高（含）硫高（含）酸原油加工工艺中的防腐研究
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摘要
高(含)硫原油具有硫含量高等特点,而高(含)酸原油具有酸值高、密度大、金属含量高、残炭高和粘度大等特点,给炼油装置的生产带来了操作、产品质量及设备腐蚀等一系列问题。
为了稳定装置的正常生产操作,做好加工高(含)硫高(含)酸原油的工艺防腐工作,为炼油二次加工装置提供合格的原料,本文研究了不同破乳剂除盐、脱水的效果,最终选用贝克白特利公司高效的CC8289C或纳尔科公司EC2452A油溶性破乳剂,应用到现有电脱盐破乳、脱盐、脱钙的成套处理技术中,除盐、脱水的效果明显。选用NCH-8E型中和缓蚀剂进行塔顶的低温硫化氢腐蚀控制,选用CK356N2型缓蚀剂进行高温部位的环烷酸腐蚀控制,通过上述工艺实施,有效地解决了装置加工高(含)硫高(含)酸原油的带来的一系列腐蚀问题,高温部位的环烷酸腐蚀也得到了有效的控制,并且达到了中石化内控指标,取得了良好的应用效果。工业生产结果表明：该技术可以处理各种劣质、重质高(含)酸原油,具有适应性较强、操作方便简单等特点。
The oil refining process is a very complicated process, in which metal corrosion including chemical and electro—chemical corrosion usually occurs. Such corrosion not only causes the loss of large quantity of metal, reducing the service life of equipment and pipeline and increasing accident rates, but also affect the products quality and energy consumption. Therefore, corrosion protection plays an important role in the oil refinery production, especially for the refinery that designs to process high sulfur or acid crude oil. Corrosion protection measures shall be put into full consideration during the whole course of refinery building from the front-end engineering, equipment material selection to the process of construction.
In addition, combining the features of the specific plant and feed—stocks used in the actual production, corrosion protection measures shall be taken on the production process and individual equipment to reduce the corrosion rates and ensure the best performance of the plant. In this paper, different demulsifier desalination, the effects of dehydration, the final choice of white Terry Baker, the company effective CC8289C or oil-soluble demulsifier EC2452A Nalco Company, applied to the existing electric desalting emulsion breaking, desalting, decalcified, high-temperature ring complete set of alkyl acid preservative treatment technology, desalination, dewatering effect is obvious. NCH-8E-type selection and an inhibitor in the top of the low-temperature hydrogen sulfide corrosion control, corrosion inhibitor for high temperature use CK356N2 parts of naphthenic acid corrosion control, through the process control device to effectively solve the processing of high (inclusive) High Sulfur (inclusive) of crude oil brought about a series of acid corrosion problems. High-temperature parts of the naphthenic acid corrosion have also been effectively controlled, and internal control targets to achieve in the petrochemical, achieved good results. The results showed that:the technology can handle a variety of low-quality, heavy high (inclusive) sour crude oil, has a strong adaptability, easy operation and simple.
为了稳定装置的正常生产操作,做好加工高(含)硫高(含)酸原油的工艺防腐工作,为炼油二次加工装置提供合格的原料,本文研究了不同破乳剂除盐、脱水的效果,最终选用贝克白特利公司高效的CC8289C或纳尔科公司EC2452A油溶性破乳剂,应用到现有电脱盐破乳、脱盐、脱钙的成套处理技术中,除盐、脱水的效果明显。选用NCH-8E型中和缓蚀剂进行塔顶的低温硫化氢腐蚀控制,选用CK356N2型缓蚀剂进行高温部位的环烷酸腐蚀控制,通过上述工艺实施,有效地解决了装置加工高(含)硫高(含)酸原油的带来的一系列腐蚀问题,高温部位的环烷酸腐蚀也得到了有效的控制,并且达到了中石化内控指标,取得了良好的应用效果。工业生产结果表明：该技术可以处理各种劣质、重质高(含)酸原油,具有适应性较强、操作方便简单等特点。
The oil refining process is a very complicated process, in which metal corrosion including chemical and electro—chemical corrosion usually occurs. Such corrosion not only causes the loss of large quantity of metal, reducing the service life of equipment and pipeline and increasing accident rates, but also affect the products quality and energy consumption. Therefore, corrosion protection plays an important role in the oil refinery production, especially for the refinery that designs to process high sulfur or acid crude oil. Corrosion protection measures shall be put into full consideration during the whole course of refinery building from the front-end engineering, equipment material selection to the process of construction.
In addition, combining the features of the specific plant and feed—stocks used in the actual production, corrosion protection measures shall be taken on the production process and individual equipment to reduce the corrosion rates and ensure the best performance of the plant. In this paper, different demulsifier desalination, the effects of dehydration, the final choice of white Terry Baker, the company effective CC8289C or oil-soluble demulsifier EC2452A Nalco Company, applied to the existing electric desalting emulsion breaking, desalting, decalcified, high-temperature ring complete set of alkyl acid preservative treatment technology, desalination, dewatering effect is obvious. NCH-8E-type selection and an inhibitor in the top of the low-temperature hydrogen sulfide corrosion control, corrosion inhibitor for high temperature use CK356N2 parts of naphthenic acid corrosion control, through the process control device to effectively solve the processing of high (inclusive) High Sulfur (inclusive) of crude oil brought about a series of acid corrosion problems. High-temperature parts of the naphthenic acid corrosion have also been effectively controlled, and internal control targets to achieve in the petrochemical, achieved good results. The results showed that:the technology can handle a variety of low-quality, heavy high (inclusive) sour crude oil, has a strong adaptability, easy operation and simple.
引文
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[3]李淑琴等.含水原油破乳脱水的声化学研究[J].天津化工,1997,4：22-24.
[4]DU Rong-xi.crude salting and dewatering by filtration technology[J].Petroleum processing petrochemicals,1999,30 (11):10-14.
[5]刘庆敏.磁处理技术在原油中的运用[J].华北石油设计,2002,69(3)：9-14.
[6]刘惠玲.微波脱水技术[J].油田地面工程,1992,11(4)：8-10.
[7]Cheng Hai-yan,QI Xin.Expeiment On crude dehydration under high pressure pulse electric filed [J].Oil &surface engineering.2000,19 (1):28,37.
[8]凌逸群.常减压蒸馏装置生产运行的主要问题及对策.2000(12)：4-7.
[9]郭丹,王德会.电脱盐操作条件的优化.炼油技术与工程.2003(11)：35-37.
[10]乔建江,徐心茹,詹敏等.石油学报,1998,14(3)：62-66.
[11]贾鹏林,石油化工腐蚀于防护,1999,16(1)：56-57.
[12]吴加平,镇海石化,2000,11(2)：19-22.
[13]吴江英,翁惠新.炼油工业中的脱钙剂[J].炼油设计,2000,30(3)：57-61.
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[15]金戈译.从原油中去除金属的生物催化剂[J].石油炼制与化工,1998,29(1)：23-27.
[16]Duffield,Randall,Yen,Ronald.sulfur compound removal from by filtration through intermetallic antimony-tin filter[P].WO 99044898.1999.
[17]Sartori,Savage,Blum,Ballinger.Removal of Calcium from crude[P].WO 14402,1998.
[18]Blum Sartori,Savage,CO2 treatment to remove Calcium from crude[P].WO 14534,1998.
[19]Kutouy oleh,Tweddle Thomaa A.A method of removing substances from fossil derived hydrocarbon liquid[P].EP 0217534,1986.
[20]John,Cerrito,David,San.Demetalation of hydrocarbonaceous feedstocks using monobasic carboxylic acids and salts thereof[P].US,US4988433.1990.
[21]John,Cerrito.Demetalation of hydrocarbonaceous feedstocks using dibasic carboxylic acids and salts thereof[P].US,US4853109.1988.
[22][P].CN86107286.1987.
[23]John,Cerrito.Demetalation of hydrocarbonaceous feedstocks using carboxylic acid and salts thereof[P].US,US4778591.1986.
[24]David.Demetalation of hydrocarbonaceous feedstocks using sulfuric acid and salts thereof[P].US,US5593573.1995.
[25]徐岳峰等.用无机含磷螯合剂从原料中脱除金属杂质[P].中国,CN1076473.1993.
[26]马永花.胜利原油脱钙技术工业应用[J].齐鲁石油化工,1997,25(3)：185-187.
[27]王中亭.用有机酸及其盐类从油料中脱除金属[P].中国,CN1120575.1996.
[28]谭丽,徐振洪,傅晓萍等.石油炼制与化工,2002,33(11)：41-44.
[29]徐振洪,于丽,谭丽等.炼油技术与工程,2004,34(11)：44-48.
[30]段海江.原油脱钙新技术应用[J].油气加工,1996,6(2)：33-35.
[31]徐岳峰.原油脱钙技术的研究[J].石油炼制与化工,1994,25(5)：41-43.
[32]李发永等.石油炼制与化工,2003,31(12)：41-44.
[33]French E C. Oil and Gas. J.May 24 1993, OGJ Sepecial 45-53.
[34]高延敏.环烷酸腐蚀研究现状和防腐对策,石油化工腐蚀与防护.2000,17(2)：6.
[35]Slavchwva E. Review of nephthenic acid corrosion in oil refining British Corrosion Journal.1999.34 (2):125.
[36]中国石化集团技术考察组.加工中东高硫原油访日、韩技术考察报告.石油化工腐蚀与防护,2001,(6),1-17.
[37]任有才,张德印.炼制高硫(含硫)原油主要装置腐蚀及防护调查.石油化工腐蚀与防护,2001,(6),18-34.
[38]王勤娜.常减压塔顶系统工艺防腐.化工进展,1999,(2),54-55.
[39]Nathan. C. C et al Mater Perform.1974, (9),29-33.
[40]许淳淳,国内外化工防腐蚀技术进展[J].化工设备与防腐蚀,2001.6：23-26.
[41]柯伟,陈进伟.炼油工业腐蚀研究进展[J].石油化工腐蚀与防护,1997,14(2)：5-7.
[42]崔新安,贾鹏林.高硫原油加工过程中的腐蚀与防护[J].石油化工腐蚀与防护,2001,18(1)：1-7.
[43]李云浩.蒸馏塔顶系统的防腐蚀措施[J].石油化工腐蚀与防护,2000.17(4)：22.
[44]侯祥麟.中国炼油技术[M].北京：中国石化出版社.1994.
[45]卢人严.面向21世纪的炼油技术发展分析[J].石油化工动态.1998.6(3)：7-16.
[2]王金斧.原油交直流电脱盐技术在南充炼油厂的应用[J].天然气与石油,1999,17(1) ：11-13.
[3]李淑琴等.含水原油破乳脱水的声化学研究[J].天津化工,1997,4：22-24.
[4]DU Rong-xi.crude salting and dewatering by filtration technology[J].Petroleum processing petrochemicals,1999,30 (11):10-14.
[5]刘庆敏.磁处理技术在原油中的运用[J].华北石油设计,2002,69(3)：9-14.
[6]刘惠玲.微波脱水技术[J].油田地面工程,1992,11(4)：8-10.
[7]Cheng Hai-yan,QI Xin.Expeiment On crude dehydration under high pressure pulse electric filed [J].Oil &surface engineering.2000,19 (1):28,37.
[8]凌逸群.常减压蒸馏装置生产运行的主要问题及对策.2000(12)：4-7.
[9]郭丹,王德会.电脱盐操作条件的优化.炼油技术与工程.2003(11)：35-37.
[10]乔建江,徐心茹,詹敏等.石油学报,1998,14(3)：62-66.
[11]贾鹏林,石油化工腐蚀于防护,1999,16(1)：56-57.
[12]吴加平,镇海石化,2000,11(2)：19-22.
[13]吴江英,翁惠新.炼油工业中的脱钙剂[J].炼油设计,2000,30(3)：57-61.
[14]Chi-Wen Huang,Bruce,Reynolds,Marinez.Catalyst system for removal of calcium from a hydrocarbon feedstock[P].US,US45143887.1992.
[15]金戈译.从原油中去除金属的生物催化剂[J].石油炼制与化工,1998,29(1)：23-27.
[16]Duffield,Randall,Yen,Ronald.sulfur compound removal from by filtration through intermetallic antimony-tin filter[P].WO 99044898.1999.
[17]Sartori,Savage,Blum,Ballinger.Removal of Calcium from crude[P].WO 14402,1998.
[18]Blum Sartori,Savage,CO2 treatment to remove Calcium from crude[P].WO 14534,1998.
[19]Kutouy oleh,Tweddle Thomaa A.A method of removing substances from fossil derived hydrocarbon liquid[P].EP 0217534,1986.
[20]John,Cerrito,David,San.Demetalation of hydrocarbonaceous feedstocks using monobasic carboxylic acids and salts thereof[P].US,US4988433.1990.
[21]John,Cerrito.Demetalation of hydrocarbonaceous feedstocks using dibasic carboxylic acids and salts thereof[P].US,US4853109.1988.
[22][P].CN86107286.1987.
[23]John,Cerrito.Demetalation of hydrocarbonaceous feedstocks using carboxylic acid and salts thereof[P].US,US4778591.1986.
[24]David.Demetalation of hydrocarbonaceous feedstocks using sulfuric acid and salts thereof[P].US,US5593573.1995.
[25]徐岳峰等.用无机含磷螯合剂从原料中脱除金属杂质[P].中国,CN1076473.1993.
[26]马永花.胜利原油脱钙技术工业应用[J].齐鲁石油化工,1997,25(3)：185-187.
[27]王中亭.用有机酸及其盐类从油料中脱除金属[P].中国,CN1120575.1996.
[28]谭丽,徐振洪,傅晓萍等.石油炼制与化工,2002,33(11)：41-44.
[29]徐振洪,于丽,谭丽等.炼油技术与工程,2004,34(11)：44-48.
[30]段海江.原油脱钙新技术应用[J].油气加工,1996,6(2)：33-35.
[31]徐岳峰.原油脱钙技术的研究[J].石油炼制与化工,1994,25(5)：41-43.
[32]李发永等.石油炼制与化工,2003,31(12)：41-44.
[33]French E C. Oil and Gas. J.May 24 1993, OGJ Sepecial 45-53.
[34]高延敏.环烷酸腐蚀研究现状和防腐对策,石油化工腐蚀与防护.2000,17(2)：6.
[35]Slavchwva E. Review of nephthenic acid corrosion in oil refining British Corrosion Journal.1999.34 (2):125.
[36]中国石化集团技术考察组.加工中东高硫原油访日、韩技术考察报告.石油化工腐蚀与防护,2001,(6),1-17.
[37]任有才,张德印.炼制高硫(含硫)原油主要装置腐蚀及防护调查.石油化工腐蚀与防护,2001,(6),18-34.
[38]王勤娜.常减压塔顶系统工艺防腐.化工进展,1999,(2),54-55.
[39]Nathan. C. C et al Mater Perform.1974, (9),29-33.
[40]许淳淳,国内外化工防腐蚀技术进展[J].化工设备与防腐蚀,2001.6：23-26.
[41]柯伟,陈进伟.炼油工业腐蚀研究进展[J].石油化工腐蚀与防护,1997,14(2)：5-7.
[42]崔新安,贾鹏林.高硫原油加工过程中的腐蚀与防护[J].石油化工腐蚀与防护,2001,18(1)：1-7.
[43]李云浩.蒸馏塔顶系统的防腐蚀措施[J].石油化工腐蚀与防护,2000.17(4)：22.
[44]侯祥麟.中国炼油技术[M].北京：中国石化出版社.1994.
[45]卢人严.面向21世纪的炼油技术发展分析[J].石油化工动态.1998.6(3)：7-16.