辽河焦化蜡油脱碱氮工艺研究

为降低焦化蜡油中碱性氮化物含量,采用糠醛溶剂精制和TTS络合脱氮两种方法对辽河焦化蜡油开展了脱碱氮工艺研究。研究发现,采用糠醛二级抽提的方法可使焦化蜡油中的碱氮脱除率达到81.3%,但糠醛对碱性氮化物的选择性较低,精制油收率不高;采用TTS络合脱氮的方法可使精制油收率达到95%,碱性氮化物的脱除率达到73.3%,TTS脱氮剂对焦化蜡油中的碱性氮化物有较好的选择性,脱碱氮效果较好。     

荆门催化装置加工未加氢焦化蜡油工业运行

中国石化荆门分公司在焦化蜡油加氢精制装置停工期间制定并实施了未加氢焦化蜡油催化裂化加工方案:1号催化装置集中加工焦化蜡油;在此期间催化裂化油浆不作为焦化原料;应用高活性抗碱氮重油催化裂化催化剂;催化裂化装置实施大剂油比、高反应温度操作。运行数据显示:加工未加氢焦化蜡油期间,1号催化裂化装置掺渣率及产品收率等情况较为理想,此工业运行为催化装置加工未加氢焦化蜡油开辟了可行的工艺途径,取得了具有工业应用价值的技术进展。     

焦化蜡油络合脱氮技术研究

为降低焦化蜡油中碱性氮化合物含量,防止碱性氮化合物毒害催化重整和催化裂化催化剂。本文在实验室条件下,以乙二酸为主脱氮剂,金属离子为辅助脱氮剂,考察了不同反应时间、脱氮剂中乙二酸含量、金属离子辅助脱氮剂种类以及金属辅助脱氮剂含量对脱氮效果的影响。结果表明,在反应温度为80℃、络合剂中乙二酸含量为0.4%、FeSO4含量为0.3%、反应时间为25min、剂油比为1:1的条件下,脱氮效果最好,焦化蜡油中碱氮脱除率可以达到60.7%。     

焦化蜡油非加氢脱碱氮技术评价

以辽河石化焦化蜡油对象,对甲酸精制、乙醇-FeCl3络合、白土吸附、硅胶氧化铝吸附、沸石吸附以及糠醛精制等非加氢脱碱氮技术进行了筛选和评价。研究表明,甲酸精制对焦化蜡油中碱氮的脱除效果显著,剂油比在1∶7时就能使碱氮从1766 mg/kg降至800 mg/kg以下,蜡油收率95%以上;FeCl3的络合作用有利于碱氮的脱除,但乙醇-FeCl3的脱氮效果并不明显,白土、硅胶氧化铝、沸石等吸附脱碱氮效果不佳;糠醛萃取也可将辽河石化蜡油中的碱氮脱至800 mg/kg以下,尽管抽余油收率相对较低(70%左右),但抽出油可作为化工原料使用,在经济成本及技术可行性上由于甲酸精制。     

焦化蜡油脱氮工艺研究

在实验室条件下考察了水浴温度、剂油比、含水量(酸的稀释比)等工艺条件对酸性试剂络合萃取脱除焦化蜡油中碱性氮化物的影响。确定了焦化蜡油脱氮的最佳工艺条件为:水浴温度50℃,剂油比1％,含水量0．12mL／g,在此条件下脱氮率为62．5％。此脱氮工艺方法可以有效的降低焦化蜡油中的碱氮含量,而且操作条件缓和,方法简单。     

CH-20型焦化蜡油加氢处理催化剂性能及工业应用

CH－20催化剂以Mo－Ni为加氢活性组分，采用Al₂（SO₄）₃和NaAlO₂为原料路线制备Al₂O₃载体，具有适宜的孔结构，加氢活性高，稳定性好，适用于CGO加氢处理制备催化裂化原料。试验结果表明。在中压（氢压6.4MPa）下，加氢处理氛含量0.49％（碱氮0.19％）、硫含量0.92％的管输CGO，其脱氮率为76％～78％，脱碱氛单～85％，脱硫率在95％以上。该催化剂于1997年2月在长岭炼油化工总厂300kt/a加红装置上工业应用，在反应器入口压力6.3MPa（氢分压5.8MPa）、人口温度340℃的条件下加工氮含量0.45％（碱氛0.165％）的CGO，加氢焦化蜡油（HT－CGO）的碱氮＜500μg/g，工业应用效果良好。     

焦化蜡油加氢精制工艺研究

辽河油田某炼油厂生产的焦化蜡油含氮量和含硫量较高,直接催化裂化反应的效果较差,需要进行一定的预处理,因此,开展了焦化蜡油加氢精制工艺优化实验研究.以目标炼油厂的焦化蜡油为研究对象,通过改变反应条件,考察了催化剂类型、实验温度、实验压力、氢油比以及反应空速对焦化蜡油加氢精制处理后脱氮率和脱硫率的影响.结果表明:随着反应温度、压力以及空速的增大,焦化蜡油的脱氮率和脱硫率逐渐升高;而随着氢油比的逐渐增大,焦化蜡油的脱氮率和脱硫率呈现出先增大后降低的趋势,存在一个最佳氢油比,使脱氮率和脱硫率达到最佳;辽河油田焦化蜡油加氢精制实验的最佳工艺条件为:催化剂PSR-102,温度380℃,压力12 MPa,氢油比1000,反应空速0.8 h-1.在此实验条件下,焦化蜡油的脱氮率可以达到60％以上,脱硫率可以达到95％以上,达到了良好的精制效果.     

未加氢焦化蜡油直接催化加工的技术改造

2011年9～10月,中国石化荆门分公司焦化蜡油加氢装置停工大修,为了解决焦化蜡油出路问题,在1#催化装置进行了未加氢焦化蜡油催化裂化的工业运行,运行方案为:①将装置催化剂更换为高活性抗碱性氮重油催化剂;②高反应温度,零回炼比操作方案;③提升管底部注入重整拔头油提高剂油比和裂化深度。运行期间,1#催化掺渣率及产品分布和收率等操作工况较为理想,该工业运行为催化裂化装置直接加工焦化蜡油开辟了一种新的可行的工艺途径,取得了具有工业应用价值的技术进展。     

XP-3复合碱氮抑制剂在催化裂化装置的应用

介绍了抚顺石化公司催化裂化装置使用XP-3复合碱氮抑制剂的情况,应用结果表明：在装置掺渣油14%～17%,焦化蜡油占催化裂化装置原料组成的25%左右时,XP-3复合碱氮抑制剂按焦化蜡油的0.18%～0.22%加注情况下,催化剂活性提高了1.1%,改善产品分布,提高轻油收率0.58%,对产品质量无不良影响。     

焦化蜡油脱碱氮技术研究进展

我国焦化蜡油具有碱性氮化物含量高的显著特点,作为催化裂化、加氢裂化的掺兑原料时,极易造成催化剂中毒,对装置的正常运行与产品分布造成不利影响。本文介绍了我国焦化蜡油的主要性质以及所含碱性氮化物对催化剂的作用机理,并对焦化蜡油加氢精制、酸处理脱氮、溶剂精制、吸附精制、络合精制等脱碱氮技术进行了综述。     

混合蜡油加氢处理改善催化裂解产品质量

原油劣质化后,要生产符合环保要求的清洁燃料,一种经济合理和行之有效的途径就是采用催化裂解原料加氢预处理技术,通过改善催化裂解原料,来降低燃料硫含量,提高催化裂解产品的质量。     

含硫VGO 和CGO 加氢预处理工艺研究

本文介绍FDS24 和CH220 型催化剂用于含硫V GO 和CGO 加氢预处理制备催化裂化和加氢裂化原料的相关效果, 考察了工艺参数对沙轻V GO 加氢脱硫的影响。试验结果表明, 在中压条件下加氢处理管输CGO , 其脱氮率为7618～ 7810% , 碱性氮脱除率为8319～ 8914% , 脱硫率在95%以上; 加氢处理伊朗V GOöCGO 混合油, 其脱硫率为8816% , 脱氮率为6711%; 含硫V GO 或CGO加氢预处理是优化催化裂化原料、改善其反应性能和扩大加氢裂化原料来源的有效途径。     

FCC汽油脱砷技术选择

为了降低FCC汽油中的硫含量和烯烃含量并适当提高其辛烷值,国内某炼厂引进了美国CDTECH公司的选择性加氢脱硫技术。其中以贵金属钯为活性中心的加氢催化剂对催化汽油中的砷化物含量有严格要求,其质量分数应小于10×10^-9,而目前国内没有催化汽油脱砷应用的先例。对FCC汽油原料脱砷技术进行了研究。结果表明,X脱砷剂在常温下脱砷可满足原料指标要求,操作费用低,寿命长,对催化汽油其它性质没有影响。     

催化裂化干气中乙烯制汽油工业实验

目前国内催化裂化干气是石油化工合理利用的盲点,大部分都作为燃料烧掉,利用率过低,造成资源浪费,找到合理利用的途径迫在眉睫。本文着重介绍了催化干气中乙烯制汽油技术的工业试验和工业应用情况。结果表明干气制汽油技术是切实可行的,有利于提高经济效益,具有很好的应用前景。     

YD-CADS汽油超深度催化吸附脱硫技术中试研究

陕西延长石油（集团）有限责任公司炼化公司和中国科学院大连化学物理研究所共同开发的YD-CADS汽油固定床超深度催化吸附脱硫组合技术,以全馏分FCC汽油为原料生产超低硫清洁汽油,采用脱二烯烃和催化吸附脱硫串联固定床工艺,具有流程短、投资低、占地少和操作简单等优点。中试结果表明,处理硫含量约100 μg·g^-1的FCC汽油时,汽油产品硫含量小于10 μg·g^-1,烯烃饱和小于2%,研究法辛烷值损失小于0.8个单位,目的产品汽油收率大于99%,化学氢耗小于0.2%。     

Hydrodesulfurization and hydroconversion of heavy FCC gasoline on PtPd/H-USY zeolite

In the search for catalysts suitable for upgrading fractions of FCC gasoline, PtPd/USY zeolite was investigated. The objectives of the work were to reduce simultaneously the sulfur, nitrogen and aromatic contents of heavy FCC gasoline having various sulfur (30–203 ppmw) and 28 ppmw nitrogen contents. The process conditions were the following: temperature: 200–300 °C; pressure: 30 bar; liquid hourly space velocity: 1.0–3.0 h⁻¹; H₂/hydrocarbon ratio: 500 m³/m³. The results indicated that PtPd/H-USY zeolite catalyst can be applied for the desulfurization of heavy FCC gasoline up to 203 ppm sulfur content. When a base heavy FCC gasoline fraction of 30 ppmw sulfur content was used the catalyst was able to reduce the aromatic content by 14 abs.% as well as sulfur and nitrogen contents to <1 ppmw in one step. Blending calculations were made to evaluate the quality of a full range FCC gasoline obtained by mixing the desulfurized heavy FCC gasoline and the untreated light cut.     

A novel catalyst system based on quadruple silicoaluminophosphate and aluminosilicate zeolites for FCC gasoline upgrading

To develop a novel catalyst system that has excellent olefin reduction capability for FCC gasoline without loss in octane number, different catalysts supported on multiple composite carriers consisting of SAPO-11, Hβ, HMOR and HZSM-5 were prepared and their catalytic performances for FCC gasoline upgrading were assessed in the present investigation. The pore structure and acidity of the catalysts were characterized by N₂ adsorption and pyridine adsorption FTIR, respectively. Based on the results obtained over the catalysts supported on binary-zeolite carriers (Hβ/HZSM-5, HMOR/HZSM-5 and SAPO-11/HZSM-5) using FCC gasoline as the feedstock, various multiple-zeolite supported catalysts were developed from different combinations of the binary-zeolite systems. It was found that the SAPO-11/HMOR/β/ZSM-5 quadruple composite zeolite supported catalyst gave higher liquid yield, improved gasoline RON, and lower coke deposit amount for the hydro-upgrading of FCC gasoline and thus can be considered as a potential catalyst system. A comprehensive analysis based on the catalytic activities and acidity measurements revealed that acid strength and acid type were two very important factors influencing hydroisomerization and aromatization activities, and the difference in catalyst acid strength determined which factor predominates.     

Correlation between feedstock SARA components and FCC product yields

Daqing, Shengli, Liaohe, Gudao, Dagang and Huabei vacuum residua were subjected to deep solvent fractionation by using the supercritical fluid extraction and fractionation, a novel separation technology recently developed by the State Key Laboratory of Heavy Oil Processing. Each residuum was fractionated to produce deasphalted oil (DAO) at four yield levels: 30, 40, 50 and 60 wt%. The saturates, aromatics, resins and asphaltenes (SARA) composition of each DAO sample was determined, indicating that the saturates and aromatic contents of DAO decreases with increased DAO yield.The DAO samples were reacted in a laboratory scale confined fluidized bed, fluid catalytic cracking (FCC) reactor. The results show that most of the gasoline yields originates from the saturate fraction of DAO. The aromatics fraction of DAO contributes to gasoline and diesel yields. Most of the coke yield is from resin fraction of DAO.Generalized empirical correlations were developed for predicting the FCC gasoline, diesel, light oil and coke yields as a function of feedstock SARA composition. These yield correlations can be used to set the upper limit of feedstock resins content for commercial FCC operations. The implications of feedstock properties on FCC products were discussed.     

反应温度对催化裂化汽油芳构化的研究

以中国石油兰州炼油石化公司催化汽油为原料,采用小型固定流化床为芳构化反应装置,考察了反应温度对芳构化产物收率、转化率、马达法和研究法辛烷值、气体产品组成和液体产品组成的影响规律。实验结果表明,随着反应温度的升高,干气、液化气和焦炭收率呈上升趋势,而汽油和柴油收率呈下降趋势,FCC汽油的转化率都在94%左右,且随反应温度的升高先增大后减小;乙烯、丙烯、丁烯、乙烯和总低碳烯烃收率单调增加,而乙烯、丙烯、丁烯、乙烯和丙烯和总低碳烯烃收率的增加幅度各不相同;异构烷烃和烯烃收率随着反应温度的升高逐渐减少,而芳烃的收率和选择性随着反应温度的升高逐渐增加,正构烷烃和环烷烃的收率随着温度的增加先增加后减少。