王超,吕高金,吉兴香,杨桂花,陈嘉川. 低共熔溶剂在木质素分离方面的研究进展[J]. 林产化学与工业, 2020, 40(3): 12-22.
[2]	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.
[3]	储秋露,陈雪艳,宋凯,王静,张晓东,施爱平. 两步法预处理对杨木酶水解及木质素吸附性能的影响[J]. 林产化学与工业, 2019, 39(6): 68-74.
[4]	卢传巍,郭晓亮,蔡青云,王春鹏,储富祥,王基夫. 甲基丙烯酸化木质素磺酸钙/聚丙烯酰胺复合水凝胶的制备与性能研究[J]. 林产化学与工业, 2019, 39(6): 75-80.
[5]	李宁,陈智糠,张一甫. 酚化木质素改性酚醛树脂胶黏剂的制备及性能表征[J]. 林产化学与工业, 2019, 39(6): 95-101.
[6]	陈雪艳, 储秋露, 王静, 张晓东, 施爱平. 两步法预处理脱除木质素对杨木酶水解的影响[J]. 林产化学与工业, 2019, 39(5): 73-79.
[7]	王兴佳, 乔炜, 肖达明, 李淑君. 铝氧单钠固体超强碱催化降解木质素的研究[J]. 林产化学与工业, 2019, 39(5): 80-86.
[8]	张清桐,运晓静,颜德鹏,李明富,王双飞,闵斗勇. 太阳光催化木质素制备银纳米颗粒[J]. 林产化学与工业, 2019, 39(4): 35-41.
[9]	孙永昌,张冰清,刘力鸣,刘肖南,史正军. 木质素基炭材料的制备及其对Cr(Ⅵ)的吸附机制研究[J]. 林产化学与工业, 2019, 39(4): 120-128.
[10]	陈超,王傲,孙康,卢辛成,许伟,蒋剑春. 生物质原料的Ni催化石墨化研究[J]. 林产化学与工业, 2019, 39(3): 94-100.
[11]	赵存异,应文俊,史正军,杨海艳,郑志锋,杨静. 羟丙基化碱木质素的制备及其对纤维素酶水解的影响[J]. 林产化学与工业, 2019, 39(2): 109-114.
[12]	许利娜,杨小华,丁海阳,李梅,夏建陵. 氧化改性木质素磺酸钠-石墨烯复合量子点的制备及性能[J]. 林产化学与工业, 2019, 39(1): 29-34.
[13]	李继辉,孙康,宋曜光,王傲,蒋剑春. 木质素基炭纳米片的制备及其电化学性能[J]. 林产化学与工业, 2019, 39(1): 67-74.
[14]	王广彬, 陈家宝, 谷利敏, 王春鹏, 许玉芝. 木质素基RAFT链转移剂的合成及其聚合特性研究[J]. 林产化学与工业, 2018, 38(6): 75-80.
[15]	周方浪, 郑志锋, 杨静, 杨海艳, 邓佳, 史正军. 木质素基酚醛树脂泡沫的制备及性能研究[J]. 林产化学与工业, 2018, 38(6): 103-109.