Reaction characteristics of maximizing light olefins and decreasing methane in C_(5) hydrocarbons catalytic pyrolysis

When converting C_(5) hydrocarbons to light olefins by catalytic pyrolysis,the generation of low value-added methane will affect the atomic utilization efficiency of C_(5) hydrocarbons.To improve the atomic utilization efficiency,different generation pathways of light olefins and methane in the catalytic pyrolysis of C_(5) hydrocarbons were analyzed,and the effects of reaction conditions and zeolite types were inves-tigated.Results showed that light olefins were mainly formed by breaking the C_(2)-C_(3) bond in the middle position,while methane was formed by breaking the C_(1)-C_(2) bond at the end.Meanwhile,it was discovered that the hydrogen transfer reaction could be reduced by about 90%by selecting MTT zeolite with 1D topology and FER zeolite with 2D topology under high weight hourly space velocity(WHSV)and high temperature operations,thus leading to the improvement of the light olefins selectivity for the catalytic pyrolysis of n-pentane and 1-pentene to 55.12% and 74.60%,respectively.Moreover,the fraction ratio of terminal C_(1)-C_(2) bond cleavage was reduced,which would reduce the selectivity of methane to 6.63%and 1.83%.Therefore,zeolite with low hydrogen transfer activity and catalytic pyrolysis process with high WHsV will be conducive to maximize light olefins and to decrease methane.

Production of Light Olefins from Biosyngas by Two-stage Catalytic Conversion Process via Dimethyl Ether

NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas （H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%） with low H/C ratio of 1.0 was used as feed gas.

Effects of zinc on Fe-based catalysts during the synthesis of light olefins from the Fischer-Tropsch process

Fe‐based catalysts for the production of light olefins via the Fischer‐Tropsch synthesis were modi‐fied by adding a Zn promoter using both microwave‐hydrothermal and impregnation methods. The physicochemical properties of the resulting catalysts were determined by scanning electron mi‐croscopy, the Brunauer‐Emmett‐Teller method, X‐ray diffraction, H2 temperature‐programed re‐duction and X‐ray photoelectron spectroscopy. The results demonstrate that the addition of a Zn promoter improves both the light olefin selectivity over the catalyst and the catalyst stability. The catalysts prepared via the impregnation method, which contain greater quantities of surface ZnO, exhibit severe carbon deposition following activity trials. In contrast, those materials synthesized using the microwave‐hydrothermal approach show improved dispersion of Zn and Fe phases and decreased carbon deposition, and so exhibit better CO conversion and stability.

TiO_2 supported cobalt-manganese nano catalysts for light olefins production from syngas

Cobalt-manganese nano catalysts were prepared by sol-gel method. This research investigated the effects of different cobalt-manganese （Co/Mn = 1/1） loading, pH and calcination conditions on the catalytic performance of Co-Mn/TiO2 catalysts for Fischer-Tropsch synthesis （FTS） in a fixed bed reactor. It was found that the catalyst containing 30wt%（Co-Mn）/TiO2 was an optimal catalyst for the conversion of synthesis gas to light olefins especially propylene. The activity and selectivity of optimal catalyst were studied under different operational conditions. The results showed that the best operational conditions were H2/CO = 1/1 molar feed ratio at 250 ℃ and GHSV = 1300 h-1 un- der atmospheric pressure. Characterization of catalysts was carried out by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, N2 adsorption-desorlation measurements.

Fe-modified HZSM-5 catalysts for ethanol conversion into light olefins

A series of Fe/HZSM-5 catalysts with different iron loadings were prepared by impregnation method.Characterization was performed by N2 adsorption-desorption,X-ray diffraction（XRD）,NH3 temperature-programmed desorption（NH3-TPD）,temperature-programmed reduction （TPR）,temperature-programmed oxidation（TPO）and thermogravimetry（TG）analysis.Iron content in the synthesized samples varied from 1.1 wt%to 20 wt%.The obtained samples have been used for ethanol conversion into light olefins.It was found that the amount of strong acidity at 300 -5 50-C on Fe-modified samples was decreased,going with another new acid site appearance at 550- 600-C and that Fe/HZSM-5 catalysts were highly selective towards light olefins,especially the 9FZ sample.In addition,Fe-modified catalysts suppressed the conversion of ethanol to aromatics and paraffins and enhanced their anti-carbon deposit ability.

Empirical modeling of normal/cyclo-alkanes pyrolysis to produce light olefins

Due to the complexity of feedstock,it is challenging to build a general model for light olefins production.This work was intended to simulate the formation of ethylene,propene and 1,3-butadiene in alkanes pyrolysis by referring the effects of normal/cyclo-structures.First,the pyrolysis of n-pentane,n-hexane,n-heptane,n-octane,n-nonane,n-decane,cyclohexane,methylcyclohexane,n-hexane and cyclohexane mixtures,and n-heptane and methylcyclohexane mixtures were carried out at 650–800℃,and a particular attention was paid to the measurement of ethylene,propene and 1,3-butadiene.Then,pseudo-first order kinetics was taken to characterize the pyrolysis process,and the effects of feedstock composition were studied.It was found that chain length and cyclo-alkane content can be qualitatively and quantitively represented by carbon atom number and pseudo-cyclohexane content,which made a significant difference on light olefins formation.Furthermore,the inverse proportional/quadratic function,linear function and exponential function were proposed to simulate the effects of chain length,cycloalkane content and reaction temperature on light olefins formation,respectively.Although the obtained empirical model well reproduced feedstock conversion,ethylene yield and propene yield in normal/cycloalkanes pyrolysis,it exhibited limitations in simulating 1,3-butadiene formation.Finally,the accuracy and flexibility of the present model was validated by predicting light olefins formation in the pyrolysis of multiple hydrocarbon mixtures.The prediction data well agreed with the experiment data for feedstock conversion,ethylene yield and propene yield,and overall characterized the changing trend of 1,3-butadiene yield along with reaction temperature,indicating that the present model could basically reflect light olefins production in the pyrolysis process even for complex feedstock.

Effects of Vanadium Oxidation Number on Light Olefins Selectivity of FCC Catalyst

Effects of vanadium on light olefins selectivity of FCC catalysts were investigated with vanadium having different oxidation numbers （hereinafter abbreviated as Oxnum）. Molecular modeling studies showed that vanadium with low Oxnum could affect the chemical conversion of large-size hydrocarbon molecules. However, the vanadium deposited on equilibrium catalyst bad high Oxnum because of the oxidation reaction taking place in the regenerator, so an activation method to reduce vanadium Oxnum named ＂selective activation＂ was introduced. It was proved by means of Electron Paramagnetic Resonance （EPR） and Temperature-Programmed Reduction （TPR） methods that the vanadium Oxnum was decreased, when the catalyst was activated. The molecular modeling studies are consistent well with the lab evaluation results. The light olefins selectivity of activated equilibrium catalysts was better than that achieved by the inactivated catalysts. Similar results were observed with the lab vanadium-contaminated catalyst. The light olefins selectivity of the catalyst was optimized when the vanadium Oxnum was close to 2 （VO）.

Effect of preparation methods on the structure and catalytic performance of Fe–Zn/K catalysts for CO2 hydrogenation to light olefins

Potassium promoted iron–zinc catalysts prepared by co-precipitation method(C–Fe–Zn/K),solvothermal method(S–Fe–Zn/K)and hydrothermal method(H–Fe–Zn/K)could selectively convert CO_2to light olefins,respectively.The physicochemical properties of the obtained catalysts were determined by SEM,N_2physisorption,XRD,H_2-TPR,CO_2-TPD and XPS measurements.The results demonstrated that preparation methods had great influences on the morphology,phase structures,reduction and adsorption behavior,and hence the catalytic performance of the catalysts.The samples prepared by hydrothermal and co-precipitation method generated small uniform particles and led to lower specific surface area.In contrast,microspheres with larger specific surface area were formed by self-assembly of nanosheets using solvothermal method.ZnFe_2O_4was the only detectable phase in the fresh C–2Fe–1Zn/K,S–3Fe–1Zn/K and S–2Fe–1Zn/K samples.ZnFe_2O_4and ZnO co-existed with increasing Zncontent in S–1Fe–1Zn/K sample,while ZnO and Fe_2O_3could be observed over H–2Fe–1Zn/K sample.All the used samples contained Fe_3O_4,ZnO and Fe_5C_2.The peak intensity of ZnO was strong in the AR-H–2Fe–1Zn/K sample while it was the lowest in the AR-C–2Fe–1Zn/K sample after reaction.The formation of ZnFe_2O_4increased the interaction between iron and zinc for C–2Fe–1Zn/K and S–Fe–Zn/K samples,causing easier reduction of Fe_2O_3to Fe_3O_4.The surface basicity of the sample prepared by co-precipitation method was much more than that of the other two methods.During CO_2hydrogenation,all the catalysts showed good activity and olefin selectivity.The CO selectivity was increased with increasing Zncontent over S–Fe–Zn/K samples.H–2Fe–1Zn/K catalyst preferred to the production of C_5^+hydrocarbons.CO_2conversion of 54.76%and C_2~=–C_4~=contents of 57.38%were obtained on C–2Fe–1Zn/K sample,respectively.

Synthesis,characterization and catalytic performance of nanosized iron-cobalt catalysts for light olefins production

Nanosized Fe-Co catalysts were prepared by co-precipitation method and studied for the conversion of synthesis gas to light olefins.In particular,the effects of a range of preparation variables such as Co/Fe molar ratios of the precipitation solution,pH value of precipitate,temperature of precipitation,promoters and loading of optimum promoter on the structure and catalytic performance are investigated.The optimal nano catalyst for light olefins （C2-C4） production was obtained over the catalyst with Co/Fe molar ratio of 3/1 which promoted with 2 wt% K.The results show that the best operational conditions were GHSV=2200 h^-1 （H2/CO=2/1） at 260℃ under atmospheric pressure.Characterization of catalysts were carried out using X-ray diffraction （XRD）,thermal gravimetric analysis （TGA）,differential scanning calorimetry （DSC）,scanning electron microscopy （SEM）,transmission electron microscopy （TEM） and N2 physisorption measurements such as Brunauer-Emmett-Teller （BET） and Barrett-Joyner-Halenda （BJH） methods.

One-step conversion of syngas to light olefins over bifunctional metal-zeolite catalyst

Light olefins(C_(2)–C_(4))are fundamental building blocks for the manufacture of polymers,chemical intermediates,and solvents.In this work,we realized a composite catalyst,comprising MnxZry oxides and SAPO-34 zeolite,which can convert syngas(CO+H_(2))into light olefins.MnxZry oxide catalysts with different Mn/Zr molar ratios were facilely prepared using the coprecipitation method prior to physical mixing with SAPO-34 zeolite.The redox properties,surface morphology,electronic state,crystal structure,and chemical elemental composition of the catalysts were examined using H_(2)-TPR,SEM,XPS,XRD,and EDS techniques,respectively.Tandem reactions involved activation of CO and subsequent hydrogenation over the metal oxide catalyst,producing methanol and dimethyl ether as the main reaction intermediates,which then migrated onto SAPO-34 zeolite for light olefins synthesis.Effects of temperature,pressure and reactant gas flow rate on CO conversion and light olefins selectivity were investigated in detail.The Mn_(1)Zr_(2)/SAPO-34 catalyst(Mn/Zr ratio of 1:2)attained a CO conversion of 10.8%and light olefins selectivity of 60.7%,at an optimized temperature,pressure and GHSV of 380℃,3 MPa and 3000h^(−1) respectively.These findings open avenues to exploit other metal oxides with CO activation capabilities for a more efficient syngas conversion and product selectivity.

The sol-gel derived Co-Mn/TiO_2 catalysts for light olefins production

在这个研究工作，二 30%(Co-Mn )/TiO2 催化剂用大音阶的第五音胶化(催化剂 A ) 和一起沉淀(催化剂 B ) 被准备方法。到在 Fischer-Tropsch 合成(英尺) 的 C24 轻石蜡的活动和选择在不同运作的条件下面在一个改正床反应堆被学习了。这些运作的条件是：温度

Effects of Light Olefins Formation during Catalytic Pyrolysis of n-Heptane

The influence of zeolite structure and process parameters (including reaction temperature and catalyst/oil ratio) on rules for formation of ethylene and propylene in the course of catalytic pyrolysis of n-heptane was studied in a small- scale fixed fluid catalytic cracking unit. Test results have revealed that compared to the USY zeolite and Beta zeolite, the catalytic pyrolysis of n-heptane in the presence of the ZRP zeolite catalyst can result in higher yield and selectivity of ethyl- ene and propylene, while a higher reaction temperature and a higher catalyst/oil ratio can promote the formation of ethylene and propylene during catalytic pyrolysis of n-heptane. The ethylene formation reaction is more sensitive to the changes in reaction temperature, whereas the changes in catalyst/oil ratio are more influential to the propylene formation reaction. This paper has made a preliminary exploration into the different reaction pathways for formation of ethylene and propylene on zeolites with different structures.

Review of Directly Producing Light Olefins via CO Hydrogenation

Directly making light olefins via CO hydrogenation is a promising process toobtain a non-petroleum based supply of alkenes. Limited by the ASF distribution function ofFischer-Tropsch synthesis, the yield of light olefins (C_2-C_4) can not reach the desired levels,which is a great challenge to overcome. Beginning with a brief introduction of F-T synthesis, thispaper provides a review of current research, including thermodynamic analysis, the ASF distributionfunction, the reaction performance of CO hydrogenation and slurry reactor studies. The problemscurrently faced by this research area are presented at the end of the article.

Light olefins synthesis from C1-C2 paraffins via oxychlorination processes

A two-step process was employed to convert methane or ethane to light olefins via the formation of an intermediate monoalkyl halide. A novel K4RuOCll0/TiO2 catalyst was tested for the oxidative chlorination of methane and ethane. The catalyst had high selectivity for methyl and ethyl chlorides, 80% and 90%, respectively. During the oxychlorination of ethane at T〉~250~C, the formation of ethylene as a reaction product along with ethyl chloride was observed. In situ Fourier transform infrared studies showed that the key intermediate for monoalkyl chloride and ethylene formation is the alkoxy group. The reaction mechanism for the oxidative chlorina- tion of methane and ethane over the Ru-oxychloride catalyst was proposed. The novel fiber glass catalyst was also tested for the dehydrochlorination of alkyl chlorides to ethylene and propylene. Very high selectivities （up to 94%-98%） for ethylene and propylene formation as well as high stability were demonstrated.

Targeted Catalytic Cracking to Olefins(TCO):Reaction Mechanism,Production Scheme,and Process Perspectives

Light olefins are important organic building blocks in the chemicals industry.The main low-carbon olefin production methods,such as catalytic cracking and steam cracking,have considerable room for improvement in their utilization of hydrocarbons.This review provides a thorough overview of recent studies on catalytic cracking,steam cracking,and the conversion of crude oil processes.To maximize the production of light olefins and reduce carbon emissions,the perceived benefits of various technologies are examined.Taking olefin generation and conversion as a link to expand upstream and downstream processes,a targeted catalytic cracking to olefins(TCO)process is proposed to meet current demands for the transformation of oil refining into chemical production.The main innovations of this process include a multiple feedstock supply,the development of medium-sized catalysts,and a diameter-transformed fluidizedbed reactor with different feeding schemes.In combination with other chemical processes,TCO is expected to play a critical role in enabling petroleum refining and chemical processes to achieve low carbon dioxide emissions.

Study on reformulation of fluid catalytic cracking gasoline and increasing production of light olefins

The effects of reaction temperature,mass ratio of catalystto oil,space velocity,andmass ratio of water to oil on the product distribution,the yields of light olefins(light olefins including ethylene,propylene and butylene)and the composition of the fluid catalytic cracking(FCC)gasoline upgraded over the self-made catalyst GL in a confined fluidized bed reactor were investigated.The experimental results showed that FCC gasoline was obviously reformulated under appropriate reaction con-ditions.The olefins(olefins with C atom number above 4)content of FCC gasoline was markedly reduced,and the aromaticscontent andoctanenumber were increased.The upgraded gasoline met the new standard of gasoline,and meanwhile,higher yields of light olefins were obtained.Furthermore,higher reaction temperature,higher mass ratio of catalyst to oil,higher mass ratio of water to oil,and lower space velocity were found to be beneficial to FCC gasoline reformulation and light olefins production.

Effect of manganese on the catalytic performance of an iron-manganese bimetallic catalyst for light olefin synthesis

A systematic study was carried out to investigate the promotion effect of manganese on the performance of a coprecipitated iron-manganese bimetallic catalyst for the light olefins synthesis from syngas. The catalyst samples were characterized by N2 physisorption, transmis- sion electron microscopy （TEM）, X-ray photoelectron spectroscopy （XPS）, powder X-ray diffraction （XRD）, Mossbauer spectroscopy, H2- differential thermogravimetric analysis （H2-DTG）, CO temperature-programmed reduction （CO-TPR） and CO2 temperature-programmed des- orption （CO2-TPD）. The Fischer-Tropsch synthesis （FTS） performance of the catalyst was measured at 1.5 MPa, 250 ℃ and syngas with H2/CO ratio of 2.0. The characterization results indicated that the addition of manganese decreases the catalyst crystallite size, and improves the catalyst BET surface area and pore volume. The presence of manganese suppresses the catalyst reduction and carburization in H2, CO and syngas, respectively. The addition of manganese improves the catalytic activity of water-gas shift reaction and suppresses the oxidation of iron carbides in the FTS reaction. The incorporation of manganese improves the catalyst surface basicity and results in a significant improvement in the selectivities to light olefins and heavy hydrocarbons （C5＋）, and furthermore an inhibition of methane formation in FTS. The pure iron catalyst （Mn-00） has the highest initial FTS catalytic activity （65%） and the lowest selectivity （17.35 wt%） to light olefins （C2=-C4=）. The addition of an appropriate amount of manganese can improve the catalyst FTS activity.

Catalyst for Increasing Ethylene and Propylene Production and Its Industrial Application in a Catalytic Pyrolysis Unit

Light olefins,particularly ethylene and propylene,are the most important building blocks for the petrochemical industry,and demand for their production has been increasing.The catalytic pyrolysis process(CPP)and the corresponding catalyst,developed by SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,are designed to maximize the light olefin yield from catalytic cracking of heavy feedstocks.However,owing to the continuing degradation of feedstocks,the original catalyst can no longer maintain its activity.Herein,we describe the rational design of the new catalyst,Epylene,from a new metal-modified hierarchical ZSM-5 zeolite and matrix.Epylene was tested in the CPP unit of Shaanxi Yanchang Coal Yulin Energy and Chemical Company.A test run and base run were conducted to demonstrate the better performance of Epylene compared with the original catalyst.The properties of the feedstocks and the operating conditions in both runs were similar.The light olefin yield was increased from 33.95%to 36.50%and the coke yield was only 9.58%in the test run,which was lower than that in the base run.

Promotion effects of alkali metals on iron molybdate catalysts for CO_(2)catalytic hydrogenation

CO_(2)hydrogenation is an attractive way to store and utilize carbon dioxide generated by industrial processes,as well as to produce valuable chemicals from renewable and abundant resources.Iron catalysts are commonly used for the hydrogenation of carbon oxides to hydrocarbons.Iron-molybdenum catalysts have found numerous applications in catalysis,but have been never evaluated in the CO_(2)hydrogenation.In this work,the structural properties of iron-molybdenum catalysts without and with a promoting alkali metal(Li,Na,K,Rb,or Cs)were characterized using X-ray diffraction,hydrogen temperatureprogrammed reduction,CO_(2)temperature-programmed desorption,in-situ^(57)Fe Mossbauer spectroscopy and operando X-ray adsorption spectroscopy.Their catalytic performance was evaluated in the CO_(2)hydrogenation.During the reaction conditions,the catalysts undergo the formation of an iron(Ⅱ)molybdate structure,accompanied by a partial reduction of molybdenum and carbidization of iron.The rate of CO_(2)conversion and product selectivity strongly depend on the promoting alkali metals,and electronegativity was identified as an important factor affecting the catalytic performance.Higher CO_(2)conversion rates were observed with the promoters having higher electronegativity,while low electronegativity of alkali metals favors higher light olefin selectivity.