Mercury (Hg) is present in petrochemical samples, including crude oils, and the processing and use of petroleum products contribute to global Hg emissions. We present a refined theory on geochemical processes controlling Hg concentrations in crude oil by studying dissolution kinetics and solubility thermodynamics of cinnabar (α-HgS(s)) in different crude oils held at reservoir temperatures. In a black light crude oil, α-HgS(s) dissolved in an apparent zero-order reaction with a rate of 0.14-0.58 µmoles m-2 s-1 at 170-230 C and an estimated activation energy of 43 kJ mole-1. For crude oil samples with a total sulfur concentration spanning 0.15-2.38% (w/w) the measured dissolution rate varied between 0.05-0.24 µmoles m-2 s-1 at 200 C. Separate tests showed that thiols and, to a lesser extent, organic sulfides increased the solubility of α-HgS(s) in isooctane at room temperature compared to thiophenes, disulfides and elemental sulfur. Long-term (14 days) α-HgS(s) solubility tests in a crude oil at 200 C generated dissolved Hg concentrations in the 0.3% (w/w) range. The high α-HgS(s) dissolving capacity of the crude oils was more than two orders of magnitude greater than the highest reported Hg concentration in crude oils globally. Based on the kinetic and solubility data it was further concluded that α-HgS(s) is not stable under typical petroleum reservoir conditions and would decompose to elemental mercury (Hg0). Our results suggest that source/reservoir temperature, abundance of reduced sulfur compounds in the crude oil, and dissolved Hg0 evasion processes are principal factors controlling the ultimate Hg concentration in a specific crude oil deposit.

中文翻译：

---

减少硫配体促进储层温度下朱砂在原油中的快速溶解

包括原油在内的石化样品中均存在汞（Hg），石油产品的加工和使用会导致全球汞排放。通过研究朱砂（α-HgS（s））在不同储层温度下在不同原油中的溶解动力学和溶解热力学，我们提出了控制原油中Hg浓度的地球化学过程的精细理论。在黑光原油中，α-HgS在170-230℃下以0.14-0.58 µmoles m-2 s-1的速率以表观零级反应溶解，估计活化能为43 kJ mol -1。对于总硫浓度为0.15-2.38％（w / w）的原油样品，在200°C下测得的溶解速率在0.05-0.24 µmoles m-2 s-1之间变化。单独的测试表明，巯基和（在较小程度上）与噻吩，二硫化物和元素硫相比，有机硫化物在室温下增加了α-HgS在异辛烷中的溶解度。在200°C的原油中进行长期（14天）α-HgS溶解度测试时，生成的溶解汞浓度为0.3％（w / w）。原油的高α-HgS溶解能力比全球原油中报告的最高Hg浓度高出两个数量级。根据动力学和溶解度数据，可以进一步得出结论，α-HgS在典型的石油储层条件下不稳定，会分解为元素汞（Hg0）。我们的结果表明，源/储层温度，原油中还原硫化合物的丰度，