Copper slag assisted coke reduction of phosphogypsum for sulphur dioxide preparation

The reduction of phosphogypsum(PG)to lime slag and SO_(2)using coke can effectively alleviate the environmental problems caused by PG.However,the PG decomposition temperature remains high and the product yield remains poor.By adding additives,the decomposition temperature can be further reduced and PG decomposition rate and product yield can be improved.However,the use of current additives such as Fe_(2)O_(3)and SiO_(2)brings the problem of increasing economic cost.Therefore,it is proposed to use solid waste copper slag(CS)as a new additive to reduce PG to prepare SO2,which can reduce the cost and meet the environmental benefits at the same time.The effects of proportion,temperature and thermostatic time on PG decomposition are investigated by experimental and kinetic analysis combined with FactSage thermodynamic calculations to optimize the roasting conditions.Finally,the reaction mechanism is proposed.It is found that adding CS to the coke and PG system can increase the rate of PG decomposition and SO_(2)yield while lowering the PG decomposition temperature.For example,when the CS/PG mass ratio increases from 0 to 1,PG decomposition rate increases from 83.38%to 99.35%,SO_(2)yield increases from 78.62%to 96.81%,and PG decomposition temperature decreases from 992.4℃to 949.6℃.The optimal reaction parameters are CS/PG mass ratio of 1,Coke/PG mass ratio of 0.06 at 1100℃for 20 min with 99.35%PG decomposition rate and 96.81%SO_(2) yield.The process proceeds according to the following reactions:2CaSO_(4)+ 0.7C + 0.8Fe_(2)SiO_(4)→0.8Ca_(2)SiO_(4)+ 0.2Ca_(2)Fe_(2)O_(5)+ 0.4Fe_(3)O_(4)+2SO_(2)+ 0.7CO_(2)Finally,a process for decomposing PG with coke and CS is proposed.

Low temperature H_2S sensor based on copper oxide/tin dioxide thick film

Nanostructured tin dioxide （SnO2） powders were prepared by a sol-gel dialytic process and and the doping of CuO on it was completed by a deposition-precipitation method.The thick film sensors were fabricated from the CuO/SnO2 polycrystalline powders.Sensing behavior of the sensor was investigated with various gases including CO,H2,NH3,hexane,acetone,ethanol,methanol and H2S in air.The as-synthesized gas sensor had much better response to H2S than to other gases.At the same time,the CuO/SnO2 sensor had enough sensitivity,together with fast response and recovery,to distinguish H2S from those gases at 160 and 210 ℃.Therefore,it might have promising applications in the future.

Extraction of copper ions by supercritical carbon dioxide

Complexation combined with supercritical fluid extraction was used to extract Cu2+ in this study. The effects of pressure, temperature, volume of CO2 on the efficiency of extraction were systematically investigated. At the optimum condition a 57.32% recovery was achieved. Addition of suitable amount of methanol (v/v = 5%) to the supercritical CO2 can increase in the extraction of Cu2+ (72.69%, RSD = 2.12%, n = 3). And the recovery can further increase in the presence of non-ionic surfactant Triton X-100 because of its function of solubilization. Surfactant was first used in the extraction of metal ions in the present study, and the results are satisfied (90.52%, RSD = 2.20%, n = 3).

Copper Ion Beam Irradiation-Induced Effects on Structural,Morphological and Optical Properties of Tin Dioxide Nanowires

The 0.8 Me V copper （ Cu） ion beam irradiation-induced effects on structural, morphological and optical properties of tin dioxide nanowires （Sn02 NWs） are investigated. The samples are irradiated at three different doses 5 × 10^12 ions/cm2, 1 ×10^13 ions/cm2 and 5 × 10^13 ions/em2 at room temperature. The XRD analysis shows that the tetragonal phase of Sn02 NWs remains stable after Cu ion irradiation, but with increasing irradiation dose level the crystal size increases due to ion beam induced coalescence of NWs. The FTIR spectra of pristine Sn02 NWs exhibit the chemical composition of SnO2 while the Cn-O bond is also observed in the FTIR spectra after Cu ion beam irradiation. The presence of Cu impurity in SnO2 is further confirmed by calculating the stopping range of Cu ions by using TRM/SRIM code. Optical properties of SnO2 NWs are studied before and after Cu ion irradiation. Band gap analysis reveMs that the band gap of irradiated samples is found to decrease compared with the pristine sample. Therefore, ion beam irradiation is a promising technology for nanoengineering and band gap tailoring.

Separation and recovery of Cu and As during purification of copper electrolyte

Cu, As, Sb and Bi in copper electrolyte could be efficiently removed by reducing with SO2 followed by evaporative crystallization. As2O3 and CuSO4·5H2O were obtained after crystallized product was treated by dissolution, oxidation, neutralization, sedimentation, filtration and evaporative crystallization. The removal rates of Cu, As, Sb and Bi are 87.1%, 83.9%, 21.0% and 84.7%, respectively, when As （Ⅴ） in copper electrolyte is fully reduced to As （Ⅲ） by SO2, and the H2SO4 in concentrated copper electrolyte is 645 g/L. The removal rate of As is 92.81% when 65 g crystallized product is dissolved in 200 mL water at 30 ℃. The CuSO4·5H2O content is 98.8% when the filtrate is purified under the conditions that n（Fe）：n（As） is 1.2, the dosage of H2O2 is 19 times the stoichiometric needed, temperature is 45 ℃, time is 40 min, pH is 3.7, and then is evaporation crystallized.

Separation and recovery of Cu and As from copper electrolyte through electrowinning and SO_2 reduction

Cu and As were separated and recovered from copper electrolyte by multiple stage electrowinning, reduction with SO2and evaporative crystallization. Experimental results showed that when the current density was 200 A/m2, the electrolyte temperature was 55 °C, the electrolyte circulation rate was about 10 mL/min and the final Cu concentration was higher than 25.88 g/L, the pure copper cathode was recovered. By adjusting the current density to 100 A/m2 and the electrolyte temperature to 65 °C, the removal rate of As was 18.25% when the Cu concentration decreased from 24.69 g/L to 0.42 g/L. After As（V） in Cu-depleted electrolyte was fully reduced to As（Ⅲ） by SO2, the resultant solution was subjected to evaporative crystallization, then As2O3 was produced, and the recovery rate of As was 59.76%. The cathodic polarization curves demonstrated that both Cu2＋ concentration and As（V） affect the limiting current of Cu2＋ deposition.

Reduction and deposition of arsenic in copper electrolyte

The influences of temperature, H2SO4 concentration, CuSO4 concentration, reaction time and SO2 flow rate on the reduction of arsenic（V） with SO2 were studied and the deposition behavior of arsenic （III） under the effect of concentration and co-crystallization was investigated in copper electrolyte. The results indicate that reduction rate of arsenic （V） decreases with increasing temperature and H2SO4 concentration, but increases with increasing SO2 flow rate and reaction time, and it can reach 92% under appropriate conditions that reaction temperature is 65 °C, H2SO4 concentration is 203 g/L, CuSO4 concentration is 80 g/L, reaction time is 2 h and SO2 gas flow rate is 200 mL/min. To remove arsenic in the copper electrolyte, arsenic （V） is reduced to trivalence under the appropriate conditions, the copper electrolyte is concentrated till H2SO4 concentration reaches 645 g/L, and then the removal rates of As, Cu, Sb and Bi reach 83.9%, 87.1%, 21.0% and 84.7%. The XRD analysis shows that crystallized product obtained contains As2O3 and CuSO4·5H2O.

Improvement of catalytic stability for CO_2 reforming of methane by copper promoted Ni-based catalyst derived from layered-double hydroxides

Copper-promoted nickel-based metal nanoparticles (NPs) with high dispersion and good thermal stability were derived from layered-double hydroxides (LDHs) precursors that were facilely developed by a co-precipitation strategy. The copper-promoted Ni-based metal NPs catalysts were investigated for methane reforming with carbon dioxide to hydrogen and syngas. A series of characterization techniques including XRD, N2adsorption and desorption, H2-TPR, XPS, CO2-TPD, TEM, TGA and in situ CH4-TPSR were utilized to determine the structure-function relationship for the obtained catalysts. The copper addition accelerated the catalyst reducibility as well as the methane activation, and made the Ni species form smaller NPs during both preparation and reaction by restricting the aggregation. However, with higher copper loading, the derived catalysts were less active during methane reforming with CO2to syngas. It was confirmed that the catalyst with 1 wt% Cu additive gave the higher catalytic activity and remained stable during long time reaction with excellent resistance to coking and to sintering. Furthermore, the mean size of metal NPs changed minimally from 6.6 to 7.9 nm even after 80 h of time on stream at temperature as high as 700 °C for this optimized catalyst. Therefore, this high dispersed anti-coking copper-promoted nickel catalyst derived from LDHs precursor could be prospective catalyst candidate for the efficient heterogeneous catalysis of sustainable CO2conversion. © 2016 Science Press

Photopromoted Carbonylation of Alkyl Bromides Catalyzed by Copper Salts under Ambient Conditions

Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.

Research on Copper Removal from Composite Wires of Copper-Stainless Steel Fibers

A method of copper removal from composite wires of copper stainless steel fibers by means of sulfuric acid solution with hydrogen dioxide is described. After removing copper, the stainless steel fibers remain smooth and uniform, keep high strength and are arranged in order. The copper sulfate with 5 H 2O (CuSO 4 5H 2O) can be crystallized directly from the reaction solution.

Synthesis of α-hydroxy ketones by copper（Ⅰ）-catalyzed hydration of propargylic alcohols: CO2 as a cocatalyst under atmospheric pressure

Inexpensive and efficient Cu(Ⅰ) catalysis is reported for the synthesis of α-hydroxy ketones from propargylic alcohols, CO2, and water via tandem carboxylative cyclization and nucleophilic addition reaction. Notably, hydration of propargylic alcohols can be carried out smoothly under atmospheric CO2 pressure, generating a series of α-hydroxy ketones efficiently and selectively. This strategy shows great potential for the preparation of valuable α-hydroxy ketones by using CO2 as a crucial cocatalyst under mild conditions.

Synthesis and Characterization of Free and Copper (II) Complex of N,N′-<i>Bis</i>(Salicylidene)Ethylenediamine for Application in Dye Sensitized Solar Cells

Dye sensitized solar cell represents a promising method for the conversion of solar energy to electric energy. In the present work free N,N'-bis(salicyli-dene)ethylenediamine and its copper (II) complex were synthesized, characterized, and investigated for use as dye sensitizers in the fabrication of dye sensitized solar cells. The dyes were characterized using UV-Vis, Steady State Florescence, and Fluorescence Lifetime, Thermogravimetric Analysis, Differential Scanning Calorimetry, and Cyclic Voltammetry. The thermogravimetric analyses of the ligand and the ligand Copper complex demonstrate the stabilizing effect of the copper ion on the ligand complex. Additionally, the copper ion is shown to stabilize the structure, as evidenced by the 150oC increase in the extrapolated onset temperature of the decomposition event. The ligand copper complex is further stabilized by the presence of the copper, which is determined by the 6.34% residue that remained at the end of the thermogravimetric analysis, compared with 0% residue when applying the same condition for the ligand without copper. The current-voltage characteristics of the cells and the electrochemical impedance were determined. The photovoltaic performance of the solar cell devices fabricated using N,N'-bis(salicylidene) ethylenediamine dye was found to be slightly better than those produced from the copper complex. The solar to electric power efficiency of the ligand-based dye sensitized solar cell was 0.14% and that of the copper complex was found to 0.12%. Although the difference in the cell efficiency is quite small, it is obvious that the insertion of Copper into the ligand did not enhance the performance of the solar cells. The photocurrent-photovoltage results are consistent with the absorption spectra that showed a more prominent band for the ligand. The free hydroxyl groups, present in the ligand but absent from the copper complex owing to their coordination with the copper metal, could be responsible for the difference in the performance of the devices. The hydroxyl groups get attached to the TiO2 and facilitate the transfer of electrons.

Copper-based bimetallic electrocatalysts for CO_(2) reduction:From mechanism understandings to product regulations

Electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)is a promising method to solve current environment and energy issues.Copper-based catalysts have been widely studied for converting CO_(2) into value-added hy-drocarbon products.Cu monometallic catalyst has been proved to have some shortcomings,including relatively high energy barriers and diverse reaction pathways,leading to low reaction activities and poor product selec-tivity,respectively.Recently copper-based bimetallic tandem catalysts have attracted extensive attentions due to their special catalyst structure,which can be easily regulated to achieve high CO_(2) RR reactivity and product selectivity.With the development of quantum chemistry calculations and spectroscopic characterization methods,deep understandings of CO_(2) RR from the mechanism perspective provide a broad horizon for the design of effi-cient catalysts.This review offers a good summary of reaction mechanisms and product regulation strategies over copper-based bimetallic catalysts,along with a brief discussion on future directions towards their practical applications.

超亲气泡沫铜纳米线电极电化学还原CO_(2)性能

利用可再生电能进行电化学还原CO_(2)被认为是一种有前景的储能和减排技术,但在阴极发生析氢副反应,将降低电化学还原CO_(2)的性能。采用泡沫铜为基底制备铜纳米线电极扩展电极的电化学活性面积,然后通过十七氟癸基三甲基硅烷对电极进行亲气处理,使电极表面从疏气状态变为超亲气状态,从而强化气相反应物CO_(2)传质,增加反应三相接触线,提高电极的电化学还原CO_(2)性能。实验结果表明:与未亲气处理的泡沫铜纳米线电极相比,所制备的超亲气泡沫铜纳米线电极虽然具有较小的电化学活性面积,但其超亲气的特性更有利于CO_(2)的传质,抑制了电解液中氢离子的传输,有效削弱了析氢副反应的发生。在电解电位为-1.5V(vs.Ag/AgCl)时,H_(2)法拉第效率降低了17.7%,电化学还原CO_(2)性能提升。

Cu/TiO_(2) Photocatalysts for CO_(2) Reduction: Structure and Evolution of the Cocatalyst Active Form

Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.

CuGa_(2)电催化CO_(2)还原制合成气

碳达峰、碳中和是实现我国绿色可持续发展发展的重大战略需求。合成气作为现代化工生产的重要基础原料,其传统的制备方法高度依赖化石能源,导致了大量的温室气体排放利用可再生电力驱动的电催化CO_(2)还原制合成气技术作为一种环保且可持续的替代方案,近年来受到广泛的研究与关注。虽然已有研究探讨了不同催化剂对电催化CO_(2)还原制合成气的V(H_(2))/V(CO)的影响,但对于在单一催化剂上实现对合成气产物中H_(2)和CO选择性的有效调控仍具有挑战性。为了实现在单一催化剂上对合成气产物中V(H_(2))/V(CO)的选择性调控,本研究采用高温固相合成工艺合成了CuGa_(2)金属间化合物,用以作为电催化剂来实现高选择性、可调性电催化CO_(2)还原制合成气,并通过SEM、EDS、XRD和XPS等一系列表征分析手段,研究了CuGa_(2)金属间化合物的理化特性与电化学性能,并探究了CuGa_(2)金属间化合物在电催化CO_(2)还原过程中的相关催化机理。研究结果表明,该催化剂作为CuGa_(2)和少量金属氧化物的混合物,能够通过改变电解液浓度、调控pH值的手段,显著调控其对于电催化CO_(2)还原反应(eCO_(2)RR)和析氢反应(HER)的选择性,从而调控合成气产物中的V(H_(2))/V(CO)。此外,不同电位对V(H_(2))/V(CO)的影响测试结果显示,通过控制施加电位,可以调节CuGa_(2)催化剂活性位点的利用率,进而改变eCO_(2)RR和HER的选择性,实现合成气产物中V(H_(2))/V(CO)在0.3~4内可调。

电解工艺条件对Cu基催化剂电化学还原CO_(2)的产物分布影响

工业化发展实现生产力飞跃的同时,化石能源的消耗导致大气中二氧化碳(CO_(2))含量升高,电化学还原CO_(2)(CO_(2)RR)制备高附加值化学品,不仅能解决温室气体带来的问题,还能够缓解能源危机。铜基催化剂是目前用于CO_(2)RR的有效催化剂之一,本研究通过对铜片表面水热处理制备氧化亚铜,将CO_(2)电化学还原为甲酸和一氧化碳,并系统性考察了电解液浓度、CO_(2)压力以及电解液温度对电化学还原产物分布的影响。实验结果发现,电解液浓度降低、CO_(2)压力增加可以抑制析氢反应,电解液温度升高有利于CO的生成。当电解液浓度1 mol/L、温度30℃,CO_(2)的压力为55 atm时,在-0.7~-1.2 V(vs.RHE)测试电压范围内,甲酸法拉第效率达70%以上,最高达可到83.6%。当电解液温度由30℃升至80℃,电压为-0.9 V(vs.RHE)时,甲酸法拉第效率由80%降低到49.7%,CO法拉第效率由4.4%增加到39.2%,表明随着电解液温度升高,甲酸法拉第效率降低。

CO_(2)加氢制甲醇铜基催化剂研究进展

大气中二氧化碳(CO_(2))浓度的增加对人类赖以生存的地球环境产生了严重的负面影响,因此,减少和降低大气中CO_(2)的浓度迫在眉睫。其中,借助太阳能、风能等可再生能源获得的绿色低成本氢气,将CO_(2)加氢转化为高附加值的甲醇,将有助于减少CO_(2)排放,助推碳中和目标的实现。铜基催化剂因其具有良好的活性和甲醇选择性,一直是CO_(2)加氢制甲醇催化领域的研究重点。本工作综述了近年来CO_(2)加氢制甲醇铜基催化剂的研究进展,首先对CO_(2)加氢制甲醇反应进行了热力学与反应机理分析;其次,探讨了助剂、载体以及制备方法对铜基催化剂物化性质及催化性能的影响;随后,讨论了CO_(2)加氢制甲醇的工业化进展;最后,对当前铜基催化剂催化CO_(2)加氢制甲醇的挑战以及未来研究趋势进行了总结与展望。

An effective catalyst carrier SiO_(2):Enhancing catalytic and combustion properties of CuFe_(2)O_(4)on energetic components

To enhance the catalytic activity of copper ferrite(CuFe_(2)O_(4))nanoparticle and promote its application as combustion catalyst,a low-cost silicon dioxide(SiO_(2))carrier was employed to construct a novel CuFe_(2)O_(4)/SiO_(2)binary composites via solvothermal method.The phase structure,morphology and catalytic activity of CuFe_(2)O_(4)/SiO_(2)composites were studied firstly,and thermal decomposition,combustion and safety performance of ammonium perchlorate(AP)and 1,3,5-trinitroperhydro-1,3,5-triazine(RDX)with it affecting were then systematically analyzed.The results show that CuFe_(2)O_(4)/SiO_(2)composite can remarkably either advance the decomposition peak temperature of AP and RDX,or reduce the apparent activation energy at their main decomposition zone.Moreover,the flame propagation rate of RDX was promoted by about 2.73 times with SiO_(2)content of 3 wt%,and safety property of energetic component was also improved greatly,in which depressing the electrostatic discharge sensitivity of pure RDX by about 1.89 times.In addition,the effective range of SiO_(2)carrier content in the binary catalyst is found to be 3 to 5 wt%.Therefore,SiO_(2)opens a new insight on the design of combustion catalyst carrier and will promote the application of CuFe_(2)O_(4)catalyst in solid propellant.

分子筛铜基催化剂的合成及其用于CO_(2)加氢制备甲醇性能研究

为解决传统甲醇合成工艺完全依赖化石燃料且伴随大量CO_(2)排放等问题,采用浸渍法制备了分子筛铜基催化剂,并将其用于CO_(2)催化加氢制备甲醇。考察了CO_(2)和氢气作为混合气的循环次数、反应温度、体积空速和反应压力等对CO_(2)加氢制备甲醇转化率和选择性影响。在反应温度为240℃、体积空速为4000h^(-1)、反应压力为5.0MPa和混合气循环3次的优化条件下,甲醇的转化率和选择性分别达到95.3%、98.5%,为CO_(2)的低成本、高效利用提供新方向。