Process analysis of resource utilization of phenol-based distillation residue from coal chemical industry

doi:10.16085/j.issn.1000-6613.2021-1535

Abstract

Abstract:

In order to solve the problems of complex composition, high toxicity and low resource utilization rate of phenolic distillation residue, a multi effect resource utilization scheme of vacuum deep drawing and thermochemical conversion was proposed according to the component characteristics of phenolic residue. And the preparation process of different products in this scheme was verified by experiments. The results showed that the main light components of phenolic residue were hydroquinones, and the proportion of phenols from the phenolic residue was 70.38%. The special resin for magnesia carbon brick refractories was prepared by condensation reaction of formaldehyde and phenol with its additive which from the deep drawing light components of phenolic residue. The performance index of the stillage residual resin can meet the enterprise standard and basically reach the industry level. The properties of MgO-C brick prepared by the residual resin of the autoclave were not significantly different from those prepared by commercial resin Nv. After chemical modification and increasing the degree of crosslinking, the residual heavy components of phenolic residue could basically meet the requirements of granular activated carbon adhesive. At the same time, from the cost-benefit point of view, a comparative evaluation was made on the utilization schemes of phenolic distillation residue. This study provides an alternative way of resource utilization for the treatment of phenolic distillation residue.

Key words: distillation residue, waste treatment, resource utilization, vacuum distillation, phenolic resin, magnesia carbon brick, activated carbon

摘要：

针对酚基精馏釜残组成复杂、毒性大且资源利用率不高的问题，根据其组分特征，本文初步提出减压深拔-热化学转化的多效资源化利用方案，并对该方案中不同产品的制备工艺进行了初步实验验证。结果表明，通过减压深拔得到的轻组分主要以苯二酚类化合物为主，且酚类物质占比70.38%（质量分数）。将深拔轻组分作为苯酚添加物与甲醛进行缩合反应，制备的镁碳砖耐火材料专用树脂，性能指标可满足企业标准，并基本达到行业水平。利用此釜残基树脂制备的镁碳砖，其性能与商用树脂Nv制备的镁碳砖性能无明显差异。深拔剩余的重组分通过化学改性，增加交联程度后可以基本达到颗粒活性炭黏结剂的指标要求。同时从成本效益上对釜残资源化利用方案进行了对比评价。本研究为酚基精馏釜残的处理提供了资源化利用可选途径。

关键词: 精馏釜残, 废物处理, 资源化利用, 减压深拔, 酚醛树脂, 镁碳砖, 活性炭

CLC Number:

CAI Sichao, ZHOU Jing, DU Jinze, LI Fangzhou, LI Yuansen, HE Lin, LI Xingang, WANG Chengyang. Process analysis of resource utilization of phenol-based distillation residue from coal chemical industry[J]. Chemical Industry and Engineering Progress, 2022, 41(6): 3360-3371.

蔡思超, 周静, 杜金泽, 李方舟, 李源森, 何林, 李鑫钢, 王成扬. 煤化工酚基精馏釜残资源化利用过程初步分析[J]. 化工进展, 2022, 41(6): 3360-3371.

Figures/Tables 22

References 23

1	DUAN Huabo, HUANG Qifei, WANG Qi, et al. Hazardous waste generation and management in China: a review[J]. Journal of Hazardous Materials, 2008, 158(2/3): 221-227.
2	王雄雷, 牛艳霞, 刘刚, 等. 煤焦油渣处理技术的研究进展[J]. 化工进展, 2015, 34(7): 2016-2022.
	WANG Xionglei, NIU Yanxia, LIU Gang, et al. Research progress of coal tar residue treatment technology[J]. Chemical Industry and Engineering Progress, 2015, 34(7): 2016-2022.
3	蒋学先. 浅论我国危险废物处理处置技术现状[J]. 金属材料与冶金工程, 2009, 37(4): 57-60.
	JIANG Xuexian. Discussion on the current status of treatment and disposal technology for hazardous waste in our country[J]. Metal Materials and Metallurgy Engineering, 2009, 37(4): 57-60.
4	STORM C, RUD¨IGER H, SPLIETHOFF H, et al. Co-pyrolysis of coal/biomass and coal/sewage sludge mixtures[J]. Journal of Engineering for Gas Turbines and Power, 1999, 121(1): 55-63.
5	MA Yuhui, SU Wei, WANG Qunhui, et al. Discharge and disposal of coking residue and distribution characteristics of PAHs in it[J]. Applied Mechanics and Materials, 2013, 448/449/450/451/452/453: 448-452.
6	ROCHA E R L, LOPES M S, MACIEL M R W, et al. Recovery and characterization of petroleum residues through the molecular distillation process[J]. Petroleum Science and Technology, 2014, 32(20): 2450-2457.
7	AN Zhenwei H, KONG Shunli, CHENG Jing, et al. Preparation of efficient carbon-based adsorption material using asphaltenes from asphalt rocks[J]. Industrial & Engineering Chemistry Research, 2019, 58(32): 14785-14794.
8	马媛, 杜金泽, 周静, 等. 酚基釜残深拔残渣分析及其热转化制备CO₂吸附材料[J]. 化学工业与工程, 2021, 38(1): 43-52.
	MA Yuan, DU Jinze, ZHOU Jing, et al. Chemical analysis of the phenolic tar residue and its potential conversion to CO₂ adsorbents by thermal treatment[J]. Chemical Industry and Engineering, 2021, 38(1): 43-52.
9	KA BE T, ISHIHARA A, QIAN E W, et al. Coal and coal-related compounds: structures, reactivity and catalytic reactions[M]. Amsterdam: Elsevier, 2004.
10	VAEZ I M, PASSANDIDEH-FARD M, MOGHIMAN M, et al. Gasification of heavy fuel oils: a thermochemical equilibrium approach[J]. Fuel, 2011, 90(2): 878-885.
11	HIR ANO K, ASAMI M. Phenolic resins—100 years of progress and their future[J]. Reactive and Functional Polymers, 2013, 73(2): 256-269.
12	黄发荣, 焦杨声. 酚醛树脂及其应用[M]. 北京: 化学工业出版社, 2003.
	HU ANG Farong, JIAO Yangsheng. Phenolic resin and its application[M]. Beijing: Chemical Industry Press, 2003.
13	DEMCHUK Y, SIDUN I, GUNKA V, et al. Effect of phenol-cresol-formaldehyde resin on adhesive and physico-mechanical properties of road bitumen[J]. Chemistry & Chemical Technology, 2018, 12(4): 456-461.
14	PYSHYE V S, DEMCHUK Y, GUNKA V, et al. Development of mathematical model and identification of optimal conditions to obtain phenol-cresol-formaldehyde resin[J]. Chemistry & Chemical Technology, 2019, 13(2): 212-217.
15	PAN H, SHUPE T F, HSE C Y. Synthesis and cure kinetics of liquefied wood/phenol/formaldehyde resins[J]. Journal of Applied Polymer Science, 2008, 108(3): 1837-1844.
16	ZHAO Yong, YAN Ning, FENG M. Synthesis and characterization of bio-based phenol-formaldehyde resol resins from bark autoclave extractives[J]. Forest Products Journal, 2016, 66(1/2): 18-28.
17	ZHOU Jing, HU Lihong, LIANG Bingchuan, et al. Preparation and characterization of novolac phenol-formaldehyde resins with enzymatic hydrolysis lignin[J]. Journal of the Taiwan Institute of Chemical Engineers, 2015, 54: 178-182.
18	SOLT P, HERWIJNEN H W G VAN, KONNERTH J. Thermoplastic and moisture-dependent behavior of lignin phenol formaldehyde resins[J]. Journal of Applied Polymer Science, 2019, 136(40): 48011.
19	YAN Liangcong, CUI Yuhu, GOU Guangjun, et al. Liquefaction of lignin in hot-compressed water to phenolic feedstock for the synthesis of phenol-formaldehyde resins[J]. Composites Part B: Engineering, 2017, 112: 8-14.
20	CHEN Min, WANG Nan, YU Jingkun, et al. Effect of porosity on carbonation and hydration resistance of CaO materials[J]. Journal of the European Ceramic Society, 2007, 27(4): 1953-1959.
21	张碧芳, 王光华. 碳质耐火材料粘结剂的研究[J]. 粘接, 1988, 9(4): 8-12.
	ZHANG Bifang, WANG Guanghua. Studies on carbon refractory bonding agent[J]. Adhesion in China, 1988, 9(4): 8-12.
22	裘晓鹏, 罗小勇, 陈亮, 等. 危险废物刚性填埋场设计与经济性分析[J]. 环境卫生工程, 2020, 28(6): 80-85.
	QIU Xiaopeng, LUO Xiaoyong, CHEN Liang, et al. Design and economic analysis of rigid landfill for hazardous waste[J]. Environmental Sanitation Engineering, 2020, 28(6): 80-85.
23	李庆辉. 药业公司危险废物资源化处理工艺方案设计[D]. 济南: 山东大学, 2016.
	LI Qinghui. Process design for treatment of hazardous waster from a pharmaceutical company[D]. Jinan: Shandong University, 2016.

精馏釜残成分	河南		新疆		云南
精馏釜残成分	0~255℃	255~450℃	0~250℃	250~450℃	0~270℃	270~550℃
苯酚	0.85	4.04	2.80	0.71	13.96	0.96
单取代基苯酚	3.27	6.06	4.01	3.29	27.16	8.10
多取代基苯酚	6.76	3.85	5.83	6.80	14.93	4.57
苯二酚	12.80	4.36	14.18	10.10	0.88	1.78
单取代基苯二酚	32.26	21.08	39.67	37.48	7.85	15.28
多取代基苯二酚	14.44	5.79	10.20	15.66	6.27	7.90
多环酚	4.97	21.95	3.13	6.15	8.91	24.17
其他芳环类	1.67	7.88	1.77	1.36	7.69	13.61
酸和酮	17.31	2.76	4.97	5.47	0.29	2.14
其他	5.67	22.24	13.44	12.97	12.06	21.49
收率	32.75	18.35	15.60	21.14	37.87	21.86

精馏釜残成分	河南		新疆		云南
精馏釜残成分	0~255℃	255~450℃	0~250℃	250~450℃	0~270℃	270~550℃
苯酚	0.85	4.04	2.80	0.71	13.96	0.96
单取代基苯酚	3.27	6.06	4.01	3.29	27.16	8.10
多取代基苯酚	6.76	3.85	5.83	6.80	14.93	4.57
苯二酚	12.80	4.36	14.18	10.10	0.88	1.78
单取代基苯二酚	32.26	21.08	39.67	37.48	7.85	15.28
多取代基苯二酚	14.44	5.79	10.20	15.66	6.27	7.90
多环酚	4.97	21.95	3.13	6.15	8.91	24.17
其他芳环类	1.67	7.88	1.77	1.36	7.69	13.61
酸和酮	17.31	2.76	4.97	5.47	0.29	2.14
其他	5.67	22.24	13.44	12.97	12.06	21.49
收率	32.75	18.35	15.60	21.14	37.87	21.86

组分	MT-LRPF1	MT-LRPF2	MT-Nv
镁砂5~3mm	11.0	11.0	11.0
镁砂3~1mm	26.0	26.0	26.0
镁砂1~0.08mm	29.0	29.0	29.0
镁砂≤80μm	20.0	20.0	20.0
石墨≤300μm	10.5	10.5	10.5
釜残树脂LRPF-1	3.5	—	—
釜残树脂LRPF-2	—	3.5
商用树脂Nv	—	—	3.5

组分	MT-LRPF1	MT-LRPF2	MT-Nv
镁砂5~3mm	11.0	11.0	11.0
镁砂3~1mm	26.0	26.0	26.0
镁砂1~0.08mm	29.0	29.0	29.0
镁砂≤80μm	20.0	20.0	20.0
石墨≤300μm	10.5	10.5	10.5
釜残树脂LRPF-1	3.5	—	—
釜残树脂LRPF-2	—	3.5
商用树脂Nv	—	—	3.5

无机盐种类	新疆	云南
Na	5.69	26.1
Al	0.189	1.47
Si	0.765	1.46
S	4.01	14.3
K	0.136	0.411
Ca	0.236	0.233
Mn	0.224	0
Fe	55.5	13.0
Ni	0.0475	1.01
Cr	0.0397	1.09
Ti	0	0.323