煤化工酚基精馏釜残资源化利用过程初步分析

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

化工进展 ›› 2022, Vol. 41 ›› Issue (6): 3360-3371.doi: 10.16085/j.issn.1000-6613.2021-1535

煤化工酚基精馏釜残资源化利用过程初步分析

蔡思超¹^,²(), 周静¹^,², 杜金泽¹^,², 李方舟³, 李源森¹^,², 何林¹^,²^,³(), 李鑫钢¹^,²^,³, 王成扬¹^,²

^1.天津大学化工学院，天津 300072
^2.精馏技术国家工程研究中心，天津 300072
^3.天津大学浙江研究院，浙江宁波 315000

收稿日期:2021-07-20 修回日期:2021-10-02 出版日期:2022-06-10 发布日期:2022-06-21
通讯作者: 何林 E-mail:sichaocai@tju.edu.cn;linhe@tju.edu.cn
作者简介:蔡思超（1998—），男，硕士研究生，研究方向为有机固废资源化与无害化转化。E-mail：sichaocai@tju.edu.cn。
基金资助:
国家重点研发计划(2018YFC1902100)

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

CAI Sichao¹^,²(), ZHOU Jing¹^,², DU Jinze¹^,², LI Fangzhou³, LI Yuansen¹^,², HE Lin¹^,²^,³(), LI Xingang¹^,²^,³, WANG Chengyang¹^,²

^1.College of Chemical Engineering, Tianjin University, Tianjin 300072, China
^2.National Engineering Research Center of Distillation Technology, Tianjin 300072, China
^3.Zhejiang Institute of Tianjin University, Ningbo 315000, Zhejiang, China

Received:2021-07-20 Revised:2021-10-02 Online:2022-06-10 Published:2022-06-21
Contact: HE Lin E-mail:sichaocai@tju.edu.cn;linhe@tju.edu.cn

摘要/Abstract

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

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

中图分类号:

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.

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.

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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

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

项目	外观	黏度（25℃）/Pa·s	水分/%	固体含量/%	残碳量/%	游离酚/%	pH
YB/T 4131—2005	棕黑色透明	1~30	≤6.5	≥75	≥40	≤12	4~7.5
Q/0100SQH 001—2018	液体	1~30	≤8.0	≥40.0	≥25.0	≤14.0	≤8.0
LRPF1	棕黑色半透明	27~31	≤2.0	≥77	≥35	≤8.5	4~7
LRPF2	棕黑色半透明	26~30	≤3.5	≥75	≥33	≤10	4~6
商用树脂Nv	红棕色透明	30~36	≤6.5	≥77	≥42	≤9.0	6.8~7.2

MgO-C砖	体积密度/g·cm^-3	显气孔率/%	常温耐压强度/MPa
MT-LRPF1	2.89±0.02	4.2±0.3	14.8±0.2
MT-LRPF2	2.90±0.03	4.1±0.5	15.3±0.3
MT-Nv	2.82±0.02	4.4±0.5	14.9±0.2

煤化工酚基精馏釜残资源化利用过程初步分析

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

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组分	质量分数/%
C₂₂H₃₃N₆O₂	36.2
C₁₉H₄₂N₃O₃	22.1
C₃₁H₆₃N₁₂O	16.3
C₂₉H₅₉N₁₂O	11.86
C₁₅H₃₄N₆NaO₂	7.31
C₁₅H₃₃N₁₂	6.17

单元	输入			输出
单元	物料能耗	质量 /kg	能耗 /MJ	物料	质量 /kg
单元-1	酚基釜残	9000		轻质酚混合物	11790
	苯酚	8842		深拔重质组分	6052
	负荷		13112
单元-2	轻质酚混合物	11790		酚醛树脂	14211
	甲醛溶液	7074		含酚废水	23010
	催化剂	378		蒸汽	1263
	水	19242
	负荷		17535
单元-3	酚醛树脂	14211		耐火材料用树脂	18650
	乙二醇	2006
	HMTA	1622
	二茂铁	811
	负荷		360
单元-4	耐火材料用树脂	18650		镁碳砖	466250
	镁砂	458257		废气	66607
	石墨	55950
	负荷		35840
单元-5	深拔重质组分	6052		活性炭黏结剂	10979
	草酸	154
	甲醛溶液	1636
	乙醇	3137
	负荷		731

项目	费用/×10³CNY·d^-1
操作费用	1860.88
原料费用	1701.13
产品销售额	1915.87
公用工程费用	0.47022
设备及安装成本	9261.33

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黏结剂	颗粒炭耐磨强度/%
高温煤沥青	98.05
FCR-0.1	98.73
FCR-0.15	96.71

处理方式	经济效益/CNY·t^-1
填埋	-1787
焚烧	829
热转化综合利用	5493