The equilibrium solubilities of 5(NH4)O·12WO3·5H2O (APT·5H2O) were determined at the terminal ammonia concentration of 2 mol/L at 87-95℃. Experimental data were regressed. The linear functional relatio...The equilibrium solubilities of 5(NH4)O·12WO3·5H2O (APT·5H2O) were determined at the terminal ammonia concentration of 2 mol/L at 87-95℃. Experimental data were regressed. The linear functional relation between the solubility of APT- 5H2O and the temperature (t /℃) is given as y = - 588.08 + 7.28t. The solubility of the species as a function of the terminal ammonia concentration (x / mol · L-1) is also achieved: y = 36.76 + 18.86x. The solubility of APT · 5H2O produced by ion-exchange method in China is much lower, which is due to much lower silica, much higher NH4Cl, and a small amount of APT · 7H2O with low solubility in the APT crystals. APT · 7H2O forms because of a large amount of NH4Cl and the low activity of water in the crystallization.展开更多
Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel m...Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel method. The catalysts were characterized by EDX, BET, FTIR, UV-Vis DRS, XRD and the results indicate that such paratungstate-loaded catalysts maintained their heptatungstate structure in the anatase titania matrix up to 400 ℃. The catalysts were tested for the heterogeneous photodegradation of chlorobenzene in aqueous media and showed a better catalytic activity than P-25 TiO_ 2 because paratungstate can prevent the recombination of the holes and electrons produced during irradiation. Moreover, the paratungstate-loaded titania catalysts can resist the disaggregation during the photoirradiation and can be easily recycled from the aqueous suspensions after reactions.展开更多
A new technology for the crystallization of ammonium paratungstate with coarse grain has beenstudied. The factors influencing the physi-chemical properties of ammonium paratungstate crystal, such astemperature, concen...A new technology for the crystallization of ammonium paratungstate with coarse grain has beenstudied. The factors influencing the physi-chemical properties of ammonium paratungstate crystal, such astemperature, concentration, seed crystal, agitation. etc. were examined. It is necessary to keep high temperature and low concentration in the process. and the addition of seed crystal and agitation with air is also in favor of the system. Ammonium paratungstate crystal with particle size of 36-42 μm and apparent density of2. 0-2. 2 g·cm- 3 were obtained by controlling suitable technological parameters.展开更多
The effects of temperature, ammonia concentration and ammonium carbonate concentration on the dissolving behavior of ammonium paratungstate were studied in（NH4）2CO3-NH3？H2O-H2O system. The results show that rising ...The effects of temperature, ammonia concentration and ammonium carbonate concentration on the dissolving behavior of ammonium paratungstate were studied in（NH4）2CO3-NH3？H2O-H2O system. The results show that rising temperature, prolonging duration, increasing ammonia concentration and decreasing ammonium carbonate concentration favor dissolving of ammonium paratungstate at temperature below 90 ℃, while the WO3 concentration decreases after a certain time at temperature above 100 ℃. Furthermore, the undissolved tungsten exists in the form of either APT·4 H2O below 90 ℃ or pyrochlore-type tungsten trioxide above 100℃. In dissolving process, the ammonium paratungstate dissolves into paratungstate ions followed by partially converting to tungstate ion, resulting in the coexistence of the both ions. This study may provide a new idea to exploit a novel technique for manufacturing ammonium paratungstate and pyrochlore-type tungsten trioxide.展开更多
Three new suprarnolecular networks based on paratungstate and N-donor bridging ligands, [H2bpmp]2,5H[H2W12O40]·2H20（1）, [H2（bpp）]2[H（py-CH3）]0.25 [H（py-C2Hs）]0.25H1.5[H2W12O40]·4H2O（2） and [H2pip]3...Three new suprarnolecular networks based on paratungstate and N-donor bridging ligands, [H2bpmp]2,5H[H2W12O40]·2H20（1）, [H2（bpp）]2[H（py-CH3）]0.25 [H（py-C2Hs）]0.25H1.5[H2W12O40]·4H2O（2） and [H2pip]3[H2W12O40]（3）[bpmp=N,N＇-bis（4-pyridylmethyl）piperazine; bpp=l,3-bis（4-pyridyl）propane; py=pyridine; pip=piperazine] were prepared by the hydrothermal synthesis and characterized by elemental analysis, infrared（IR）, thermogravimetric（TG） analysis and single-crystal X-ray diffraction（XRD）. All the compounds show high-dimen- sional suprarnolecular networks based on [H2W12O40]^6- and the protonated N-donor ligands via the N-H.…O-W hydrogen bonds and/or π…πstacking interactions. Their luminescent properties were investigated.展开更多
Both paratungstate A and paratungstate B（para A and para B for short）are distinct isopolytungstates with Z value（H<sup>+</sup>/W）of 1.14. When WO<sub>4</sub><sup>2-</sup> aqueou...Both paratungstate A and paratungstate B（para A and para B for short）are distinct isopolytungstates with Z value（H<sup>+</sup>/W）of 1.14. When WO<sub>4</sub><sup>2-</sup> aqueous solution is acidised to Z=1.14, para A forms rapidly, while para B forms only after heating fora long time. Because the transformation rate from para A to para B is extremely slow and there is no reli-展开更多
The production of ammonium paratungstate(APT) is riddled with the generation of wastewater,which causes environmental problems.To solve the problem of wastewater generation at source,a membrane electrolysis-NH3·H...The production of ammonium paratungstate(APT) is riddled with the generation of wastewater,which causes environmental problems.To solve the problem of wastewater generation at source,a membrane electrolysis-NH3·H2O precipitation method,which prevents wastewater generation and recycles the reagents used in the process,was proposed and investigated in this study.The electrolysis process was investigated based on parameters such as initial cathodic and anodic NaOH concentrations,and current density.The results showed that an increase in current density and initial cathodic NaOH concentration and a decrease in the initial anodic NaOH concentration would enhance the separation of tungsten and sodium.The optimum condition was found at a current density of 666 A·m^(-2),initial anodic and cathodic NaOH concentrations of 69 g·L^(-1) and 40 g·L^(-1),with a current efficiency of 75.40%,and energy consumption for producing 1 ton of NaOH was 2184 kW·h.The precipitation process was investigated based on the acidic high W/Na molar ratio solution obtained by the electrolysis process with NH3·H2O as the precipitant.Parameters such as excessive coefficient,temperature,and W/Na molar ratio were studied.The result showed that the variation of excessive coefficient and solution temperature had an opposite effect on the purity of the APT,while an increase in the W/Na molar ratio would increase the product purity.The precipitation product obtained had a purity of 99.6% and was characterized using X-ray diffraction,inductively coupled plasma,and scanning electron microscopy.The methods proposed in this study could provide fundamental information for the design of a cleaner APT production process.展开更多
The reaction behaviors of silicate species in （NH4）2WO4-（NH4）2CO3-NH3-H2O system are crucial to developing a greenmanufacture technique for ammonium paratungstate. In order to efficiently remove silicon from the s...The reaction behaviors of silicate species in （NH4）2WO4-（NH4）2CO3-NH3-H2O system are crucial to developing a greenmanufacture technique for ammonium paratungstate. In order to efficiently remove silicon from the system, the reaction behaviors ofsilicate species were systematically investigated by thermodynamic analysis. The thermodynamic analysis shows that silicate in thetungstate clinker partly decomposes in the leaching process, with 150-160 mg/L silicon thermodynamically at 25 ℃. The dissolvedsilicon can be removed by magnesium salts via forming insoluble MgSiO3. The low carbonate and high ammonia concentrations inthe system are beneficial to the removal of silicon, with silicon concentration reaching 8-10 mg/L thermodynamically, whereasMgSiO3 precipitation is hardly formed when the concentration of total carbonate is more than 1.5 mol/L. The reaction behaviors ofcalcium and magnesium were also studied in the system. The results in the verification experiments consist with the theoreticalcalculation.展开更多
文摘The equilibrium solubilities of 5(NH4)O·12WO3·5H2O (APT·5H2O) were determined at the terminal ammonia concentration of 2 mol/L at 87-95℃. Experimental data were regressed. The linear functional relation between the solubility of APT- 5H2O and the temperature (t /℃) is given as y = - 588.08 + 7.28t. The solubility of the species as a function of the terminal ammonia concentration (x / mol · L-1) is also achieved: y = 36.76 + 18.86x. The solubility of APT · 5H2O produced by ion-exchange method in China is much lower, which is due to much lower silica, much higher NH4Cl, and a small amount of APT · 7H2O with low solubility in the APT crystals. APT · 7H2O forms because of a large amount of NH4Cl and the low activity of water in the crystallization.
文摘Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel method. The catalysts were characterized by EDX, BET, FTIR, UV-Vis DRS, XRD and the results indicate that such paratungstate-loaded catalysts maintained their heptatungstate structure in the anatase titania matrix up to 400 ℃. The catalysts were tested for the heterogeneous photodegradation of chlorobenzene in aqueous media and showed a better catalytic activity than P-25 TiO_ 2 because paratungstate can prevent the recombination of the holes and electrons produced during irradiation. Moreover, the paratungstate-loaded titania catalysts can resist the disaggregation during the photoirradiation and can be easily recycled from the aqueous suspensions after reactions.
文摘A new technology for the crystallization of ammonium paratungstate with coarse grain has beenstudied. The factors influencing the physi-chemical properties of ammonium paratungstate crystal, such astemperature, concentration, seed crystal, agitation. etc. were examined. It is necessary to keep high temperature and low concentration in the process. and the addition of seed crystal and agitation with air is also in favor of the system. Ammonium paratungstate crystal with particle size of 36-42 μm and apparent density of2. 0-2. 2 g·cm- 3 were obtained by controlling suitable technological parameters.
基金Project(51274243) supported by the National Natural Science Foundation of China
文摘The effects of temperature, ammonia concentration and ammonium carbonate concentration on the dissolving behavior of ammonium paratungstate were studied in（NH4）2CO3-NH3？H2O-H2O system. The results show that rising temperature, prolonging duration, increasing ammonia concentration and decreasing ammonium carbonate concentration favor dissolving of ammonium paratungstate at temperature below 90 ℃, while the WO3 concentration decreases after a certain time at temperature above 100 ℃. Furthermore, the undissolved tungsten exists in the form of either APT·4 H2O below 90 ℃ or pyrochlore-type tungsten trioxide above 100℃. In dissolving process, the ammonium paratungstate dissolves into paratungstate ions followed by partially converting to tungstate ion, resulting in the coexistence of the both ions. This study may provide a new idea to exploit a novel technique for manufacturing ammonium paratungstate and pyrochlore-type tungsten trioxide.
基金Supported by the National Natural Science Foundation of China(No.91027002)the Fundamental Research Funds for the Central Universities,China(No.11CXPY002)
文摘Three new suprarnolecular networks based on paratungstate and N-donor bridging ligands, [H2bpmp]2,5H[H2W12O40]·2H20（1）, [H2（bpp）]2[H（py-CH3）]0.25 [H（py-C2Hs）]0.25H1.5[H2W12O40]·4H2O（2） and [H2pip]3[H2W12O40]（3）[bpmp=N,N＇-bis（4-pyridylmethyl）piperazine; bpp=l,3-bis（4-pyridyl）propane; py=pyridine; pip=piperazine] were prepared by the hydrothermal synthesis and characterized by elemental analysis, infrared（IR）, thermogravimetric（TG） analysis and single-crystal X-ray diffraction（XRD）. All the compounds show high-dimen- sional suprarnolecular networks based on [H2W12O40]^6- and the protonated N-donor ligands via the N-H.…O-W hydrogen bonds and/or π…πstacking interactions. Their luminescent properties were investigated.
文摘Both paratungstate A and paratungstate B（para A and para B for short）are distinct isopolytungstates with Z value（H<sup>+</sup>/W）of 1.14. When WO<sub>4</sub><sup>2-</sup> aqueous solution is acidised to Z=1.14, para A forms rapidly, while para B forms only after heating fora long time. Because the transformation rate from para A to para B is extremely slow and there is no reli-
基金financially supported by National Key R&D Program of China (Nos.2020YFC1909703)the Natural Science Foundation of China (Nos.52104403)+1 种基金HBIS Group Co.,Ltd. Key R&D Program (No.20210036)Lv Liang Key R&D Program (No.2020GXZDYF7)。
文摘The production of ammonium paratungstate(APT) is riddled with the generation of wastewater,which causes environmental problems.To solve the problem of wastewater generation at source,a membrane electrolysis-NH3·H2O precipitation method,which prevents wastewater generation and recycles the reagents used in the process,was proposed and investigated in this study.The electrolysis process was investigated based on parameters such as initial cathodic and anodic NaOH concentrations,and current density.The results showed that an increase in current density and initial cathodic NaOH concentration and a decrease in the initial anodic NaOH concentration would enhance the separation of tungsten and sodium.The optimum condition was found at a current density of 666 A·m^(-2),initial anodic and cathodic NaOH concentrations of 69 g·L^(-1) and 40 g·L^(-1),with a current efficiency of 75.40%,and energy consumption for producing 1 ton of NaOH was 2184 kW·h.The precipitation process was investigated based on the acidic high W/Na molar ratio solution obtained by the electrolysis process with NH3·H2O as the precipitant.Parameters such as excessive coefficient,temperature,and W/Na molar ratio were studied.The result showed that the variation of excessive coefficient and solution temperature had an opposite effect on the purity of the APT,while an increase in the W/Na molar ratio would increase the product purity.The precipitation product obtained had a purity of 99.6% and was characterized using X-ray diffraction,inductively coupled plasma,and scanning electron microscopy.The methods proposed in this study could provide fundamental information for the design of a cleaner APT production process.
基金Project(51274243)supported by the National Natural Science Foundation of ChinaProject(2015CX001)supported by the Innovation-driven Plan of Central South University,China
文摘The reaction behaviors of silicate species in （NH4）2WO4-（NH4）2CO3-NH3-H2O system are crucial to developing a greenmanufacture technique for ammonium paratungstate. In order to efficiently remove silicon from the system, the reaction behaviors ofsilicate species were systematically investigated by thermodynamic analysis. The thermodynamic analysis shows that silicate in thetungstate clinker partly decomposes in the leaching process, with 150-160 mg/L silicon thermodynamically at 25 ℃. The dissolvedsilicon can be removed by magnesium salts via forming insoluble MgSiO3. The low carbonate and high ammonia concentrations inthe system are beneficial to the removal of silicon, with silicon concentration reaching 8-10 mg/L thermodynamically, whereasMgSiO3 precipitation is hardly formed when the concentration of total carbonate is more than 1.5 mol/L. The reaction behaviors ofcalcium and magnesium were also studied in the system. The results in the verification experiments consist with the theoreticalcalculation.
