过程工业尾气封闭循环原理与应用（Ⅱ）：绿电制硝酸

doi:10.11949/0438-1157.20210389

摘要/Abstract

摘要：

针对传统氨-空气氧化制硝酸工艺尾气NO_x和N₂O排放，通过化工过程自由能耗散比模型分析指出污染物扩散所致环境自由能耗散可达产品加工有效自由能的66.2%。为此提出绿电制硝酸（GPtNA）尾气封闭循环新工艺，将电解水制氢/氧和空分制氧/氮两个单元耦合嵌入合成氨与硝酸工艺圈，以电代碳，提供绿色氢、氧、氮资源；与传统硝酸工艺相比，吨产品（HNO₃ 100%）减碳0.356 t、CO₂减排1.31 t、回收NO_x与N₂O各1.01~1.70 kg，对硝酸工业减碳降污具有重要意义。新工艺开发依托成熟的合成氨、硝酸与空分技术，利用绿电制氢电耗4.3 kW·h/m³等前沿成就，硝酸产品理论电耗为2560 kW·h/t、其成本可与传统硝酸工艺理论氨耗269.8 kg/t相竞争，当可再生（水、风、光）电价低于0.22 CNY/（kW·h），GPtNA工艺具有资源、环境和经济性全面竞争优势。

关键词: 过程系统, 硝酸工艺, 污染控制, 封闭循环, 二氧化碳减排, 绿电制氢

Abstract:

Based on a model analysis of free energy dissipation in chemical processes it is pointed out that the ambient air quality decline, induced by dispersion of NO_x_{and N₂O emission from traditional ammonia/air oxidation nitric acid (AAtNA) process, accounted as environment loss of free energy will reach 66.2% of that effectively consumed in production. Hence a new process of green power to nitric acid (GPtNA) is proposed for elimination of pollution source by enclosed exhaust cycling. For the purpose of carbon replacement by power, the units of water electrolysis and air separation are coupled into the loops of high pressure catalytic ammonia synthesis and dual-pressure catalytic oxidation/absorption nitric acid to supply green hydrogen, oxygen and nitrogen sources. Compared with AAtNA process, 0.356 t carbon consumption can be avoid therefore 1.31 t CO₂ emission abated, plus 1.01—1.70 kg NO_x and 1.01—1.70 kg N₂O recovered for per ton nitric acid (100% HNO₃) produced by GPtNA process, meaningful to carbon reducing and pollution abatement for nitric acid industry. Based on the mature industrial technologies of ammonia, nitric acid and air separation, the new process development is also benefited from the frontier achievement of green power to hydrogen. Under the current available power-hydrogen efficiency of 4.3 kW·h/m³, a theoretic power consumption of 2560 kW·h/t for GPtNA process can be competitive to the cost of theoretic ammonia consumption of 269.8 kg/t for AAtNA process under certain power/ammonia price ratio. When the renewable (water, wind, light) electricity price is lower than 0.22 CNY/(kW·h), the GPtNA process has a comprehensive competitive advantage in resources, environment and economy.}

Key words: process system, nitric acid process, pollution control, closed loop, CO₂ emission reduction, hydrogen production from green power

中图分类号:

TQ 021.4

朱家骅,卢蔚,彭玉凤,李季. 过程工业尾气封闭循环原理与应用（Ⅱ）：绿电制硝酸[J]. 化工学报, 2021, 72(10): 5265-5272.

Jiahua ZHU,Wei LU,Yufeng PENG,Ji LI. Principles and application of enclosed exhausts cycling for process industry (Ⅱ): Production of nitric acid from green power[J]. CIESC Journal, 2021, 72(10): 5265-5272.

图/表 3

图1 煤基合成氨氧化制硝酸与GPtNA封闭循环工艺物流路线对比图（图中数值为摩尔比）

Fig.1 Comparative process flow diagrams of nitric acid manufacturing from coal-based ammonia oxidation and enclosure GPtNA

表1 GPtNA关键工艺部位物流组成

Table 1 Composition of process flow at critical loop position of GPtNA

工艺部位	工艺气体组成/%（mol）
工艺部位	NH₃	NO_x	O₂	N₂
氨氧化炉前	10.19		28.54	60.38
氧化吸收塔后		<0.2	13.50	85.50

图2 传统硝酸工艺氨耗与GPtNA工艺电耗成本比对图

Fig.2 Costs comparison between supplies of ammonia for traditional ammonia oxidation and power for GPtNA

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