Gygax冷却失效模型在化工过程反应安全风险评估应用的局限性

doi:10.16085/j.issn.1000-6613.2023-1709

摘要/Abstract

摘要：

目前我国精细化工的反应安全风险评估技术主要是使用Stoessel反应危害分级方法而得出1~5级的工艺危险度等级，本文提出该方法是基于Gygax冷却失效模型建立的，即评估冷却失效工况下反应体系的工艺危险度等级。而国内外的化工反应安全事故统计结果表明，冷却失效工况仅是反应安全事故起因的很小部分（约3%）。以硝化工艺为例，文献报道的基于冷却失效的反应危害分级方法得出大部分硝化反应工艺处于低风险，这与实际生产中硝化反应事故数与死亡数占比最多存在矛盾。主要原因是由于该方法只评估间歇反应釜的冷却失效工况，而忽略其他众多复杂的事故起因。这表明该分级方法无法准确评估出实际工艺生产中的反应危害，无法较全面地涵盖化工反应安全事故起因并提出有效的事故管控措施，具有一定局限性。而化工过程全流程的反应危害分析（RHA）是根据从异常工况起因至最后反应事故发生的事故链以提出相应保护层，进而确定具体事故防范措施。相比Stoessel反应危害分级方法更适合实际生产工艺安全的提升。因此，建议对化工过程的反应安全风险评估作全流程RHA分析，特别是危险工艺和4~5级的高风险工艺。

关键词: Stoessel反应危害分级, 冷却失效工况, 全流程反应危害分析, 安全, 反应, 化学过程

Abstract:

At present, the reaction safety risk assessment technology in China's fine chemical industry mainly uses the Stoessel criticality classification method and ranks the reaction process hazard levels from 1 — 5 class. This method is based on the Gygax cooling failure model, which evaluates the reactivity hazard level of reaction systems under the assumption of a cooling failure condition. However, statistics on chemical reactivity safety incidents, both domestically and internationally, indicate that the cooling failure condition only accounts for a very small portion of the causes of such incidents (about 3%). Taking nitration processes as an example, the literature reports using the Stoessel criticality classification method indicate that most nitration reaction processes are classified as low risk levels. This contradicts with the fact that based on actual production incidents, nitration process is the dangerous process with the highest fatalities in China. The primary reason for this is that the Stoessel method only assesses the cooling failure scenarios in batch reaction vessels while it overlooks many other complex incident causes. This indicates that this classification method cannot accurately assess the reactivity hazards in actual chemical production, because it fails to cover most of the causes of chemical reactivity safety incidents and to propose effective accident control measures. On the other hand, the full-process reactivity hazard analysis (RHA) is based on assessing the accident chain of a chemical process from identifying the root causes of abnormal conditions to simulating the occurrence of reaction runaways, proposing corresponding protective layers, and thereby determining specific accident prevention measures. This approach is more suitable for enhancing actual process safety compared to the Stoessel criticality classification method. Therefore, it is recommended to conduct a comprehensive RHA analysis for the reactivity risk assessment of actual chemical plants, especially for hazardous processes rated at levels 4 and 5 high risk.

Key words: Stoessel criticality classification, cooling failure scenario, full-process reactivity hazard analysis, safety, reaction, chemical processes

中图分类号:

TQ014

杨钰涛, 王达, 吴展华, 盛敏. Gygax冷却失效模型在化工过程反应安全风险评估应用的局限性[J]. 化工进展, 2024, 43(11): 6379-6389.

YANG Yutao, WANG Da, WU Zhanhua, SHENG Min. Limitations of the application of the Gygax cooling failure model for reactivity hazards assessment of chemical processes[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6379-6389.

图/表 9

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时间	事故	伤亡，经济损失	事故简介	起因类别
2020/2/11	辽宁葫芦岛辽宁先达农业科学有限公司爆炸事故	5死10伤， 1200万元	误将丙酰三酮加入到氯代胺储罐，反应飞温，导致爆炸	加错料
2020/8/3	湖北仙桃蓝化有机硅有限公司闪爆事故	6死4伤	分层塔出料不完全，致丁酮肟盐酸盐进入静置槽内反应放热最后爆炸	产品分离过滤出错
2020/9/14	山西孝义山西晋茂能源科技有限公司中毒事故	4死1伤	误将酸洗塔废液和碱洗塔废液同时排入地下槽，反应产生硫化氢气体致中毒	加错料
2020/9/14	甘肃张掖耀邦化工科技有限公司中毒事故	3死，450万元	误将盐酸加入硫化物废水，反应产生硫化氢气体致中毒	加错料
2020/9/28	湖北天门楚天生物科技有限公司爆炸事故	6死1伤， 542.5万元	进行压滤二硝基蒽醌时，致其分解爆炸	产物分解（可能是压敏物）
2020/11/9	浙江衢州中天东方氟硅材料有限公司火灾事故	过火面积约2000m²	甲基氯硅烷高沸物泄漏，误用熟石灰粉中和，反应产热着火，引燃化学品致火灾扩大	加错料
2021/2/26	湖北仙隆化工股份有限公司爆炸事故	4死4伤	o,o-二甲基二硫代磷酸酯蒸馏提纯时，停搅拌至局部热点后导致爆炸	停搅拌

时间	事故	伤亡，经济损失	事故简介	起因类别
2020/2/11	辽宁葫芦岛辽宁先达农业科学有限公司爆炸事故	5死10伤， 1200万元	误将丙酰三酮加入到氯代胺储罐，反应飞温，导致爆炸	加错料
2020/8/3	湖北仙桃蓝化有机硅有限公司闪爆事故	6死4伤	分层塔出料不完全，致丁酮肟盐酸盐进入静置槽内反应放热最后爆炸	产品分离过滤出错
2020/9/14	山西孝义山西晋茂能源科技有限公司中毒事故	4死1伤	误将酸洗塔废液和碱洗塔废液同时排入地下槽，反应产生硫化氢气体致中毒	加错料
2020/9/14	甘肃张掖耀邦化工科技有限公司中毒事故	3死，450万元	误将盐酸加入硫化物废水，反应产生硫化氢气体致中毒	加错料
2020/9/28	湖北天门楚天生物科技有限公司爆炸事故	6死1伤， 542.5万元	进行压滤二硝基蒽醌时，致其分解爆炸	产物分解（可能是压敏物）
2020/11/9	浙江衢州中天东方氟硅材料有限公司火灾事故	过火面积约2000m²	甲基氯硅烷高沸物泄漏，误用熟石灰粉中和，反应产热着火，引燃化学品致火灾扩大	加错料
2021/2/26	湖北仙隆化工股份有限公司爆炸事故	4死4伤	o,o-二甲基二硫代磷酸酯蒸馏提纯时，停搅拌至局部热点后导致爆炸	停搅拌

事故可能原因	事故数	事故占比/%	伤亡数	伤亡占比/%
设备缺陷	34	12.5	80	7.2
杂质	21	7.7	59	5.3
工艺设计	17	6.3	48	4.3
技术故障	8	3.0	12	1.1
工厂设计	7	2.6	43	3.9
搅拌/冷却	7	2.6	29	2.6
停电	6	2.2	5	0.5
其他	4	1.5	17	1.5
操作员错误	96	35.4	321	29.0
管理不当	20	7.4	372	33.7
清理不充分	9	3.3	24	2.2
操作步骤错误	7	2.6	18	1.6
反应物错放	5	1.8	23	2.1
应急程序不完善	4	1.5	29	2.6
极端天气	4	1.5	0	0
非正常温度	3	1.1	0	0
未知	19	7.0	25	2.3

事故可能原因	事故数	事故占比/%	伤亡数	伤亡占比/%
设备缺陷	34	12.5	80	7.2
杂质	21	7.7	59	5.3
工艺设计	17	6.3	48	4.3
技术故障	8	3.0	12	1.1
工厂设计	7	2.6	43	3.9
搅拌/冷却	7	2.6	29	2.6
停电	6	2.2	5	0.5
其他	4	1.5	17	1.5
操作员错误	96	35.4	321	29.0
管理不当	20	7.4	372	33.7
清理不充分	9	3.3	24	2.2
操作步骤错误	7	2.6	18	1.6
反应物错放	5	1.8	23	2.1
应急程序不完善	4	1.5	29	2.6
极端天气	4	1.5	0	0
非正常温度	3	1.1	0	0
未知	19	7.0	25	2.3

事故起因		事故数	事故起因		事故数
加料问题（占21%）	进料过多	12	温度控制问题（占19%）	蒸汽过热、过长	6
	进料过快	8		测温位置不当	6
	加错料	5		温度控制系统	7
	顺序错误	4		冷却失效	5
	进料太少	3		人为读温度错误	4
	进料方式不当	2		离其他热源过近	2
	进料过慢	1		开车时加热过快	1
化学工艺问题（占34%）	放大时冷却设计不足	8		温度计外部结垢	1
	产物分解	7	维护保养问题（占15%）	泄漏问题	7
	生成不稳定副产物	6		管道堵塞问题	6
	一次性投料致事故	4		溶剂冷凝器回流阀关	3
	氧化副反应	3		上批反应残留	2
	反应物溶度过高	2		管道中残留水	3
	杂质催化	2		反应时修补设备	2
	温度过低致物料累积	1		未经审批的变更	1
	产物发生相变	1		气动器件的供气问题	1
搅拌问题（占10%）	搅拌设计不够	4	人为操作失误（占6%）	不按规章操作	4
	机械故障	3		反应未完成出料	3
	没开启搅拌或不及时	6		换班时交接问题	3
	停电	2		产品过滤出错	1
	因投料停止搅拌	2	反应物杂质问题（占15%）	含水	9
	因投料停止搅拌	2	反应物杂质问题（占15%）	其他杂质	6