TSR模拟实验研究与地质实际的异同及可能原因分析

罗厚勇; 王万春; 刘文汇

doi:10.11781/sysydz201202186

TSR模拟实验研究与地质实际的异同及可能原因分析

doi: 10.11781/sysydz201202186

1.
中国科学院油气资源研究重点实验室, 兰州 730000
2. 中国科学院研究生院, 北京 100049
3. 中国石油化工集团公司油气成藏重点实验室, 江苏无锡 214126

基金项目: 中国科学院知识创新工程重要方向项目(KZCX2-YW-Q05-03-03);国家重点基础研究发展计划(973计划)项目(2012CB214800)资助

详细信息

作者简介:
罗厚勇(1985- ),男,博士研究生,从事油气地球化学研究.E-mail:luohouyong8@163.com.

中图分类号: TE12
计量
- 文章访问数: 3605
- HTML全文浏览量: 40
- PDF下载量: 1695
- 被引次数: 0
出版历程
- 收稿日期: 2011-10-19
- 修回日期: 2012-02-20
- 刊出日期: 2012-03-28

Similarities and differences between simulation experiments on TSR and geological observations and possible causes

1.
Key Laboratory of Petroleum Resource Research, Institute of Geology and Geophysics, Chinese Academy of Sciences, Lanzhou, Gansu 730000, China
2. Graduate University of Chinese Academy of Sciences, Beijing 100049, China
3. Key Laboratory of Petroleum Accumulation, SINOPEC, Wuxi, Jiangsu 214126, China

摘要

摘要: 通过对比分析与热化学硫酸盐还原反应(TSR)相关的模拟实验研究和地质实际研究的异同后认为,TSR模拟实验能够再现地质实际过程的某些现象,如生成物、反应温度和催化剂等.但目前的TSR模拟实验与地质实际过程之间存在较大的差距,TSR模拟实验反应物相对简单,实验时间有限,催化剂较少,致使实际地质过程中存在的一些复杂连锁反应不能在模拟实验中发生,一些反应也没有达到地质条件下反应进行的程度,因此难以再现地质实际情况下观察到的诸多现象.TSR模拟实验与地质实际情况下硫化氢的硫同位素和烃类组分的碳同位素分馏存在较大的差异.未来的TSR模拟实验研究应设计更为复杂的反应物和反应体系,应用多种反应催化剂,以深入探讨TSR的反应机理和动力学过程,有效解决与TSR相关的地质地球化学问题.
- 碳同位素 /
- 硫同位素 /
- 催化剂 /
- TSR /
- 模拟实验 /
- 油气地球化学
Abstract: The similarities and differences between simulation experiments on thermochemical sulfate reduction (TSR) and geological observations have been compared.Some results of the TSR simulation experiments are consistent with the natural TSR process in terms of products,reaction temperature,catalysts,etc.; however,there is a big gap between current TSR simulation experiments and actual geological process.Owing to relatively simple reactants,limited experimental time as well as comparatively less catalysts,some complex chain reactions during the actual geological processes fail to occur in the TSR simulation experiments,preventing some of the reactions from achieving the extent of reaction under geological conditions.Therefore,the TSR simulation experiments fail to reproduce the phenomena observed under actual geological conditions.Significant differences exist between simulation experiments and geological observations on the sulfur isotopic fractionations of hydrogen sulphide and the carbon isotopic fractionations of n-alkanes.In order to carry forward the study of TSR reaction mechanisms and dynamics and to efficiently figure out TSR-related geological and geochemical issues,the future TSR simulation experiments should use more complex reactants,systems and all kinds of catalysts.
- carbon isotope /
- sulfur isotope /
- catalyst /
- TSR /
- simulation experiment /
- petroleum geochemistry

HTML全文

参考文献(66)

[1]	Kiyosu Y,Krouse H R.Carbon isotope effect during abiogenic oxidation of methane[J].Earth and Planetary Science Letters,1989,95:302-306.
[2]	Worden R H,Smalley P C,Oxtoby N H.Gas Souring by thermochemical sulfate reduction at 140℃[J].AAPG Bulletin,1995,79:854-863.
[3]	Machel H G.Gas souring by thermochemical sulfate reduction at 140℃:discussion[J].AAPG Bulletin,1998,82:1870-1873.
[4]	Cai C F,Worden R H,Bottrell S H,et al.Thermochemical sulphate reduction and the generation of hydrogen sulphide and thiols (mercaptans) in Triassic carbonate reservoirs from the Sichuan Basin,China[J].Chem Geol,2003,202:39-57.
[5]	Bildstein O,Worden R H,Brdsse E.Assessment of anhydrite dissolution as the rate limiting step during thermochemical sulfate reduction[J].Chemical Geology,2001,176:173-189.
[6]	马喜斌,张建勇,张燕,等.川东北高含硫天然气形成机理[J].断块油气田,2008,15(6):13-17.
[7]	Cross M M,Manning D A C,Bottrell S H,et al.Thermochemical sulphate reduction(TSR):experimental determination of reaction kinetics and implications of the observed reaction rates for petroleum reservoirs[J].Organic Geochemistry,2004,35:393-404.
[8]	Machel H G.Bacterial and thermochemical sulfate reduction in diagenetic settings:old and new insights[J].Sedimentary Geology,2001,140:143-175.
[9]	Machel H G,Krouse H R,Sassen R.Products and distinguishing criteria of bacterial and thermochemical sulfate reduction[J].Appl Geochem,1995,10:373-389.
[10]	Zhang T W,Ellis G S,Wang K S,et al.Effect of hydrocarbon type on thermochemical sulfate reduction[J].Organic Geochemistry,2007,38:897-910.
[11]	Pan C C,Yu L P,Liu J Z,et al.Chemical and carbon isotopic fractionations of gaseous hydrocarbons during abiogenic oxidation[J].Earth and Planetary Science Letters, 2006,246:70-89.
[12]	张建勇,刘文汇,腾格尔,等.硫化氢形成与C₂₊气态烷烃形成的同步性研究:几个模拟实验的启示[J].地球科学进展,2008,23(4):390-400.
[13]	张建勇,刘文汇,腾格尔,等.硫酸盐热还原作用模拟实验装置的材料选择[J].石油实验地质,2010,32(4):400-404.
[14]	张建勇,刘文汇,范明,等.TSR产物对碳酸盐岩储层是否具有改良作用:实验地质学的依据[J].海相油气地质,2008,13(2):57-61.
[15]	范明,胡凯,蒋小琼,等.酸性流体对碳酸盐岩储层的改造作用[J].地球化学,2009,38(1):20-26.
[16]	Stasiuk L D.The origin of pyrobitumens in upper Devonian Leduc Formation gas reservoirs,Alberta,Canada:an optical and EDS study of oil to gas transformation[J].Marine and Petroleum Geology,1997,14:915-929.
[17]	Heydari E.The role of burial diagenesis in hydrocarbon destruction and H₂S accumulation,Upper Jurassic smackover formation,Black Creek Field,Mississippi[J].AAPG Bulletin,1997,81:26-45.
[18]	Worden R H,Smalley P C,Oxtoby N H.The effects of thermochemical sulfate reduction upon formation water salinity and oxygen isotopes in Carbonate reservoirs[J].Geochimica et Cosmochimica Acta,1996,60:3925-3931.
[19]	Cai C F,Xie Z Y,Worden R H.Methane-dominated thermochemical sulphate reduction in the Triassic Feixianguan Formation East Sichuan basin, China: towards prediction of Fatal H₂S concentrations[J].Marine and Petroleum Geology,2004,21:1265-1279.
[20]	郑冰,腾格尔,张建勇,等.川东北地区飞仙关组油气藏H₂S由TSR和TDR两种方式形成[J].石油与天然气地质,2010,31(6):847-857.
[21]	张建勇,刘文汇,腾格尔,等.建南气田长兴组-飞仙关组天然气特征及气源分析[J].天然气地球科学,2010,21(6):1004-1010.
[22]	刘文汇,腾格尔,高波,等.四川盆地大中型天然气田(藏)中H₂S形成及富集机制[J].石油勘探与开发,2010,37(5):513-522.
[23]	Cai C F,Worden R H,Wang Q H,et al.Chemical and isotopic evidence for secondary alteration of natural gases in the hetianhe field,Bachu Uplift of the Tarim basin[J].Organic Geochemistry,2002,33:1415-1427.
[24]	Cai C F,Hu G Y,He H,et al.Geochemical characteristics and origin of natural gas and thermochemical sulphate reduction in Ordovician carbonates in the Ordos Basin,China[J].Journal of Petroleum Science and Engineering,2005,48:209-226.
[25]	Heydari E,Moore C H.Burial diagenesis and thermochemical sulfate reduction,Smackover Formation, southeastern Mississi-ppi Salt Basin[J].Geology,1989,12:1080-1084.
[26]	Toland W G.Oxidation of organic compounds with aqueous sulfate[J].Journal of the American Chemical Society,1960,82:1911-1916.
[27]	丁康乐,李术元,岳长涛,等.原油中有机硫化物成因的硫酸盐热化学还原反应模拟研究[J].燃料化学学报,2008,36(1):48-54.
[28]	李术元,丁康乐,岳长涛,等.含水条件下正己烷与硫酸镁热化学还原反应体系模拟[J].中国石油大学学报(自然科学版),2009,33(1):120-126.
[29]	丁康乐,李术元,岳长涛,等.硫酸盐热化学还原反应基元步骤与反应机理初探[J].燃料化学学报,2008,36(6):706-711.
[30]	陈腾水,何琴,卢鸿,等.饱和烃与硫酸钙和元素硫的热模拟实验对比研究:H₂S成因探讨[J].中国科学D辑:地球科学,2009,39(12):1701-1708.
[31]	李开开,蔡春芳,蔡镠璐,等.塔中地区上奥陶统热液流体与热化学硫酸盐还原作用[J].石油与天然气地质,2008,28(2):217-222.
[32]	蔡春芳,李宏涛.沉积盆地热化学硫酸盐还原作用评述[J].地球科学进展,2005,20(10):1100-1105.
[33]	丁康乐,李术元,岳长涛,等.硫酸盐热化学还原反应的研究进展[J]石油大学学报(自然科学版),2005,29(1):150-155.
[34]	朱光有,张水昌,梁英波,等.TSR对深部碳酸盐岩储层的溶蚀改造[J].岩石学报,2006,22(8):2182-2194.
[35]	王一刚,文应初,洪海涛,等.四川盆地三叠系飞仙关组气藏储层成岩作用研究拾零[J].沉积学报,2007,25(6):831-839.
[36]	Dixon S A,Summers D M,Surdam R C.Diagenesis and preservation of porosity in Norphlet Formation (Upper Jurassic),southern Alabama[J].AAPG Bulletin,1989,73:707-728.
[37]	Powell T G,MacQueen R W.Precip itation of sulfide ores and organic matter:Sulfade reactions at Pine Point,Canada [J].Science,1984,224:63-66.
[38]	Cai C F,Hu W S,Worden R H.Thermochemical sulphate reduction in Cambro-Ordovician carbonates in central Tarim[J].Marine and Petroleum Geology,2001,18:729-741.
[39]	朱光有,张水昌,梁英波,等.川东北地区飞仙关组高含H₂S天然气TSR成因的同位素证据[J].中国科学D辑:地球科学,2005,35(11):1037-1046.
[40]	张水昌,朱光有,何坤.硫酸盐热化学还原作用对原油裂解成气和碳酸盐岩储层改造的影响及作用机制[J].岩石学报,2011,27(3):809-826.
[41]	Worden R H,Smalley P C.H₂S-producing reactions in deep carbonate gas reservoirs:Khuff Formation, Abu Dhabi[J].Chemical Geology,1996,133:157-171.
[42]	Anisimov L A.Conditions of a biogenic reduction of sulfide in oil and gas-bearing basins[J].Geochemistry International,1978,15:63-71.
[43]	Goldhaber M B,Orr W L.Kinetic controls on thermochemical sulfate reduction as a source of sedimentary H₂S[M]//Vairavamurthy M A,Schoonen M A A. eds.Geochemical Transformations of Sedimentary Sulfur.American Chemical Society Symposium Series 612.Washington,D.C:Am Chem Soc, 1995:412-425.
[44]	代金友,陈安定,何顺利,模拟硫化氢生成的热化学还原反应实验研究[J].石油实验地质,2008,30(2):200-202.
[45]	Claypool G E,Mancini E A.Geochemical relationships of petroleum in Mesozoic reservoirs to carbonate source rocks of Jurassic Smackover Formation,southwestern Alabama[J].AAPG Bulletin,1989,73:904-924.
[46]	Rooney M A.Carbon isotopic evidence for the accelerated destruction of light hydrocarbons by thermochemical sulfate reduction//Thermochemical Sulphate Reduction (TSR) and Bacterial Sulphate Reduction (BSR) workshop.Calgary:University of Calgary,1996.
[47]	Orr W L.Changes in Sulfur Content and Isotopic Ratios of Sulfur during Petroleum Maturation:Study of Big Horn Basin Paleozoic Oils[J].AAPG Bulletin,1974,58(11):2295-2318.
[48]	Hao F,Guo T L,Zhu Y M,et al.Evidence for multiple stages of oilcracking and thermochemical sulfate reduction in the Puguang gas filed,Sichuan Basin,China[J].AAPG Bulletin,2008,92:611-637.
[49]	Tang Y C,Ellis G S,Zhang T W,et al.Effect of aqueous che-mistry on the thermal stability of hydrocarbons in petroleum re-servoirs[J].Geochimica et Cosmochimica Acta,2005,69:559.
[50]	Ellis G S,Zhang T,Ma Q,et al.Empirical and theoretical evidence for the role of MgSO₄ contact ion-pairs in thermochemical sulfate reduction[C]//American Geophysical Union,Fall Meeting,2006:59.
[51]	Ellis G S,Zhang T,Ma Q,et al.Kinetics and mechanism of hydrocarbon oxidation by thermochemical sulfate reduction[C]//23rd IMOG meeting,2007.
[52]	Zhang T W,Amrani A,Ellis G S,et al.Experimental investigation on thermochemical sulfate reduction by H₂S initiation[J].Geochimica et Cosmochimica Acta,2008,72:3518-3530.
[53]	Amrani A,Zhang T W,Ma Q S,et al.The role of labile sulfur compounds in thermochemical sulfate reduction[J].Geochimica et Cosmochimica Acta,2008,72:2960-2972.
[54]	Ma Q S,Ellis G S,Amrani A,et al.Theoretical study on the reactivity of sulfate species with hydrocarbons[J].Geochimica et Cosmochimica Acta,2008,72:4565-4576.
[55]	Trudinger P A,Chambers L A.Low temperature sulfate reduction:biological versus abiological[J].Canadian Journal of Earth Sciences,1985,22:1910-1918.
[56]	Orr W L.Rate and mechanism of nonmicrobial sulfate reduction:thermochemiacal sulfate reduction[C]//95th Annual Geological Society of America Meeting,1982.
[57]	Machel H G.Saddle dolomite as a by-product of chemical compaction and thermochemical sulfate reduction[J].Geology,1987,15:936-940.
[58]	谢增业,李剑,李志生,等.四川盆地飞仙关组气藏硫化氢成因及其依据[J].沉积学报,2008,26(2):314-323.
[59]	张水昌,帅燕华,朱光有.TSR促进原油裂解成气:模拟实验证据[J].中国科学D辑:地球科学,2008,38(3):307-311.
[60]	刘文汇,张殿伟,王晓锋.加氢和TSR反应对天然气同位素组成的影响[J].岩石学报,2006,22(8):2237-2242.
[61]	朱光有,张水昌,梁英波.天然气中高含H₂S的成因及其预测[J].地质科学,2006,41(1):152-157.
[62]	Xiang C F,Pang X Q,Wang J Z,et al.Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China:Evidence from Formation Water and Natural Gas Geochemistry[J].Acta Geologica Sinica,2010,84(2):358-369.
[63]	Manzano B K,Fowler M G,Machel H G.The influence of thermochemical sulphate reduction on hydrocarbon composition in Nisku reservoir,Brazeau river area,Alberta,Canada[J].Organic Geochemistry,1997,27(7/8):507-521.
[64]	Belenitskaya G A.Distribution pattern of hydrogen sulphide-bearing gas in the former Soviet Union[J].Petroleum Geo science,2000,6:175-187.
[65]	张水昌,朱光有,陈建平,等.四川盆地川东北部飞仙关组高含硫化氢大型气田群气源探讨[J].科学通报,2007,52(增刊1):86-94.
[66]	刘全有,金之钧,高波,等.川东北地区酸性气体中CO₂成因与TSR作用影响[J].地质学报,2009,83(8):1195-1202.