一种耐硫催化脱氧剂及其生产方法

本发明为一种耐硫催化脱氧剂及其生产方法，涉及催化技术领域。一种以活性氧化铝为载体，金属铂和钼为复合活性组分的催化脱氧剂及其制备方法，金属铂质量占催化剂总质量的0．03％～0．5％，钼占0．5％～15％。本催化脱氧剂应用范围较广，使用空速可达5000～10000h^-1，催化脱氧深度可从入口O2体积分数的5×10^-3脱除至1×10^-7以下。本发明的脱氧剂具有抗硫性，用于含硫场合，可将有机硫转化为H2S。本催化剂适用于各类含氢气体中精脱除杂质氧，尤其是合成气中氧的脱除。

采用新型高效脱氧剂生产高纯氮

我们知道，工业气体常见的纯化方法主要有化学反应法(又称催化反应法)，选择吸附法，低温精馏法，金属吸气法和薄膜扩散法等。在实际应用中，往往是几种方法同时采用，如用低温精馏法+选择吸附法来制职纯氩气。本文介绍一种化学反应法+吸附法——采用新型高效催化脱氧剂3093和3093A脱氧，并用5A分子筛吸附杂质，制取高纯氮的应用实例。

全自动循环氮气脱氧净化系统

介绍了为国内化纤厂聚合车间的切片干燥工艺研制的全自动循环氮气脱氧净化系统 ,该系统由全自动加氢控制系统和装填 HDC- 10 .3型高效脱氧催化剂的脱氧反应器组成。

NH_3 selective catalytic reduction of NO: A large surface TiO_2 support and its promotion of V_2O_5 dispersion on the prepared catalyst

A titania support with a large surface area was developed, which has a BET surface area of 380.5 m^2/g, four times that of a traditional titania support. The support was ultrasonically impregnated with 5 wt% vanadia. A special heat treatment was used in the calcination to maintain the large surface area and high dispersion of vanadium species. This catalyst was compared to a common V2O5-TiO2 catalyst with the same vanadia loading prepared by a traditional method. The new catalyst has a surface area of 117.7 m^2/g, which was 38% higher than the traditional V2O5-TiO2 catalyst. The selective catalytic reduction（SCR） performance demonstrated that the new catalyst had a wider temperature window and better N2 selectivity compared to the traditional one. The NO conversion was 80% from 200 to 450 °C. The temperature window was 100 °C wider than the traditional catalyst. Raman spectra indicated that the vanadium species formed more V-O-V linkages on the catalyst prepared by the traditional method. The amount of V-O-Ti and V=O was larger for the new catalyst. Temperature programmed desorption of NH3, temperature programmed reduction by H2 and X-ray photoelectron spectroscopy results showed that its redox ability and total acidity were enhanced. The results are helpful for developing a more efficient SCR catalyst for the removal of NOx in flue gases.

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.

Electrospinning synthesis of porous boron-doped silica nanofibers for oxidative dehydrogenation of light alkanes

The discovery of the high activity and selectivity of boron-based catalysts for oxidative dehydrogenation(ODH)of alkanes to olefins has attracted significant attention in the exploration of a new method for the synthesis of highly active and selective catalysts.Herein,we describe the synthesis of porous boron-doped silica nanofibers(PBSNs)100-150 nm in diameter by electrospinning and the study of their catalytic performance.The electrospinning synthesis of the catalyst ensures the uniform dispersion and stability of the boron species on the open silica fiber framework.The one-dimensional nanofibers with open pore structures not only prevented diffusion limitation but also guaranteed high catalytic activity at high weight hourly space velocity(WHSV)in the ODH of alkanes.Compared to other supported boron oxide catalysts,PBSN catalysts showed higher olefin selectivity and stability.The presence of Si-OH groups in silica-supported boron catalysts may cause low propylene selectivity during the ODH of propane.When the ODH conversion of ethane reached 44.3%,the selectivity and productivity of ethylene were 84%and 44.2%g_(cat)^(-1)s^(-1),respectively.In the case of propane ODH,the conversion,selectivity of olefins,and productivity of propylene are 19.2%,90%,and 76.6 jimol g_(cat)^(-1)s^(-1),respectively.No significant variations in the conversion and product selectivity occurred during 20 h of operation at a high WHSV of 84.6 h^(-1).Transient analysis and kinetic experiments indicated that the activation of O2 was influenced by alkanes during the ODH reaction.

Ru nanoparticles supported on hydrophilic mesoporous carbon catalyzed low-temperature hydrodeoxygenation of microalgae oil to alkanes at aqueous-phase

The processing of an energy carrier such as microalgae oil into valuable fuels and chemicals is quite promising.Aqueous-phase processing is suitable for this purpose because the separation of intrinsic water from the algae cell is difficult.In this study,we synthesized ruthenium(Ru)nanoparticles supported on highly hydrophilic mesoporous carbon to catalyze the quantitative hydrodeoxygenation(HDO)of microalgae oil to alkanes in a one-pot process at a low temperature(140℃)in the aqueous phase.The mesoporous carbon was obtained by single-step calcination of starch and zinc chloride in nitrogen.The as-obtained carbon showed high surface areas and pore volumes,allowing high dispersion of Ru nanoparticles.The surface of the carbon material was rich in hydroxyl groups,as evidenced by X-ray photoelectron spectroscopy(XPS),infrared(IR)spectroscopy,and thermogravimetric analysis(TGA)measurements.As a result,the carbon material contacted preferably with the water phase versus the organic phase,improving the accessibility of substrates.On the other hand,the contact angle test results speculated the superior hydrophilic nature of mesoporous Ru/C(ZnCl2,starch)than commercial Ru/C.Both kinetics modeling and in situ IR monitoring in water revealed the superior performance of the hydrophilic mesoporous and hydrophilic Ru/C compared to a commercial Ru/C for the tandem hydrogenation of stearic acid and decarbonylation of stearyl alcohol.The herein designed hydrothermal carbon material was highly active,environmentally benign,sustainable,and recyclable material,and could be potentially used for other hydrogenation reactions in the aqueous phase.

Ordered macroporous boron phosphate crystals as metal-free catalysts for the oxidative dehydrogenation of propane

Ordered macroporous materials with rapid mass transport and enhanced active site accessibility are essential for achieving improved catalytic activity.In this study,boron phosphate crystals with a three-dimensionally interconnected ordered macroporous structure and a robust framework were fabricated and used as stable and selective catalysts in the oxidative dehydrogenation(ODH)of propane.Due to the improved mass diffusion and higher number of exposed active sites in the ordered macroporous structure,the catalyst exhibited a remarkable olefin productivity of^16 golefin gcat^-1 h^-1,which is up to 2–100 times higher than that of ODH catalysts reported to date.The selectivity for olefins was 91.5%(propene:82.5%,ethene:9.0%)at 515℃,with a propane conversion of 14.3%.At the same time,the selectivity for the unwanted deep-oxidized CO2 product remained less than 1.0%.The tri-coordinated surface boron species were identified as the active catalytic sites for the ODH of propane.This study provides a route for preparing a new type of metal-free catalyst with stable structure against oxidation and remarkable catalytic activity,which may represent a potential candidate to promote the industrialization of the ODH process.

Oxidative Desulfurization of Model Sulfur Compound by Potassium Ferrate in the Presence of Phosphomolybdic Acid Catalyst

In this work, the removal of thiophene from simulated oil has been studied by using the adsorption, extraction and oxidation/adsorption methods, respectively. In the adsorptive desulfurization process, different commercial adsorbents were used to eliminate thiophene at ambient pressure and mild temperature, and the results showed that carbon powder had the best adsorption ability. In the extractive desulfurization process, the best desulfurization result was obtained when DMF is used. In the oxidative/adsorptive desulfurization procedure using synthesized potassium ferrate as the oxidant and phosphomolybdic acid solution as the catalyst, thiophene was oxidized and removed from hydrocarbons in combination with active carbon adsorption, and the residual sulfur content of simulated oil could be reduced to 15.3mg/L from the original level of 200mg/L, with the desulfurization rate reaching 92.3%.

Preparation of Alumina Binder-Added PtSnNa/AlSBA-15 Catalyst for Propane Dehydrogenation

Abstract： The present article compares the propane dehydrogenation performance of alumina binder-added PtSnNa/ A1SBA-15 catalysts prepared via three different procedures in comparison with the performance of a binder-free PtSnNa/ AISBA-15 catalyst. All these catalysts have been investigated by reaction tests and some physico-chemical characterizations such as BET, H2 chemisorption, catalytic grain crushing strength, NHa-TPD and TPO analyses. Test results showed that the addition of alumina binder could enhance the mechanical strength of catalyst evidently. Moreover, the different preparation procedures not only modified the characteristics of both acid and metal functions but also affected the coke deposition on the catalysts. Among these catalysts studied, the catalyst prepared by impregnation followed by the agglomeration of alumi- na binder had exhibited the highest catalytic activity and stability compared with other catalyst samples undergoing different preparation procedures. The possible reason may be attributed to the highest metallic dispersion and the strong interactions among Pt, Sn and the support.

Effects of indium on Ni/SiO_2 catalytic performance in hydrodeoxygenation of anisole as model bio-oil compound: Suppression of benzene ring hydrogenation and C–C bond hydrogenolysis

SiO2‐supported monometallic Ni and bimetallic Ni‐In catalysts were prepared and used for hydrodeoxygenation of anisole,which was used as a model bio‐oil compound,for BTX(benzene,toluene,and xylene)production.The effects of the Ni/In ratio and Ni content on the structures and performances of the catalysts were investigated.The results show that In atoms were incorporated into the Ni metal lattice.Although the Ni‐In bimetallic crystallites were similar in size to those of monometallic Ni at the same Ni content,H2uptake by the bimetallic Ni‐In catalyst was much lower than that by monometallic Ni because of dilution of Ni atoms by In atoms.Charge transfer from In to Ni was observed for the bimetallic Ni‐In catalysts.All the results indicate intimate contact between Ni and In atoms,and the In atoms geometrically and electronically modified the Ni atoms.In the hydrodeoxygenation of anisole,although the activities of the Ni‐In bimetallic catalysts in the conversion of anisole were lower than that of the monometallic Ni catalyst,they gave higher selectivities for BTX and cyclohexane as a result of suppression of benzene ring hydrogenation and C–C bond hydrogenolysis.They also showed lower methanation activity.These results will be useful for enhancing carbon yields and reducing H2consumption.In addition,the lower the Ni/In ratio was,the greater was the effect of In on the catalytic performance.The selectivity for BTX was primarily determined by the Ni/In ratio and was little affected by the Ni content.We suggest that the performance of the Ni‐In bimetallic catalyst can be ascribed to the geometric and electronic effects of In.

Synthesis of Silica-Dispersed NiMo Hydrodesulfurization Catalysts

Silica-dispersed NiMo hydrodesulfurization catalysts were synthesized by the deposition-precipitation method. For comparative purposes, bulk NiMo catalysts were obtained by co-precipitation. The silica-dispersed NiMo catalyst had highly active metals content. Silica was employed to disperse active metals for full utilization of active components. The BET analysis showed that the silica-dispersed NiMo catalysts had a high surface area （147.0 m2/g） and pore volume （0.27 mL/g）, whereas the bulk NiMo catalysts exhibited a very low surface area （87.5 m2/g）. Transmission electron microscopy results proved that the active components were dispersed on the SiO2 substrate. X-ray diffraction patterns of the silicadispersed NiMo catalyst and the bulk NiMo catalyst were indexed to NiMoO4. The hydrodesulfurization activity of silicadispersed NiMo catalysts was much higher than that of reference catalysts and could be up to twice greater than those of commercial NiMo alumina-supported systems per gram of catalyst. The activity testing results also demonstrated that the silica-dispersed NiMo catalyst was an effective hydrodesulflarization catalyst.

Preparation of Bi_2WO_6 Photocatalyst and Its Application in the Photocatalytic Oxidative Desulfurization

A type of visible light photocatalyst Bi2WO6 was prepared from Bi(NO3)3.5H2O and Na2WO4.2H2O by means of hydrothermal method and was characterized by UV-vis diffuse reflectance spectrometry and XRD.Oxidative desulfurization via photocatalysis was investigated using thiophene dissolved in octane as the model compound,with hydrogen peroxide used as the oxidant.The effects of hydrogen peroxide mass fraction,irradiation time,dosage of photocatalyst Bi2WO6 on the desulfurization efficiency were also investigated.Under suitable conditions,the desulfurization rate of model compound reached over 70%.

Selection of Chelated Fe(Ⅲ)/Fe(Ⅱ) Catalytic Oxidation Agents for Desulfurization Based on Iron Complexation Method

Optimization of factors influencing the experiments on reactions involving 8 different chelating agents and soluble Fe(III)/Fe(II) salts was carried out to yield chelated iron complexes. A combination of optimized influencing factors has resulted in a Fe chelating capacity of the iron-based desulfurization solution to be equal to 6.83—13.56 g/L at a redox potential of 0.185—0.3. The desulfurization performance of Fe(III)/Fe(II) chelating agents was investigated on a simulated sulfur-containing industrial gas composed of H2 S and N2 in a cross-flow rotating packed bed. Test results have revealed that the proposed iron-based desulfurization solution showed a sulfur removal efficiency of over 99% along with a Fe chelating capacity exceeding 1.35 g/L. This desulfurization technology which has practical application prospect is currently in the phase of commercial scale-up study.

Preparation of Cu-BiVO_4 and Its Photocatalytic Properties for Desulfurization of Model Oil

A photocatalyst Cu-BiVO4 was synthesized by the hydrothermal method and was characterized by XRD, UV-vis DRS, and N2 adsorption-desorption measurement. The catalytic activity of the Cu-BiVO4 samples was studied on desulfurization of thiophene dissolved in n-octane, which was used as a model light oil, via photocatalytic oxidation reaction under illumination by visible light. The catalyst characterization results indicated that the loading of Cu on the catalyst did not change the crystal phase of BiVO4, and the crystallinity of the Cu-BiVO4 sample was found to be better at pH=7. The Cu-BiVO4 samples presented a significant bathochromic shift of the absorption band in the visible region, and the absorption intensity increased for the composite catalyst. The desulfurization experiments showed that the Cu-BiVO4 sample prepared at a pH value of 7 had a better catalytic activity. Under proper operating conditions, the desulfurization rate of the model compound achieved by Cu-BiVO4 sample prepared at pH=7 could reach as high as 90%.

Influence of Alumina Content on Catalytic Performance of PtSn/Al_2O_3/SBA-15 Catalysts for Propane Dehydrogenation

The alumina-modified SBA-15 （A12OJSBA-15） zeolite was prepared in a non-aqueous system by using toluene as the solvent, and was used to support the PtSn-based catalyst for propane dehydrogenation. The BET surface area mea- surements, hydrogen chemisorption, FT-IR spectroscopy, NH3-TPD, XPS and TPO techniques were used to characterize the catalysts. Test results showed that the addition of alumina not only could modify the acid function of the support but also the structure of the metallic phase, thus affecting their catalytic properties. Among these catalysts studied, the PtSn/AI203 （5%）/ SBA-15 catalyst exhibited a best catalytic performance in terms of propane conversion and selectivity to propene. The high catalytic performance might be attributed to the relatively good Pt metal dispersion and/or the strong interaction between Pt and Sn species.

Oxidative Desulfurization of Diesel Fuel with Hydrogen Peroxide Using Na_2WO_4 as Catalyst

Oxidative desulfurization was performed on Na2WO4 catalyst in the presence of hydrogen peroxide and acetic acid under mild reaction conditions （atmospheric pressure and temperature range of 293--343 K）. Different organic compounds including benzothiophene （BT）, dibenzothiophene （DBT）, 4, 6-dimethyl dibenzothiophene （4, 6-DMDBT） were used to investigate the reactivity of this catalyst, and the effect of various parameters, such as temperature, solvents and the amount of oxidant reagent used in oxidative desulfurization reaction, was also examined. The results showed that the Na2WO4- H202 system was very effective for oxidative desulfurization, and the oxidation of BT, DBT and 4, 6-DMDBT was influenced by different parameters.

Influence of dehydrating agents on the oxidative carbonylation of methanol for dimethyl carbonate synthesis over a Cu/Y-zeolite catalyst

The influence of the dehydration by metal oxides on the synthesis of dimethyl carbonate （DMC） via oxidative carbonylation of methanol was studied. A Cu/Y-zeolite catalyst was prepared by the ion exchange method from CuCl2.2H2O and the commercial NH4-form of the Y type zeolite, The catalyst was characterized by X-ray fluorescence （XRF）, N2 adsorption （BET method）, X-ray diffraction （XRD）, and temperature-programmed de- sorption of ammonia （NH3-TPD） to evaluate its Cu and Cl content, surface area, structure, and acidity. Reaction tests were carried out using an autoclave （batch reactor） for 18 h at 403 K and 5.5 MPa （2CH3OH ＋ 1/2O2 ＋ CO （CH3O）2CO ＋ H2O）. The influence of various dehydrating agents （ZnO, MgO, and CaO） was examined with the aim of increasing the methanol conversion （XMeOH, MeOH conversion）. The MeOH conversion increased upon addition of metal oxides in the order CaO 〉〉 MgO 〉 ZnO, with the DMC selectivity （SDMC） following the order MgO 〉 CaO 〉 ZnO. The catalysts and dehydrating agents were characterized before and after the oxidative carbonylation of methanol by thermogravimetric and differential thermogravimetric （TG/DTG）, and XRD to con- firm that the dehydration reaction occurred via the metal oxide （MO ＋ H2O →M（OH）2）. The MeOH conversion increased from 8.7% to 14.6% and DMC selectivity increased from 39.0% to 53.1%, when using the dehydrating azent CaO.

Effect of Preparation Method on the Physicochemical Properties of MoVNbTe Catalyst for Propane Ammoxidation to Acrylonitrile

MoVNbTe catalyst has been found to be the most active and selective catalyst in the ammoxidation of propane to ACN, the selective oxidation of propane to acrylic acid and in the oxidative dehydrogenation of ethane to ethylene. However, in our previous work, when 0.5 mL of MoVNbTe catalyst prepared using slurry method was tested in the propane ammoxidation to ACN, it only shows 1% conversion of propane with about 55% selectivity to CAN, thus giving only 0.6% yields to ACN. The poor catalyst activity is attributed to insufficient formation of crystalline phases essential for the propane activation process. In an attempt to improve the physicochemical properties of this catalyst, several preparation methods have been used, namely hydrothermal, reflux, changing the solvent and changing the calcinations temperature. The modified catalysts have been characterized using X-Ray Diffraction （XRD） and N2 physisorption （BET）. The MoVNbTe catalyst prepared by hydrothermal method shows a remarkable improvement in the formation of crystalline phases.