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.

Insights into kinetics and reaction mechanism of acid-catalyzed transesterification synthesis of diethyl oxalate

The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated.The effects of different factors(e.g.,acidity,electron accepting capacity,cations type and crystalline water)on the catalytic activity of acidic catalysts were investigated respectively.It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid(FeCl3)and a Bronsted acid(H2SO4)follows a first-order kinetic reaction process.In addition,the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism.This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis,diminishing the industrial production cost of diethyl oxalate,and developing downstream bulk or high-value-added industrial products.

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.

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.

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.

Honeycomb-structured solid acid catalysts fabricated via the swelling-induced self-assembly of acidic poly(ionic liquid)s for highly efficient hydrolysis reactions

The development of heterogeneous acid catalysts with higher activity than homogeneous acid catalysts is critical and still challenging.In this study,acidic poly(ionic liquid)s with swelling ability(SAPILs)were designed and synthesized via the free radical copolymerization of ionic liquid monomers,sodium p-styrenesulfonate,and crosslinkers,followed by acidification.The 31P nuclear magnetic resonance chemical shifts of adsorbed trimethylphosphine oxide indicated that the synthesized SAPILs presented moderate and single acid strength.The thermogravimetric analysis results in the temperature range of 300–345°C revealed that the synthesized SAPILs were more stable than the commercial resin Amberlite IR-120(H)(245°C).Cryogenic scanning electron microscopy testing demonstrated that SAPILs presented unique three-dimensional(3D)honeycomb structure in water,which was ascribed to the swelling-induced self-assembly of the molecules.Moreover,we used SAPILs with micron-sized honeycomb structure in water as catalysts for the hydrolysis of cyclohexyl acetate to cyclohexanol,and determined that their catalytic activity was much higher than that of homogeneous acid catalysts.The equilibrium concentrations of all reaction components inside and outside the synthesized SAPILs were quantitatively analyzed using a series of simulated reaction mixtures.Depending on the reaction mixture,the concentration of cyclohexyl acetate inside SAPIL-1 was 7.5–23.3 times higher than that outside of it,which suggested the high enrichment ability of SAPILs for cyclohexyl acetate.The excellent catalytic performance of SAPILs was attributed to their 3D honeycomb structure in water and high enrichment ability for cyclohexyl acetate,which opened up new avenues for designing highly efficient heterogeneous acid catalysts that could eventually replace conventional homogeneous acid catalysts.

Preparation of solid acid catalyst SO4^2-/TiO2/γ-Al2O3 for esterification: A study on catalytic reaction mechanism and kinetics

In this work, a series of SO4^2-/TiO2/γ-Al2O3 solid acid catalysts were synthesized by impregnation method, in which nano-TiO2 was prepared by sol–gel method, and then the nano-TiO2 sol was loaded on porous γ-Al2O3 supporter through impregnation. The structure and property of catalyst were characterized by XRD, N2-BET,SEM, TEM, XPS, NH3-TPD, Pyridine-IR and FT-IR. In addition, the catalyst of chelate bidentate coordination acid center model was established. The catalytic performance test was carried out in the esterification of n-butyl alcohol with lauric acid and the catalyst showed excellent activity. The experimental results showed that the medium strength acid sites were more dominant active sites than the strong and weak acid sites for the rapid esterification reaction. Its kinetic behaviors and activation energy were studied for the esterification under the catalytic reaction condition.

Oxidation of glyoxal to glyoxylic acid by oxygen over V_2O_5/C catalyst

A novel vanadium oxide catalyst supported on active carbon was prepared by an incipient wetness impregnation method, and the precursor was obtained from oxalic acid aqueous solutions of NH4VO3. The catalyst was applied liquid phase oxidation of glyoxal to glyoxylic acid. It was found that V2O5/C catalyst exhibited obvious activity for glyoxal oxidation. Glyoxylic acid could be obtained without pH regulation during the reaction. By using this catalyst, the conversion of glyoxal and the yield of glyoxalic acid were 29.2% and 13.6%, respectively at 313 K and oxygen flow 0.1 L/rain after reaction for 10 h.

Ketalization of Catechol with Carbonyl Compounds Catalyzed by Metal p-Toluenesulfonate as Biphasic Acid Catalyst

Ketalization of catechol was studied with various carbonyl compounds using metal p-toluenesulfonate as biphasic catalysts. The results showed that copper p-toluenesulfonate was the most efficient catalysts for the reaction. The advantages of high activity, stability, reusability and low cost for the simple synthetic procedure made the catalyst one of the best choice for the reaction.

Preparation of Cs-Rb-V series sulphuric acid catalyst

Cs Rb V series low temperature sulphuric acid catalyst was prepared for the first time by using carbonized mother liquor containing alkali metal salts. The results show that the conversion of SO 2 on catalyst prepared directly with carbonized mother liquor could reach to 24.8% at 410?℃. If n (Na)/ n (V) was adjusted properly, the conversion of SO 2 could be increased to 35.6% at 410?℃. Refined carbonized mother liquor could make the catalytic activity even higher at low temperature, the conversion of SO 2 could be increased to 36.65% at 410?℃. The catalyst was examined with differential thermal analysis. It was found that both endothermic peaks and exothermic peaks of catalyst shifted forward obviously and the catalyst possessed higher activity at low temperature.

Biodiesel Production from Crude Jatropha curcas L.Oil with Trace Acid Catalyst

Biodiesel produced from crude Jatropha curcas L.oil with trace sulfuric acid catalyst(0.02%-0.08% oil) was investigated at 135-184 ℃.Both esterification and transesterification can be well carried out simultane-ously.Factors affecting the process were investigated,which included the reaction temperature,reaction time,the molar ratio of alcohol to oil,catalyst amount,water content,free fatty acid(FFA) and fatty acid methyl ester(FAME) content.Under the conditions at 165 ℃,0.06%(by mass) H2SO4 of the oil mass,1.6 MPa and 20:1 methanol/oil ratio,the yield of glycerol reached 84.8% in 2 hours.FFA and FAME showed positive effect on the transesterification in certain extent.The water mass content below 1.0% did not show a noticeable effect on trans-esterification.Reaction kinetics in the range of 155 ℃ to 175 ℃ was also measured.

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.

Laboratory Research on Tahe AR Fluid Coking on Weak Acid Catalysts

Fluid coking on micro-spherical particles with acid sites on them could produce more light oils from Tahe AR.The conversion rate could increase by about 20% on the catalyst B compared to that obtained on the catalyst A and the light oil yield could increase by about 12%.The yield of gasoline and diesel was more than 50% from Tahe AR over the catalyst B.Tests on acidity of the catalyst B by pyridine FT-IR spectrometry showed that the total acid content and the ratio of weak acid number to total acid number were higher than other catalysts.

Synthesis and Performance of Mesoporous Phosphotungstic Acid/Alumina Composite as a Novel Oxidative Desulfurization Catalyst

A series of mesoporous phosphotungstic acid/alumina composites （HPW/Al_2O_3） with various HPW contents were synthesized by evaporation-induced self-assembly method. These composites were characterized by nitrogen adsorption-desorption, TEM, FTIR, and UV-vis, and were tested as catalysts in oxidation desulfurization of model fuel composed of dibenzothiophene （DBT） and hydrocarbon, using H202 as the oxidant. These composites exhibited high activity in catalytic oxidation of DBT in model fuel and good reusing ability. The best performance was achieved by using the mesoporous HPW/Al_2O_3 with 15wt% HPW content, which resulted in a DBT conversion of 98% after 2 h reaction at 343 K, and it did not show significant activity degradation after 3 recycles. Characterization results showed that the mesoporous structure of alumina and the Keggin structure of HPW were preserved in the formed composite. These results suggested that HPW/ Al_2O_3 could be a promising catalyst in oxidative desulfurization process.

Direct conversion of corn cob to formic and acetic acids over nano oxide catalysts

Considering energy shortage, large molecules in corn cob and easy separation of solid catalysts, nano oxides are used to transform corn cob into useful chemicals. Because of the microcrystals, nano oxides offer enough accessible sites for cellulose, hemicellulose and monosaccharide from corn cob hydrolysis and oxidant. Chemical conversion of corn cob to organic acids is investigated over nano ceria, alumina, titania and zirconia under various atmospheres. Liquid products are mainly formic and acetic acids. A small amount of other compounds, such as D-xylose,D-glucose, arabinose and xylitol are also detected simultaneously. The yield of organic acids reaches 25%–29% over the nano oxide of ceria,zirconia and alumina with 3 h reaction time under 453 K and 1.2 MPa O2. The unique and fast conversion of corn cob is directly approached over the nano oxides. The results are comparative to those of biofermentation and offer an alternative method in chemically catalytic conversion of corn cob to useful chemicals in a one-pot chemical process.

Novel efficient procedure for biodiesel synthesis from waste oils with high acid value using 1-sulfobutyl-3-methylimidazolium hydrosulfate ionic liquid as the catalyst

Preparation of biodiesel from waste oils containing 72% of free fatty acids catalyzed by a novel Br?nsted acidic ionic liquid 1-sulfobutyl-3-methylimidazolium hydrosulfate([BHSO_3MIM][HSO_4]) was systematically investigated.The optimum molar ratio of methanol to waste oils,catalyst amount,reaction temperature and reaction time were 8/1,10%(based on the mass of waste oils),140°C and 6 h,respectively,under which the obtained yield of biodiesel reached 94.9%.Also,[BHSO_3MIM][HSO_4] as a catalyst still retained around 97% of its original catalytic activity after successive re-use of 5 batches(6 h per batch),showing the excellent operational stability.Moreover,the acidic IL [BHSO_3MIM][HSO_4] was able to ef ficiently catalyze conversions of waste oils with different amounts of FFAs(free fatty acids) into biodiesel,and showed tremendous application potential.Therefore,an ef ficient and environmentally friendly catalyst is provided for the synthesis of biodiesel from waste oils with high acid value.

Effects of Calcination Temperature on the Acidity and Catalytic Performances of HZSM-5 Zeolite Catalysts for the Catalytic Cracking of n-Butane

The acidic modulations of a series of HZSM-5 catalysts were successfully made by calcination at different treatment temperatures, i.e. 500, 600, 650, 700 and 800 ℃, respectively. The results indicated that the total acid amounts, their density and the amount of B-type acid of HZSM-5 catalysts rapidly decreased, while the amounts of L-type acid had almost no change and thus the ratio of L/B was obviously enhanced with the increase of calcination temperature （excluding 800 ℃）. The catalytic performances of modified HZSM-5 catalysts for the cracking of n-butane were also investigated. The main properties of these catalysts were characterized by means of XRD, N2 adsorption at low temperature, NH3-TPD, FTIR of pyridine adsorption and BET surface area measurements. The results showed that HZSM-5 zeolite pretreated at 800 ℃ had very low catalytic activity for n-butane cracking. In the calcination temperature range of 500-700 ℃, the total selectivity to olefins, propylene and butene were increased with the increase of calcination temperature, while, the selectivity for arene decreased with the calcination temperature. The HZSM-5 zeolite calcined at 700 ℃ produced light olefins with high yield, at the reaction temperature of 650 ℃ the yields of total olefins and ethylene were 52.8% and 29.4%, respectively. Besides, the more important role is that high calcination temperature treatment improved the duration stability of HZSM-5 zeolites. The effect of calcination temperature on the physico-chemical properties and catalytic performance of HZSM-5 for cracking of n-butane was explored. It was found that the calcination temperature had large effects on the surface area, crystallinity and acid properties of HZSM-5 catalyst, which further affected the catalytic performance for n-butane cracking.

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.