The correlation between nitrogen species in coke and NOx formation during regeneration☆

Nitrogen oxides(NO x)emission during the regeneration of coked fluid catalytic cracking(FCC)catalysts is an environmental issue.In order to identify the correlations between nitrogen species in coke and different nitrogencontaining products in tail gas,three coked catalysts with multilayer structural coke molecules were prepared in a fixed bed with model compounds(o-xylene and quinoline)at first.A series of characterization methods were used to analyze coke,including elemental analysis,FT-IR,XPS,and TG–MS.XPS characterization indicates all coked catalysts present two types of nitrogen species and the type with a higher binding energy is related with the inner part nitrogen atoms interacting with acid sites.Due to the stronger adsorption ability on acid sites for basic nitrogen compounds,the multilayer structural coke has unbalanced distribution of carbon and nitrogen atoms between the inner part and the outer edge,which strongly affects gas product formation.At the early stage of regeneration,oxidation starts from the outer edge and the product NO can be reduced to N_2 in high CO concentration.At the later stage,the inner part rich in nitrogen begins to be exposed to O_2.At this period,the formation of CO decreases due to lack of carbon atoms,which is not bene ficial to the reduction of NO.Therefore,nitrogen species in the inner part of multilayer structural coke contributes more to NO X formation.Based on the multilayer structure model of coke molecule and its oxidation behavior,a possible strategy to control NO X emission was discussed merely from concept.     

分子筛催化剂积炭失活行为探讨

反应过程中生成的重质副产物积炭堵塞孔道是造成酸性分子筛催化剂失活的主要因素.影响积炭的因素有催化剂的孔道结构、酸性以及操作条件.对分子筛催化剂积炭失活机理、积炭表征技术、影响因素和抑制措施进行了综述,并介绍了一种积炭分离方法,对分子筛催化剂积炭研究的发展趋势进行了分析.     

Deactivation by coke of a catalyst based on a SAPO‐34 in the transformation of methanol into olefins

When methanol is converted to olefins on a SAPO‐34 catalyst between 350 and 425°C, there is a rapid initial formation of coke, followed by a slower rate of coke deposition. The rate of coke formation decreases with increasing temperature, and with progression through the catalyst bed. The coke completely blocks the internal channels of the SAPO‐34 crystals and subsequently blocks the mesopores (intercrystalline and those of the bentonite). Coke deposition mainly blocks sites of acidic strength above 175 kJ mol⁻¹. The presence of water in the feed lessens coke formation, either by converting Lewis to Brønsted sites or by competing for surface sites with coke precursors. © 1999 Society of Chemical Industry     

Study of Coke and Coke Precursors During Catalytic Cracking of n-Hexane and 1-Hexene over Ultrastable Y Zeolite

In this paper we report about coke formation during catalytic cracking of n-hexane and 1-hexene over acidic ultrastable Y zeolite in a fixed-bed reactor. The study is based on a classification between coke precursors, whose amount is estimated through volatilisation by nitrogen purging, and coke, large formed coke molecules that remain during nitrogen purging even at 873 K and whose amount is estimated by oxidation at that temperature. The role of coke precursors on the coking process and catalytic cracking reaction is discussed as well as differences in coking tendencies between the two reactants. The results show that the amount of coke precursors and/or coke may decrease with reaction temperature resulting into a reversal of the coking dependence upon temperature.     

Spectroscopic investigations on deactivation of zeolite catalysts during reactions of olefins

Coke formation over acidic zeolite catalysts upon reaction of olefins is investigated using in-situ IR spectroscopy, i.e. an IR cell which simultaneously serves as a fixed-bed flow reactor and is attached to a gas chromatograph. Zeolites HY, dealuminated H-MOR with two different Si/Al ratios and H-ZSM-5 are compared. The effects of the number of active sites and the pore volume of the zeolites on the initial rate of coke formation and the final coke level are studied.

The final level of coke deposition reflects to some extent the pore volume of the zeolite catalyst. In all cases a considerable amount of coke formed remained inside the pore structure but another fraction was deposited onto the external surface. Both findings were confirmed by sorption measurements on samples before and after loading with coke.

Possible mechanisms of deactivation through coke formation, viz, poisoning, consumption or blockage of sides are briefly considered. In-situ IR spectroscopy revealed that at most a small fraction of the active sites of HY, HMOR or HZSM-5 disappeared during coke deposition suggesting that deactivation is caused by site blocking rather than by poisoning or consumption of the acidic centres.

Finally, in-situ IR spectroscopy turned out to be a useful tool for discriminating between low-temperature coke (formed below about 500 K) and high-temperature coke (deposited above 500 K).     

Effect of acid strength distribution on de-t-butylation rate and catalyst fouling rate

De-t-butylation of t-butylbenzenes was carried out over a pyridine poisoned solid acidic catalyst to determine the effect of acid strength distribution on the reaction rate and catalyst fouling rate. The acid sites on the solid acidic catalyst were divided into three groups by their acid strength. Moderate acid sites, which were effective for the de-t-butylation but ineffective for the coke formation, were exclusively left on the catalyst surface by the partial poisoning. It is found that the present modification of the catalyst is useful in preparing an acid catalyst without catalyst fouling by coke deposition.     

Reduction of nitrogen dioxide by propene over acidic mordenites: influence of acid site concentration, formation of by-products and mechanism

The reduction of nitrogen dioxide to nitrogen by propene was studied over a variety of acidic mordenite zeolites differing in their Si : Al ratio and thus, in their concentration of acid sites. The formation of by-products was monitored applying an ion–molecule reaction (IMR) mass spectrometer. It was found that at fixed conditions the yield of nitrogen increases with increasing concentration of acid sites, confirming that acid sites are the active catalytic centres in the reaction. Apart from nitrogen and nitric oxide, acrylonitrile and ammonia are formed as nitrogen containing gas-phase products in the reaction. In separate experiments, it was shown that acrylonitrile is hydrolysed by water over the acidic zeolites to yield ammonia and acrylic acid. When acrylonitrile is used as reducing agent for nitrogen dioxide, formation of nitrogen is strongly enhanced in the presence of water. Water also has a promoting effect on the formation of nitrogen in the reaction between nitrogen dioxide and propene. Acrylonitrile and its product of hydrolysis, ammonia, are considered to be intermediates of nitrogen dioxide reduction to nitrogen by propene over acidic zeolites.     

金属助剂对邻二甲苯氧化制苯酐催化剂影响的研究进展

介绍了邻二甲苯氧化制苯酐的反应机理及其催化剂的制备、评价与分析方法,重点就金属助剂对催化剂影响的研究进展进行了分析。结果表明,添加金属助剂可改变V-Ti系催化剂的活性、稳定性和对苯酐的选择性,其中Rb、K、Sb的引入可减少邻二甲苯的深度氧化,提高催化剂对苯酐的选择性;Nb、Sn、W和Cs的引入会改变催化剂表面的酸性位点和浓度,对催化剂的活性和选择性造成不同影响;Zr的引入提高了催化剂的热稳定性和选择性;稀土元素La、Pr、Sm、Nd的引入可提高苯酐的收率和选择性。     

MCM-48负载SO42-/ZrO2定位催化硝化合成3,4-二甲基硝基苯

采用液相沉积法制备了由MCM–48介孔分子筛负载SO42－／ZrO2的催化剂,探讨了催化剂表面的成酸过程和催化定位硝化反应机理,并以邻二甲苯和硝酸定位硝化反应为探针反应,考察了催化剂的性能;用酸碱滴定、TEM、N2吸附-脱附和Hammett指示法表征了固体超强酸。结果表明,固体超强酸保持了MCM-48的介孔结构,BET表面积高达208 m2/g,表面含有质子酸和路易斯酸中心,且具有强酸性（H0＜－13.75）;得到适宜的工艺条件：催化剂培烧温度500 ℃,反应温度60 ℃,n(硝酸)/n(邻二甲苯)＝2.5,m(邻二甲苯)/m(催化剂)＝25,反应时间3 h,产物收率为91.8%,含量达到82.1%。     

有机含氮化合物对深度加氢脱硫反应的影响

从燃料油中含氮化合物和含硫化合物特点出发,介绍了含氮化合物对加氢脱硫（HDS）催化剂活性、选择性以及失活等性能的影响。研究表明,含氮化合物主要通过与含硫化合物在催化剂表面的竞争吸附,强烈抑制HDS催化剂活性。含氮化合物对含硫化合物加氢（HYD）和氢解（HYG）两条并行反应路径均有抑制作用,但对HYD反应路径的抑制作用更为强烈。含氮化合物还能通过毒化催化剂酸中心进而影响催化剂HDS活性和选择性,而其在催化剂表面的强烈吸附也是引发催化剂结焦和失活的重要因素。     

Mechanism of coke deposition on the surface of molybdenite

The formation of coke is studied by SEM/TEM on the basal plane of a thin (ca. 500 Å) single-crystal film of MoS₂. From exposure to benzene at 550 and 700 °C, which is exothermic in decomposition, carbon islands are formed on the face opposite to the exposure face; whereas for the endothermic decomposition of methane (at 700 °C), carbon islands are formed on the exposure face. This result provides a direct evidence for the carbon diffusion mechanism for coke deposition in which a temperature gradient is the driving force for carbon diffusion. It is demonstrated that the formation and growth of thin (perhaps monolayer) carbon islands can be studied by gold decoration/TEM. A gold-decoration/TEM study of coke formation of benzene on MoS₂ show that screw dislocations are not preferred sites for carbon deposition, and that steps on the basal plane are likely the active sites for decomposition of benzene.     

β分子筛的金属离子改性及其择形催化性能研究

从β分子筛的改性入手,考察各种离子浸渍改性对β分子筛催化萘烷基化反应的影响。通过催化剂表面酸性和晶体结构等的表征,探讨不同离子改性对催化剂性能的影响规律及其改性机制。结果表明,5％的硝酸铜改性Hβ的效果较好,在保证转化率基本不变的前提下,β,β-DIPN选择性以及2,6-DIPN与2,7-DIPN的比值均有所提高,而多取代产物比例下降。酸性与BET表征结果表明,铜改性后选择性的提高是由于外表面酸性活性位的降低,同时,由于CuO对孔口有一定的修饰作用,同时拥有适度的生焦,从而使产物分布发生变化,提高了催化剂的选择性,而分子筛的有效孔径并未发生改变。     

Effect of the metallic/acid site (nPt/nA) ratio on the transformation of acetone towards methyl isobutyl ketone

Methyl isobutyl ketone (MIBK) was synthesized from acetone (Ac) and hydrogen over Pt-HZSM5 bifunctional catalysts. The reaction was carried out at 160°C, atmospheric pressure, and with a P_H2/PAc molar ratio = 0.33, using a fixed bed and dynamic flow reactor. The results show that catalytic properties and coke formation largely depend on the ratio between the number of accessible hydro-dehydrogenation sites and the number of theoretical acidic sites (nPt/nA). This revised version was published online in July 2006 with corrections to the Cover Date.     

石油加工过程中焦炭形成的原因、类型及影响因素

回顾了多种烃类分子裂解生焦的机理,指出多环芳烃是石油加工过程中焦炭形成的反应中间体。从分子化学反应水平上综述了3种生焦机理:多相催化结焦、多相非催化结焦、均相非催化结焦,研究表明:较高温度下烷烃催化裂解过程中,焦炭的组成与裂解反应深度有关,但不受烷烃分子结构的影响;热裂解过程中,异构烷烃的生焦速率大于正构烷烃,烯烃、芳烃具有较大的生焦趋势,且芳烃裂化的生焦量与物质的碱性对数线性相关。依据显微结构的不同,焦炭可以分为3类:点状焦炭、镶嵌状焦炭和纤维状焦炭,相关研究表明:焦的结构特性与中间相形态有关,可塑性好的碳质中间相易聚合、溶并形成各向异性的纤维状焦炭。工艺过程中,原料的性质、催化剂及添加剂种类、工艺操作条件等因素都会影响焦炭的生成。     

烃类裂解结焦机理的研究

烃类高温裂解生产乙烯过程中 ,炉管管壁结焦不仅导致传热系数下降 ,压力降增大 ,管子腐蚀 ,还会堵塞炉管 ,影响裂解炉正常运转 ,因此研究结焦机理 ,从而更有效地抑制结焦一直受到人们的重视。结焦过程涉及到不同形式的焦油和炭的复杂过程 ,虽报道的文章很多 ,但确切机理尚不清楚。目前综合国内外的有关文献报道 ,对烃类热裂解过程中的结焦机理进行了详细综述 ,着重阐述了以金属碳化物为中间产物的金属催化反应 ,即金属催化结焦 ;非催化结焦 ;自由基结焦三种结焦机理。同时叙述了用此三种结焦机理如何解释实验室和工业装置的结焦状况。为进一步探索结焦机理开发新的结焦抑制技术奠定了一定的基础。     

乙烯裂解炉结焦抑制技术研究

介绍了乙烯裂解炉的结焦机理、影响结焦的主要因素和抑制炉管结焦的主要技术。     

乙烯裂解炉结焦抑制技术研究

介绍了乙烯裂解炉的结焦机理、影响结焦的主要因素和抑制炉管结焦的主要技术。     

Kinetic investigations of the deactivation by coking of a noble metal catalyst in the catalytic hydrogenation of nitrobenzene using a catalytic wall reactor

The vapour phase hydrogenation of nitrobenzene to aniline is a highly exothermic reaction deactivated by coking of the palladium catalyst supported on -alumina carrier. For studying the deactivation of the catalyst a catalytic wall reactor was used in order to ensure isothermal reaction conditions for the kinetic measurements. Furthermore, the catalytic wall reactor allowed the determination of axial coke profiles by total carbon analysis of different wall segments. On the assumption that the main reaction and the deactivation of the catalyst can be assumed separable both the steady state and the unsteady state kinetics were studied. Nitrobenzene was identified as the relevant coke precursor whereas aniline has neither an influence on the main reaction nor on the deactivation. It could be shown that the hydrogenation of nitrobenzene to aniline follows a Langmuir–Hinshelwood mechanism considering the surface reaction of the adsorbed nitrobenzene molecule and one adsorbed hydrogen atom as the rate determining step. The differentiation of coke on the active sites and coke on the support must be taken into account to model the kinetics of coke formation with sufficient accuracy.     

催化裂化结焦反应的研究进展

综述了近年来催化裂化结焦反应的研究进展情况,重点介绍了结焦反应的影响因素、焦炭对催化反应的影响、结焦机理以及焦炭的表征4个方面。研究认为,原料的性质、反应温度、催化剂的类型等因素均会对焦炭的生成产生影响。焦炭可以导致催化剂的失活,而位于孔道内部的焦炭对反应物或产物的扩散不利,进而影响产物的分布。研究表明,各种烃类组分形成焦炭的过程都必须经历芳香烃这一步。对于结焦催化剂可以采取多种表征手段,其中利用XPS以及GC-MS对焦炭进行表征的报道日益增多。尽管国内外对于催化裂化结焦反应的研究开展较早,然而探究焦炭的具体成分仍存在不小的困难,通过先进的表征手段鉴定焦炭中高缩合度芳烃组分以及如何减小催化裂化催化剂的结焦量将成为未来的研究方向。     

Coking characteristics of reforming catalysts

Coking rates were measured for two different γ-aluminas, each with and without platinum, under near commercial conditions using a gravimetric reactor. Coke on catalyst was characterized by a Temperature-Programmed Oxidation (TPO) technique. With a naphtha feed, coke formed on both aluminas at rates related to the respective population of α-sites as measured by IR. For the corresponding Pt on alumina catalysts, coke, as measured by TPO, predominantly formed on sites associated with alumina (“alumina coke”), while coke associated with Pt (“Pt coke”), was relatively minor. With a n-heptane feed, under the same conditions, coke formation on both aluminas was much less than with the naphtha feed. However, the corresponding Pt on alumina catalysts generated comparatively more coke with a higher proportion associated with Pt. A correspondence between this proportion of “Pt coke” and the decline in reforming activity was observed. It is postulated that most of the coke produced during naphtha reforming with an active catalyst is formed by a reaction between α-sites on alumina and certain components in the feed via a polymerization mechanism. This type of coke has minimal effect on the reforming reactivity of the catalyst. However, in n-heptane reforming, about 50% of the coke also results from precursors formed from reactions with Pt. In either case, coke associated with Pt appears to be the probable cause of deactivation.