生物油含氧化合物加氢脱氧反应机理研究进展

分析了不同原料制备的生物油含氧化合物的组成差异,综述了生物油中典型含氧化合物（酚类化合物、呋喃类化合物、醚类化合物、酸类和酯类化合物）的加氢脱氧机理,重点介绍了含氧化合物加氢脱氧动力学数据及反应路径;同时,还对生物油加氢精制过程进行了描述,主要论述了生物油加氢精制过程的机制以及O、S、N等杂原子在不同催化剂下的脱除活性;最后指出生物油加氢精制面临的问题是人们对其反应机理了解不够深入,而模型化合物加氢脱氧无法真实反映生物油的反应过程,今后应重点研究不同类型含氧化合物的相互作用和真实生物油的反应机理。     

小球藻热解油在Ni-Cu/ZrO_2催化剂上的加氢脱氧

在小型固定床反应器中以Ni-Cu/ZrO2为催化剂,对小球藻热解油进行催化加氢脱氧,以改善生物油性能。利用XRD、H2-TPR、TG、NH3-TPD等技术对催化剂进行了结构表征。结果表明,Cu的加入有效促进了Ni-Cu/ZrO2催化剂活性相的表面分散,提高了该催化剂对小球藻热解油加氢脱氧反应的催化活性。在2 MPa、350℃反应条件下,随Cu/Ni的增大,Ni-Cu/ZrO2的催化活性先升高后降低,Cu/Ni质量比为0.40时的催化性能最好,连续运行3 h后所得精制生物油脱氧率达82.0%。Ni-Cu/ZrO2催化剂在反应过程中,表面结焦少,活性粒子及催化剂性能稳定,连续运行24 h后所得精制生物油脱氧率依然维持在77.0%以上。小球藻热解油经催化加氢脱氧所得的精制生物油,低位热值由31.5 MJ·kg-1提高至35.0 MJ·kg-1,40℃运动黏度由20.5 mm2·s-1降至9.5 mm2·s-1,且油品中水分更易于脱除。精制生物油中高级脂肪酸的含量减少,油品稳定性大幅提高。     

渣油和生物油加氢制柴油的研究

实验利用国内炼油厂的渣油和生物油混合,首先在催化剂NiMo-Al2O3的作用下进行初步加氢对原料油进行脱氧脱水,得到的中间油含水率为280×10-6。裂解催化剂和精制催化剂在固定床反应器内分层依次填装,然后对中间油进行加氢精制。研究柴油和汽油的收率,探究柴油最大收率的反应条件,并考察了温度、压力以及空速对柴油和汽油收率的影响。实验表明,加氢精制效果最佳条件为温度350℃、压力11MPa、空速0.8h-1和氢气流量1 300mL/h,所得柴油收率为60.1%,汽油收率为9.7%,尾油收率为28.9%,液化气及其它气体为2.8%。其中,液体收率98.7%,总收率101.5%。     

小球藻热解油在Ni-Cu/ZrO2催化剂上的加氢脱氧

在小型固定床反应器中以Ni-Cu/ZrO₂为催化剂,对小球藻热解油进行催化加氢脱氧,以改善生物油性能。利用XRD、H₂-TPR、TG、NH₃-TPD等技术对催化剂进行了结构表征。结果表明,Cu的加入有效促进了Ni-Cu/ZrO₂催化剂活性相的表面分散,提高了该催化剂对小球藻热解油加氢脱氧反应的催化活性。在2 MPa、350 ℃反应条件下,随Cu/Ni的增大,Ni-Cu/ZrO₂的催化活性先升高后降低,Cu/Ni质量比为0.40时的催化性能最好,连续运行3 h后所得精制生物油脱氧率达82.0%。Ni-Cu/ZrO₂催化剂在反应过程中,表面结焦少,活性粒子及催化剂性能稳定,连续运行24 h后所得精制生物油脱氧率依然维持在77.0%以上。小球藻热解油经催化加氢脱氧所得的精制生物油,低位热值由31.5 MJ·kg^-1提高至35.0 MJ·kg^-1,40℃运动黏度由20.5 mm²·s^-1降至9.5 mm²·s^-1,且油品中水分更易于脱除。精制生物油中高级脂肪酸的含量减少,油品稳定性大幅提高。     

生物油催化加氢综述

从生物油催化加氢工艺流程、加氢催化剂及技术经济方面出发,综述了生物油催化加氢近年来的研究进展。并从技术经济角度,分析了借助现有石化炼油设备对生物油进行催化加氢精制在经济性方面的优势。最后,针对现阶段存在的催化剂稳定性和加氢成本较高的问题,提出需要从降低催化剂积炭性能及开发经济合理的加氢工艺方面入手,提高加氢产物性质,降低催化加氢成本。     

焦化柴油氧化法脱碱性氮研究

针对抚顺石油三厂焦化柴油进行氧化法非加氢预精制研究,选用实验室所开发出的氧化剂,采用单因素试验方法,考察反应温度、反应时间、氧化剂与油的质量比和催化剂与油的质量比等因素对精制效果及收率的影响,确定出适宜的工艺条件为:m(催化剂)/m(油)为0.010～0.020,m(氧化剂)/m(油)为0.010～0.015,反应温度30～40℃,沉降时间为20～30 min,反应时间10～20min。在此工艺条件下,碱性氮脱除率达到96%以上,柴油颜色呈现较好的浅黄色,可有效缓和后序加氢精制操作条件。     

煤焦油中的蒽油加氢制柴油的方法

正一种蒽油加氢制柴油的方法,先将蒽油在含有第一催化剂的加氢反应区中反应,再将加氢反应区中所得产物油进入含有第二催化剂的加氢裂化反应区中反应制得柴油组分成品,本发明的优点在于:本发明的加氢精制催化剂在对煤焦油加氢脱硫、加氢脱氮、加氢脱氧的同时,能提高活性,使芳烃饱和及开环,并且由于催化剂中加入了助剂钾,抑制了煤焦油中易生焦物质的结焦堵塞反应器,提高了催化剂的     

油页岩干馏瓦斯中丙烯积炭模拟

通过自建实验台模拟瓦斯全循环油页岩干馏工艺并进行积炭实验,以丙烯为碳源气,考察反应时间、壁面温度和气体流量对积炭的影响。结果表明,积炭量随反应时间和壁面温度(800℃以下)的增加而增加,随气体流量的增加先增加,流量达到30 m L/min后积炭量开始减少。各因素对积炭的影响程度从大到小依次为反应时间、气体流量和壁面温度,且各因素间无交互作用。     

石油系加氢精制剂用于煤直接液化油的研究

以煤直接液化低分油为原料,对几种国内外的石油系加氢精制催化剂进行了不同工艺的条件实验.结果表明,催化剂Cat-A具有相对好的加氢脱氮率,催化剂Cat-B具有相对好的加氢脱硫率,而催化剂Cat-C具有非常好的加氢脱硫率,但其氮脱除率很低.实验得到加氢精制较适宜的反应条件为:压力10MPa,温度350℃,氢油体积比800:1左右.实验发现几种催化剂较易失活,在微反装置上连续运转一周后,催化剂Cat-A的活性下降20%左右.     

提高页岩油加氢精制脱氮率工艺的研究

本文提出了以全馏分页岩油作为原料,经两次加氢精制工艺生产低硫低氮柴油,并副产高附加值的LPG和加氢石脑油,解决了目前页岩油加氢精制工艺中存在柴油产品的安定性差,加氢精制催化剂操作运转周期短的技术问题,可同时实现轻质油产品深度脱硫的目的。为从事页岩油深加工企业提供了一种提高页岩油加氢精制脱氮率的有效工艺方法。     

己内酰胺加氢精制过程的影响因素分析

介绍了己内酰胺加氢精制的工艺流程,总结了国内某15万t/a固定床己内酰胺加氢精制装置的运行数据,探究了反应压力、温度和催化剂等对加氢精制效果的影响。结果表明:当反应压力在由0.3 MPa升高至0.5 MPa时,加氢出口高锰酸钾吸收值(PAN值)逐渐降低,继续提高反应压力,PAN值变化不明显;当反应温度在50℃~60℃时,PAN值基本可稳定在0.8~1.6,碱度在0.13 mmol/kg左右波动,可保证己内酰胺水溶液质量达标;经过加氢反应,己内酰胺水溶液吸光度小幅降低、碱度小幅升高,但不会影响成品己内酰胺的质量;固定床加氢催化剂寿命较短,其活性下降的主要原因是催化剂结块和表层被己内酰胺覆盖。     

Preparation method for supported metal catalysts using w/o microemulsion: Study on immobilization conditions of metal particles by hydrolysis of alkoxide

It was previously found that the silica-supported rhodium catalyst prepared using water-in-oil microemulsion had rhodium particles partly, or wholly, embedded in silica. In this work, consequently, we investigated the effect of hydrolysis conditions of tetraethylorthosilicate, employed as the source of silica, on the atomic ratio of surface rhodium in contact with the gas phase, to total surface rhodium of nanoparticles. This ratio is denoted as R in this paper. R became higher when the catalyst was prepared under the following hydrolysis conditions: a shorter hydrolysis time and a smaller amount of tetraethylorthosilicate. On the other hand, R showed the minimum value when the water content in the preparation solution was 33 vol%. From these results, it is demonstrated that it was important to form silica as early as possible in hydrolysis of TEOS in order to increase R values. In addition, the effect of R on the catalytic behavior in CO hydrogenation was investigated. At R values below 30%, the turnover frequencies increased with a decrease in R.     

生物油金属水热原位加氢提质技术研究进展

水热液化技术可以将秸秆等木质纤维素类生物质转化为生物油,生物油提质可制备液体燃料和高附加值化学品。但生物油成分复杂,研发适宜的提质方法与工艺是当前的热点。金属水热原位加氢提质是一种新兴生物油提质技术,具有原料适应性广、成本低和效率高等优势,受到国内外广泛关注。本文从木质纤维素类生物质水热加氢提质原理、金属水热原位加氢最新研究进展及相关数值模拟方法三方面进行了综述,在此基础上指出目前该技术存在的主要问题,并指明未来研究方向。目前金属水热原位加氢提质过程活性氢和氢气作用机制尚不明晰;明确加氢催化剂与金属/金属氧化物的相互作用是制备高效加氢催化剂的关键;集总动力学和分子模拟等方法是金属水热原位加氢提质技术在理论计算领域未来的发展方向,有待进行深入研究。     

Preparation of tartaric acid modified Raney nickel catalysts: study of modification procedure

Chiral modification of Raney nickel using (2R,3R)-tartaric acid was studied. The prepared catalyst was used in enantioselective hydrogenation of methylacetoacetate (MAA) to methyl-(3R)-hydroxybutyrate. The influence of the most important modification parameters, such as pH, temperature, time, concentration of the modifier and the presence of a co-modifier, on the optical yield of MAA hydrogenation was systematically investigated. From the data obtained, a considerable influence of modifying conditions on the resulting enantioselectivity of the catalyst was evident. The optical yield increased with an increasing of the modifying temperature and time. Dependencies of the optical yield on the tartaric acid concentration and on the modifying pH passed through a maximum. Therefore, there exists an optimal value of modifying pH, at which a minimal catalyst amount is leached to the modifying solution. Furthermore, significant adsorption of tartaric acid and subsequent complex formation of nickel and tartaric acid occurs on the catalyst surface. It was found that the presence of sodium bromide in the modifying solution resulted in a lower degree of the nickel leaching, and a decrease of the residual aluminum content in the catalyst increased the optical yield of the reaction.     

The hydrogenation of isophorone to trimethyl cyclohexanone using the downflow single capillary reactor

Despite many innovations in the intensification of catalytic multiphase reactors for the small and medium scale manufacture of chemicals, there have as yet been relatively few commercial successes. One reason for this might be that many of these developments inherently incorporate a fixed catalyst, which may not suit an industry that is based on principles of batch manufacture and multi-product plant. This study evaluates an intensified reactor that encompasses the opportunities demonstrated from structured flows and thin channels, together with a mobile, slurry catalyst, namely a capillary reactor with gas/liquid/suspended catalyst flow. A downflow single capillary reactor (SCR) was designed, built and evaluated for the selective hydrogenation of isophorone to trimethyl cyclohexanone using commercial Pd- and Rh-based catalysts. Using the single capillary arrangement, the reaction was shown to be operating under kinetic control.

Comparison of the rate of hydrogenation with autoclave showed a significant increase of the reaction rate when capillary reactor was used. The temperature of reaction is a crucial factor in tuning the reaction towards different products. The constant relative reaction rate obtained for different catalyst loading as well as the calculated value of the apparent activation energy show that the reaction of hydrogenation of isophorone is not mass transfer limited in the single capillary reactor.     

劣质催化柴油中多环芳烃选择加氢工艺评价

选取商品柴油加氢精制催化剂和催化柴油选择加氢裂化催化剂,采用N_2吸附-脱附、XRD、TPD、Py-IR等对催化剂进行表征,结果表明,选择加氢裂化催化剂较加氢精制催化剂具有更大的比表面积和孔容,具有更多的中强酸量和较少的弱酸量,并具有更多的B酸中心。以中石化青岛炼化公司生产的高密度、低十六烷值的FCC柴油为原料,对商品加氢精制催化剂和加氢精制/选择加氢裂化组合催化剂进行FCC柴油中多环芳烃选择加氢工艺条件的考察,结果表明,加氢精制催化剂适宜的反应条件为370℃、1.25 h~(-1)、8.0 Mpa,加氢精制/选择加氢裂化催化剂适宜的反应条件为350℃、1.25 h~(-1)、8.0 MPa,组合催化剂的多环芳烃选择加氢效果较好。     

The effect of oxygen and the reduction temperature of the Pt/Al2O3 catalyst in enantioselective hydrogenation of 1-phenyl-1,2-propanedione

The effect of oxygen and catalyst reduction temperature in enantioselective hydrogenation of 1-phenyl-1,2-propanedione over commercial Pt/Al₂O₃ catalyst was investigated. Dichloromethane was used as solvent. The catalyst was modified in situ with (−)-cinchonidine. Relatively high enantiomeric excesses (65%) of (R)-1-hydroxy-1-phenyl-2-propanone were obtained with the solvent used as received, i.e. containing traces of dissolved oxygen and other impurities. Dichloromethane dissociated partially on the Pt/Al₂O₃ surface causing desorption of methane, ethene and HCl from the catalyst during TPD according to mass spectrometric analysis. Under anaerobic conditions the reaction rate was low giving only about 40% enantiomeric excesses of (R)-1-hydroxy-1-phenyl-2-propanone. When injecting 5 mm³ of oxygen into the reactor a beneficial effect was observed (i.e. higher reaction rate and enantiomeric excess) in comparison with anaerobic conditions. Poisoning effect of oxygen was observed when injecting 500 mm³ of oxygen into the reactor. Effect of catalyst reduction temperature was studied at three different temperatures (170, 400 and 455°C). Highest reaction rates and enantiomeric excesses were obtained with the catalyst reduced at 400°C. Methane was desorbed from the catalyst at temperatures between 263 and 383°C which could be the explanation for the lower activity of the catalyst reduced at 170°C. It was demonstrated that small amounts of oxygen can have a beneficial effect in enantioselective hydrogenation of 1-phenyl-1,2-propanedione and also that catalyst reduction temperature plays an important role in obtaining high enantiomeric excesses.     

稻壳快速热解制取生物质油的试验研究

目前生物质快速热解高温热解气主要利用间壁式冷却器进行冷凝,容易造成冷却管道的结焦堵塞问题,本试验根据流化床稀相输送特点、生物质的热解特性以及生物质油的冷凝收集特点,设计了生物质快速热解反应装置,改进生物质物快速冷凝系统,以稻壳为原料进行快速热解制取生物质油的试验研究,分别考察单因素反应温度、流化气量以及进料速度对生物质油产率的影响。试验表明:稻壳热解气能够快速顺利地得到冷凝,反应系统能够连续顺利运行,随着反应温度、流化气量、进料速度的增大,生物质油的产率都呈现先增大后减小的趋势。另外对产出的生物质油用气质联用设备进行了成分分析,得出了生物质油的主要成分,其中酸类、酮类、脂类以及酚类的含量相对较高。     

影响Claus尾气加氢催化剂性能的动力学研究

实验室通过对低温Claus尾气加氢催化剂动力学研究,考察了Claus尾气含硫化合物加氢反应的规律。通过对影响Claus尾气加氢催化剂性能的主要因素分析,阐述了过程气中烃类反应导致的催化剂积炭速率与烃含量、催化剂使用温度、催化剂运转时间的关系;通过使用XRD、SEM等技术手段,对热老化前后Claus尾气加氢催化剂晶相、金属分散、孔结构等性质进行测试和表征。从不同角度研究、探讨影响催化剂性能的因素,对于低温Claus尾气加氢催化剂及其配套工艺的开发和应用具有指导意义。     

超临界乙醇体系中苯酚催化加氢的降解规律

目前,液化的生物油与石油粗油成分接近,通常环类化合物含量高,如煤焦油中酚及其衍生物含量占40%以上,急需加氢升级技术。超临界乙醇（243.1℃,6.38MPa）温度、压力条件低,具有良好的传质性能,且为绿色、可再生溶剂。在超临界乙醇体系下的催化加氢是一种油升级有效方式。本文以苯酚为生物油中环类化合物典型模型,在300～400℃、Pt/C催化剂下,探讨超临界乙醇体系下苯酚催化加氢过程。研究分析了超临界乙醇中温度、氢气压力和反应时间对苯酚催化加氢降解规律的影响,并建立了能很好地描述过程中苯酚转化率的动力学模型（R2 = 0.989）。实验表明：该体系下的苯酚催化加氢降解反应的级数为二级,反应的活化能为51.7kJ/mol;尽管升高温度和氢气压力均能提高苯酚的转化率,但温度对转化率的影响更为显著。本研究将为更好地控制反应过程和提高超临界乙醇体系中苯酚的转化率提供参考。