Techno-economic study of the formic acid conversion towards commodity chemicals

西格玛储能（SES）致力于通过提供清洁能源存储技术来应对气候变化。SES开发了一种集成热回收的混合热压缩储能（HT-CAES）技术，克服了CAES系统的典型缺点，即往返效率低，与电池相比能量密度低，需要可靠和不间断的可再生能源供应。SES的技术可以从废气中捕获大部分二氧化碳。压缩气体在液态二氧化碳和压缩空气中分离，存放在地上的储存系统或天然圆顶中。SES申请了一项工艺专利，该工艺利用石墨烯纳米片负载的Cu电催化剂，将二氧化碳还原为甲酸（HCOOH），其法拉第效率（FE）超过40%，电流密度达到35 mA cm-2。从电解槽中得到的氢氧化氢被浓缩，可以以1000加元/吨的价格出售，也可以气化生产能源。然而，HCOOH市场规模小且饱和（< 100万吨/年）。寻找新的途径转化HCOOH对于确保SES的HT-CAES/电催化二氧化碳减排（ECR）的商业成功及其在加拿大减少温室气体排放的应用至关重要。然而，所有有趣的HCOOH还原途径都涉及二氧化碳的产生，而限制其进化绝对是SES的目标。在这个Engage项目中，我们探索了在限制二氧化碳形成的同时转化HCOOH的新途径。我们采用有利可图的方法将HCOOH转化为商品化学品，包括甲醇、高级醇、甲醛和酰胺，这将在几个月内摊销ECR的成本。具有挑战性的反应途径包括在压力高于40 bar和温度< 150 °C的条件下将HCOOH还原为CH3OH，并使用HCOOH作为氢甲酰化剂。我们将在实验中探索的更直接的途径是HCOOH在低温下直接转化为HCHO，并以HCOOH作为甲酰化剂在酸性催化剂上得到橡胶添加剂。我们将探索使用微波（MW）辐射作为替代加热技术。该项目的实现和成功为加拿大带来了几个好处，包括温室气体减排带来的环境效益，将氢氧化氢转化为商品化学品的有利可图的技术经济优势，以及基于MW的创新过程。与该项目成功相关的社会效益包括改善空气质量和培养参与该项目实现的高素质人才。

Sigma Energy Storage (SES) is committed to fight climate change by providing clean energy storage technologies. SES developed a Hybrid Thermal- Compressed Energy Storage (HT-CAES) technology with integrated heat recovery that overcomes the typical drawbacks of CAES systems, i.e. low round trip efficiency, lower energy density compared to batteries, and need for reliable and uninterrupted energy supply from renewables. SES's technology can capture most of CO2 from the exhaust. The compressed gases are separated in liquid CO2 and compressed air in above-ground storage systems or natural domes. SES patented a process exploiting graphene nanoflakes-supported Cu electrocatalysts that reduce CO2 to formic acid (HCOOH) with unprecedented faradaic efficiencies (FE) of over 40 % and current densities > 35 mA cm-2. HCOOH from the electrolyser is concentrated and could be either sold at 1000 CA$/ton or gasified to produce energy. However, HCOOH market is small and saturated (< 1 M ton/y). Finding new avenues to convert HCOOH is of paramount importance to ensure the commercial success of SES`s HT-CAES/Electrocatalytic CO2 reduction (ECR) and its application to reduce GHG in Canada. All interesting HCOOH reduction pathways involve however the production of CO2, while to limit its evolution is definitely a target for SES. In this Engage project we explore new avenues to convert HCOOH while limiting at the same time CO2 formation. We tackle profitable ways to convert HCOOH to commodity chemicals, including methanol, higher alcohols, formaldehyde and amides, which will amortize the cost of the ECR in few months. Challenging reaction pathways include reducing HCOOH to CH3OH at pressure above 40 bar and T < 150 °C, and using HCOOH as a hydroformylation agent. More direct pathways that we will explore experimentally are the direct conversion of HCOOH to HCHO at low temperature and adopting HCOOH as a formylating agent to obtain formanilide (rubber additive) over acid catalysts. We will explore the use of microwaves (MW) irradiation as alternative heating technique.This realization and success of this project encompasses several benefits for Canada, including environmental benefits deriving from GHG emission reduction, techno-economical advantages deriving from a profitable conversion of HCOOH into commodity chemicals to and from an innovative process based on MW. Social benefits linked to the success of this project include the improvement air quality and the formation of highly qualified personnel (HQP) involved in its realization.