当前煤气的净化处理主要应用低温甲醇洗工艺进行脱硫脱碳，含硫尾气中富集的H₂S主要通过Claus工艺进行回收生产硫磺，该工艺产品附加值较低且耗能大。因此，本研究旨在寻找一种对H₂S高附加值利用的工艺路线。

H₂S与CO经由羰基硫（COS）可以合成高附加值的二硫化碳（CS₂），但该反应需要较高浓度的H₂S气体作为原料。经典的低温甲醇洗工段得到的含硫尾气中H₂S占比仅30~40 mol%。本研究在原工艺吸收塔T101的脱碳段与脱硫段富液解吸之前，分别增加闪蒸器以脱除大量的CO₂减少后续含硫尾气中CO₂的占比。使用商业软件Aspen Plus对改造工艺进行了可行性研究，结果表明可将含硫尾气中H₂S浓度提高到60 mol%。

通过用户模型将动力学参数嵌入到Aspen的RPLUG平推流反应器，构建了H₂S和CO羰基化反应器的机理模型。针对反应的进料组成，空速，反应温度进行了分析与优化，结果表明使用绝热固定床反应器在170℃时进料配比1:3（H₂S:CO），COS产率最高。由于H₂S和COS能够形成共沸物，为了避免引入新的杂质和过高的分离成本，本研究使用变压精馏方法进行分离，以年度总费用（TAC）作为评判标准确定了高压塔与低压塔的最优操作参数，得到90 mol% COS。将高浓度的COS通过Gibbs反应器转化为CS₂，最后通过常规精馏将CS₂提纯至99 mol%作为产品。最终将CS₂合成工段与低温甲醇洗工段耦合，将羰基化反应剩余的硫化物循环到吸收塔以回收利用，使含硫尾气中H₂S的H以74%转化为H₂，S以99.93%转化为CS₂。

本研究模拟的两个工段进行耦合的工艺，得到高附加值产品CS₂，同时H₂S中潜在氢源得到了回收利用。整个工艺流程低能耗、低污染、H₂S转化率高，为含硫尾气中H₂S的高附加值应用提供了新思路。

Currently, the purification process of gas mainly uses the low-temperature methanol washing technology for desulfurization and decarbonization. The H₂S enriched in the tail gas acidic gas is mainly recovered and produced into sulfur through the Claus process, which has low added value and consumes a lot of energy. Therefore, this study aims to find a process route for high added value utilization of H₂S.

H₂S can be synthesized into high added value carbon disulfide (CS₂) through carbonyl sulfide (COS) reaction with CO, but this reaction requires a high concentration of H₂S gas as raw material. The classic low-temperature methanol washing process only yields acid gas with H₂S content of 30-40mol%. In this study, flash tanks were added before the decarbonization and desulfurization sections of absorber tower T101 in the original process to remove a large amount of CO₂ and reduce the proportion of CO₂ in the subsequent acid gas. The feasibility of the modified process was studied using commercial software Aspen Plus, and the results showed that the H₂S concentration in the acid gas could be increased to 60 mol%.

The kinetic parameters were embedded into Aspen's RPLUG plug flow reactor using a user model, and a mechanism model of the H₂S and CO carbonylation reactor was constructed. Analysis and optimization were conducted on the feed composition, space velocity, and reaction temperature, and the results showed that the highest COS yield could be achieved using an adiabatic fixed bed reactor with a feed ratio of 1:3 (H₂S:CO) at 170°C. As H₂S and COS can form azeotropes, a variable pressure distillation method was used for separation to avoid introducing new impurities and high separation costs. The optimal operating parameters for the high-pressure tower and low-pressure tower were determined based on the total annual cost (TAC), and 90 mol% COS yield was obtained. The high concentration of COS was then converted to CS₂ through a Gibbs reactor, and the CS₂ was purified to 99 mol% as the final product through conventional distillation. Finally, the CS₂ synthesis section was coupled with the low-temperature methanol washing section, and the remaining sulfides from the carbonylation reaction were recycled to the absorber tower for recovery, resulting in 74% conversion of H₂S to H₂ and 99.93% conversion of S to CS₂ in the acid gas.

The process of coupling the two simulated sections in this study resulted in the production of high-value-added product CS₂, while the potential hydrogen source in H₂S was recovered and utilized. The entire process has low energy consumption, low pollution, and high H₂S conversion rate, providing a new approach for the high-value application of H₂S in acidic gases.

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