Analytical methods for the determination of mercury species in natural gas condensate
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摘要: 天然气凝析油是优质石脑油原料，作为天然气的伴生品，其中，含有少量的汞及其化合物。汞不仅危害人体健康，而且在凝析油的加工转化过程中还会腐蚀热交换器等单元设备，进而引起生产安全隐患。明晰凝析油中汞的存在方式及形态演变，是天然气化工领域一个富有挑战性的课题。本文系统介绍天然气凝析油中汞的化学形态及分析技术，详细比较和讨论了凝析油等液烃中汞的萃取工艺及汞形态的检测手段，综合评价了不同检测技术的优缺点。已有研究结果表明，采用气相色谱-电感耦合等离子体质谱联用技术，汞回收率接近100%，汞的测定精度高，是一种检测凝析油等液烃中汞组成及化学形态的可靠技术手段。此外，凝析油中汞的形态及其含量是确定脱汞工艺、装置规格及脱汞剂的两个关键因素，而研发一套高精度的快速检测汞形态的新方法，是天然气化工领域需要关注的一个新方向。
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关键词:
- 凝析油 /
- 汞形态 /
- 检测技术 /
- 气相色谱-电感耦合等离子体质谱联用技术
Abstract: Natural gas condensate, a by-product in natural gas exploitation and utilization, is an excellent raw material for naphtha production. However, the natural gas condensate always contains a trace amount of mercury, which may damage the human health and corrode the downstream processing units such as heat exchangers. It is highly demanded that the mercury in natural gas condensate can be identified specifically and analyzed accurately and quickly, which remains a big challenge in natural gas processing industry up to now. This paper reviewed the analytical methods for the determination of mercury species in natural gas condensate, by evaluating the advantages and disadvantages of various measures in terms of mercury extraction and detection in natural gas condensate. It was observed that the gas chromatography-inductively coupled plasma-mass spectrometer with high accuracy and high mercury recovery rate is the best technique at present to determine the mercury species in the natural gas condensate. The state of mercury species and content of mercury are two key factors to govern the selection and optimization of the adsorbent and the process for the efficient removal of mercury in natural gas condensate in different scales, which exacts a novel technique for the fast yet accurate characterization of various mercury species to meet the demands in the natural gas industry. -
表 1 部分地区天然气和凝析油中汞含量[9]
Table 1 Mercury contents in the natural gas and natural gas condensate from different regions[9]
Region Natural gas/(μg·m-3) Natural gas condensate/(μg·kg-1) Europe 100-150 ND South America 50-120 50-100 Gulf of Thailand 100-400 400-1200 Africa 80-100 500-1000 North Africa 50-80 20-50 Malaysia 1-200 10-100 Indonesia 200-300 10-500 ND: not detected 
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表 2 煤、石油、天然气和凝析油中汞化合物的自然丰度
Table 2 Natural abundance of mercury species in coal, crude oil, natural gas and natural gas condensate
Mercury species Coal Crude oil Natural gas Natural gas condensate Hg0 ≤1% main main main (CH3)2Hg NS ≤1% ≤1% ≤1% HgCl2 10%-50% 10%-50% ND 10%-50% HgS NS solid particles ND solid particles HgO ≤1% ND ND ND CH3HgCl NS ≤1% ND ≤1% NS: not sure; ND: not detected
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表 3 Bloom等对凝析油和原油中的汞形态测定结果(ng/g)[19]
Table 3 Mercury species in natural gas condensate and crude oil (ng/g)[19]
Sample Unfiltered mercury 0.8 μm nitrocellulose membrane filtered mercury total Hg0 dissolved Hg2+ CH3Hg Natural gas #1 20700 3060 5210 2150 3.74 condensate #2 49400 34500* 36800 237 6.24 Crude oil #1 1990 408 821 291 0.25 #2 4750 1120 1470 433 0.26 #3 4610 536 1680 377 0.27 #4 4100 1250 1770 506 0.62 #5 15200 2930 3110 489 0.45 #6 1.51 0.09 1.01 0.39 0.15 #7 0.42 0.17 0.41 0.02 0.11 *: this sample contained particulate Hg0 that was re-dissolved in hexane
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表 4 不同凝析样品油中汞化合物含量(μg/L)[20]
Table 4 ontents of mercury compound in various natural gas condensates (μg/L)[20]
Sample Injection model Hg0 HgCl2 DMeHg MeEtHg DEtHg MeHgCl EtHgCl Total Organic mercury ratio Condensate #1 pulsed splitless ND 30.9 < < < < < 32.4 - on-column 1.53 ND < < < < < #2 pulsed splitless ND 8.13 2.06 3.2 0.86 0.21 0.05 15.1 42% on-column 0.52 ND 1.99 3.2 1.01 < < #3 pulsed splitless ND 116 9.23 13.1 5.07 0.32 < 173 16% on-column 28.8 ND 9.31 14.9 5.18 < < #4 pulsed splitless ND 7.44 0.78 0.97 0.11 0.09 < 12.2 16% on-column 2.66 ND 1.1 1.03 0.1 < < #5 pulsed splitless ND 26.8 < < < < < 27.7 - on-column 0.86 ND < < < < < #6* pulsed splitless ND 48.4 < < < < < 48.4 - on-column < ND < < < < < #7* pulsed splitless ND 0.68 23.4 29.1 5.81 0.51 < 59.5 99% on-column < ND 21.4 28.6 6.28 < < #8* pulsed splitless ND 0.14 3.98 3.19 0.14 0.13 0.07 7.68 98% on-column 0.03 ND 3.91 2.98 0.21 < < Crude oil #9 pulsed splitless ND 0.60 < < < < < 0.63 on-column 0.03 ND < < < < < ND: not detected; < : below detection limit; the average values of both injection models were adopted for DMeHg, MeEtHg and DEtHg;
*: condensate naphtha；-: not calculated
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表 5 凝析油中汞化合物的不同检测方法的检测限
Table 5 Detection limit of various methods for mercury speciation in natural gas condensate
Mercury species Limit of detection /(μg·L-1) Ref. Hg0 Hg2+ MeEtHg MeHg+ (MeHg) EtHg+ (EtHg) Me2Hg MePrHg Et2Hg MeBuHg Pr2Hg Bu2Hg GC-MIP-AES ND 0.56 ND 0.56 ND 0.24 ND ND ND ND ND [27] 0.98 ND ND ND ND 1.32 0.16 0.08 0.14 0.20 0.11 [26] GC-ICP-MS 0.15 0.34 0.019 0.074 0.05 0.2 ND 0.035 ND ND 0.05 [20] ND 0.03 ND 0.09 ND ND ND ND ND ND ND [36] HPLC-CVAFS ND ND ND 0.05 0.07 ND ND ND ND ND ND [39] ND: not detected
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表 6 不同检测方法对凝析油或原油中形态汞的汞回收率以及相对标准偏差的影响
Table 6 Mercury recovery rate and relative standard deviation of mercury species in natural gas condensate or crude oil analyzed by various methods
Analysis method MeHg EtHg DMeHg DEtHg MeHgCl EtHgCl Hg2+ Hg0 Ref. CVAFS mercury recovery rate /% 105.5 ND ND ND ND ND 93.1 98.7 [19] GC-MIP-AES mercury recovery rate /% ND ND 94.7 ND 108.9 ND 99.2 ND [27] GC-ICP-MS(a) mercury recovery rate /% ND ND 168.9 99.9 103.1 100.1 114 ND RSD /% ND ND 3.2 3.0 2.6 1.6 3.2 3.4 GC-ICP-MS(b) mercury recovery rate /% ND ND 223 90.2 94.9 92.1 ND 77.5 RSD /% ND ND 1.6 (5.1c) 2.5 (4.4c) 2.7 2.6 ND 2.2 (3.9c) [20] HPLC-CVAFS mercury recovery rate /% 86.7 70.6 ND ND ND ND ND ND [39] RSD(%) 1.8 2.1 ND ND ND ND ND ND a: pulsed splitless injection mode; b: on-column injection mode; c: crude oil or condensate gas
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Process Solid adsorption Decomposition-adsorption Decomposition-stripping-adsorption Total mercury content medium high higher Organic mercury lower high higher Mercury adsorbents Ag molecular sieve, metal iodide & metal sulfide sorbent Ag, S or metal sulfide sorbent metal sulfide sorbent Catalyst - Pt, Pd(temp. 160-200 ℃) Pt, Pd(temp. 160-200 ℃) Stripping gas - - natural gas & air Characteristics simple process, mature technology a little more complicated process, medium cost complex process, high cost Atmosphere dry gas dry gas dry gas & wet gas
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Table 8 Comprehensive evaluation of adsorbent for removal of mercury from natural gas condensate[17, 42]
Adsorbents Metal halide adsorbent Ag Molecular sieve Metal sulfide adsorbent(CuS) Regeneration non-regenerable regenerable non-regenerable Atmosphere dry gas dry gas & wet gas dry gas & wet gas Secondary pollution with without without Applicability Hg0, Hg2+ & organic mercury Hg0 Hg0, part of organic mercury stability low high medium Industrialization low light hydrocarbon high
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