A-Site Effect on the Conversion of Bio-Ethanol into Isobutene over Ternary A1ZnyZrzOn Catalysts

Ternary multifunctional A1ZnyZrzOn catalysts are prepared by introducing A-site transition metals with the redox capability into binary Zn1Zr8On. Structure and morphology were investigated by means of XRD, BET and FESEM, respectively. Activity data showed that Cr addition exhibited obvious beneficial effect to promote isobutene production from direct conversion of bio-ethanol compared to other A-site metal dopants. A significant higher yield of isobutene over Cr-promoted Zn1Zr8On catalyst was also observed with respect to its binary Zn1Zr8On counterpart. The choice of A-site metal is of prime importance in the isobutene production, catalyzing mainly the ethanol dehydrogenation, meanwhile the appropriate addition of zinc on the catalyst surface is also essential for good isobutene yield.

Deactivation mechanism of acetone to isobutene conversion over Y/Beta catalyst

The conversion of acetone derived from biomass to isobutene has attracted extensive attentions.In comparison with Brønsted acidic catalyst,Lewis acidic catalyst could exhibit a better catalytic performance with a higher isobutene selectivity.However,the catalyst stability remains a key problem for the long-running acetone conversion and the reasons for catalyst deactivation are poorly understood up to now.Herein,the deactivation mechanism of Lewis acidic Y/Beta catalyst during the acetone to isobutene conversion was investigated by various characterization techniques,including acetone-temperature-programmed surface reaction,gas chromatography-mass spectrometry,in situ ultraviolet-visible,and ^(13)C cross polarization magic angle spinning nuclear magnetic resonance spectroscopy.A successive aldol condensation and cyclization were observed as the main side-reactions during the acetone conversion at Lewis acidic Y sites.In comparison with the low reaction temperature,a rapid formation and accumulation of the larger cyclic unsaturated aldehydes/ketones and aromatics could be observed,and which could strongly adsorb on the Lewis acidic sites,and thus cause the catalyst deactivation eventually.After a simple calcination,the coke deposits could be easily removed and the catalytic activity could be well restored.

Alkylation of Isobutane and Isobutene in Acidic Polyether Ionic Liquids

The Br?nsted-acidic polyether ionic liquids(ILs)with different polymerization degrees(n value)were prepared via the reaction of tetramethylguanidine and epoxy ethane,followed by successive reactions with 1,3-propane sultone and trifluoromethanesulfonic acid(TfOH).The prepared ILs were characterized by infrared spectroscopy and 1H nuclear magnetic resonance spectroscopy,and their thermal stability was determined by thermal gravimetry.The synthesized polyether ILs coupled with TfOH were used to catalyze the alkylation reaction of isobutane and isobutene for the preparation of alkylate gasoline.The polyether ILs could improve the substrate dissolution and promote the separation of the catalyst from the products.The ideal IL(n=94)was determined.The optimized alkylation reaction conditions covered:a VTfOH/VIL ratio of 0.35,a reaction temperature of 40℃,a reaction time of 50 min,and a stirring speed of 800 r/min.The conversion of isobutene was 92.4%and the selectivity for the C8-product was 81.6%.Under optimal conditions,the catalyst life was determined and TfOH showed improved cyclic performance in the polyether ILs.After 8 operating cycles,the catalytic activity of the catalyst showed negligible decline.

Influence of Geometric Structure of Immobilized Aluminium Chloride Catalyst on Catalytic Property in Isobutene Polymerization

The catalytic property of AICl(3) catalyst immobilized on gamma -Al2O3 for isobutene polymerization has been studied. It was found that the activity, selectivity and stability of the catalyst are dependent greatly on geometric characteristic pf the pore structure and size of catalyst. Although the activity and selectivity of the catalysts with micro- and meso-pore structure are all high in initial stage, but their stability is low, while those with bimodal meso- and macro-pore structure are excellent. Increasing granularity of the catalyst(particle become fine) brings about an increase in isobutene conversion, but a decrease in selectivity, resulting in lower average molecular weight and iis broader distribution.

A shaped binderless ZSM-11 zeolite catalyst for direct amination of isobutene to tert-butylamine

A shaped binderless and two binder‐containing ZSM‐11 zeolite catalysts were prepared and characterized by powder X‐ray diffraction, N2 adsorption‐desorption, and pyridine adsorption‐infrared measurements. The binderless catalyst was synthesized using a dry‐gel conversion technique, inwhich 1,6‐hexanediamine and tetrabutylammonium bromide were used as structure‐directingagents and no other alkaline materials were added. The catalytic performance of the zeolites in the direct amination of isobutene to tert‐butylamine was evaluated in a fixed‐bed reactor. By virtue of its high crystallinity as well as its good mechanical strength, the shaped binderless ZSM‐11 catalyst showed a higher rate of formation of tert‐butylamine than did the binder‐containing catalysts.

Selective Oxidation of Isobutene over CsFeCoBiMnMoO_x Mixed Oxide Catalyst

Mixed oxide catalyst Cs0.1Fe2Co6BiMnMo12Ox was prepared by the coprecipitation method. Selective oxidation of isobutene was carried out in a fixed-bed reactor over Cs0.1Fe2Co6BiMnMo12Ox. The results showed that the catalyst had high catalytic activity. Under the optimum reaction conditions (n(i-C4=):n(O2)=1:2-1:4, space velocity=180 h-1, T=360℃), the yields of methacrolein and methacrylic acid can reach 80% and 8%, respectively. The total yield of liquid products (methacrolein, methacrylic acid and acetic acid) can reach about 90%.

Tuning the crystallite size of monoclinic ZrO_(2) to reveal critical roles of surface defects on m–ZrO_(2) catalyst for direct synthesis of isobutene from syngas

The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_(2) catalysts for isobutene synthesis were studied.We prepared a series of monoclinic ZrO_(2) catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas.ZrO_(2) with small crystalline size showed higher CO conversion and isobutene selectivity,while samples with large crystalline size preferred to form dimethyl ether(DME)instead of hydrocarbons,much less to isobutene.Oxygen defects(ODefects)analyzed by X-ray photoelectron spectroscopy(XPS)provided evidence that more ODefectsoccupied on the surface of ZrO_(2) catalysts with smaller crystalline size.Electron paramagnetic resonance(EPR)and ultraviolet–visible diffuse reflectance(UV–vis DRS)confirmed the presence of high concentration of surface defects and Zr3+on mZrO_(2)-5.9 sample,respectively.In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS)analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased.These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species,and thus the products distribution changed.This study provides an in-depth insight for active sites regulation of ZrO_(2) catalyst in CO hydrogenation reaction.

Promoting di-isobutene selectivity over ZnO/ZrO_(2)-SO_(4) in isobutene oligomerization

Isooctane attracts great interest in recent years because of its promising potential as friendlyenvironmental gasoline,which is obtained by dimerization of isobutene with a hydrogenation step.Herein,a solid acid catalyst sulfated zirconia modified by ZnO was prepared.The oligomerization of isobutene had been investigated over ZrO_(2)-SO_(4) and ZnO(X)/ZrO_(2)-SO_(4) catalyst in order to find efficient catalysts for the production of isobutene oligomers.The presence of ZnO obviously enhanced the dimerization of isobutene and ZnO(X)/ZrO_(2)-SO_(4) exhibited the highest di-isobutene yield of 60%.Kinetic studies showed the higher trimerization-to-dimerization activation energy ratios of ZnO(X)/ZrO_(2)-SO_(4) than those of ZrO_(2)-SO_(4) from 353 to 393 K.In addition,reaction rate of dimerization was higher than trimerization over ZnO(X)/ZrO_(2)-SO_(4).The high L/B ratio manifested the capability to enhance the selectivity of C8 in isobutene dimerization.Furthermore,ZnO(X)/ZrO_(2)-SO_(4) exhibited stable conversion for the dimerization of isobutene.

Kinetic studies on the dimerization of isobutene with Ni/Al_2O_3 as a catalyst for reactive distillation process

Isooctane is a promising gasoline additive that could be produced by dimerization of isobutene(IB) with subsequent hydrogenation.In this work,the dimerization of IB has been carried out in a batch reactor over a temperature range of 338-383 K in the presence of laboratory prepared Ni/Al_2O_3 as a catalyst and n-pentane as solvent.The influence of various parameters such as temperature,catalyst loading and initial concentration of IB was examined.A Langmuir-Hinshelwood kinetic model of IB dimerization was established and the parameters were estimated on the basis of the measured data.The feasibility of oligomerization of IB based on the reactive distillation was simulated in ASPEN PLUS using the kinetics developed.The simulation results showed that the catalyst of Ni/Al_2O_3 had higher selectivity to diisobutene(DIB) and slightly lower conversion of IB than ion exchange resin in the absence of polar substances.

Oxidative Dehydrogenation of Isobutane to Isobutene on FSM-16 Doped with Cr and Related Catalysts

The oxidative dehydrogenation of isobutane to isobutene was examined for the use in the preparation of FSM-16 and related compounds doped by chromium with expectations that a yield of isobutene of greater than 8% could be achieved. The activity depended on the molding procedure of the catalyst and the doping method of the chromium species. In the present study, 8.8% and 8.3% of the yield of isobutene were obtained at 0.75 h and 6 h on-stream for the catalyst （Cr-loading; 6.2 wt.%） molded using wet treatment hut not pressurization treatment, in which the chromium species were directly added into the aqueous solution containing raw FSM-16 （hydrated sodium silicate powder） at an initial stage of the catalyst preparation. The structure information was based on XRD （X-ray diffraction）, the specific surface area was determined using a conventional BET （Brunauer-Emmett-Teller） nitrogen adsorption and the loading of chromium was estimated using ICP （inductively coupled plasma）. All those parameters combined with the molding method indicated that the catalytic activity was more influenced by the loading of chromium into bulk but not on surface of the catalyst rather than by the hexagonal structure of FSM-16 and the surface area.

Production of bio-ethanol by consecutive hydrogenolysis of corn-stalk cellulose

Current bio-ethanol production entails the enzymatic depolymerization of cellulose,but this process shows low efficiency and poor economy.In this work,we developed a consecutive aqueous hydrogenolysis process for the conversion of corn-stalk cellulose to produce a relatively high concentration of bio-ethanol(6.1 wt%)without humin formation.A high yield of cellulose(ca.50 wt%)is extracted from corn stalk using a green solvent(80 wt%1,4-butanediol)without destroying the structure of the lignin.The first hydrothermal hydrogenolysis step uses a Ni–WO_(x)/SiO_(2)catalyst to convert the high cumulative concentration of cellulose(30 wt%)into a polyol mixture with a 56.5 C%yield of ethylene glycol(EG).The original polyol mixture is then subjected to subsequent selective aqueous-phase hydrogenolysis of the C–O bond to produce bioethanol(75%conversion,84 C%selectivity)over the modified hydrothermally stable Cu catalysts.The added Ni component favors the good dispersion of Cu nanoparticles,and the incorporated Au3+helps to stabilize the active Cu^(0)-Cu^(+)species.This multi-functional catalytic process provides an economically competitive route for the production of cellulosic ethanol from raw lignocellulose.

Concentration of Bio-Ethanol through Cellulose Ester Membranes during Temperature-Difference Controlled Evapomeation

To evaluate the high-performance of membrane materials in the concentration of an aqueous solution of dilute bioethanol under temperature-difference controlled evapomeation (TDEV), asymmetric porous cellulose nitrate (CN) and cellulose acetate (CA) membranes were prepared by a phase inversion method. In the concentration of dilute ethanol under TDEV, these membranes showed a high permeation rate and high ethanol/water selectivity. In membranes with almost the similar pore size, the ethanol/water selectivity was considerably higher for the CN membrane than the corresponding CA membrane. This result suggested that the affinity between the membrane material and the permeant is an important factor in the separation selectivity.

Energy-Efficient Production of Cassava-Based Bio-Ethanol

Fuel ethanol is an important renewable and sustainable fuel, produced in China by fermentation of mostly corn, wheat and cassava feedstock. Fermentation produces an ethanol-lean broth (10 to 12 vol%). Ethanol is recovered by distillation, followed by a molecular sieve drying beyond the azeo-tropic point. The distillation and molecular sieve operations consume most of the total energy used, with the steam consumption currently being ~1.8 kg/kg ethanol, including 0.5 kg/kg ethanol in the final molecular sieve stage during regeneration. The objectives of the paper are fourfold: 1) firstly to study the distillation process of a large-scale cassava-based fuel ethanol production (200,000 tons per year), by field measurements and by using an Aspen Plus V8.2 simulation, with and without energy integration of condensers and reboilers, resulting in a distillation steam consumption of ~1.3 kg/kg ethanol;2) secondly, to examine the effects of using Very High Gravity (VHG) fer-mentation of cassava meal mash. By using VHG fermentation, the ethanol concentration in the fermenter broth is significantly increased, to about 19 vol% (15.4 wt%). The steam consumption is then reduced to ~0.94 kg/kg, representing a considerable saving in comparison with the current operation. Applying VHG fermentation needs minor additional investment, rapidly recovered through the energy savings and the smaller size of equipment;3) thirdly, to assess the application of a hybrid operation, where pervaporation will be used to selectively and continuously remove ethanol from the fermenter broth, thus slightly increasing the fermentation yield by reducing the risk of ethanol inhibition, whilst producing an ehtanol-rich permeate (about 30 wt%);and finally 4) to demonstrate that the production cost of cassava-based ethanol can substantially be reduced by applying the proposed improvements.

Evaluation of Plantain Biomass (<i>Musa paradisiaca</i>L.), as Feedstock for Bio-Ethanol Production

This study investigated the viability of post-harvested plantain biomass as a promising feedstock for the production of Bioethanol. The properties of the derived bio-ethanol were determined to examine its suitability as a promising and sustainable alternative to petroleum-based ethanol The research revealed that Plantain biomass is made up of Lignocellulosic contents such as extractive, Lignin, cellulose, hemicelluloses, ash and moisture in different proportions. The different parts of the biomass such as the flower, stem and leaves were hydrolyzed using H2SO4. Optimum hydrolysis conditions of 6%w/v acid concentration, 30 min contact time and 80°C working temperature were established for Plantain stem and flower. However, hydrolysis of Plantain leaves was at the best under the experimental conditions of acid concentration (10% w/v), contact time (120 min) and temperature (120°C). The highest yield of the bio-ethanol produced was obtained from Plantain stem biomass with a record of 8.04% followed by Plantain flower with a yield of 7.73% and 757% from Plantain leaves The hydrolyzate was fermented using Baker’s yeast (Saccharomyces cerevisiae) at a room temperature of 25°C and pH of 4.5 for 4 D. The structural determination of the derived bioethanol was conducted using FT-IR analysis and the fuel properties were found to be consistent with those of the conventional ethanol. The SEM analysis conducted on the post hydrolysed biomass confirmed the effectiveness of the hydrolysis scheme adopted as evident on the surface morphology of the biomass. This study confirmed the viability of Plantain biomass as promising feedstock for Bio-ethanol production under the established hydrolysis conditions.

Life-Cycle Analysis of Bio-Ethanol Fuel Emissions of Transportation Vehicles in Greater Houston Area

Study is conducted on the life cycle assessment of bio-ethanol used for transportation vehicles and their emissions. The emissions that are analyzed include greenhouse gases, volatile organic compounds, sulfur oxide, carbon monoxide, nitrous oxide, particulate matter with the size less than 10 and 2.5 microns. Furthermore, various blends of bio-ethanol and gasoline are studied to learn about the impacts of higher blend on emissions. The Greenhouse Gases, Regulated Emissions, and Energy Use in Transportation (GREET) model software are used to simulate for emissions. The research analyzes two pathways of emissions: Well-to-Pump and Pump-to-Vehicle analyses. It is found that the fuel cell vehicles using 100% bio-ethanol have shown the most reduction in the amount of all the pollutants from the Pump-to-Vehicle emission analysis. The Well-to-Pump analysis shows that only greenhouse gases (GHGs) reduce with higher blends of bio-ethanol. All other pollutants VOC, CO, NOx, SOx, PM10 and PM2.5 emissions increase with the higher blending ratios. The Pump-to-Vehicle analysis shows that all the pollutant emissions reduce with the percentage increase of bio-ethanol in the fuel blends.

不同分子筛催化乙苯与异丁烯液相烷基化反应制对叔丁基乙苯性能

关键化学品对叔丁基乙苯(p-TBEB)在工程塑料、高铁航空和电子信息等领域有广阔的应用前景。目前烷基化生产p-TBEB过程存在原料受限、催化剂失活快等弊端,同时也缺乏针对不同构型分子筛用于制备p-TBEB性能的系统研究。分别选取具有BEA、FAU、MOR、MWW和MTW拓扑结构的HBeta、HUSY、HMOR、HMCM-22和HZSM-12氢分子筛,采用XRD、SEM、NH3-TPD和N2物理吸/脱附对分子筛的结构和性质等进行了表征。结果表明,所选取的分子筛皆为纯相分子筛,具有各自典型的形貌和酸分布。在反应温度为200℃、反应压力为2.5 MPa、乙苯与异丁烯进料物质的量之比为4.0和异丁烯质量空速为1.0 h-1的反应条件下,系统研究了不同拓扑结构分子筛用于乙苯与异丁烯液相烷基化制备p-TBEB的催化性能。结果表明,酸量与分子筛的反应活性和目标产物选择性的关联度不高,孔道结构是影响其烷基化性能的关键因素。和其他几种分子筛相比,具有一维十二元环孔道的HZSM-12氢分子筛不仅能维持较高的乙苯转化率(≈20%),还具有高目标产物选择性,是最优的乙苯与异丁烯反应制p-TBEB的分子筛催化材料。

Mo_(12)Bi_(1.2)Fe_(3)Co_(8)K_(0.4)用于异丁烯气相氧化制甲基丙烯醛

以(NH_(4))_(6)Mo_(7)O_(24)·4H_(2)O、Bi(NO_(3))_(3)·5H_(2)O、Fe(NO_(3))_(3)·9H_(2)O、Co(NO_(3))_(2)·6H_(2)O和KNO_(3)为前驱体金属盐,通过共沉淀法制备了一系列MoBiFeCoK混合氧化物催化剂,考察了主金属Mo、Bi,助金属Fe、Co和掺杂金属K含量对催化剂催化异丁烯气相氧化反应的影响,通过SEM、EDX、XRD、NH_(3)-TPD对掺杂K前后的催化剂进行了表征,同时对催化异丁烯气相氧化反应条件进行了优化,并测试其100 h的催化稳定性。结果表明,Bi、Fe、Co和K的含量对MoBiFeCoK混合氧化物催化剂催化异丁烯气相氧化反应的性能有显著影响,其中,Mo_(12)Bi_(1.2)Fe_(3)Co_(8)K_(0.4)表现出最优催化性能;K的掺杂降低了催化剂酸量(从Mo12Bi1.2Fe3Co8的15.27μmol/g降至Mo_(12)Bi_(1.2)Fe_(3)Co_(8)K_(0.4)的5.91μmol/g),并明显提升主产物甲基丙烯醛(MAL)的选择性;异丁烯气相氧化反应的最佳条件为:以0.66 g Mo_(12)Bi_(1.2)Fe_(3)Co_(8)K_(0.4)为催化剂,反应温度320℃,n(O_(2))∶n(异丁烯)(氧烯比)=10∶1,体积空速(GHSV)=2000h^(-1)。在该条件下,Mo_(12)Bi_(1.2)Fe_(3)Co_(8)K_(0.4)在100h的催化异丁烯气相氧化反应中表现稳定,异丁烯转化率保持在98.6%,MAL选择性保持在86.4%。

Catalytic behavior of Mo-Bi-Fe-Co-K-M-O(M=Ce,Gd,CeGd)catalysts for selective oxidation of isobutene

The further improvement of methacrolein(MAL)selectivity from isobutene(IB)oxidation is crucial and challenging.In this study,based on the typical Mo-Bi-Fe-Co-K-O mixed metal oxide,the rare earth element Gd-doped,Ce-doped and CeGd co-doped catalysts were prepared by co-precipitation strategy to increase the selectivity of MAL from 47.9%to 49.8%,64.2% and 68.6%,respectively.In order to elucidate in-depth the promoting effect of Ce and/or Gd,various characterizations were utilized including X-ray diffraction patterns(XRD),Raman,X-ray fluorescence spectrometry(XRF),X-ray photoelectron spectroscopy(XPS),O_(2)-temperature programmed desorption(O_(2)-TPD),H2-temperature programmed reduction(H2-TPR),CO_(2)-temperature programmed desorption(CO_(2)-TPD),IB-temperature programmed desorption(i-C4-TPD)and in-situ IB-Fourier transform infrared spectroscopy(IB-FTIR).Both Ce and Gd finely regulate the bulk and surface structure of the catalyst,thus altering the redox ability,oxygen mobility and storage ability and basicity.Compared with Ce,Gd addition slightly regulates the variation of Co^(2+)/Co^(3+)redox couples,greatly enhances the interaction among the components on the catalyst,thus only increases the content of surface oxygen species and has little effect on their mobility.While Cecontaining catalyst performs stronger oxygen storage and migration ability,thus leading to the overproduction of surface Odefectspecies,which are proposed to be the active sites for the production of MAL and COx.The CeGd co-doped catalyst possesses the proper content of surface Odefectspecies,thus exhibits much higher MAL selectivity.Moreover,the promoting mechanism of Ce and/or Gd over IB oxidation is proposed.Therefore,this work is helpful for understanding the influence of rare earth elements on the structure of mixed metal oxides and the olefin selective oxidation reaction.

混合碳四中异丁烯叠合催化剂工业应用及优化

从操作参数、混合碳四组成、混合碳四水含量、催化剂等几个方面对异丁烯叠合催化剂进行分析和比较。研究发现,采用离子交换树脂的异丁烯叠合催化剂含有一定量的水分,在操作参数和混合碳四组成变化不大的情况下,催化剂自身水含量和混合碳四中的水含量是影响催化剂性能的关键因素。催化剂水含量越低,遇水后体积膨胀率越大,催化剂破碎、粉化越严重,最终导致催化剂性能下降,反应器受损。催化剂含水量越高,遇水后体积膨胀率越小,催化剂越不易破碎,温度对催化剂膨胀率的影响越小。但催化剂含水量过大,会影响异丁烯的转化效果,为了控制催化剂的膨胀率,保证催化剂的活性,催化剂的水含量最好控制在20%~25%,混合碳四中的水含量在0.05%以下,防止夹带明水,避免引起催化剂的膨胀和破碎。经过优化后,催化剂可稳定运行2年左右,反应器出口异丁烯含量在0.5%以下。