环保型催化剂负压抽吸正压输送筛分系统改进与设计

介绍了硫酸装置催化剂筛分系统采用负压连续吸取筛分、正压稀相气力输送装填系统的工作流程,并对系统的相关工艺参数进行了核定和计算。该系统具有粉尘无泄漏,催化剂取出、筛分、回填损失小的特点,不仅改善了催化剂筛分过程中的作业环境,且减少了催化剂损耗。

催化剂负压连续输送筛分系统的设计与应用

某硫酸装置催化剂筛分系统采用了负压连续输送筛分的方式,介绍了其系统设计分析和工作流程,并对该系统的相关工艺参数进行了核定和计算。根据在3套硫酸装置的催化剂筛分系统中的应用效果来看,与传统主要依靠人工方式的催化剂筛分系统相比,大大减少了劳动力,改善了催化剂筛分过程中的作业环境,对催化剂筛分系统自动化研究具有一定的借鉴意义。

催化裂化装置再生器跑剂原因分析及对策

某公司180×10^(4)t/a催化裂化装置自2019年装置大检修以后出现再生器跑剂问题。文中结合装置检修内容、改造项目以及历年来出现过的问题,逐项分析再生器跑剂可能的原因,最终判断为再生器2级旋风分离器升气管出现问题,并得以验证。通过装置窗口检修期间对损坏部位进行修复,最终解决了再生器跑剂问题。

Adsorptive and catalytic properties in the removal of volatile organic compounds over zeolite-based materials

Volatile organic compounds（VOCs） are a major component in air pollutants and pose great risks to both human health and environmental protection. Currently, VOC abatement in industrial applications is through the use of activated carbons as adsorbents and oxide-supported metals as catalysts. Notably, activated carbons easily adsorb water, which strongly hinders the adsorption of VOCs; conventional oxides typically possess relatively low surface areas and random pores, which effectively influence the catalytic conversion of VOCs. Zeolites, in contrast with activated carbons and oxides, can be designed to have very uniform and controllable micropores, in addition to tailored wettability properties, which can favor the selective adsorption of VOCs. In particular, zeolites with selective adsorptive properties when combined with catalytically active metals result in zeolite-supported metals exhibiting significantly improved performance in the catalytic combustion of VOCs compared with conventional oxide-supported catalysts. In this review, recent developments on VOC abatement by adsorptive and catalytic techniques over zeolite-based materials have been briefly summarized.

PtSnNa/SUZ-4:An efficient catalyst for propane dehydrogenation

The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO techniques combined with propane dehydrogenation tests.It has been shown that SUZ-4-supported PtSnNa（PtSnNa/SUZ-4） was determined to be a better catalyst for propane dehydrogenation than conventional catalysts supported on ZSM-5,owing to its higher catalytic activity and stability.Dibenzothiophene poisoning experiments were performed to investigate the detailed structures of the two supported catalysts.The characterization of the two catalysts indicates that the distribution of Pt on the porous support affects the activity.In contrast to ZSM-5-supported catalysts,Pt particles on the PtSnNa/SUZ-4 are primarily dispersed over the external surface and are not as readily deactivated by carbon deposition.This is because that the strong acid sites of the SUZ-4 zeolite evidently prevented the impregnation of the Pt precursor H_2PtCl_6 into the zeolite.In contrast,the weak acid sites of the ZSM-5 zeolite led to more of the precursor entering the zeolite tunnels,followed by transformation to highly dispersed Pt clusters during calcination.In the case of the PtSnNa/ZSM-5,the interactions between Sn oxides and the support were lessened,owing to the weaker acidity of the ZSM-5 zeolite.The dispersed Sn oxides were therefore easier to reduce to the metallic state,thus decreasing the catalytic activity for hydrocarbon dehydrogenation.

Catalytic Synthesis of Geranyl Propionate

[Objective] The aim was to explore the optimal conditions for the catalytic synthesis of geranyl propionate. [Method] The synthesis of mesoporous molecular sieves Al-MCM-41 was carried out in an open-vessel. The mesoporous structure of as-synthesized Al-MCM-41 was characterized by X-ray diffraction （XRD） pattern, Fourier transform infrared （FT-IR） spectrum, NH3-Temperature Programmed Desorption （TPD）, and N2 adsorption-desorption isotherms. The catalytic performances of Al-MCM-41 for the synthesis of geranyl propionate （GP） with geraniol and propionic acid as reagents also were investigated. [Result] The as-synthesized Al-MCM-41 possesses typical hexagonal mesoporous structure with high long-range order and crystalline degree. Based on the systematic investigation of reaction time, temperature, amount ratio of reagents and regeneration of catalyst, the optimum reaction conditions were obtained with molar ratio of geraniol to propionic acid of 1.0∶1.5, reaction temperature of 120 ℃ and reaction time of 8 h. The high GP selectivity of 70.01% with geraniol conversion of 40.01% was achieved under above optimum conditions. The catalyst inactivation can be observed after five catalytic cycles. The regeneration of inactivated catalyst with high activity and selectivity can be achieved by calcination treatment to remove the carbon deposition, which covers the acid site of catalyst. [Conclusion] The optimal conditions for the synthesis of geranyl propionate were obtained.

Production of Low-carbon Light Olefins from Catalytic Cracking of Crude Bio-oil

Low-carbon light olefins are the basic feedstocks for the petrochemical industry. Catalytic cracking of crude bio-oil and its model compounds （including methanol, ethanol, acetic acid, acetone, and phenol） to light olefins were performed by using the La/HZSM-5 catalyst. The highest olefins yield from crude bio-oil reached 0.19 kg/（kg crude bio-oil）. The reaction conditions including temperature, weight hourly space velocity, and addition of La into the HZSM-5 zeolite can be used to control both olefins yield and selectivity. Moderate adjusting the acidity with a suitable ratio between the strong acid and weak acid sites through adding La to the zeolite effectively enhanced the olefins selectivity and improved the catalyst stability. The production of light olefins from crude bio-oil is closely associated with the chemical composition and hydrogen to carbon effective ratios of feedstock. The comparison between the catalytic cracking and pyrolysis of bio-oil was studied. The mechanism of the bio-oil conversion to light olefins was also discussed.

100万吨/年ARGG装置油浆固含量高原因分析

介绍大庆炼化公司100万吨/年ARGG装置在生产期间出现固含量突然升高时进行的操作调整,并对影响油浆固含量高的各因素进行分析,得出油浆固含量高的原因。

Catalytic Transformation of Bio-oil to Olefins with Molecular Sieve Catalysts

Catalytic conversion of bio-oil into light olefins was performed by a series of molecular sieve catalysts, including HZSM-5, MCM-41, SAPO-34 and Y-zeolite. Based on the light olefins yield and its carbon selectivity, the production of light olefins decreased in the following order： HZSM-5〉SAPO-34〉MCM-41〉Y-zeolite. The highest olefins yield from bio-oil using HZSM- 5 catalyst reached 0.22 kg/kgbio-oil with carbon selectivity of 50.7% and a nearly complete bio-oil conversion. The reaction conditions and catalyst characterization were investigated in detail to reveal the relationship between the catalyst structure and the production of olefins. The comparison between the pyrolysis and catalytic pyrolysis of bio-oil was also performed.

Nanosized and hierarchical zeolites: A short review

Zeolites are crystalline aluminosilicates with three‐dimensional microporous structures. They have been used as ion‐exchangers, catalysts, and adsorbents in various fields such as oil refining, petro‐chemistry, agriculture, and water and wastewater treatment. Their wide use is because of their many beneficial properties, such as framework and compositional flexibilities, physical and hydro‐thermal stabilities, non‐toxicity, high surface areas, exchangeable cations, and good cost‐benefit ratios. Although many zeolite applications depend on their microporous structures, this can cause diffusional constraints for bulky reactant and product molecules. There have been many efforts to overcome the intrinsic limitations of conventional zeolites by preparing nanosized and hierarchi‐cally structured zeolites. As a result of these efforts, several strategies have been established and the use of new zeolitic materials in various catalytic and adsorptive reactions has been investigated. Longer lifetimes, high catalytic performances, and postponed coking and catalyst deactivation can be achieved using hierarchical and nanosized zeolites. The aim of this review is to provide an over‐view of the enhanced properties of hierarchical and nanosized zeolites, and recent development methods for their synthesis. The advantages and disadvantages of each route are discussed, and the catalytic applications of nanozeolites and zeolites with secondary porosity, and a comparison with conventional zeolites, are briefly presented.

Methane combustion over palladium catalyst within the confined space of MFI zeolite

Isolated cationic Pd species encapsulated in MFI zeolite,i.e.,Pd@MFI,have been successfully prepared via in situ hydrothermal route followed by oxidative treatment.The as-prepared Pd@MFI samples are investigated as promising catalysts in the reaction of methane combustion.Typically,Pd@H-ZSM-5 shows remarkable activity in methane catalytic combustion with a low apparent activation energy value of 70.7 kj/mol as well as good catalytic stability even in excess water vapor.Detailed characterization results demonstrate the strong interaction between Pd sites and zeolite framework in Pd@ZSM-5 and the efficient stabilization of isolated Pd sites by zeolite thereof.Spectroscopy analyses reveal that the presence of BrΦnsted acid sites is beneficial to methane adsorption and its subsequent activation on adjacent Pd sites,constructing cooperation between Bronsted acid sites and Pd sites within the confined space of MFI zeolite toward high-efficiency methane catalytic combustion.The reaction mechanism of methane combustion catalyzed by Pd@H-ZSM-5 model catalyst is finally discussed.

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study,various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5.The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied.The results of XRD,TEM N_2-adsorption-desorption,NH_3-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals,and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5.Catalytic cracking of n-dodecane(550℃,4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance,with the improvement higher than 87%in the catalytic activities and 21%in the deactivation rate compared with untreated zeolites.This could be ascribed to their suitable pore structure,which enhanced the diffusion of reactant molecules in pores of catalysts.

Disproportionation of Toluene by Modified ZSM-5 Zeolite Catalysts with High Shape-selectivity Prepared Using Chemical Liquid Deposition with Tetraethyl Orthosilicate

Shape-selective catalysts for the disproportionation of toluene were prepared by the modification of the cylinder-shaped ZSM-5 zeolite extrudates with chemical liquid deposition with TEOS （tetraethyl orthosilicate）.Various parameters for preparing catalysts were changed to investigate the suitable conditions.The resulting cata-lysts were tested in a pressured fixed bed reactor and characterized by SEM （scanning electron microscopy）.The conversion of toluene and para-xylene selectivity were influenced remarkably by the n（SiO2）/n（Al2O3） ratio of ZSM-5 zeolite,the type and amount of deposition agent,acid and solvent used,and the time and cycle of deposition treatment.TEOS was proved to be a more efficient agent than the conventional polysiloxanes when the deposition amount was low.The catalyst prepared at the suitable conditions exhibited a high para-xylene selectivity of 91.1% with considerable high conversion of 25.6%.SEM analyses confirmed the formation of a layer of amorphous silica on the external surface of ZSM-5 zeolie crystals,which was responsible for the highly enhanced shape-selectivity.

Synthesis of ZSM-5/MOR Co-crystalline Zeolite without Template and the Catalytic Application Thereof

A ZSM-5/MOR co-crystalline zeolite was synthesized without using the template. The physico-chemical properties of the zeolite were characterized by XRD, FT-IR, SEM and TPD and then compared with the co-crystalline zeolite synthesized with a template. Analytical results indicated that they were similar in structure and composition. The influences ofpH value and Si/Al ratio on synthesis were studied. It was found that a high pH value or a low Si/AI ratio could provide better environment for mordenite （MOR） crystallization. The zeolites applied as catalysts in naphtha catalytic cracking for producing ethylene and propylene showed outstanding catalytic performance with the total yield of ethylene and propylene reaching 55 m%. The process could achieve most favorable efficiency when the catalyst contained 5 m% of MOR.

Catalytic cracking of 1-butene to propylene by Ag modified HZSM-5

Silver modified HZSM-5 （AgHZ） zeolite catalysts were prepared by ion exchange method and their catalytic properties in the l-butene cracking reaction were measured. The catalysts were characterized by infrared spec- troscopy with pyridine adsorption （Py-IR）, N2 adsorption and X-ray diffraction （XRD）. The effects of Ag loading and steaming treatment on catalytic performances were studied. It is found that the activity ofHT_SM-5 （HZ） catalyst significantly decreases with the steaming time, whereas AgHZ catalysts show stable activity in the steaming time of 24-48 h and their activities increase with the Ag loading. When the steaming time is 24-48 h, the yield of propylene over HZ catalyst significantly decreases, whereas it is stable over AgHZ catalysts. The AgHZ catalysts with Ag loadings of 0.28%-0.43% （by mass） show similar propylene yields （-30%）, which are higher than that over the AgHZ catalyst with a Ag loading of 0.55% （by mass）. These results indicate that the steam-treated AgHZ catalysts with optimum Ag loadings have higher yield of propylene and are more stable than the steam- treated HZ catalyst. The regeneration stability measurement in butene cracking also shows that the AgHZ catalyst steam-treated under a suitable condition has better stability than the HZ catalyst.

Single-step conversion of lignin monomers to phenol: Bridging the gap between lignin and high-value chemicals

Transformation of lignin into high-value chemicals is hampered by the complexity of monomers obtained from lignin depolymerization. Here we report a strategy, composed of hy-dro-demethoxylation and de-alkylation reactions, that is able to chemically converge various lig-nin-derived phenolic monomers into phenol in a single-step. Using 2-methoxy-4-propylphenol as a model compound, Pt/C exhibited the best performance in hydro-demethoxylation reaction afford-ing 80% 4-propylphenol from 2-methoxy-4-propylphenol, while H-ZSM-5 was identified as the most suitable catalyst for de-alkylation, achieving 83% yield of phenol from 4-propylphenol. Since the two catalysts operate under compatible conditions, combining the two catalysts to simultane-ously promote both hydro-demethoxylation and de-alkylation reactions was achieved. Configura-tion of how to organize the catalysts is a critical parameter, where the physical mixture of the two was most effective, providing over 60% phenol from 2-methoxy-4-propylphenol in a single-step.

Tandem Lewis acid catalysis for the conversion of alkenes to 1,2‐diols in the confined space of bifunctional TiSn‐Beta zeolite

The generation of multifunctional isolated active sites in zeolite supports is an attractive method for integrating multistep sequential reactions into a single‐pass tandem catalytic reaction.In this study,bifunctional TiSn‐Beta zeolite was prepared by a simple and scalable post‐synthesis approach,and it was utilized as an efficient heterogeneous catalyst for the tandem conversion of alkenes to 1,2‐diols.The isolated Ti and Sn Lewis acid sites within the TiSn‐Beta zeolite can efficiently integrate alkene epoxidation and epoxide hydration in tandem in a zeolite microreactor to achieve one‐step conversion of alkenes to 1,2‐diols with a high selectivity of>90%.Zeolite confinement effects result in high tandem rates of alkene epoxidation and epoxide hydration as well as high selectivity toward the desired product.Further,the novel method demonstrated herein can be employed to other tandem catalytic reactions for sustainable chemical production.

Stabilizing copper species using zeolite for ethanol catalytic dehydrogenation to acetaldehyde

The selective dehydrogenation of ethanol to acetaldehyde is a promising route for acetaldehyde production.Although Cu-based catalysts exhibit high activity in ethanol dehydrogenation,a rapid deactivation due to Cu sintering always occurs.In this study,highly dispersed Cu species were stabilized using the silanol defects in Beta zeolite(denoted as Beta)resulting from dealumination,and applied as robust catalysts for ethanol-to-acetaldehyde conversion.Typically,a long catalyst lifetime of 100 h with an acetaldehyde yield of^70%could be achieved over 5%Cu/Beta.The presence of Cu^+and Cu0 species and the agglomeration of Cu particles after a long-term reaction for 180 h were revealed by transmission electron microscopy,thermogravimetric analysis,and CO-diffuse-reflectance infrared Fourier transform spectroscopy,and were responsible for the deactivation of the Cu/Beta catalyst in the ethanol-to-acetaldehyde conversion.

Direct hydrothermal synthesis of Mo-containing MFI zeolites using Mo-EDTA complex and their catalytic application in cyclohexene epoxidation

A series of Mo-containing MFI zeolites with different Mo loadings(Mo-MFI-n,n represent the initial Si/Mo molar ratio)was hydrothermally synthesized by using tetrapropylammonium hydroxide as the template and Mo-EDTA complex as the Mo source.Various characterization results demonstrated that the use of the Mo-EDTA complex is beneficial for the incorporation of more Mo species into the MFI-type zeolites.The special complexing capability of EDTA^(2–)plays a critical role in adjusting the release rate of the Mo species to combine with the Si tetrahedron species during the zeolite growth process,thus leading to a uniform distribution of Mo in the MFI framework.In addition,a small portion of extra-framework Mo clusters may be distributed inside the channels or near the pore window of the zeolites.The catalytic properties of these Mo-containing MFI zeolites were evaluated for the epoxidation of cyclohexene with H_(2)O_(2)as the oxidant.The composition-optimized catalyst,Mo-MFI-50,efficiently converted cyclohexene to the corresponding epoxide with a relatively high conversion(93%)and epoxide selectivity(82%)at 75℃after 9 h of reaction.Moreover,the resultant Mo-containing MFI catalyst exhibited excellent structural stability and recoverability and was easily recycled by simple filtration without the need for calcination treatment.

Study of M-ZSM-5 nanocatalysts(M: Cu, Mn, Fe, Co …) for selective catalytic reduction of NO with NH_3: Process optimization by Taguchi method

A series of different transition metals(V,Co,Cr,Mn,Fe,Ni,Cu and Zn) promoted H-ZSM-5 catalysts were prepared by impregnation method and characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The catalytic activity of these catalysts was evaluated for the selective catalytic reduction(SCR) of NO with NH_3 as reductant in the presence of oxygen.The results revealed that the catalytic activity of Cu-ZSM-5 nanocatalyst for NO conversion to N_2 was 80%at 300 ℃,which was the best among various promoted metals.Design of experiments(DOEs) with Taguchi method was employed to optimize NH_3-SCR process parameters such as NH_3/NO ratio,O_2 concentration,and gas hourly space velocity(GHSV) over Cu-ZSM-5 nanocatalyst at 250 and 300 ℃.Results showed that the most important parameter in NH_3-SCR of NO is O_2 concentration;followed by NH_3/NO ratio and GHSV has little importance.The NO conversion to N_2 of 63.1%and 94.86%was observed at 250℃ and 300℃,respectively under the obtained optimum conditions.