甲醇制烯烃再生催化剂催化裂解混合碳四的可行性分析

随着开工建设及运行的甲醇制烯烃工业装置越来越多,如何利用碳四并将其转化为低碳烯烃变得越来越重要。为探究甲醇制烯烃再生催化剂裂解混合碳四的可行性,首先,对甲醇制烯烃工业装置副产混合碳四与石脑油蒸汽裂解和炼油催化裂化产生的碳四产品组分进行分析,得出甲醇制烯烃工业装置副产的混合碳四中烯烃含量较高且无丁二烯的结论;其次,梳理碳四催化裂解转化的研究成果,得出SAPO-34及ZSM-5分子筛都可以作为裂解碳四的催化剂且ZSM-5分子筛性能更优的结论;再者,对混合碳四转化工艺,即以碳四烯烃歧化反应和催化裂解为主的工艺进行分析与对比,总结各种工艺的特点。最终得出结论:利用高温再生催化剂裂解甲醇制烯烃副产的混合碳四是可行的,无需再建设反应器及再生器,可节省成本,具有一定的优势和经济效益,但下游烯烃分离系统处理碳四的能力会影响碳四的裂解负荷。     

甲醇制烯烃装置再生器热点成因及其对设备安全影响的探究

在甲醇制烯烃装置中，再生器的作用是烧去催化剂上携带的碳组分，恢复催化剂活性。同时通过循环流化将催化剂输送至反应器，提供反应器反应时所需温度。设备运行时内部高温且存在大量流化状态的催化剂及一氧化碳，通过内部设置隔热耐磨衬里，保护设备器壁不受磨损及高温侵蚀。某甲醇制烯烃装置运行期间再生器器壁出现高温热点，分析研究再生器热点成因及其对设备安全的影响。     

裂解碳八、碳九加氢技术

以乙烯裂解碳八、碳九为原料,采用两段加氢工艺,一段加氢采用镍系加氢催化剂,二段加氢采用活性金属催化剂。二段催化剂均可再生,运行周期长。混合油品可先脱胶质,再经一段使双烯烃加氢成单烯烃,二段单烯烃加氢饱和、脱硫氮氧等,使原料不饱和组分大幅降低,提高了裂解碳八、碳九油品品质。     

利用Aspen Plus模拟碳四加氢反应装置的应用

新建于内陆地区的炼化一体化装置运行过程中,轻烃回收产生部分重碳四、丁二烯抽提和MTBE产生部分剩余碳四,混合这部分碳四烃类,经饱和加氢后作为乙烯裂解原料,使原料得以充分利用。模拟不同烯烃含量的混合碳四饱和加氢过程,并将其结果分别与设计要求和实际运行结果对比,讨论装置的运行状况及产品的应用。     

碳四烯烃制丙烯催化剂及其工业应用

研究碳四烯烃催化裂解制丙烯BOC-1催化剂的放大制备及其工业应用,详细介绍催化剂放大制备后实验室小试和工业应用评价结果。BOC-1催化剂在工业生产装置中运行和再生性能良好,丙烯单程收率28.5%,碳四烯烃转化率82.1%,催化剂使用周期17天,各项性能指标均超过洛阳炼化宏力化工有限责任公司的工业催化剂水平,适合进一步推广使用。建立由烯烃催化裂解、吸收稳定、气分、MTBE醚化和烷烃分离5个单元组成的碳四烯烃资源综合利用工艺流程,并使用VMGSim流程模拟软件进行模拟计算。结果表明,采用新工艺流程,碳四烯烃综合利用率99.3%,聚合级丙烯收率35.19%。     

甲醇制烯烃工业装置催化剂的再生研究

基于某180万t/a甲醇制烯烃工业装置催化剂再生数据,研究了催化剂的烧焦特性,建立了本征和经验动力学模型并对工业催化剂再生数据进行了拟合。在分析工业上催化剂再生过程特点及再生器操作条件复杂性的基础上,对工业与实验烧焦动力学模型精确度存在差距的原因进行了分析。阐述了甲醇制烯烃工业装置运行中遇到的问题及解决方案,并总结了工业催化剂再生器较优的操作区间。对再生剂和新鲜剂的催化性能进行了比较,发现再生过程中保留少量的积炭有助于避免或缩短反应的诱导期,提高低碳烯烃的选择性。     

双催化剂催化裂化工艺

为了获取更高的低碳烯烃收率,开发了双催化剂催化裂化技术。该技术采用反应并联、催化剂分区再生的技术手段,同时使用Y型催化剂和ZSM-5分子筛催化剂。反应部分采用双提升管工艺,重油与轻油分别匹配不同的催化剂和工艺条件在不同的提升管内进行反应。再生部分采用分区再生、烟气串联的两段再生技术,避免2种催化剂混合,同时保证轻油裂化所需的热量。中试试验结果表明,该技术可以显著提高催化裂化装置的低碳烯烃产率。     

中国石油碳二加氢催化剂在煤制烯烃应用

由中国石油石油化工研究院开发的碳二加氢催化剂在中国神华包头600kt·a-1煤制烯烃装置投入工业运行，反应器出口未检出乙炔含量，催化剂性能完全满足装置要求。这是该大型煤制烯烃工业化装置的碳二加氢单元首次开车，标志着煤制烯烃装置的聚合级烯烃精制技术已经成熟，煤制烯烃技术产业链将延伸到高附加值产品领域。     

甲醇制烯烃催化剂再生的影响因素及问题分析

甲醇制烯烃的过程中催化剂的再生方式不同于传统的催化裂化的完全再生,它属于不完全再生。催化剂因反应结焦失去活性,需要经过再生器的烧焦再生才能恢复活性。在催化剂再生过程中,由于再生温度、主风量、反应进料负荷、再生器的藏量等因素的变化都会影响再生催化剂的定碳,从而影响催化剂的活性。在实际生产过程中,再生器平稳运行直接影响到装置的生产情况,因此在操作过程中控制好再生温度、主风量等参数的变化对再生催化剂活性的恢复至关重要。     

烯烃分离装置乙炔转化器布置及相关管道设计

烯烃分离装置正常运行时一段时间后,乙炔转化器内部的催化剂需要再生。为保证连续生产,烯烃分离装置共设两台乙炔转化器,一台运行,一台催化剂再生或备用。文章结合某采用LUMMUS工艺包的烯烃分离装置中乙炔转化器相关设计内容,就乙炔转化器平面及竖面布置需要考虑的因素及应对措施,提出了设计时应把握的原则;就乙炔转化器相关管道设计需要考虑的因素及应对措施,从管道布置、管道应力分析、管道等级选用及管道等级分界、管道支吊架设计等几方面阐述了乙炔转化器相关管道的设计要点,为后续类似设备布置及管道设计提供了借鉴。     

再生时间对甲醇制烯烃催化剂水蒸气再生过程的影响

对甲醇制烯烃（MTO）过程失活催化剂采用水蒸气再生不仅可以减少二氧化碳排放,而且能提高低碳烯烃选择性,具有很好的应用前景。本文针对工业MTO过程使用的SAPO-34分子筛催化剂,研究了再生时间对水蒸气再生过程的影响。采用XRD、NH₃-TPD、TGA、FTIR、GC-MS以及N₂物理吸脱附表征手段对再生催化剂样品的晶体结构、酸性、残炭性质以及结构参数进行了表征,并考察再生催化剂的MTO反应性能。结果表明,再生时间越长,再生催化剂上残炭量越低,其酸性、比表面积和孔结构等能较好地恢复,在MTO反应中表现出更长的催化寿命。在再生过程中,催化剂上的残炭物种由芘、菲等大分子量的有机物转变为对MTO具有反应活性的萘等小分子有机物;但是可溶性残炭物种随着再生时间的延长而减少,从而使得初始低碳烯烃选择性有所降低。     

Advanced Catalytic Dehydrogenation Technologies for Production of Olefins

Catalytic dehydrogenation is a critical and growing technology for the production of olefins, especially for propylene production. This paper will give an overview of advances in the catalysis science and technology for production of olefins by catalytic dehydrogenation, including the concomitant removal of H₂ by selective oxidation. For light paraffin dehydrogenation, UOP has licensed the Oleflex? process widely for production of polymer-grade propylene as well as isobutylene with over 12 million metric tons of capacity announced. Today there are nine UOP C₃ Oleflex? units in operation accounting for 55?% of the installed world-wide propylene production capacity from propane dehydrogenation technology. The heart of the process is a noble metal multi-metallic catalyst and the continuous catalyst regeneration (CCR) process. The coupling of catalytic dehydrogenation with selective oxidation of hydrogen allows one to design a process, which greatly improves equilibrium conversions while maintaining very high selectivity to olefin. The Lummus/UOP SMART? SM process (Styrene Monomer Advanced Reheat Technology) allows 30?C70?% capacity expansion, achieves a higher per-pass ethylbenzene conversion, and provides the most cost-effective revamp for higher capacity. Styrene Monomer Advanced Reheat Technology (SMART?) uses an oxidation catalyst and novel reactor internals to allow oxidative reheating between dehydrogenation stages. In the case of selective oxidation catalysts containing dispersed metal active sites, the role of diffusion and pore architecture is as important as the active metal sites.     

Synthesis of ethylene and propylene on a SAPO-34 silica—alumina—phosphate catalyst

A process for the preparation of ethylene and propylene from methanol on a microporous silica—alumina—phosphate SAPO-34 catalyst is described. The influence of the temperature and the nature and concentration of the diluting agent on the catalyst activity, its selectivity with respect to C₂₌-C₄₌ olefins, and ability to be regenerated were studied. The SAPO-34 catalyst was shown to be highly effective in the selectivity of ethylene and propylene formation; the total yield of C₂₌-C₄₌ olefins at 350–450°C was 77–84% and methanol conversion was up to 96–99%. In the conversion of methanol under helium at 450°C, the yield of ethylene (∼36%) was higher than at 375°C (∼29%), while the yield of propylene (∼30%) was lower (∼38%). The use of water and helium vapors as a diluent increased the yield of ethylene to ∼36% at 375°C and to ∼50% at 450°C. In the conversion of methanol at 450°C in water vapors without helium, the yield of ethylene reached ∼44–49% and the yield of propylene was 24–29%. The C₃₌ to C₂₌ ratio in the process varied from ∼0.5 to 1.5. The high efficiency of the SAPO-34 catalyst is the consequence of the microporous structure of zeolite and the high content of acid centers of medium strength. In the course of methanol conversion, the catalyst was deactivated due to coking. After regeneration with air at 550°C, the catalyst activity was completely restored, while the crystal structure and the acid properties did not change. The activity of the catalyst in a cycle is prolonged if water vapors are used as a diluent and the catalyst is processed at a high temperature with vapors. The industrial processes for the production of ethylene and propylene from nonpetroleum materials are not used in Russia. The results of this study are comparable to the data obtained from the UOP/Norsk Hydro process on the SAPO-34 catalyst. The catalyst can be recommended for further trials on an FCC type pilot plant with a moving catalyst bed.     

α-甲基苯乙烯加氢工业催化剂失活分析及再生

苯酚丙酮装置副产的α-甲基苯乙烯影响装置物耗,通常采用加氢将其转化为异丙苯作为原料循环使用,可提高装置运行效率、降低单耗,提高技术经济指标。α-甲基苯乙烯具有高度聚合性,易形成低聚物,同时含水、苯酚、碱性物等杂质,从而导致加氢催化剂失活。针对某工业装置运行中α-甲基苯乙烯加氢催化剂出现的失活现象进行剖析,并根据分析结果进行再生试验。结果表明,加氢催化剂失活原因主要是由于钠、铁杂质沉积以及苯酚、苯乙酮的聚合物覆盖所致。基于失活原因,重点比较了不同再生方案对加氢催化剂性能的影响,结果发现,水洗可以去除钠杂质,热异丙苯清洗或焙烧加氢催化剂可以除去表面的聚合物,使加氢催化剂性能完全恢复,产物中α-甲基苯乙烯残余量约500×10^-6,通过再生试验为工业α-甲基苯乙烯加氢催化剂的长周期稳定运行提供技术支撑。     

新型液固循环移动床反应器中直链烷基苯合成研究

For the alkylation of benzene with long-chain olefins, using Hβ zeolite catalyst as replacement of HF or A1Cl3 has the advantages of no corrosion, less environmental pollution, and much more 2-phenyl isomer, which has the highest biodegradability and solubility, and better detergent properties among the related isomers. The characterization of the coke shows that the deactivation of catalyst is caused by the jam of bulkier molecules, such as naphthalene, indane and linear alkylbenzenes, which are too big to move quickly in the intracrystalline pores of catalyst. The deactivated catalyst can be regenerated by benzene washing at higher temperature. To make the processes of reaction and regeneration continuous, a novel moving bed reactor is developed. Comparing with the processes with fixed bed reactors, the processes in this work have the advantages of continuous operation, low temperature, low pressure, low mole ratio of benzene to olefins, and high weight hourly space velocity.Keywords t3 zeolite, alkylation, linear alkylbenzene, moving bed reactor     

V-Mg-O催化剂上丁烷氧化脱氢动力学研究

制备了V－Mg-O催化剂,并测定了在该催化剂上进行丁烷氧化脱氢的反应动力学。应用BET和X射线衍射技术对催化剂进行了表征,在反应温度793－873K范围内,改变接触时间（W／F）和丁烷与氧气的分压进行了动力学实验。在所有的实验条件下,产物主要有脱氢产物（丁烯、丁二烯）、CO和CO2。提出了一个包括C4烯烃、COx生成反应的反应网络;从所测量的动力学数据中得到了合适的幂率型动力学方程。因为氧化脱氧反应的表观活化能比深度氧化反应的表观活化能大,在相同转化率时,C4烯烃选择性随着反应温度的提高而增加。     

用于二甲醚催化裂解的下行式循环流化床

从天然气或煤制合成气等非石油资源（经由二甲醚）制取低碳烯烃的工艺中，二甲醚催化裂解制烯烃是决定性的步骤．采用新型的并流下行循环流化床（CDCFB），能较好地解决反应热的导出，以维持反应温度的均衡，保持反应的高转化率与高选择性，并可使反应和再生操作能连续平稳地进行本文提出了一种用于实施二甲醚催化裂解反应的CDCFB结构形式，并用实验考察了整套装置的可操作性及各种操作与结构参数对催化裂解工艺的适应性，测定了反应再生系统的流体力学性能，为热态试验装置提供了设计依据     

RN-1加氢精制催化剂的器外再生

通过对RN-1型加氢精制催化剂的器外再生以及其再生前后操作数据的对比可以看出，器外再生能够满足扩能改造后的生产要求,在超负荷的情况下,产品质量仍能达到各项指标。     

Kinetics of steam regeneration of SAPO-34 zeolite catalyst in methanol-to-olefins (MTO) process

Methanol-to-olefins(MTO) is industrially applied to produce ethylene and propylene using methanol converted from coal,synthetic gas,and biomass.SAPO-34 zeolites,as the most efficient catalyst in MTO process,are subject to the rapid deactivation due to coke deposition.Recent work shows that steam regeneration can provide advantages such as low carbon dioxide emission and enhanced light olefins yield in MTO process,compared to that by air regeneration.A kinetic study on the steam regeneration of spent SAPO-34 catalyst has been carried out in this work.In doing so,we first investigated the effect of temperature on the regeneration performance by monitoring the crystal structure,acidity,residual coke properties and other structural parameters.The results show that with the increase of regeneration temperature,the compositions of residual coke on the catalyst change from pyrene and phenanthrene to naphthalene,which are normally considered as active hydrocarbon pool species in MTO reaction.However,when the regeneration temperature is too high,nitrogen oxides can be found in the residual coke.Meanwhile,as the regeneration temperature increases,the quantity of residual coke reduces and the acidity,BET surface area and pore structure of the regenerated samples can be better recovered,resulting in prolonging catalyst lifetime.We have further derived the kinetics of steam regeneration,and obtained an activation energy of about 177.8 kJ·mol~(-1).Compared that with air regeneration,the activation energy of steam regeneration is higher,indicating that the steam regeneration process is more difficult to occur.     

TA精制催化剂在线再生工艺条件的优化

介绍了PTA装置加氢反应Pd/C催化剂失活后在线再生的方法,并详细探讨了不同再生工艺条件对催化剂恢复活性的影响和Pd/C催化剂的在线再生机理,同时提出了PTA加氢反应催化剂在线再生最佳的工艺条件。