加氢裂化装置掺炼辽河原油焦化蜡油技术分析

通过分析加氢裂化装置掺炼焦化蜡油的原料性质,发现掺炼后原料（CGO,VGO）的密度、C,不溶物及氮含量高于设计值,而硫含量低于设计值,这样的原料不利于精制和裂化反应.掺炼CGO后主要操作参数方面：精制床层平均温度增加8℃,总温升增加5℃;加氢裂化床层平均温度增加10℃,总温升没有变化;装置C5＋液收高于掺炼之前;尾油外甩增加.装置运行方面：高氮低硫原料导致精制反应器和裂化反应器的操作条件出现矛盾;循环氢中氨含量过高对裂化剂活性有强烈的抑制作用,并且热高分气换热器结盐速度明显加快.针对这些问题提出了相对应解决措施：确定合理原料掺炼比例;尽可能避免选择高氮低硫原料;增上装置洗盐技术设施.     

加氢裂化装置热高分气换热器结盐分析与控制

中国石油天然气股份有限公司锦州石化分公司加氢裂化装置掺炼减三线油,并大量采用重整氢作为新氢后,热高分至冷高分间的压力降开始上升(由0.20 MPa上升到0.59 MPa)。掺炼焦化蜡油后,压力降最高达到1.17 MPa,只能采取在热高分顶压力引出位置临时注水的方式进行洗盐处理。通过对洗盐前和洗盐过程中冷高分酸性水的采样结果对比分析,认为主要是由于高压换热器E1003氯化铵结盐造成的热高分至冷高分间压力降升高。分析了氯化铵中氮和氯的来源,并根据装置不同进料时氮含量的变化分别计算出氯化铵解离平衡常数Kp值,再结合氯化铵结晶热平衡数据查询结盐温度与装置实际运行温度对比,找出结盐的原因及影响因素,采取在E1003前增加长期连续注水点、提高换热器E1003的入口温度、降低混合进料中的氮含量等控制措施,有效地解决了高压换热器E1003的结盐问题。     

加氢裂化装置掺炼不同二次加工油的研究

对比了中国石化北京燕山分公司2.0 Mt/a加氢裂化装置分别掺炼催化裂化柴油（简称催化柴油）和焦化蜡油对工艺参数、设备、产品以及能耗的影响。结果表明：与掺炼催化柴油相比,装置掺炼焦化蜡油后,加氢精制反应器和加氢裂化反应器的平均温度均有所升高,加氢精制反应器的总温升降低;高压换热器结盐速率加快;相同喷气燃料收率下,总氢耗降低,重石脑油芳烃潜含量降低,喷气燃料、柴油和尾油质量得到改善,综合能耗增加。两种工况下,通过工艺参数的调整,均可得到优质石脑油、喷气燃料、柴油和尾油。     

加氢裂化装置掺炼不同二次加工油的研究

对比了中国石化北京燕山分公司2.0 Mt/a加氢裂化装置分别掺炼催化裂化柴油（简称催化柴油）和焦化蜡油对工艺参数、设备、产品以及能耗的影响。结果表明：与掺炼催化柴油相比，装置掺炼焦化蜡油后，加氢精制反应器和加氢裂化反应器的平均温度均有所升高，加氢精制反应器的总温升降低；高压换热器结盐速率加快；相同喷气燃料收率下，总氢耗降低，重石脑油芳烃潜含量降低，喷气燃料、柴油和尾油质量得到改善，综合能耗增加。两种工况下，通过工艺参数的调整，均可得到优质石脑油、喷气燃料、柴油和尾油。     

焦化蜡油、催化油浆做加氢裂化原料的研究

焦化蜡油和催化油浆若直接作为加氢裂化原料，蜡油中的焦粉含量及催化油浆中的催化剂细粉会滞留在加氢精制催化剂床层上结焦，沉积引起床层压降超高的情况发生。通过选择适宜的过滤器进行的过滤试验结果表明：经适宜精度过滤后焦化蜡油采用适当比例与减压蜡油混合则完全满足加氢裂化对原料的要求，加氢裂化装置掺炼焦化蜡油是完全可行的；随着滤芯孔径的减小，过滤后催化油浆中的固体物含量也会进一步降低，但过滤后催化油浆中Na和Ni的金属含量、残碳和密度仍无法满足加氢裂化对原料的要求。     

加氢裂化装置加工焦化蜡油的难点分析与对策

以国外某炼油厂1.0 Mt/a加氢裂化装置为例,对焦化蜡油与直馏蜡油的理化性质进行了对比,分析出加氢裂化装置加工焦化蜡油的难点为硫、氮、不饱和烃、芳烃及焦粉含量高,原料干点偏高且重杂质多。针对焦化蜡油加工难点提出了以下对策:尽量控制焦化蜡油干点不高于520℃;原料油和注水罐设置氮气气封;适当注入质量分数为50~100μg/g的阻垢剂;加强注水管理,优先选用加氢类汽提水、加氢裂化塔顶凝结水、除氧水等优质水源;优化设备设计与选材;设置焦化蜡油预过滤器等一系列针对性措施,有利于加氢裂化装置的长周期稳定运行。对进料中含有焦化蜡油的加氢裂化装置的设计具有一定的指导意义。     

焦化蜡油加氢裂化试验

由于大庆原油的定量供应,我厂加氢裂化装置又不断扩建,作为加氢裂化主要原料的减二、三线蜡油已远远不能满足我厂加氢裂化的需要,我们进行了焦化蜡油加氢裂化试验.因焦化蜡油的胶质和焦粉含量较高,用焦化蜡油与常三、减二蜡油混对进料.针对焦化蜡油杂质较高,先用3822催化剂以较大空速进行加氢精制,再加氢裂化(用3812催化剂),两个反应器串联.为了对比考察,另用一套装置单装3812催化剂(原料油不经预精制)同时试验.     

加氢裂化装置掺炼焦化蜡油的技术经济分析

在以减压蜡油为原料的加氢裂化装置上,按合适的掺炼比加工焦化蜡油可以改善装置的操作性能,并可以发挥焦化蜡油的潜在经济价值.本文根据加氢裂化装置掺炼焦化蜡油的实际情况,探讨了焦化蜡油的合理加工方案和经济效果.     

中压加氢裂化装置原料油换热器传热系数下降的原因及对策

介绍了1.30Mt/a中压加氢裂化装置原料油换热器在运行过程中的结垢问题.通过对结垢原因的分析和处理措施的探讨,指出预防加氢裂化装置原料油换热器结垢要采取以下措施：（1）在原料罐顶加氮封;（2）做好原料油过滤;（3）控制原料和新氢中的氯含量.对结垢后的换热器,可以采取如下处理办法：（1）用催化裂化柴油冲洗;（2）向原料油中注入防垢剂.     

蜡油加氢裂化装置高压换热器垢样分析及建议

针对某炼油厂蜡油加氢裂化装置高压换热器因结垢而换热效率大幅降低、压降上涨的现象,在停工消缺过程中对高压换热器进行清洗并取样分析。对所取垢样进行甲苯抽提处理后采用X射线荧光光谱仪、扫描电子显微镜和X射线衍射仪等手段进行检测。结果表明：垢样的主要无机成分为Fe2P4O12和FeS,此外还有少量含Si、含Na的无机物以及少量的有机垢。对此,建议炼油厂严格控制加氢裂化原料油中含磷物质的携带,同时要尽可能做好环烷酸对设备和管线腐蚀的防护。     

Kinetics of Hydrocracking and Hydrotreating of Coker and Oilsands Gas Oils

Two-stage hydrocracking of gas oils involves a complex set of hydrogenation, heteroatom removal, and cracking reactions. Feeds from coking processes and oilsands bitumen are richer in aromatics and heteroatoms, which increases the importance of the reactions of these components. The hydrocracking and hydrotreating kinetics of a series of conventional, coker and oilsands gas oils were measured using a laboratory microreactor. The kinetics were then correlated with the composition of the feed oils. The conversion of gas oil to middle distillate during hydrotreating was correlated with sulfur content and polyaromatic hydrocarbon content. Hydrocracking of the gas oil in the second stage of reaction followed a Langmuir-Hinshelwood rate expression based on the inlet concentration of total nitrogen. The resulting composite rate expression gave good prediction of gas oil conversion kinetics for the full range of gas oils. The inhibition of hydrocracking by nitrogen was more important for cracking than the differences in the homologous series in the gas oils of different origins.     

辽河原油延迟焦化馏出油全馏分加氢精制

延迟焦化馏出油（包括汽油、柴油及蜡油）的烯烃含量和氮含量高,必须进行加氢精制.石油化工科学研究院组合使用活性支撑物RP-1和国产RN-1催化剂对辽河原油焦化馏出油全馏分进行加氢精制,其生成油质量大幅度提高.使烯烃饱和.氮含量降低,为催化裂化和加氢裂化装置扩大了原料来源.     

Kinetics of Hydrocracking and Hydrotreating of Coker and Oilsands Gas Oils

Abstract

Two-stage hydrocracking of gas oils involves a complex set of hydrogenation, heteroatom removal, and cracking reactions. Feeds from coking processes and oilsands bitumen are richer in aromatics and heteroatoms, which increases the importance of the reactions of these components. The hydrocracking and hydrotreating kinetics of a series of conventional, coker and oilsands gas oils were measured using a laboratory microreactor. The kinetics were then correlated with the composition of the feed oils. The conversion of gas oil to middle distillate during hydrotreating was correlated with sulfur content and polyaromatic hydrocarbon content. Hydrocracking of the gas oil in the second stage of reaction followed a Langmuir-Hinshelwood rate expression based on the inlet concentration of total nitrogen. The resulting composite rate expression gave good prediction of gas oil conversion kinetics for the full range of gas oils. The inhibition of hydrocracking by nitrogen was more important for cracking than the differences in the homologous series in the gas oils of different origins.     

1.0Mt/a加氢裂化装置运行状况标定

对中国石油辽阳石化公司100万t/a加氢裂化装置的运行状况进行了标定。结果表明,标定期间,当原料为常减压直馏蜡油和焦化蜡油的混合物(二者质量比为9∶1),进料量为150 t/h时,原料密度、含硫质量分数和氮含量的标定值均低于相应的设计值;加氢精制催化剂KF-848与加氢裂化催化剂FC-14具有较好的匹配性。     

焦化蜡油脱氮精制-催化裂化组合工艺研究

介绍了焦化蜡油脱氮精制-催化裂化组合工艺的实验室研究情况.该工艺采用研制的脱氮用精制剂,该精制剂为一种酸性络合剂,能选择性脱除焦化蜡油中的碱性氮化物,精制后油的收率97%以上.研究结果表明,在一定条件下,焦化蜡油脱氮精制前后的催化裂化产品收率表现出明显差异,精制后焦化蜡油催化裂化液化石油气、汽油和柴油三项收率之和比未精制油高10个百分点以上;焦化蜡油(25%)与直馏蜡油(75%)的混合油催化裂化时,焦化蜡油精制后的混合油催化裂化液化石油气、汽油和柴油三项收率之和比未精制油高近4个百分点.     

Properties and Chemical Composition of Typical Coker Gas Oil

The coker gas oil from Daqing, Shengli, and Liaohe, which are three famous oil fields in China, are studied. The properties, chemical composition, and structural composition of coker gas oil from Daqing, Shengli, and Liaohe saturated hydrocarbon are analyzed. The results show that nitrogen and sulfur content in Daqing coker gas oil is the lowest, and saturated hydrocarbon content is the highest, and Daqing coker gas oil is the most easily processed raw material, and Liaohe coker gas oil mediates between two raw materials, but Shengli coker gas oil is the most difficult to process. By comparing with vacuum gas oil and nitrogen, sulfur content and carbon residue in the coker gas oils is higher and saturated hydrocarbon content is lower. Shengli coker gas oil is a somewhat inferior raw material. The factor of effecting on the processing and use of coker gas oil are analyzed, and the processing ways of coker gas oil are put forward.     

焦化蜡油溶剂精制油的加氢裂化工艺研究

为合理利用焦化蜡油、洛阳石化工程公司炼制研究所开发了焦化蜡油溶剂精制－加氢裂化组合工艺,中型试验结果表明,焦化蜡油经溶剂精制可以脱除80％的氮和40％的硫,得到的精制油质量接近相应的直馏蜡油,可以直接作为加氢裂化原料,抽出的重芳烃可作为化工原料,抽出的轻芳烃的某一段窄馏分再掺入加氢裂化原料可以提高加氢裂化重石脑油的芳烃潜含量。     

Properties and Chemical Composition of Typical Coker Gas Oil

Abstract

The coker gas oil from Daqing, Shengli, and Liaohe, which are three famous oil fields in China, are studied. The properties, chemical composition, and structural composition of coker gas oil from Daqing, Shengli, and Liaohe saturated hydrocarbon are analyzed. The results show that nitrogen and sulfur content in Daqing coker gas oil is the lowest, and saturated hydrocarbon content is the highest, and Daqing coker gas oil is the most easily processed raw material, and Liaohe coker gas oil mediates between two raw materials, but Shengli coker gas oil is the most difficult to process. By comparing with vacuum gas oil and nitrogen, sulfur content and carbon residue in the coker gas oils is higher and saturated hydrocarbon content is lower. Shengli coker gas oil is a somewhat inferior raw material. The factor of effecting on the processing and use of coker gas oil are analyzed, and the processing ways of coker gas oil are put forward.