利用焦化干气制氢的可行性研究

对焦化干气作为低价原料在中国石油辽河石化分公司制氢装置上的应用进行了可行性研究,并对改造方案的选择和优化进行了讨论,结果表明,通过对原天然气制氢装置进行原料精制部分和压缩机系统改造,采用等温-绝热加氢-脱硫工艺和西北化工研究院开发的JT-1G/JT-4加氢精制催化剂,可满足焦化干气作制氢原料的要求;以产氢能力15 000 m3·h^－1计,焦化干气的制氢成本为0.441元·m^－3,与以天然气为原料制氢相比,每年可节约1 380万元。     

加氢精制催化剂在焦化干气制氢装置上的应用

介绍了JT-4和JT-1G加氢催化剂在中国石化荆门分公司焦化干气制氢改造中的使用情况。结果表明，两种加氢催化剂具有良好的烯烃和有机硫低温加氢活性。焦化干气经加氢精制后，完全满足制氢工艺要求。     

JT-4型焦化催化干气加氢催化剂在制氢装置上的应用

为解决干气不平衡问题,制氢装置在加氢反应器中使用西北化工研究院开发的JT-4型焦化催化干气加氢催化剂,以满足干气制氢的需要。使用结果表明,焦化干气经JT-4型催化剂加氢转化后,完全满足制氢工艺要求,解决了全厂干气不平衡问题,大幅度降低了制氢成本。     

JT-1G型和JT-4型炼厂干气加氢精制催化剂的开发及工业应用

介绍了炼厂焦化干气加氢精制催化剂的开发研制过程及其在炼厂制氢、大中型合成氨原料路线改造工程中的应用概况。并对研制开发的JT-1G和JT-4型加氢催化剂应用于国内炼厂富气汽柴油吸收串绝热等,炼厂干气绝热床循环法加氢以及等温-绝热加氢等三种工艺流程的操作运行工况作了说明。     

JT-1G/JT-4型加氢精制催化剂在逆流等温-绝热加氢精制工艺上的应用

介绍了JT-1G/JT-4型加氢精制催化剂首次配合逆流等温-绝热加氢精制工艺,用于焦化富气制氢装置的使用情况。工业应用表明,JT-1G/JT-4型加氢精制催化剂在生产过程中催化性能良好,完全满足焦化富气作为制氢原料对烯烃饱和的要求,并将有机硫加氢转化为无机硫,经氧化锌脱硫剂脱硫后,原料中硫的质量分数降至0.2×10^-6。     

加氢精制催化剂在催化干气变温-加氢净化工艺中的应用

介绍了JT-4和JT-1G型加氢精制催化剂在制氢装置催化干气变温-加氢净化工艺中的应用情况。结果表明,两种催化剂具有良好的烯烃和有机硫低温加氢活性。催化干气经变温-加氢精制后,完全满足制氢工艺要求。     

焦化干气加氢催化剂在制氢装置的长期稳定运行

介绍了JT-1G型加氢转化催化剂在锦州石化分公司的工业应用。生产运行表明，该催化剂具有很强的有机硫加氢转化活性，完全满足在制氢装置生产过程中对制氢原料的净化要求。     

JT-1G型加氢催化剂在甲醇装置的应用

介绍了西北化工研究院研制开发的JT-1G型加氢催化剂在中国石油天然气股份有限公司青海油田格尔木炼油厂甲醇装置的应用。为不断降低天然气制甲醇装置的生产成本,在不改变现有工艺流程的基础上,将甲醇装置富裕的氢气提供给炼油装置使用,将炼油装置的副产物炼油干气用于制取甲醇原料,从而提高甲醇的利润空间。JT-1G型加氢催化剂可将炼油厂炼油干气提氢后得到解吸气中的烯烃饱和并进行硫转化,以满足蒸汽转化催化剂及合成甲醇的要求,从而替代部分原料天然气,达到降低甲醇生产成本的目的。     

用催化干气作制氢原料的工艺路线及其操作要点

用催化干气作制氢原料工艺相对复杂，就杭州炼油厂的制氢工艺两条路线(等温-绝热、变温-绝热)、三种取热方式的优劣进行讨论；并对适合该工艺的JT-4，JT-1G加氢催化剂延长使用寿命的操作方法进行探讨。通过各类数据的比较，说明现有的工艺选择，能充分满足该厂的生产需要。     

烯烃饱和工艺和双功能催化剂在焦化富气制氢中的应用

逆流等温绝热烯烃饱和工艺和JT-1G、JT-4型催化剂首次在焦化富气制氢中应用.应用结果表明,该工艺能够将焦化富气中体积分数15%以上的烯烃在加氢饱和过程中放出的热量取出,有效控制了催化剂床层温升;该催化剂可以对原料中体积分数15%以上的烯烃进行饱和及有机硫转化为无机硫.分析了该工艺及催化剂在使用中存在的问题,探讨了优化措施,总结了在使用过程中的经验.     

采用JT-1G 型加氢催化剂优化制氢工艺

长岭炼油化工总厂20000Nm³/h 制氢装置通过采用JT-1G 型加氢催化剂, 反应器入口温度降至200℃, 停开干法脱硫循环机, 加氢后气体的质量指标达到后工序要求。不但降低了成本, 而且简化了工艺, 操作更方便, 并为制氢工艺进一步优化后, 停开制氢干法脱硫反应器奠定了基础。     

逆流等温-绝热烯烃饱和技术在制氢原料精制中的应用

介绍逆流等温-绝热加氢工艺流程在高烯烃含量的炼厂气用作制氢装置原料时,有效控制原料烯烃饱和过程中加氢反应器催化剂床层的温度的原理以及该工艺在中石油辽河石化焦化富气制氢中的使用情况,结果表明,该工艺解决了烯烃加氢饱和过程中的放热取出问题,实现了焦化富气用作制氢原料,拓宽了制氢原料来源.     

Noncatalytic conversion of residuum in two-stage coal liquefaction

An experimental investigation was conducted to ascertain the contribution of thermal reactions in the hydroprocessing reactor of two-stage liquefaction processes. Various solvent/residuum feedstocks were reacted in the absence of a catalyst at temperatures ranging from 655K to 728K. Detailed characterization of the composite and fractionated feedstock and product samples was performed to ascertain the extent of residuum conversion, heteroatom removal, and hydrogen rearrangement. The results showed that hydrogenation of the solvent portion of the feedstock neither enhances residuum conversion nor results in the transfer of hydrogen from the solvent to the residuum. Higher reaction temperatures also had little effect on the reactions involved. These results suggest that the conversion of residuum in the hydroprocessing reactor of two-stage liquefaction processes must occur catalytically rather than thermally.     

重油催化裂解制低碳烯烃工艺条件研究

采用固定流化床催化裂化试验装置,以中国石油兰州石化公司3.0 Mt·a-1重油催化裂化装置所用原料油为原料,考察反应温度和剂油质量比对重油催化裂解制低碳烯烃性能的影响,在确定的适宜操作条件下研究中国石油兰州石化公司重催装置原料在不同催化剂上的催化裂解制低碳烯烃的反应性能。结果表明,较适宜的操作条件为:反应温度590℃,剂油质量比为7,与降烯烃催化剂和重油裂解催化剂相比,多产丙烯催化剂的低碳烯烃产率可达25.53%,更适合作为重油催化裂解制低碳烯烃时使用。     

Intensification of the processes of dehydrogenation and dewaxing of middle distillate fractions by redistribution of hydrogen between the units

The dehydrogenation and dewaxing of hydrocarbons of middle-distillate fractions, which proceed in the hydrogen medium, are of great importance in the petrochemical and oil refining industries. They increase oil refining depth and allow producing gasoline, kerosene, and diesel fractions used in the production of hydrocarbon fuels, polymer materials, synthetic detergents, rubbers, etc. Herewith, in the process of dehydrogenation of hydrocarbons of middle distillate fractions (C₉–C₁₄) hydrogen is formed in the reactions between hydrocarbons, and the excess of hydrogen slows the target reaction of olefin formation and causes the shift of thermodynamic equilibrium to the initial substances. Meanwhile, in the process of hydrodewaxing of hydrocarbons of middle distillate fractions (C₅–C₂₇), conversely, hydrogen is a required reagent in the target reaction of hydrocracking of long-chain paraffins, which ensures required feedstock conversion for production of low-freezing diesel fuels. Therefore, in this study we suggest the approach of intensification of the processes of dehydrogenation and dewaxing of middle distillate fractions by means of redistribution of hydrogen between the two units on the base of the influence of hydrogen on the hydrocarbon transformations using mathematical models. In this study we found that with increasing the temperature from 470 °C to 490 °C and decreasing the hydrogen/feedstock molar ratio in the range of 8.5/1.0 to 6.0/1.0 in the dehydrogenation reactor, the production of olefins increased by 1.45–1.55%wt, which makes it possible to reduce hydrogen consumption by 25,000 Nm³/h. Involvement of this additionally available hydrogen in the amount from 10,000 to 50,000 Nm³/h in the dewaxing reactor allows increasing the depth of hydrocracking of long-chain paraffins of middle distillate fractions, and, consequently improving low-temperature properties of produced diesel fraction. In such a way cloud temperature and freezing temperature of produced diesel fraction decrease by 1–4 °C and 10–25 °C (at the temperature of 300 °C and 340 °C respectively). However, when the molar ratio hydrogen/hydrocarbons decreases from 8.5/1.0 to 6.0/1.0 the yield of side products in the dehydrogenation reactor increases: the yield of diolefins increases by 0.1–0.15%wt, the yield of coke increases by 0.07–0.18%wt depending on the feedstock composition, which is due to decrease in the content of hydrogen, which hydrogenates intermediate products of condensation (the coke of amorphous structure). This effect can be compensated by additional water supply in the dehydrogenation reactor, which oxidizes the intermediate products of condensation, preventing catalyst deactivation by coke. The calculations with the use of the model showed that at the supply of water by increasing portions simultaneously with temperature rise, the content of coke on the catalyst by the end of the production cycle comprises 1.25–1.56%wt depending on the feedstock composition, which is by 0.3–0.6%wt lower that in the regime without water supply.     

流化催化裂化提升管进料段混合研究进展

流化催化裂化是最重要的重油加工工艺之一,提升管反应器是催化裂化装置的关键部分,提升管反应器的进料混合段存在返混严重;油剂两相在提升管截面上浓度分布不均匀等问题。进料段内油滴和催化剂的混合状况对产品的收率与分布有着极为重要的影响。从喷嘴和进料段结构对改善提升管进料段的混合效果进行了分析,同时介绍了近年来研究的新成果,以及设备应用的新进展。     

JT-1G型加氢催化剂在焦化干气制氢中的应用

本文主要从应用的角度探讨了焦化干气制氢及ＪＴ－１Ｇ型加氢催化剂的使用情况。     

F-T合成加氢裂化催化剂的工业应用

F-T合成油低温工艺产物中有大于质量分数40%的石蜡生成,必须对其进行加氢裂化生产优质的中间馏分油。加氢裂化关键在于高性能催化剂的研究开发,概述了近年来加氢裂化催化剂在国内外的应用现状。FC-14及SC-I催化剂在内蒙古伊泰煤制油有限责任公司的运行结果表明,SC-I催化剂表现出良好的活性及较高的中间馏分油选择性,在总进料20 t·h^-1、反应器入口氢分压7.0 MPa、氢油体积比800和总体积空速（2.0~15.0） h^-1条件下,反应器出口温度约340 ℃,总温升14 ℃,表现出较高的反应活性及灵活的温度调控性,柴油收率上升约3~4个百分点,具有较高的中油选择性。     

Some effects of carbon monoxide in hydroprocessing of heavy feedstocks

Hydroprocessing routes, when utilized for upgrading bituminous feedstocks and heavy oils, represent versatile means for production of additional liquid fuels. Production of pure hydrogen involves expensive gas purification and shift conversion steps so that by-passing these would be economically beneficial. Experiments undertaken to determine the effect of the presence of carbon monoxide (CO) in the hydrogen stream on the hydrocracking of Athabasca bitumen in a high-pressure continuous-flow system showed that CO content up to 50 mol % in the hydrogen feed would not affect thermal hydrocracking detrimentally. The use of a catalyst with stabilizing capability emphasized the apparent non-interference of CO with thermal cracking. On the other hand, significant performance inhibition of molybdenum-containing multi-functional catalysts indicated surface poisoning by CO adsorption which was partially alleviated in the presence of steam. On the addition of water to the feedstock, the latter catalysts caused substantial water-gas shift reaction to take place, accompanied by less extensive methanation. These reactions were less apparent with the other type of catalysts. Depending upon feedstock characteristics it may be possible to incorporate catalytic components allowing the presence of CO in the feed. In the overall evaluation, other important effects of CO presence would have to be examined in connection with the coking propensity of the feedstock and the reactor temperature control.     

反应温度对低温煤焦油加氢产物性质及化学组成的影响

使用工业催化剂Ni-Mo/Al2O3,在固定床反应器上对360℃前馏分煤焦油进行加氢处理实验,研究反应温度(320~400)℃对煤焦油加氢产物分布及化学组成的影响。实验过程中,反应条件设定为:压力10 MPa,空速0.5 h~(-1),氢油体积比1 600∶1。使用GC-MS分析煤焦油加氢前后的化学组成变化,结果表明,升高反应温度对煤焦油中芳烃类物质的加氢饱和反应不利,但有利于杂原子的脱除以及油品的轻质化。煤焦油中最主要的两类化合物是烷基萘与酚类物质,加氢过程中主要转化为二环癸烷与烷基环己烷。