STUDY ON THE MECHANICAL PROPERTIES OF SOLID CATALYSTS

The mechanics of porous catalyst paricles has been discussed and outlined. Concept of brittle fracture, statistical model of single-particle strength, and bulk crushing strength model were introduced. It is elucidated that the objective of catalyst mechanics research is to establish mechanical reliability model of converters using solid catalysts.

Catalytic Performance of Aquathermolysis and Viscosity Reduction of Heavy Oil over a WO_(3)/ZrO_(2) Solid Acid

Tungstated zirconia(WO_(3)/ZrO_(2))solid acid catalysts with different WO_(3) contents were prepared by a hydrothermal method and then used in the catalytic aquathermolysis of heavy oil from Xinjiang.The WO_(3)/ZrO_(2) solid acid catalyst was characterized by a range of characterization methods,including X-ray diffraction,NH3-temperature programmed desorption,and pyridine infrared spectroscopy.The WO_(3) content of the WO_(3)/ZrO_(2) catalysts had an important impact on the structure and property of the catalysts.When the WO_(3) mass fraction was 20%,it facilitated the formation of tetragonal zirconia,thereby enhancing the creation of robust acidic sites.Acidity is considered to have a strong impact on the catalytic performance of the aquathermolysis of heavy oil.When the catalyst containing 20%WO_(3) was used to catalyze the aquathermolysis of heavy oil under conditions of 14.5 MPa,340℃,and 24 h,the viscosity of heavy oil decreased from 47266 to 5398 mPa·s and the viscosity reduction rate reached 88.6%.The physicochemical properties of heavy oil before and after the aquathermolysis were analyzed using a saturates,aromatics,resins,and asphaltenes analysis,gas chromatography,elemental analysis,densimeter etc.After the aquathermolysis,the saturate and aromatic contents significantly increased from 43.3%to 48.35%and 19.47%to 21.88%,respectively,with large reductions in the content of resin and asphaltene from 28.22%to 25.06%and 5.36%to 2.03%,respectively.The sulfur and nitrogen contents,and the density of the oil were significantly decreased.These factors were likely the main reasons for promoting the viscosity reduction of heavy oil during the aquathermolysis over the WO_(3)/ZrO_(2) solid acid catalysts.

Preparation and Catalytic Application of Novel Water Tolerant Solid Acid Catalysts of Zirconium Sulfate/HZSM-5

Esterification of acrylic acid（AA） to produce AA esters has widespread application in the chemical industry. A series of water tolerant solid acid catalysts was prepared, and characterized by XRD, nitrogen adsorption, TGA-DTA, XPS, and ammonia adsorption FTIR. The effects of Si/Al ratio, zirconium sulfate（ZS） loading on HZSM-5 and calcination temperature on the esterification were investigated. When 20% （mass fraction） ZS is loaded on HZSM-5, the conversion of AA reaches 100%. XRD analysis indicates that ZS is highly dispersed on HZSM-5 because no crystalline structure assigned to ZS is found. Catalytic activity and hydrophobicity of ZS supported on HZSM-5 are higher compared with those of parent ZS or HZSM-5. Results show that this kind of novel catalysts is an efficient water tolerant solid acid catalyst for esterification reactions.

MECHANICAL STRENGTH AND RELIABILITY OF SOLID CATALYSTS

The mechanical strength of solid catalysts is one of the key parameters for reliable and efficient perform-ance of a fixed bed reactor. Some recent developments and their basic mechanics within this context are reviewed. The main concepts discussed are brittle fracture which leads to the mechanical failure of the catalyst pellets, measurement and statistical properties of the catalyst strength data, and mechanical reliability of the catalyst pellets and their packed bed. The scientific basis for the issues on the catalyst mechanical properties calls yet for further elucidation and ad-vancement.

Biochar-based Solid Acids as Catalysts for Carbohydrate Hydrolysis: A Critical Review

Recently, increasing interest has been focused on the hydrolysis of carbohydrates to monosaccharides, among which, glucose and xylose as typical platform sugars can be used to produce chemicals and biofuels. As heterogeneous catalysts, solid acids have gained extensive attention for biomass biorefinery and could replace the conventional process owing to their excellent properties, including acceptable acidity and easy separation. In particular, biochar-based solid acids derived from biomass are promising for biomass conversion owing to the low-cost of feedstocks and the simple preparation procedure. Herein, we attempt to provide a critical overview of biochar-based solid acids for hydrolysis of carbohydrates into glucose and xylose. The preparation methods and properties of biochar-based catalysts as well as the influence of their properties on catalytic performance were discussed in detail. We also highlight the major challenges facing the use of biochar-based solid acids for carbohydrate hydrolysis.

Efficient production of 5-hydroxymethylfurfural from hexoses using solid acid SO_4^(2-)/In_2O_3-ATP in a biphasic system

A natural attapulgite （ATP）‐based catalyst, sulfated In2O3‐ATP （SO42-/In2O3‐ATP）, was obtained by an impregnation‐calcination method and was used to efficiently and selectively produce the useful platform chemical 5‐hydroxymethylfurfural （HMF） from hexoses. Some important reaction param‐eters were studied, revealing that Lewis and Br-nsted acid sites on SO42-/In2O3‐ATP catalyze glu‐cose isomerization and fructose dehydration. The yields of HMF from glucose and fructose were 40.2%and 46.2%, respectively, using the optimal conditions of 180℃ for 60 min with 10 wt%of solid acid catalyst in a mixture of γ‐valerolactone‐water （9：1）.

Integrating theory with the nanoreactor concept to synthesize hollow carbon sphere-encapsulated PtNi alloys for enhanced H_(2) generation

The rational design of efficient bimetallic nanoparticle(NP)catalysts is challenging due to the lack of theoretical understanding of active components and insights into the mechanisms of a specific reaction.Here,we report the rational design of nanoreactors comprising hollow carbon sphere-confined PtNi bimetallic NPs(PtNi@HCS)as highly efficient catalysts for hydrogen generation via ammonia borane hydrolysis in water.Using both density functional theory calculations and molecular dynamics simulations,the effects of an active PtNi combination and the critical synergistic role of a hollow carbon shell on the molecule diffusion adsorption behaviors are explored.Kinetic isotope effects and theoretical calculations allow the clarification of the mechanism,with oxidative addition of an O-H bond of water to the catalyst surface being the rate-determining step.The remarkable catalytic activity of the PtNi@HCS nanoreactor was also utilized for successful tandem catalytic hydrogenation reactions,using in situ-generated H_(2) from ammonia borane with high efficiency.The concerted design,theoretical calculations,and experimental work presented here shed light on the rational elaboration of efficient nanocatalysts and contribute to the establishment of a circular carbon economy using green hydrogen.

Simulation of biodiesel industrial production via solid base catalyst in a fixed-bed reactor

Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can describe the transesterification reaction well. The Antoine equation of biodiesel is regressed with the vapor-liquid data cited of literature. The non-random two liquid （NRTL） model is applied to describe the system of fatty acid methyl ester （FAME）, methanol and glycerol and parameters are obtained. The Ternary phase map is obtained from Aspen Plus via the liquid-liquid equilibrium （LLE） data. In order to describe the production in a fixed-bed performs in industrial scale after being magnified 1 000 times, the Aspen Plus simulation is employed, where two flowsheets are simulated to predict material and energy consumption. The simulation results prove that at least 350. 42 kW energy consumption can be reduced per hour to produce per ton biodiesel compared with data reported in previous references.

Preparation,characterization and catalytic properties of S_2O_8^(2-)/ZrO_2-CeO_2 solid superacid catalyst

A novel solid superacid catalyst S2O8^2-/ZrO2-CeO2 was prepared by a coprecipitation method and characterized by means of XRD FTIR, BET, TEM and DSC/TG analysis methods. The results indicated that incorporation of appropriate amounts of Ce into the catalyst was beneficial to the formation of sole tetragonal ZrO2 and effectively prevented from the formation of monoclinic ZrO〉 and restrained the loss of sulfated species. XRD revealed the presence of tetragonal Ce0.16Zr0.84O2phase in the case of S2O8^2-/ZrO2-CeO2 calcined above 500 ℃. Catalytic activities of S2O8^2-/ZrO2-CeO2 for the esterification of lactic acid with n-butanol was studied. The results showed that the optimum conditions were as follows： calcination temperature of the catalyst 600 ℃, n（lactic acid）：n（n-butyl alcohol）=1.0：3.0, w（S2O8^2-/ZrO2- CeO2）=12.0%, reaction temperature 145 ℃, and reaction time 2 h. The esterification efficiency of lactic acid was about 96.6%.

A new solid acid SO_4^(2-)/TiO_2 catalyst modified with tin to synthesize 1,6-hexanediol diacrylate

A new solid acid catalyst,SO4^2-/TiO2 modified with tin,was prepared using a sol-gel method and its physicochemical properties were revealed by nitrogen adsorption-desorption,X-ray powder diffraction,scanning electron microscopy,Fourier transform infrared spectroscopy,infrared spectroscopy of adsorbed pyridine,temperature-programmed desorption of ammonia and thermal gravimetric analysis.The structure,acidity and thermal stability of the SO4^2-/TiO2-SnO2 catalyst were studied.Incorporating tin enlarged the specific surface area and decreased crystallite size of the SO4^2-/TiO2 catalyst.The total acid sites of the modified catalyst increased and Bronsted acid strength remarkably increased with increasing tin content.The decomposition temperature of sulfate radical in the modified catalyst was 100 ℃ greater and its mass loss was more than twice that of the SO4^2-/TiO2 catalyst.The SO4^2-/TiO2-SnO2 catalyst was designed to synthesize 1,6-hexanediol diacrylate by esterification of 1,6-hexanediol with crylic acid.The yield of 1,6-hexanediol diacrylate exceeded 87% under the optimal reaction conditions：crylic acid to 1,6-hexanediol molar ratio = 3.5,catalyst loading = 7%,reaction temperature = 130 ℃ and reaction time = 3 h.The modified catalyst exhibited excellent reusability and after 10 cycles the conversion of 1,6-hexanediol was above 81%.

Reaction Kinetics of Biodiesel Synthesis from Waste Oil Using a Carbon-based Solid Acid Catalyst

The kinetics of simultaneous transesterification and esterification with a carbon-based solid acid catalyst was studied.Two solid acid catalysts were prepared by the sulfonation of carbonized vegetable oil asphalt and petroleum asphalt.These catalysts were characterized on the basis of elemental analysis,acidity site concentration,the Brunauer-Emmett-Teller（BET）surface area and pore size.The kinetic parameters with the two catalysts were determined,and the reaction system can be described as a pseudo homogeneous catalyzed reaction.All the forward and reverse reactions follow second order kinetics.The calculated concentration values from the kinetic equations are in good agreement with experimental values.

Research on KOH/La-Ba-Al_2O_3 catalysts for biodiesel production via transesterification from microalgae oil

Alumina supports modified by lanthanum （La） and barium （Ba） were prepared by peptization. Catalysts with different KOH contents supported on modified alumina were prepared by impregnation method. Various techniques, including N2 adsorption-desorption （Brunauer-Emmet-Teller method, BET）, X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and fourier transform infrared absorption spectroscopy （FT-IR）. Catalytic activity for microalgae oil conversion to methyl ester via transesterification was evaluated and analyzed by GC-MS and GC. BET results showed that the support possessed high specific surface area, suitable pore volume and pore size distribution. Activity results indicated that the catalyst with 25 wt% KOH showed the best activity for microalgae oil conversion. XRD and SEM results revealed that Al-O-K compound was the active phase for microalgae oil conversion. The agglomeration and changing of pore structure should be the main reasons for the catalyst deactivation when KOH content was higher than 30 wt%.

Geometric effect promoted hydrotalcites catalysts towards aldol condensation reaction

In solid basic catalysis field,how to achieve optimized activity and desired stability through elaborate control over basic site properties remains a challenge.In this work,taking advantage of the structure memory effect of layered double hydroxides(LDHs),rehydrated Ca4 Al1-x Gax-LDHs and Ca4 Al1-x Inx-LDHs catalysts were prepared and applied in aldol condensation reaction that isobutyraldehyde(IBD)reacts with formaldehyde(FA)to obtain hydroxypivalaldehyde(HPA).Notably,the resulting re-Ca4 Al0.90Ga0.10-LDHs exhibits an extraordinarily-high catalytic activity(HPA yield:72%),which is to our best knowledge the highest level in this reaction.The weak Br?nsted basic site,7-coordinated Ca-OH group,which serves as an active site,catalyzes the condensation process and promotes the product desorption.Studies on structure-property correlations demonstrate that Ga as a structural promoter induces a moderate expansion of the laminate lattice,which results in a significant increase in the concentration of weak basic sites in re-Ca4Al0.90Ga0.10-LDHs,accounting for its high catalytic activity.This work illuminates that geometric structure of basic active sites can be tuned via introducing catalyst additive,which leads to a largely improved performance of hydrotalcite solid basic catalysts towards aldol condensation reaction.

One Step Preparation of Sulfonated Solid Catalyst and Its Effect in Esterification Reaction

A carbon-based sulfonated catalyst was prepared by direct sulfonation and carbonization （in moderate conditions：200 ＆#176;C, 12 h） of red liquor solids, a by-product of paper-making process. The prepared sulfonated cata-lyst （SC） had aromatic structure, composed of carbon enriched inner core, and oxygen-containing （SO3H, COOH, OH） groups enriched surface. The SO3H, COOH, OH groups amounted to 0.74 mmol·g^-1, 0.78 mmol·g^-1, 2.18 mmol·g^-1, respectively. The fresh SC showed much higher catalytic activity than that of the traditional solid acid catalysts （strong^-acid 732 cation exchange resin, hydrogen type zeolite socony mobile-five （HZSM-5）, sulfated zir-conia） in esterification of oleic acid. SC was deactivated during the reactions, through the mechanisms of leaching of sulfonated species and formation of sulfonate esters. Two regeneration methods were developed, and the catalytic activity can be mostly regenerated by regeneration Method 1 and be fully regenerated by regeneration Method 2, respectively.

Alkylation of Catechol with tert-Butyl Alcohol Catalyzed by Mesoporous Acidic Montmorillonite Heterostructure Catalysts

The liquid phase alkylation of catechol with tert-butyl alcohol to produce4-tert-butyl catechol (4-TBC) was carried out over MCM-41, HZSM-5, H-exchanged montmorillonite andnovel acidic porous montmorillonite heterostructures (PMHs). Upon all catalysts tested, 4-TBC is themain product and 3-tert-butyl catechol (3-TBC) and 3,5-di-tert-butyl catechol are the sideproducts. The synthetic PMHs showed higher conversion of catechol and better selectivity to 4-TBCcompared to other solid acid catalysts tested. Over the PMHs derived from H-exchangedmontmorillonite through template extraction processes, the suitable reaction temperature is ca 410K, the ratio of catechol to tert-butyl alcohol is 1:2. Increasing the amount of catalyst (lowerweight hourly space velocity) can improve the conversion of catechol and influence the selectivityslightly. The reasonable reaction time is ca 8 h. The type and strength of acidity ofH-montmorillonite and PMH were determined by pyridine adsorption FT-IR and ammoniatemperature-programmed desorption techniques. The medium and strong acid sites are conducive toproducing 4-TBC and the weak acid sites to facilitating the 3-TBC formation. The differences betweenthe PMHs from calcination and those from extraction are attributed to proton migration and aciditychange in the gallery surface.

Clean Aerobic Liquid Oxidation of Aldehydes with Solid Catalyst

Clean liquid oxidation of aldehydes can be accomplished using solid catalyst in the presence of molecular oxygen at room temperature, which is a valuable alternative to traditional counterparts.

Friedel-Crafts Acylation of Ferrocene Catalyzed by Solid Superacid,Silica-supported Polytrifluoromethanesulfosiloxane

Solid superacid, silica-supported polytrifluoromethanesulfosiloxane (SiO2-Si-SCF3) wasfirstly used in the Friedel-Crafts acylation of ferrocene as a novel catalyst. IR spectra, WAXD andspecific surface area of the superacid SiO2-Si-SCF3 were also investigated.

Rare earth metals modified Ni-S2O8^2-/ZrO2-Al2O3 catalysts for n-pentane isomerization

The effects of adding rare earth(RE) metals,such as Ce,Yb and Pr to Ni-S_2O_8^(2-)/ZrO_2-Al_2O_3(Ni-SZA) on the structure of catalysts as well as their isomerization performance were studied.The prepared catalysts were characterized by XRD,BET,FT-IR,Py-IR,and H_2-TPR,The results showed that the addition of RE metals can increase the strength and amounts of the acid sites,improve the redox properties of catalysts.The Yb-Ni-SZA catalyst showed the best redox properties,which could provide enough metallic sites.In addition,it provided the largest amounts of weak and moderately strong acid sites.Among RE metals modified Ni-SZA catalyst,Yb-Ni-SZA exhibited the highest isopentane yield of 61.7%at 160 °C.The optimum isomerization catalytic performance of the catalysts decreased in the order of Yb-Ni-SZA > Pr-Ni-SZA > Ni-SZA > Ce-Ni-SZA.

Construction of a Bronsted-Lewis solid acid catalyst La-PW-SiO_(2)/SWCNTs based on electron withdrawing effect of La(Ⅲ)onπbond of SWCNTs for biodiesel synthesis from esterification of oleic acid and methanol

A novel solid Bronsted-Lewis acid catalyst La-PW-SiO_(2)/SWCNTs(single-wall carbon nanotubes)was synthesized from the synergistic modification of H_(3)PW_(12)O_(40)(HPW)by single-walled carbon nanotubes functionalized with sidewall hydroxyl groups(SWCNTs–OH)and La^(3+) via sol–gel method.The freshly prepared catalyst was characterized by several methods,and the catalytic activity and stability of it were studied from the esterification of oleic acid and methanol.Results showed that the highest conversion of oleic acid was 93.1%(mass)and maintained as high as 88.7%(mass)after six cycles of La-PW-SiO_(2)/SWCNTs.The high catalytic activity and stability of La-PW-SiO_(2)/SWCNTs can be attributed to the strong electron withdrawing effect of La^(3+) on π bond of SWCNTs,because it can facilitate the formation of a large number of strong Lewis acid sites.Therefore,the reduction of catalytic activity of a solid acid catalyst due to the fact that hydration reaction of its Bronsted acid sites can be effectively reduced.La-PW-SiO_(2)/SWCNTs can be an efficient and economical catalyst,because it shows good catalytic activity and stability.

Catalysts derived from waste slag for transesterification

MgO-CaO/SiO2 solid catalysts derived from waste slag （WS） of metal magnesium plant were prepared. The catalytic performances were evaluated in the transesterification of rapeseed oil with methanol to biodiesel in a 500 mL three-necked reactor under atmospheric pressure. The basic strengh of the catalyst reached 22.0 measured by indicators accroding to Hammett scale. The results show that the MgO-CaO/SiO2 is an excellent catalyst for transesterification, and the conversion of rapeseed oil reach 98% under the optimum condition.