直馏柴油脱酸工艺研究进展

综述了直馏柴油脱酸方法的发展。氯法化学萃取是目前直馏柴油脱酸工艺的研究热点,能否取代直馏柴油碱洗电精制一硫酸中和法工艺,其关键在于新型破乳剂、高效率萃取设备和三相分离器的开发。介绍了作者开发的SW－1破乳剂在直馏柴油氯精制工艺中的应用研究。     

采用新方法对直馏柴油进行脱酸的工艺研究

采用氨法对直馏柴油进行脱酸的中试研究结果表明，对于酸度大于30mgKOH／100ml柴油原料，该工艺的脱酸效果较好，且具有无高压电场、不使用强酸强碱、无“三废”排放及溶剂可循环使用等优点，是直馏柴油碱洗电精制的理想替代工艺。     

馏分油脱酸剂技术(Ⅱ型)的工业应用

介绍了馏分油脱酸剂技术(Ⅱ型)在无锡石油化工总厂常压蒸馏装置上的应用情况.和传统的碱洗电精制工艺相比,该工艺仅需一个一级高压电场沉降分离罐,无需水洗操作,另外增加了脱酸剂回收装置.工业应用结果表明,直馏柴油经精制后其质量完全达到柴油质量标准要求,与该厂原来采用的碱洗精制工艺相比,柴油收率由99.00%提高到99.97%,碱渣和废水排量大大降低.     

采用碱性白土脱除直馏柴油环烷酸的工艺研究

采用湿法将氢氧化钙负载于活性白土上制备了碱性白土,再使用碱性白土脱除直馏柴油中环烷酸.考察了脱酸温度、脱酸时间、碱性白土用量及柴油酸度对脱酸效果的影响,并采用二次逆流脱酸工艺.结果表明,当柴油酸度为34 mgKOH/100 mL时,在60℃下,碱性白土用量为每升柴油8.3 g,脱酸60 min,柴油酸度可降至2.03 ...     

直馏柴油无碱脱酸方法及效果评价

介绍了采用脱酸剂s对直馏柴油进行脱酸精制方法，结果表明，当原料酸度为20．00mgKOH／100mL时，S剂的加入量为400μg／g即可，S剂的加入量应随原料油酸度而变化；精制脱酸油的酸度应以尽量接近0为宜。对采用脱酸剂S精制柴油的效果进行评价，结果表明，对成品柴油质量无不良影响，在柴油罐底水中加入3％的抗乳化剂A和0．2％抗酸度回升剂E可解决脱酸油乳化及遇水酸度回升问题。直馏柴油无碱脱酸成本简要概算为2．922元／t油。     

直馏柴油碱洗-吸附分离脱酸技术的实验研究

针对直馏柴油碱洗电精制脱酸工艺存在的不足,研发了一种新的直馏柴油碱洗-吸附分离脱酸技术。采用自制的实验装置,在评选出的最佳柴油脱酸操作条件下(氢氧化钠与环烷酸的摩尔比为1.05,碱液中氢氧化钠质量分数为15%,温度为60℃,空速为3.0 h~(-1),洗水用量为0.5%),对酸度为101.8 mg/(100 mL)的直馏柴油进行了连续脱酸处理,精制柴油酸度小于7 mg/(100 mL),回收环烷酸粗酸值为192.71 mg/g,可满足一级品85号酸的质量标准[SH/T0530—92(1998)]。结果表明:与传统的柴油碱洗电精制脱酸工艺比较,该工艺碱液中氢氧化钠质量分数提高了7.5～15.0倍,完全消除乳化,洗水回用率57.5%,碱渣排放量减少86.7%～93.3%,具有一定的工业应用前景。     

胜华直馏柴油的固定床催化酯化脱酸

 针对柴油碱洗脱酸精制易乳化、收率低的问题，研究了催化酯化脱酸的技术来替代柴油碱洗脱酸。考察了在固定床催化剂存在下，影响柴油酯化脱酸的因素，并评价了酯化脱酸技术的经济性。结果表明，反应温度、空速、醇/油质量比、甲醇水含量等是影响柴油酯化脱酸的重要因素。反应温度高、空速降低、加大醇/油质量比有利于酯化反应的进行。甲醇中水的质量分数低于5%时，对酯化反应影响大，随水含量的增加，脱酸率显著降低；水的质量分数在5%~10%范围，脱酸率不再随水含量的增加而变化。对胜华直馏柴油来说，在反应温度280～300℃、反应空速1.5h^-1、醇/油质量比0.01条件下，脱酸效果明显。直馏柴油酯化脱酸比碱洗脱酸具有更好的经济效益。     

直馏柴油纤维膜接触器绿色脱酸技术的实验研究

针对直馏柴油纤维膜接触器脱酸技术的不足,采用西南石油大学研制的绿色脱酸剂对中国石油克拉玛依石化公司生产的直馏柴油进行脱酸试验;采用水解法对废脱酸剂进行再生,同时得到石油酸副产品。结果表明：在绿色脱酸剂中有机胺质量分数为15%、剂油体积比为0.3、反应温度（相分离温度）为40 ℃、相分离时间为80 min的条件下,脱酸剂有效循环次数达到13次;废脱酸剂在再生温度为90 ℃、再生时间为8 h、溶剂油用量为4 mL/g的条件下进行高温水解再生,得到的再生脱酸剂用于柴油脱酸的有效循环次数可达12次;回收的石油酸的粗酸值达到205.5 mgKOH/g,满足一级品75号酸的质量标准要求(SH/T0530-1992)。纤维膜接触器绿色脱酸工艺完全消除乳化现象,脱酸剂可再生和循环使用,无三废排放。     

聚乙烯胺用于直馏柴油脱酸的实验研究

采用以聚乙烯胺（PVAm）作主剂的脱酸剂对直馏柴油进行了脱酸实验,并考察了柴油脱酸过程中主要因素的影响。结果表明,在脱酸剂中PVAm与原料油中环烷酸的摩尔比为5.0、剂油体积比为0.02、反应温度和相分离温度均为50℃、反应时间20s、相分离时间为60min、萃取级数为3的操作条件下,脱酸剂可将苏丹柴油酸度从102.7 mgKOH/（100mL）降至6.0 mgKOH/（100mL）,脱酸率高达94.2%,精制油收率达到99.6%,精制油质量达到GB 252－2000产品质量指标。脱酸剂经高温水解再生,可以重复使用。此脱酸剂用于直馏柴油脱酸具有脱酸剂用量小、可循环利用、再生能耗低、绿色环保等优点。     

直馏柴油碱洗新工艺研究

介绍了利用膜分散技术进行克拉玛依石化公司直馏柴油碱洗脱酸工艺研究。讨论了溶剂组成、脱酸温度、剂油质量相比、连续相流量对脱酸效果的影响。研究表明,对连续相流通截面积为0．2cm。的膜分散萃取反应器,当脱酸溶剂中氨,乙醇,水的质量比例为4／40／50,试验温度65℃,连续相流量450g／min条件下,剂油作用比0．07时,能够将直馏柴油酸度降低到7mgKOH／100mL以下,并同时抽出粗酸值在170mgKOH／g以上的石油酸,石油酸纯度在70％以上。     

柴油纤维液膜碱洗脱酸精制技术工业试验研究

克拉玛依石化分公司的50 m3/h常压柴油碱洗脱酸精制装置采用了以纤维液膜反应器为核心设备的新型脱酸技术,工业试验结果表明,经过该工艺处理,柴油酸度全部达标,碱渣中柴油质量分数小于4%。对试验过程中出现的水溶性碱超标问题进行的理论分析认为,柴油中水溶性碱超标的原因主要是由于小液滴的分散造成的,并在流态试验装置上得到了验证,为工业化装置提供了经验。     

Microwave Demulsification in Removing Naphthenic Acids from Diesel Oil

Emulsification is an undesired phenomenon in the refining of highly acidic oil by alkali-washing electro-refining. In this article, a novel microwave method is applied for demulsification in the removing of naphthenic acid from diesel oil. The internal heating is attributed to molecular rotation and ionic conduction. The decrease of interface zeta-potential and the viscosity of diesel oil are responsible for the demulsification with microwave irradiation. The results exhibited that the demulsification rate is maximized when the optimum microwave irradiation power, exposure time, and irradiation pressure for Anshan and Liaohe diesel oil are deemed to be 375 W, 5/6 min and 0.05 MPa, respectively.     

轻柴油馏份中环烷酸含量的测定及提取方法

利用小油珠碱洗法成功地测定了35~#轻柴油馏份环烷酸的含量,与作者推导的公式计算结果相等。文中给出了轻柴油馏份环烷酸的提取工艺流程和最佳条件。此外介绍了轻柴油环烷酸的理化性质和应用结果。     

环烷酸在酸性催化剂上的催化转化研究

在重油微反装置上进行了环烷酸在酸性催化剂上的催化转化研究,考察了反应温度、催化剂装填量以及掺混直馏柴油对环烷酸转化率和脱酸效果的影响,并与环烷酸的热转化反应进行了比较。结果表明,环烷酸在酸性催化剂上的催化脱酸反应很容易进行,在较低的反应温度下(400℃)脱酸率接近100%;而相同条件下的热脱酸效果较差。反应温度和催化剂装填量的改变不影响环烷酸的脱酸率,但是会影响转化率与产物分布,其影响规律与常规催化裂化相似。环烷酸的脱酸反应生成CO和CO_2,但以CO为主。直馏柴油的加入并不影响环烷酸的催化脱酸效果。     

A Study on Removing Naphthenic Acid From Diesel Oil by Salt

Abstract

Sodium carbonate as deacidification agent was used to remove naphthenic acid from diesel oil. The influence of affect factors about treating conditions on the acid removal of diesel oil was investigated, such as volume ratio of deacidification agent-to-oil (VRDO), reaction temperature, stirring time, and resting time. Orthogonal tests were done to conform the optimum process condition. The results showed that the optimum condition is that VRDO was 0.40, reaction temperature was 330 K, stirring time was 6 min, and resting time was 35 min. Under the optimum condition, acidity of diesel oil was reduced to 5.15 mgKOH/100 mL from 135.52 mgKOH/100 mL, and if deacidification rate of naphthenic acid reached 96.8%, diesel oil recovery could reach 92.6%. The quality index of diesel met the national standard.     

Microwave Demulsification in Removing Naphthenic Acids from Diesel Oil

Abstract

Emulsification is an undesired phenomenon in the refining of highly acidic oil by alkali-washing electro-refining. In this article, a novel microwave method is applied for demulsification in the removing of naphthenic acid from diesel oil. The internal heating is attributed to molecular rotation and ionic conduction. The decrease of interface zeta-potential and the viscosity of diesel oil are responsible for the demulsification with microwave irradiation. The results exhibited that the demulsification rate is maximized when the optimum microwave irradiation power, exposure time, and irradiation pressure for Anshan and Liaohe diesel oil are deemed to be 375 W, 5/6 min and 0.05 MPa, respectively.     

Study on the Removal of Naphthenic Acid From Diesel Oil by Salt Under Supersonic Strengthening

The naphthenic acid in diesel oil was removed by sodium carbonate as deacidification agent under strengthening of supersonic. The influence of affect factors about treating conditions on the acid removal of diesel oil was investigated, such as ultrasonic frequency, volume ratio of sodium carbonate solution to oil (VRSO), ultrasonic work function, and ultrasonic strengthening time. Orthogonal tests were done to confirm the optimum process condition. The results showed that the optimum condition was that ultrasonic frequency was 28 KHz, VRSO was 0.30, ultrasonic work function was 350 W, and ultrasonic strengthening time was 6 min. Under this optimum condition, acidity of diesel oil was reduced to 4.88 mgKOH/100 mL from 135.52 mgKOH/100 mL, and deacidification rate of naphthenic acid reached 96.4%.     

Removing Naphthenic Acids from Diesel Oil by Microwave Irradiation

Microwave technology is introduced for removal of naphthenic acid from diesel oil. The decrease of Zeta-potential of interface and the viscosity of diesel oil are responsible for the acceleration of separation of naphthenic acid with microwave irradiation. It was observed that the separation percentage changed with the dosage of alkali compound solvent, irradiation pressure, irradiation time, irradiation power, settling time, and oil phase-to-solvent phase volume ratio (O/S). The removal rate of naphthenic acid was maximum when the optimum conditions were suggested to be M_p/M_T = 1.5, 0.05 MPa, 6 min, 375 W, 25 min, and O/S = 10, respectively.     

超高酸原油中环烷酸类型及分布规律研究

通过对国内某原油进行实沸点切割和环烷酸分离,采用电位滴定仪、红外光谱仪及质谱仪等研究原油、馏分油中环烷酸分布及类型.研究结果表明:原油酸值为13.18 mg(KOH)/g,属于超高酸原油,其环烷酸主要集中为400～425℃,425～450℃和>450℃馏分,分别占原油总酸质量的4.68％,5.34％和54.44％;超高...