制氢装置烯烃饱和催化剂积碳原因分析及建议

永坪炼油厂制氢装置采用催化干气为原料,由于原料烯烃含量比较高,原料精制部分采用变温加氢+绝热加氢+Zn O脱硫工艺。装置平稳运行一年后,绝热加氢反应器出口温度超温,装置被迫切料停工,进行检修,发现变温加氢反应中烯烃饱和催化剂积碳严重,部分列管已经堵塞,更换新的催化剂后,绝热加氢反应器出口操作正常。本论文对造成烯烃饱和催化剂积碳多方面的原因进行分析,提出了操作建议。     

脱硫干气制氢工艺的应用

介绍了制氢装置采用廉价的脱硫干气作为主要原料,天然气作为补充原料的制氢工艺,以及原料气预处理和加氢处理的工艺过程。总结了脱硫干气制氢生产过程中应注意的问题。对脱硫干气制氢的工程设计提出了建议。     

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。     

燃料油加氢深度脱硫催化剂及工艺技术进展

分析了燃料油中硫化物的形态及加氢脱硫反应机理；介绍了国内外加氢深度脱硫催化剂的研究现状；评述了现有加氢深度脱硫反应工艺及反应器技术。     

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.     

新型焦炉煤气净化工艺的开发及进展

简述了焦炉煤气净化技术的现状及现有干法净化工艺的技术缺陷,重点介绍了两级加氢的新型干法净化工艺及其加氢催化剂的研发进展,从加氢催化剂的脱硫试验和工业应用等方面分析评述了新型焦炉煤气净化工艺的技术优势,表明其工艺装置可安全、稳定、高效及长周期运行。     

炼油厂产品深度脱硫工艺的研究进展

综述了国内外开发和应用的脱硫技术,通过一系列实例阐述了近年来催化加氢脱硫及非加氢脱硫的工艺进展。该技术主要有催化加氢脱硫（改进催化剂的合成、先进的反应器设计、蒸馏与加氢脱硫组合等）及非加氢脱硫技术（烷基化脱硫、溶剂萃取脱硫、沉淀脱硫、吸附脱硫、氧化脱硫和膜分离脱硫等）;评述了催化加氢脱硫、烷基化脱硫、吸附脱硫和氧化脱硫等脱硫技术的特点和研究应用前景。     

制氢装置混合气作为原料的操作优化

介绍了永坪炼油厂联合三车间20000m3/h干气制氢装置采用天然气、催化干气、加氢干气三气混合后作为制氢的原料气,从操作参数、操作方式等方面提出了一些优化措施。天然气作为制氢原料最突出的问题就是组分中无烯烃含量,甲烷含量较多,易造成反应器床层无温升的现象。因此在操作中相继配入催化干气与加氢干气作为补充烯烃,解决反应器床层无温升的现象。本文通过对天然气、催化干气、加氢干气的配比和反应器入口温度、压力等操作的优化调整进行了深入的分析和探讨,为以后使用天然气、催化干气、加氢干气三气作为制氢的原料气,提供一定的技术思路。     

煤焦油加氢脱硫研究进展

介绍了煤焦油中主要的含硫化合物类型及含量,总结了其中典型含硫化合物的加氢反应。综述了近年来加氢脱硫催化剂的研究情况和加氢工艺及其工艺条件对加氢脱硫效果的影响,在高温、高压和较低空速条件下能达到较好的脱硫效果。最后针对煤焦油组分极其复杂的情况,在开发新型催化剂、工艺、反应器上做了展望。     

水煤气加氢水解精脱硫工艺的改造及应用实践

为了充分利用水煤气中的有效成分CO生产甲醇,某公司采用了"两级加氢+水解工艺"对水煤气进行精脱硫。介绍了该精脱硫工艺的流程和运行情况,讨论了温度、空速对精脱硫工艺系统的影响,并采用微量硫色谱分析仪对工艺系统各设备进出口气体中硫化物含量进行了分析。结果表明:采用Co-Mo型加氢催化剂,在加氢温度140℃～160℃、加氢反应器中空速1 000 h~(-1)～2 500 h~(-1)条件下,出口总硫质量浓度达2 mg/m~3～5 mg/m~3,未达到总硫质量浓度低于0.1 mg/m~3的设计值。后将"两级加氢+水解工艺"改造为"三级加氢工艺",实现了系统出口总硫质量浓度在0.1 mg/m~3以下,并通过对一级氧化锌槽流程优化,将装置运行周期从3个月提高到5个月。     

焦化干气制氢的投产情况及改进措施

简述了我厂用焦化干气制氢的投产情况。针对生产不稳、干气用量不多的现象分析出影响焦化干气正常使用的主要问题是干气中总硫超标, 为解决这一问题, 建议适当扩大加氢精制和脱硫反应器, 并采用加氢干气与焦化干气混合制氢的方法。     

焦炉气生产甲醇精脱硫工艺优化改进

分析了天浩公司焦炉气制甲醇精脱硫工艺中存在的问题,介绍了精脱硫工艺的优化改进情况。在不改变精脱硫整体工艺的情况下,将原一级加氢转化器改为预加氢转化器,将原中温脱硫槽C槽改为一级加氢转化器,不仅降低了一级加氢转化器的催化剂的消耗,而且更换一级加氢转化器的催化剂时,不再需要甲醇系统停车,实现了生产的长周期运行。     

影响干气脱硫效果因素分析

炼油厂气体脱硫工艺装置中影响脱硫效果的因素主要有:脱硫塔操作温度、脱硫塔操作压力、贫液浓度、贫液中H2S含量、脱硫塔的塔板数等。以塔河分公司硫磺回收车间脱除加制氢和延迟焦化两个车间的混合干气为例,根据硫磺回收车间干气脱硫塔的运行情况,对上述影响因素进行数据计算和定量分析,从而选择合适的工艺设备、确定最佳的操作条件。     

联醇工艺中脱硫工艺技术的发展

论述和对比了联醇工艺中原料气脱硫所采用的栲胶脱硫工艺、ADA脱硫工艺、PDS脱硫工艺、氧化锌脱硫工艺、氧化铁脱硫工艺、活性炭脱硫工艺、铁钼加氢转化法脱硫工艺、有机硫水解脱硫工艺的技术原理和工艺特点;提出了将湿法脱硫与干法脱硫工艺进行合理组合,并结合有机硫水解装置的脱硫工艺选择理念;总结了“3次脱硫2次转化”脱硫工艺在联醇生产中的重要作用.     

Mechanism of coal hydrogenation—liquefaction; Effect of temperature and coal particle size

The effect of coal particle size, hydrogen pressure and temperature on the extent of coal conversion in an entrained flow reactor is presented. Coal hydrogenation is done by feeding dry coal with ZnCl₂ catalyst into a continuous stream of hydrogen. The hydrogen-coal stream enters a long, small internal-diameter reactor (coiled tube reactor) controlled at about 500°C and 12.4 MPa hydrogen. At these conditions the coal particles become plastic and sticky. The hydrogen provides the energy to force the sticky coal particles through the reactor. Conversion of 85% of the coal to liquids and gases is easily attained. A physical mechanism is presented based on the unreacted-core-shrinking model. This mechanism aids in the explanation of the effect of process variables on reaction rates. Projections beyond the range of the variables studied are presented. These projections indicate that the pressure of coal liquefaction processes may be reduced by (1) the use of dry coal particles and (2) the reduction of the particle size. Significant reaction rates may be attained at pressures as low as 0.7 MPa by proper adjustment of particle size and temperature.     

Selectivity improvement in the SRC process

The selectivity for hydrodesulfurization over hydrogenation has been examined in a new short residence time catalytic two-stage SRC process, which has the potential of producing a low-sulfur solid SRC product to meet the newly proposed EPA new point source emission standards (NPSES). In the first stage of the process, residence time and hydrogen consumption are minimized through the use of an inexpensive mineral catalyst (SRC residue ash) that has been treated under a combustion environment to improve its selectivity for hydrodesulfurization over hydrogenation. The second stage of the process involves hydrotreating the filtered liquid product with a commercial Co-Mo-Al catalyst, before splitting into a solid SRC and solvent recycle by distillation. Several process variables — such as type of coal, catalyst, temperature, hydrogen partial pressure, and reaction time — have been examined to provide information on hydrogen consumption, product distribution, sulfur removal, SRC yield and solvent quality. The results show that the ash of SRC residue can be used to selectively catalyze desulfurization over hydrogenation in SRC processing. Selectivity for desulfurization in two stage hydrodesulfurization of coal is improved by using high reaction temperatures, short residence times, the ash of SRC residue as a first stage catalyst, and Co-Mo-Al as a second stage catalyst. Two stage catalytic SRC processing is more selective for hydrodesulfurization than catalytic or non-catalytic single stage SRC processing.     

生产清洁燃料的氧化脱硫技术新进展

简要介绍了油品中硫的分布及主要脱硫技术的特点，对ASR－2和SulphCo氧化脱硫技术的反应机理、工艺流程及技术经济等方面进行了详细的介绍。与常规的加氢脱硫技术相比，氧化脱硫技术的投资少，操作条件缓和且不消耗氢气，有广阔的市场前景。     

Ethylene selectivity variation in acetylene hydrogenation reactor with the hydrogen/acetylene ratio at the reactor inlet

Variation in the selectivity of ethylene produced by acetylene hydrogenation in an integral reactor was analyzed as a function of the hydrogen/acetylene ratio in the reaction stream at the reactor inlet. The analyses were made for two sample catalysts, which showed different dependence of the ethylene selectivity on the reactant composition. Even a small mismatch between the hydrogen/acetylene ratio at the reactor inlet and the ratio for converted reactants caused a large change in the ethylene selectivity along the reactor position, particularly when the conversion was high. The results of this study indicate two important factors to be considered in the design and operation of acetylene hydrogenation process: the hydrogen/acetylene ratio in the reactor inlet should be controlled close to the ratio for converted reactants; and catalysts showing high ethylene selectivity over a wide range of the hydrogen/ acetylene ratio are required for the design of a highly selective hydrogenation process. This paper is dedicated to Professor Wha Young Lee on the occasion     

蒽醌法制过氧化氢用氢化反应器的研究进展

综述了近年来蒽醌法生产过氧化氢用悬浮氢化反应器和固定床氢化反应器的研究进展。着重介绍了管式和鼓泡床 悬浮氢化反应器的改进和泡沫固定床三相反应器用于蒽醌氢化过程可显著提高反应时空收率和选择性的优势。指出泡沫固定 床是蒽醌氢化反应器研究开发中的新思路,也是气-液-固三相反应器研究的新方向。     

预加氢催化剂RS-30（S）器外预硫化的应用分析

通过预加氢系统的催化剂装填、开工过程、开工前后精制油指标对比等方面对RS-30（S）催化剂进行评价。结采表明RS-30（S）催化剂加氯脱硫、脱氮活性较高．在反应器入口温度为280℃、高分压力为2．8MPa、氢油体积比为90v／v、体积空运为3h。的条件下,可以原料油精制得到硫含量、氮含量均小于0．5pP=的预加氢精制油,完全能够满足永坪炼油厂连续重整装置预加氢单元满负荷生产的需要。