络合脱钙计剂用于原油脱钙工业侧线试验

中国石油克拉玛依石化公司2.00 Mt/a II套蒸馏装置引出1.5 m3/h的试验原油,采用自行研发的络合脱钙剂,在自建的小型工业电脱盐试验装置进行脱钙试验。结果表明：对于含钙量较低的原油,在注水率为6%、脱钙剂加剂量为60 μg/g时,通过结构通道混合器与管填料混合器的两级油剂混合作用,金属钙、镁、铁的脱除率分别为71.5%～78.2%,32.3%～45.5%,30.0%～38.2%,脱钙油含水量小于0.3%,脱钙后排水的各项指标达到工业水车间进水要求。     

劣质原油脱钙技术在常减压装置的工业应用

中国石油天然气股份有限公司乌鲁木齐石化分公司6 Mt/a常减压装置加工北疆原油时掺炼20%~30%高钙风城稠油,采用TS-888脱钙剂对该劣质原油进行脱钙工业试验。结果表明:(1)当剂钙比为(3.0~3.5)∶1时,原油脱钙率达到65%~68%;(2)当剂钙比提高到4∶1时,原油脱钙率超过70%,加注期间脱后原油含盐合格率为97.78%,脱后原油水分最大值0.030%,含盐污水化学需氧量最大值为1 927 mg/L,氨氮最大值为64.3 mg/L,加注脱钙剂后原油含盐含水和外排含盐污水指标合格,加注脱钙剂对电脱盐装置运行没有影响;(3)当剂钙比为(3.0~3.5)∶1时,减四线脱钙率达到59.00%,渣油脱钙率达到64.60%,加热炉温升由0.51℃/d下降到0.18℃/d,焦炭灰分由0.91%降至0.72%,减压渣油钙含量降低,焦化装置加热炉运行工况明显改善。     

原油循环脱钙技术在焦化装置的应用及改进

中国石油天然气股份有限公司克拉玛依石化分公司1．5Mt／a稠油原油延迟焦化装置针对焦炭灰分含量高的问题,采用了络合循环脱钙技术。结果表明,采用先进的原油循环脱钙技术,使原油中钙质量分数由178．7μg／g降到47．8μg/g,脱钙率稳定在72％以上,焦炭灰分由0．98％降到最低0．40％,焦炭质量等级由3B上升至3A,甚至提升3个档次上升至1B,焦炭带来的年利润（含成本）提高了1250×10^4 RMB￥以上,经济效益显著。     

KR-1原油脱钙剂对辽河超稠原油脱钙、脱盐效果的影响

对国内钙离子含量较高、密度和黏度很大的辽河超稠原油,利用自行开发的KR-1原油脱钙剂,采用萃取脱钙技术进行了几种脱钙工艺研究,对影响脱钙效果的主要因素进行了分析。结果表明,在脱钙剂/原油中钙离子摩尔比为1.50∶1.00,注水质量分数为8%,稀释油质量分数10%,混合温度95℃,混合强度20次,电场强度1 000 V/cm,电场停留时间40 m in,电场脱盐温度140℃的条件下,采用KR-1原油脱钙剂,应用一级脱钙、二三级脱盐回注脱钙工艺,可使原油脱钙率达到95.6%,脱镁率、脱钒率、脱铁率分别为77.2%,68.5%,61.3%,净化原油含盐量(NaC l)达到2.2 mg/L,含水质量分数为0.12%。     

HF-101原油脱钙剂的工业应用

采用大港油田集团油田化学有限公司研制的HF-101脱钙剂对中国石油锦州石化分公司炼油厂掺炼杜巴原油进行了工业试验。应用结果表明:使用HF-101脱钙剂后原油中的钙平均脱除率可达到90.89%,脱后原油的平均钙质量分数为24.81μg/g;原油的灰分由脱钙前的0.065%降至0.030%左右;原油的盐含量和水含量也大幅度下降。锦州石化分公司使用脱钙剂后,满足石油焦和煅烧普通焦的灰分质量要求,经济效益显著,并且使用HF-101脱钙剂可使电脱盐装置的操作电流下降50%,具有较好的节能降耗作用。     

原油脱钙剂作用机理及其脱钙效果

通过对不同化学剂诸如EDTA钠盐、六偏磷酸钠盐、盐酸和RPD作为原油脱钙剂时对原油脱钙的试验研究,分析了原油脱钙剂的作用机理。结果表明,在原油脱钙过程中,脱钙剂与原油中石油酸钙的作用类似于复分解反应,原油中的环烷酸钙转化为环烷酸钠或环烷酸。不同化学剂与原油中钙之间存在化学计量关系,EDTA钠盐和六偏磷酸钠盐类化学剂在络合脱除原油中钙的同时会使原油中钠离子增加。RPD新型脱钙剂避免了钠盐化学剂的缺点,对新疆克拉玛依九区稠油、北疆原油及苏丹稠油等不同性质高钙原油,在剂钙质量比为4.0时脱钙率达90％以上。原油脱钙后,原油中的石油酸钙盐转化生成石油酸组分,不给原油引入新的有害杂质。     

脱金属剂在原油电脱盐工艺中的应用

介绍了脱金属剂在原油电脱盐工艺中脱金属原理。考察了脱钙剂品种和浓度对原油脱金属率、电脱盐工艺中电压、电流以及对含油污水的影响。结果表明,当A型脱钙剂浓度为80mg／L时,脱钙率由11．9％提高到71．2％;电脱盐工艺中加入脱钙剂,电流下降约50％,电压上升约20％,有利于装置平稳操作,节能效果明显;A型脱钙剂对含油污水处理有明显不利影响,增加环保成本,而FT-2型脱钙剂对含油污水处理影响不大。     

高钙高酸原油脱钙技术及工业试验

原油含钙影响后续加工和产品质量，针对苏丹六区高含钙含酸原油特性， 采用化学剂方法，在100万t/a焦化装置原油电脱盐工序将原油中钙铁等金属盐脱 除，取得了比较理想的结果。     

作为焦化原料的风城超稠油电脱盐、脱钙工业试验

针对风城超稠油黏度大、密度大的特点,在1.50 Mt/a延迟焦化装置采用稀释降黏的加工工艺,同时使用KR-1脱钙剂对风城超稠油进行脱钙工业试验。结果表明:稀释油掺入量(w)为20%时,风城超稠油100℃运动黏度从350mm2/s降低到60.03mm2/s,同时脱后原油的水、盐含量均明显下降,大大缓解了电脱盐装置脱盐、脱水效果差的问题;脱前原油钙质量分数为359μg/g,经适度脱钙,原油中钙脱除量为100~180μg/g,脱钙率为30%~40%;脱钙试验期间,电脱盐一级、二级、三级电流分别为150~180,140~180,160~210A,电脱盐电流整体波动较小;脱钙工业试验期间的焦炭灰分基本在1.2%以下,最低可达0.7%。     

SF型脱钙剂在高酸多巴原油上的应用

 采用SF型高效脱钙剂和破乳剂SP-169对多巴原油进行脱钙研究。考察SF型脱钙剂加剂量、反应温度、注水率、沉降时间等因素对脱钙效果的影响。结果表明,SF型脱钙剂与破乳剂SP-169配伍对多巴原油具有较好的脱钙效果和优良的破乳效果,在剂钙质量比为2.5、破乳剂SP-169加入量为100 μg/g、反应温度为90 ℃、注水率为15%、反应时间为10 min、沉降时间为15 h的条件下,脱钙率达到87.7%,同时具有较好的脱铁效果,脱铁率达到68.2%。脱后原油钙含量为34.9 μg/g,盐含量为2.018 mg NaCl/L,原油水含量为0.17%,排水中油质量浓度小于50 mg/L。     

加工多巴原油的问题与对策

介绍了多巴（Doba）原油的性质，分析了加工该类原油对生产操作、产品质量和设备腐蚀等方面可能造成的影响。Doba原油属中间基重质原油，酸值和钙含量很高，盐含量和残炭也较高，而轻质油收率很低；与众不同的是其环烷酸主要分布在渣油部分。认为采取与低酸含硫原油混炼、对装置进行配套改造、提高设备材质、重视脱盐操作、选用高效的破乳剂、脱钙剂和高温缓蚀剂等措施可以有效缓解高酸值原油对设备的腐蚀问题。     

HF-101原油脱钙剂的工业应用研究

采用大港油田集团油田化学有限公司研制的HF-101脱钙剂对中国石油锦州石化分公司炼油厂掺炼的杜巴原油脱钙效果进行了实验室评价及工业试验。实验室评价结果表明,在剂钙质量比为2:1、注水量为5%、电脱盐温度130℃、破乳剂加量30μg/g的条件下,原油脱钙率达到90.89%～91.43%,显示了良好的脱钙效果。工业应用试验结果表明,使用HF-101脱钙剂后原油中的钙平均脱除率可达到90.89%,脱后原油的平均钙含量为24.81μg/g;原油的灰分由脱钙前的0.065%降至0.030%左右;原油的盐含量和含水量也大幅度下降。并且使用HF-101脱钙剂可使电脱盐装置的操作电流下降50%,具有较好的节能降耗作用。     

双进油双电场电脱盐脱水技术及其在大港石化的应用

中国石油大港石化分公司5.0 Mt/a电脱盐装置原采用高速电脱盐技术和交直流电脱盐技术,投运之后脱后盐含量、水含量均不合格。采用双进油双电场技术进行改造后,脱后原油盐（NaCl）含量（质量浓度）小于3 mg/L、水质量分数小于0.2%,合格率为100%;脱后排水油含量（质量浓度）小于150 mg/L,合格率95%～100%;在脱钙剂注入量为25～35 μg/g时,脱后原油钙质量分数小于10 μg/g 。     

塔河原油电脱盐助剂筛选及工艺优化

为解决塔河原油电脱盐脱水难题,选取多种不同类型破乳剂进行高温电脱盐评价实验,从中筛选出效果较好的进口油溶性破乳剂PR2.针对塔河原油高沥青质、胶质含量,存在结晶盐及极性物质吸附的特点,筛选了性能良好的脱盐助剂T6,并对电脱盐工艺和脱盐助剂用量进行优化.实验结果表明,在温度为140℃,电场强度为1000 V/cm,注水20％,混合强度为手摇400次,油溶性破乳剂PR2添加量为20 μg/g,脱盐助剂T6每级添加量20 μg/g的优化条件下,塔河原油三级脱后含盐低至2.34 mg/L,脱后含水小于0.3％.并在动态电脱盐实验装置上得到验证,为解决塔河原油脱盐脱水难题,实现原油深度脱盐脱水提供了技术支撑.     

Technology for Coking of Heavy Crude Oil with High Acid Number

Sudan Khartoum Refinery Co. has selected a unique route featuring delayed coking of crude in connection with the highly sour and high-calcium heavy crude extracted from Sudanese oil block No. 6.The crude oil after pretreatment for calcium removal is subjected to coking for removal of acids and metals with the coker products being further processed. The crude oil extracted from Sudanese oil block No. 6 contains as high as 13 mg KOI-Jdg of crude in addition to a calcium content of 1600 ppm. This article makes an analysis on problems related with the operation of commercial delayed coking unit for processing of highly sour crude and bring forth measures to solve these problems. The liquid yield resulted from coking of crude oil can reach 82 m%, and the petroleum coke can meet the quality requirement for class 3B petroleum coke.     

Effects of Process Conditions on Desalting and Demetalization of Crude Oil

The efficiency of desalting for six crude oils was studied with a SY-1 dynamic simulation experimental installation. The demulsifier DC2 was examined for 1#, 2#, and 4# crude oil and DC4 was used for 3#, 5#, and 6# crude oil. The effects of temperature, electric field gradient, dosage of demulsifier, and washing water on the desalting efficiency of six crude oils were investigated. The results showed that at the optimization process condition after desalting, the desalting efficiency and the salt content of 1# crude oil reached 89.17% and 1.92 mg/L; that of 2# crude oil reached 85.08% and 1.04 mg/L; that of 3# crude oil reached 91.06% and 1.35 mg/L; that of 4# crude oil reached 81.67% and 1.51 mg/L; that of 5# crude oil reached 81.03% and 2.32 mg/L; and that of 6# crude oil reached 86.64% and 2.67 mg/L. Different crude oils have different metal contents. Three assistants, ammonium nitrate (TJ1), nitric acid (TJ3), and polyamine carboxylate (TJ4), were used to improve the efficiencies of desalting and demetalization of six crude oils. TJ4 was more efficient in removing calcium and iron for 1# and 2# crude oil. TJ1 was more efficient in desalting and demetalizing 5# crude oil. The efficiencies for removal of calcium, iron, nickel, and vanadium respectively reached 99.89%, 98.33%, 20.58%, and 43.02%. TJ3 has better efficiency desalting and demetalizing for 6# crude oil. With the concentration of TJ3 increasing from 0 to 80 mg/L, the desalting efficiency increases from 31.22% to 73.54%, and the iron removal efficiency increases from 56.0% to 74.05%.     

Effects of Process Conditions on Desalting and Demetalization of Crude Oil

Abstract

The efficiency of desalting for six crude oils was studied with a SY-1 dynamic simulation experimental installation. The demulsifier DC2 was examined for 1#, 2#, and 4# crude oil and DC4 was used for 3#, 5#, and 6# crude oil. The effects of temperature, electric field gradient, dosage of demulsifier, and washing water on the desalting efficiency of six crude oils were investigated. The results showed that at the optimization process condition after desalting, the desalting efficiency and the salt content of 1# crude oil reached 89.17% and 1.92 mg/L; that of 2# crude oil reached 85.08% and 1.04 mg/L; that of 3# crude oil reached 91.06% and 1.35 mg/L; that of 4# crude oil reached 81.67% and 1.51 mg/L; that of 5# crude oil reached 81.03% and 2.32 mg/L; and that of 6# crude oil reached 86.64% and 2.67 mg/L. Different crude oils have different metal contents. Three assistants, ammonium nitrate (TJ1), nitric acid (TJ3), and polyamine carboxylate (TJ4), were used to improve the efficiencies of desalting and demetalization of six crude oils. TJ4 was more efficient in removing calcium and iron for 1# and 2# crude oil. TJ1 was more efficient in desalting and demetalizing 5# crude oil. The efficiencies for removal of calcium, iron, nickel, and vanadium respectively reached 99.89%, 98.33%, 20.58%, and 43.02%. TJ3 has better efficiency desalting and demetalizing for 6# crude oil. With the concentration of TJ3 increasing from 0 to 80 mg/L, the desalting efficiency increases from 31.22% to 73.54%, and the iron removal efficiency increases from 56.0% to 74.05%.     

新型高效原油脱钙剂的研制

利用分子设计原理,从研究络合脱钙机理出发,研制出新型高效原油脱钙剂WA。评价结果表明,WA型脱钙剂对新疆混合原油中ca金属元素的脱除率大于80％,对其中Ca、Fe、Mg、Cu等金属元素的总脱除率接近60％。同时发现,经WA处理后,原油的黏度、密度和灰分均有所降低,即WA可部分改善原油品质,有利于原油的后续加工。利用L9(3^4)实验考察了反应温度、反应时间、加剂量和脱钙剂溶液pH值等因素对脱钙效果的影响作用,并为工业应用提供了有价值的工艺参数。     

MPTT型原油脱钙剂的实验研究

利用SH-Ⅰ型电脱盐试验仪对MPTT原油脱钙剂进行了实验研究,考察剂钙摩尔比、破乳剂加入量、注水量、反应温度、电场场强以及沉降时间对脱钙效果的影响.结果表明:针对辽河及多巴混合原油的性质研制的MPTT型脱钙剂在剂钙比为1.0～1.2、温度为135℃、注水量为6％、破乳剂加入量30μg/g、弱电场场强400V/cm、强电...     

胜利高硫高酸原油破乳脱盐研究

以胜利炼油厂第四常减压装置加工的胜利高硫高酸原油为研究对象,在实验室模拟评价装置上进行了原油综合处理剂(包括低温破乳剂、脱钙剂、高温破乳剂)的评价筛选试验,并且对电脱盐排水进行了可生化性能研究。结果表明:选用的2种原油综合处理剂,对胜利原油均有一定的破乳效果。