Cu改性吸附脱硫剂的表征及其脱硫性能

采用等体积浸渍法对ZnO-活性炭吸附脱硫剂进行Cu改性,并采用XRD、BET、TPR等手段对脱硫剂进行表征。以硫质量分数78.2μg/g的胜华炼油厂催化加氢汽油为原料,采用10mL固定床微型反应器评价脱硫剂的脱硫性能,考察Cu的负载量、反应温度、反应压力、氢/油体积比对脱硫剂的脱硫性能影响。结果表明,研制的Cu改性吸附脱硫剂具有较好的选择性深度脱硫能力,烯烃饱和也得到了较好的抑制;最优的工艺条件为反应温度300℃、反应压力1 MPa、液体空速1.0h-1、氢/油体积比100。Cu负载量为4%的Cu改性脱硫剂ADS-Cu-4具有优异的脱硫性能,在最优工艺条件下得到硫质量分数低于10μg/g且辛烷值损失仅为0.3个单位的产品。

锰氧化物改性炭基铁酸锌吸附脱硫剂的制备及其表征

利用锰氧化物脱硫剂机械强度高,反应速率快的特性,对炭基铁酸锌进行改性。在超声波辅助下共沉淀法制备活性炭负载复合金属氧化物(Fe,Zn,Mn)脱硫剂。采用XRD、SEM-EDS及XPS分析手段进行表征,分析其晶型结构、分散度、孔隙结构及其表面元素结构分布。结果表明,负载型铁锌锰金属氧化物在500℃下煅烧后,ZFM(1∶2∶0.6)形成的物相有Zn Mn O3,(Zn,Mn)Fe2O4,几乎没有单一金属氧化物的特征峰出现,说明铁锰锌氧化物之间均能形成复合晶相,其晶粒粒径大小随温度的升高而增加。复合金属氧化物在活性炭上高度分散,且形成大量孔隙,且Mn以Mn3+,Mn4+存在。

应用于流化床/传输反应器的新型ZnO可再生吸附脱硫剂

美国GTI开发出一种新型的吸附剂合成技术,它是以无机和有机原料的溶胶处理工艺为基础,制备具有独特性能的ZnO可再生吸附脱硫剂,而不再需要采用传统的吸附剂制备技术,如共沉淀或者固体氧化物混合后进行挤条、造粒或喷雾干燥等方法来获取。

负载活性炭吸附脱除液态丙烯中二甲基硫醚技术研究

利用不同金属氯化物对活性炭材料进行表面改性,制备出新型的负载吸附脱硫剂。通过对开发的脱硫剂脱硫性能的评价实验,确定以氯化亚铜为活性组分制备出的脱硫剂脱除效果最好。评价结果表明,该新型负载吸附脱硫剂对中石化济南分公司聚丙烯保安精制装置中产生的二甲基硫醚的脱除效果较好,可脱除液态丙烯中微量的二甲基硫醚,进而可提高丙烯聚合催化剂的活性,降低聚合催化剂的消耗,改善聚丙烯产品的质量,为企业带来良好的经济效益。

移动式集成设备设计及其在化学清洗废水处理中的应用

采用吸附型脱硫剂对石化企业停工检修和化学清洗过程产生的废水进行处理试验与性能评价,并在此基础上设计制造了移动式集成设备用于化学清洗废水预处理,可有效去除该废水中的硫化物、有机胺等恶臭污染物,出水水质可就地通过污水管网排入企业污水处理系统,能有效缩短化学清洗废水的处理周期,减少化学清洗废水的转运。运行效果表明,该设备对产生高浓度化学清洗废水的企业具有应用价值。

Comparison of desulfurization kinetics of copper oxide sorbent

Desulfurization experiments of CuO, γ-Al2O3 and CuO/γ-Al2O3 were made in simulated flue gas by means of thermogravimetric analysis. It is found that reaction activities of CuO supported on γ-Al2O3 could be highly improved. Desulfurization kinetics of CuO/γ-Al2O3 was studied in the temperature range of 250 °C-400 °C and SO2 concentration of 0.1%-0.9%. The experimental data were tested and compared with kinetics models of volume reaction model(VRM), grain size model(GSM), random pore model(RPM) and pore-blocking model(PBM). Correlation analysis shows that VRM and RPM models do not fit experimental data well. GSM contradicts with the changes in the physical and chemical properties of Cu O/γ-Al2O3 as the desulfurization proceeds. It is found that PBM is consistent with the change of pore structure of CuO/γ-Al2O3 sorbent during desulfurization process and predicts the conversion-time curves of the sorbent well. Meanwhile, kinetics parameters are obtained and discussed.

Deep Desulfurization via Adsorption by Silver Modified Bentonite

In order to further reduce the sulfur content in liquid hydrocarbon fuels,a desulfurization process by adsorption for removing alkyl dibenzothiophenes was investigated.Desulfurization of model gasoline by bentonite adsorbents loaded with silver nitrate was studied.The test results indicated that the bentonite adsorbents loaded with Ag + ions were effective for adsorbing the alkyl dibenzothiophenes.The crystal structure of bentonite adsorbents was characterized by X-ray diffraction (XRD) and their acidity was measured by Fourier transform infrared (FT-IR) spectroscopy.Several factors influencing the desulfurization capability,including the Ag + loading,the baking temperature,as well as the reaction temperature,were investigated.The desulfurization efficiency was enhanced by increasing the Ag + loading and the best result was obtained at a silver loading of 7 m%.It was found that the adsorption capacity of the alkyl dibenzothiophenes on bentonite loaded with Ag + ions increased with a decreasing temperature.Baking of the adsorbent could also improve the desulfurization capacity,and the optimum baking temperature was 423 K.

一体化集成设备在炼化企业化学清洗废水处理中的应用

采用吸附型脱硫剂对炼化企业停工检修,设备钝化和化学清洗过程产生的废水进行处理试验与性能评价,并在此基础上设计制造了一体化集成设备用于化学清洗废水预处理,可有效去除该废水中的硫化物、有机胺等恶臭污染物,出水水质可以显著缩短化学清洗废水的处理周期。

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%.

Study on Reduction of Sulfur Content in FCC Gasoline

Reduction of sulfur content in FCC gasoline was studied in a fixed fluid bed (FFB) unit by using metal-modified LV-23 FCC catalyst. The results showed that the sulfur content in FCC gasoline could be reduced with LV-23 catalyst modified with zinc, palladium, zinc-palladium, zinc-cobalt, and zinc-nickel. Among these metals or metal combinations, palladium-containing catalyst was the most effective. Desulfurization of the heavy fraction of FCC gasoline was more effective than full-range gasoline under the same conditions with palladium-containing catalysts. A high reaction temperature was favorable to desulfurization, but it would reduce the yield of liquid product. After desulfurization reaction, the olefin content of product gasoline decreased while the aromatic and iso-alkane contents increased. Removal of thiophene and benzothiophene is higher.

Removal of Thiophenic Sulfur Compounds from Oil Using Chlorinated Polymers and Lewis Acid Mixture via Adsorption and Friedel-Crafts Alkylation Reaction

For efficient removal of thiophenic sulfur （S-） compounds from oils, a novel method is proposed here, i.e. one-pot alkylation desulfurization （OADS）, in which oil insoluble chlorinated polymer such as polyvinyl chlo- ride （PVC） is used as the alkylating regent with Lewis acid as catalyst. The aromatic S-compounds are grafted to the polymer through Friedel-Crafts reaction and removed facilely along with the polymer. The OADS mechanism is identified by scanning electron microscope and analyzer with surface area and pore size of the polymer. The influ- ence of some factors on the OADS is studied, e.g. the type and amount of chlorinated polymers and Lewis acids. It is nroved that thionhene and benzothioDhene can be removed efficiently from oil by PVC＋AlCl3 mixture even in the presence of 25% （by mass） of benzene due to the synergetic effects of the adsorptive desulfurization of AlCl3 and the alkylation desulfurization of PVC.

Effects of steam on CO2 absorption ability of calcium-based sorbent modified by peanut husk ash

The CO_2 absorption ability of synthetic calcium-based sorbent modified by peanut husk ash (PHA) was tested by Thermal Gravimetric Analyzer (TGA), and the effects of steam and calcination temperature were investigated. The PHA composition was analyzed by X-Ray Fluorescence (XRF), the apparent morphology was characterized by scanning electron microscope (SEM), and the phases of the sorbent before and after calcination were examined by X-ray diffraction (XRD). The addition of PHA effectively improved the cyclic stability of the calcium-based sorbent. The optimal molar ratio of SiO_2 in PHA to CaO was around 0.07. Steam had positive effect on keeping porosity of the sorbent at the chemical reaction stage, and improved its CO_2 absorption ability. Steam also reduced the diffusion resistance of the product layer, and depressed the influence of high temperature calcination. It was also found that the steam hydration after calcination was an effective way to recover the absorption ability of the sorbent, while the hydration duration of 10 min was enough.