高酸值原油脱酸过程研究
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摘要
随着采油技术不断提高和石油资源的枯竭，越来越多的含酸原油被开采上来。石油酸是造成炼油设备腐蚀的主要因素，同时也会影响油品使用性能。另一方面环烷酸是一系列精细化工产品的原料，具有很高的工业应用价值。脱酸工艺日益受到炼油工业界的重视，各种新的脱酸方法不断出现，使该领域研究日益活跃。
本课题主要以苏丹Fula-North-3B原油为研究对象，对高酸值原油中环烷酸脱除过程进行了理论和实验方面的研究。研究内容包括：
1、首次对我国在苏丹和山东蓬莱等地区新开采的高酸值原油基本性质的进行了详细地评价和对其中的环烷酸组成结构进行了详细地分析；
2、对脱酸过程相平衡原理和传质动力学进行了探讨，并研究了重质原油油剂界面特性和乳化机理，同时考察了相关工艺条件。
3、通过正交实验，研究了复合溶剂各组分对脱酸过程的影响，并对其进行筛选，确定了最佳的溶剂组成和工艺条件。对于本试验而言，异丙醇浓度为20％，乙醇浓度25％，UD10为60ppm，氨浓度为8％，并对脱酸温度，搅拌强度，反应静置时间等工艺条件进行了考察。为高酸值原油的加工和环烷酸的综合利用提供了科学的决策依据。
As the decrease of petroleum resourse and the improvement of oil exploration technique, more and more crude oils with high TAN are extracted than before, The acid substances in crude oil are mainly composed of naphthenic acids(NA), which mainly lead to the heavy corrosive of the refinery equipment and degrade the oil product. On the other hand, naphthenic acid is a useful fine chemical material, and It widely used in many fields, such as drier, petroleum additive, wood preservative. Therefore, the process for extraction of NA directly from crude oil is high valued by oil refine industry.
Up to now, the separation of oil and NA is focused on two ways. First, traditional alkali-or ammonia solute neutrlization is conducted deeply by optimizating of the process and alterating the technology. Second, the naphthenic acid separated from oil is refined by means of adsorption and extraction. The latter is feasible on the level of laboratory bench procedure theoretically. At present time it is the only the former method that can be widely used in industry. By analysing the process for
acid removal from crude oil, an effective extraction technique is
proposed. Consequently the purpose of removal naphthenic acid from crude oil was reached and the problem of acid corrosion in oil refinery processing was solved. The main research contents and conclusions are as follows:
1.Based on the basic principle of colloidal chemistry, principle of acid removal from crude oil is proposed. By using combined solute composing of alcohol, isopropanol, ammonia, the optional process conditions are determined by experiments carefully. The key to the process of the present process is its solvent system, the solvent system contains alcohol, ammonia and water in certain critical ratios. The mass ratio of ammonia is about 8%, alcohol above 25% and isopropanol 20% by weight.
2.The properties of two kinds of crude oil and corresponding NA characteristics are analyzed, naphthenic acids existing as a complex mixture of compounds and can be catalogued into proportions of isomers further characterization of the mixture into relative proportions of l-,2-,3- ringed structures is determined..The results show that naphthenic acids the molecular weight of carboxylic acids widely range from 100~1000, Carbon number is between 7~70.and the contents of mono~tetracyclic naphthenic acid dominate .
本课题主要以苏丹Fula-North-3B原油为研究对象，对高酸值原油中环烷酸脱除过程进行了理论和实验方面的研究。研究内容包括：
1、首次对我国在苏丹和山东蓬莱等地区新开采的高酸值原油基本性质的进行了详细地评价和对其中的环烷酸组成结构进行了详细地分析；
2、对脱酸过程相平衡原理和传质动力学进行了探讨，并研究了重质原油油剂界面特性和乳化机理，同时考察了相关工艺条件。
3、通过正交实验，研究了复合溶剂各组分对脱酸过程的影响，并对其进行筛选，确定了最佳的溶剂组成和工艺条件。对于本试验而言，异丙醇浓度为20％，乙醇浓度25％，UD10为60ppm，氨浓度为8％，并对脱酸温度，搅拌强度，反应静置时间等工艺条件进行了考察。为高酸值原油的加工和环烷酸的综合利用提供了科学的决策依据。
As the decrease of petroleum resourse and the improvement of oil exploration technique, more and more crude oils with high TAN are extracted than before, The acid substances in crude oil are mainly composed of naphthenic acids(NA), which mainly lead to the heavy corrosive of the refinery equipment and degrade the oil product. On the other hand, naphthenic acid is a useful fine chemical material, and It widely used in many fields, such as drier, petroleum additive, wood preservative. Therefore, the process for extraction of NA directly from crude oil is high valued by oil refine industry.
Up to now, the separation of oil and NA is focused on two ways. First, traditional alkali-or ammonia solute neutrlization is conducted deeply by optimizating of the process and alterating the technology. Second, the naphthenic acid separated from oil is refined by means of adsorption and extraction. The latter is feasible on the level of laboratory bench procedure theoretically. At present time it is the only the former method that can be widely used in industry. By analysing the process for
acid removal from crude oil, an effective extraction technique is
proposed. Consequently the purpose of removal naphthenic acid from crude oil was reached and the problem of acid corrosion in oil refinery processing was solved. The main research contents and conclusions are as follows:
1.Based on the basic principle of colloidal chemistry, principle of acid removal from crude oil is proposed. By using combined solute composing of alcohol, isopropanol, ammonia, the optional process conditions are determined by experiments carefully. The key to the process of the present process is its solvent system, the solvent system contains alcohol, ammonia and water in certain critical ratios. The mass ratio of ammonia is about 8%, alcohol above 25% and isopropanol 20% by weight.
2.The properties of two kinds of crude oil and corresponding NA characteristics are analyzed, naphthenic acids existing as a complex mixture of compounds and can be catalogued into proportions of isomers further characterization of the mixture into relative proportions of l-,2-,3- ringed structures is determined..The results show that naphthenic acids the molecular weight of carboxylic acids widely range from 100~1000, Carbon number is between 7~70.and the contents of mono~tetracyclic naphthenic acid dominate .
引文
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[3]．徐英．高酸值原油加工过程中存在的问题与对策[J]．石油化工腐蚀与防护，2003．20(1)：10．
[4]．安辉，赵岩．加工高酸值原油及带炼高馏油蒸馏装置的腐蚀[J]．石油化工腐蚀与防护，2001．18(5)．
[5]．高延敏，陈家坚，雷良才．环烷酸腐蚀研究现状和防护对策[J]．石油化工腐蚀与防护，2001．17(2)：7-11．
[6]. Tebbal, S. Critical review of naphthenic acid corrosion, in NACE National Conference: Corrosion'99. 1999.
[7]. Tortes, J.L.H.O.Y.L. Classifying crude oils according to corrosivity using the Fe powder test. in:National Association of Corrosion Engineers. 2000.
[8]. Phillips, D.D.B.M.T. Corrosion in the refinery industry[J]. British Corrosion Journal, 2001.36(3): 174-175.
[9]. Ke, X.Q.W.H.M.J.Y.G.Z.Z.M.Y.W. Corrosion and erosion-corrosion behaviors of carbon steel in naphthenic andmedia[J]. Werkstoffe und Korrosion, 2002. 53(11): 833-844.
[10]. J.W.Palmer, G.B. Crude oil corrosion[J]. Hydrocarbon Engineering, 2002. 7(3): 89-90.
[11]．武文广，薛英．试论我厂加工高酸值原油的技术措施[J]．化工设备与管道，2003．40(3)：52-56．
[12]．宫秀珍．辽河油加工中的环烷酸的腐蚀和防护[J]．石油炼制，1988(1)：29-33．
[13]. We, J.H.Z.Y.Y.Z.K. Study on Erosion-Corrosion of CrSMo in Oil Containing naphthenic Acid atEievated Temperature. in China Chemical Anticorrosion Technology Association. 2000.
[14]．李国英，范惠明，孙晓瑜，刘新果．全氢工艺生产优质环烷基润滑油[J]．润滑油，2001．16(6)：23-27．
[15]．黄明福，赵杉林，杨柯，黎渊博．微波作用下直馏柴油脱酸新方法的研究[J]．石油与天然气化工，2003．32(5)：283-286．
[16]. R.C.Robinson, N.A.T.R.E.W.J.H.S. On the Nature and Origin of Acidic Species in Petroleum. 1. Detailed AcidType Distribution in a California Crude Oil[J]. Energy & Fuels, 2001.15(6): 1498-1504.
[17]．刘长久，张文林，石油及石油中的非烃化合物[M]．1991：中国石化出版社．
[18]．刘溆番，石油非烃化学[M]．1990，石油工业出版社：北京．p．245-260．
[19]．冯丽．环烷酸与高级脂肪醇直接酯化的初步研究[J]．新疆石油学院学报，1999．11(1)：25-29．
[20]. VOLLE, A.GM.B.C.H.J.-L. stability of water in acidic crude oil emulsions[J]. 3rd International Conference on Petroleum Phase Behavior and Fouling, Mar10-14, 2002, New Orleans, LA, 2002: 386-400.
[21]. Rogers, J.B.M.P.M.M.M.M. Removal of naphthenic Acid from Tailings Pond Water Via pH Adjustment, Coagulation and Sand Filtration[J]. chemosphere, 1999. 738-754.
[22]．陶嘉琳，周健，李燕萍．从新疆石油重质馏分中提取环烷酸的研究[J]．石油炼制，1991(12)：26-28．
[23]．唐晓东，高纯林．直馏柴油萃取精制工艺研究进展10．炼油设计，2001．31(2)：8-11．
[24]. Alan, G.M., Method for reducing the naphthenic acid content of crude oil and its fractions[P]. 2001: us63251415.
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