Reaction Calorimetry and Scale-Up Considerations of Bromo- and Chloro-Boron Subphthalocyanine

IF 2.9 Q2 PUBLIC, ENVIRONMENTAL & OCCUPATIONAL HEALTH
Benjamin J. Knapik, Rachel Zigelstein, Marko Saban and Timothy P. Bender*, 
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Abstract

The formation mechanism of boron subphthalocyanines (BsubPcs) has thus far evaded researchers, making it nearly impossible to accurately estimate the overall reaction enthalpy─a critical metric for determining chemical process safety for scale-up. To address this gap, reaction calorimetry was used to collect thermokinetic data for a baseline Br-BsubPc reaction at three temperatures and two BBr3 reagent ratios and a proposed semibatch process for Cl-BsubPc. For the Br-BsubPc process, the magnitude of the enthalpy of reaction (ΔHr) increased with increasing reaction temperature, from −244.6 kJ/mol-BBr3 at 25 °C to −332.7 kJ/mol-BBr3 at 50 °C to −391.3 kJ/mol-BBr3 at 75 °C. However, this increase in the magnitude of ΔHr did not result in a noticeable increase in Br-BsubPc yield, achieving 50%, 49%, and 52% yields at 25 °C, 50 °C, and 75 °C, respectively. When the molar equivalence of BBr3 was increased by 1.5× at 25 °C, the magnitude of ΔHr increased slightly (−252.2 kJ/mol-BBr3), but the yield did not improve (47%). Therefore, further attempts were made to try and improve the yield of Br-BsubPc by increasing the molar equivalence of BBr3. It was found that BBr3 equivalencies greater than 0.48 resulted in significant reductions in Br-BsubPc yield. The ΔHr of the semibatch Cl-BsubPc process was −266.5 kJ/mol-BCl3 with a yield of 33%. These processes were assessed based on criticality criteria and were both found to be “Criticality Class 1”, which is relatively safe for scale-up. Based on the calorimetry measurements, preliminary estimates for process conditions and reactor design for scale-up are provided.

Abstract Image

溴和氯硼亚酞菁的反应量热法和放大考虑
硼亚酞菁(BsubPcs)的形成机制迄今为止一直被研究人员所回避,几乎不可能准确估计整个反应焓─用于确定扩大规模的化学过程安全性的关键指标。为了解决这一差距,使用反应量热法来收集在三个温度和两个BBr3试剂比下的基线Br-BsubPc反应的热动力学数据,以及Cl-BubPc的拟议半间歇过程。对于Br-BsubPc过程,反应焓(ΔHr)的大小随着反应温度的升高而增加,从25°C时的−244.6 kJ/mol-BBr3增加到50°C下的−332.7 kJ/mol/BBr3,再到75°C下为−391.3 kJ/mol-BBr3。然而,ΔHr幅度的增加并没有导致Br-BsubPc产量的显著增加,在25°C、50°C和75°C时分别达到50%、49%和52%的产量。当BBr3的摩尔当量在25°C下增加1.5倍时,ΔHr的大小略有增加(−252.2 kJ/mol-BBr3),但产率没有提高(47%)。因此,进一步尝试通过增加BBr3的摩尔当量来提高Br-BsubPc的产率。发现大于0.48的BBr3当量导致Br-BsubPc产率的显著降低。半间歇Cl-BsubPc工艺的ΔHr为−266.5kJ/mol-BCl3,产率为33%。这些过程是根据临界标准进行评估的,都被发现是“临界等级1”,这对于扩大规模来说是相对安全的。基于量热法测量,提供了对工艺条件和放大反应器设计的初步估计。
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来源期刊
ACS Chemical Health & Safety
ACS Chemical Health & Safety PUBLIC, ENVIRONMENTAL & OCCUPATIONAL HEALTH-
CiteScore
3.10
自引率
20.00%
发文量
63
期刊介绍: The Journal of Chemical Health and Safety focuses on news, information, and ideas relating to issues and advances in chemical health and safety. The Journal of Chemical Health and Safety covers up-to-the minute, in-depth views of safety issues ranging from OSHA and EPA regulations to the safe handling of hazardous waste, from the latest innovations in effective chemical hygiene practices to the courts'' most recent rulings on safety-related lawsuits. The Journal of Chemical Health and Safety presents real-world information that health, safety and environmental professionals and others responsible for the safety of their workplaces can put to use right away, identifying potential and developing safety concerns before they do real harm.
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