Absorptive separation for resource utilization by selective SO2 removal from flue gas is a potential method applicable in practice. A flue gas desulfurization process for SO2 utilization by selective absorption in a l...Absorptive separation for resource utilization by selective SO2 removal from flue gas is a potential method applicable in practice. A flue gas desulfurization process for SO2 utilization by selective absorption in a lab-scale absorption tower at atmospheric pressure using N-formylmorpholine (NFM) as the absorbent is developed to capture and concentrate the SO2 from flue gas, in which the CO2 content is several orders higher than that of SO2. The investigation of the effects of different operating conditions on the SO2 removal efficiency shows that the SO2 removal efficiency can be obviously enhanced by increasing NFM concentration, or decreasing the absorption temperature, the superficial gas velocity, the gas-liquid ratio, or the SO2 concentration in absorption solution. Under the optimum operating conditions (covering a temperature of 40 °C, a superficial gas velocity of <0.0165 m/s, a gas-liquid ratio of 200—250, a SO2 concentration in lean NFM solution of 0—10 mg/L, and a NFM concentration of 3 mol/L), the SO2 removal rate reaches over 99.5% while the absorption of CO2 is negligible. Similarly, the SO2 removal rate is as high as 99.5% obtained in consecutive absorption-desorption cycles. Desorption experiment results indicate that the absorption of sulfur dioxide is completely reversible and the release of SO2 from NFM is very easy and rapid at 104 °C. The absorption simulation result for desulfurization of flue gas vented from the industrial catalytic cracking regenerator shows that 98.0% of SO2 can be absorbed in the absorber and most of them are released in the desorber. The experimental and simulated results show that the desulfurization ability and regenerability of NFM solution is encouraging for the development of FGD process to capture the SO2 from flue gas.展开更多
A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste...A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.展开更多
With the rapid development of industry and energy,the emission of a large number of SO2 has brought serious harm to the global environment.This paper introduces several main SO2 control technologies and describes the ...With the rapid development of industry and energy,the emission of a large number of SO2 has brought serious harm to the global environment.This paper introduces several main SO2 control technologies and describes the progress of the advanced desulfurization technologies at home and abroad.At last,higher requirements on desulfurization technology are raised.展开更多
Research and development of efficient, economical and resource-based flue gas desulfurization technology has always been a hot spot in the field of air pollution control. Molecular sieve materials have been paid atten...Research and development of efficient, economical and resource-based flue gas desulfurization technology has always been a hot spot in the field of air pollution control. Molecular sieve materials have been paid attention to by SO<sub>2</sub> adsorbent researchers due to their huge specific surface area. In this paper, 13X zeolite was modified with Cu(NO<sub>3</sub>) <sub>2</sub>·3H<sub>2</sub>O to obtain 13x-Xwt %CuO (calculated by the amount of CuO loaded). The adsorption time and capacity of SO<sub>2</sub> penetration sorbent and the isothermal curve of N<sub>2</sub> adsorption-desorption were studied. The results are as follows: 13X-3wt%CuO has the best adsorption effect, the penetration adsorption time is 110 min, the penetration adsorption capacity is 43.41 mg·g<sup>-1</sup>, the saturation adsorption capacity is 49.27 mg·g<sup>-1</sup>;The amount of CuO loading has a great influence on the adsorption effect of modified 13X molecular sieve on SO<sub>2</sub>. SEM and BET characterization showed that CuO modification did not change the external morphology of 13X molecular sieve, changed the pore size, but did not block the original channel of the molecular sieve, before and after modification belong to the type I adsorption isothermal curve. The pore size distribution and type of molecular sieve, as well as the content and type of alkali metal cations jointly control the adsorption process of SO<sub>2</sub> by 13X-xwt %CuO. XPS characterization showed that Cu(NO<sub>3</sub>) <sub>2</sub> decomposed into CuO and Cu<sub>2</sub>O during roasting at 450°C, CuO/Cu<sub>2</sub>O ≈ 1.5. The R<sup>2</sup> values of the quasi-second-order kinetic models obtained from the 13X-Xwt %CuO particle diffusion kinetic models were all above 0.99, indicating that the quasi-second-order kinetic equations were more relevant. Particle diffusion dynamics model in fitting results show that the adsorption process can be divided into two stages, the first phase of surface adsorption and diffusion rate in the granules common control process, more accurate dynamics model of the secondary in the second phase particle diffusion rate control stage, mainly for the micropore adsorption or chemical adsorption, quasi level 2 dynamic model conformity of variation;C is a constant not equal to 0, indicating that the adsorption of SO<sub>2</sub> is not completely through the form of intra-particle diffusion, and a small amount of chemisorption exists. And it is the compound effect of multiple adsorption mechanisms.展开更多
An organic macromolecule, poly(1-vinylimidazole), with an appropriate polymerization degree was proposed and mixed with water to form a novel aqueous absorbent for SO_2 capture. This aqueous solution absorbent has the...An organic macromolecule, poly(1-vinylimidazole), with an appropriate polymerization degree was proposed and mixed with water to form a novel aqueous absorbent for SO_2 capture. This aqueous solution absorbent has the advantages of simple preparation, good physicochemical properties, environment-friendliness, high ability in deep removal of SO_2, and excellent reusability. Moreover, pH-responsive behavior, pH buffering absorption mechanism, and their synergistic effect on absorption performance were revealed. The solubilities of SO_2 in the absorbent were measured in detail, and the results demonstrated excellent absorption capacity and recyclability. Then, mathematic models that describe SO_2 absorption equilibrium were established, and the corresponding parameters were estimated. More importantly, on the basis of model and experimental data, the absorption and desorption could maintain high efficiency within a wide operating region. In summary, this work provided a low-cost, efficient, and unique absorbent for SO_2 capture and verified its technical feasibility in industrial application.展开更多
In order to improve the slurry pH control accuracy of the absorption tower in the wet flue gas desulfurization process,a model free adaptive predictive control algorithm for the desulfurization slurry pH which is base...In order to improve the slurry pH control accuracy of the absorption tower in the wet flue gas desulfurization process,a model free adaptive predictive control algorithm for the desulfurization slurry pH which is based on a cyber physical systems framework is proposed.First,aiming to address system characteristics of non-linearity and pure hysteresis in slurry pH change process,a model free adaptive predictive control algorithm based on compact form dynamic linearization is proposed by combining model free adaptive control algorithm with model predictive control algorithm.Then,by integrating information resources with the physical resources in the absorption tower slurry pH control process,an absorption tower slurry pH optimization control system based on cyber physical systems is constructed.It is turned out that the model free adaptive predictive control algorithm under the framework of the cyber physical systems can effectively realize the high-precision tracking control of the slurry pH of the absorption tower,and it has strong robustness.展开更多
Based on the TiO2 photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO2 photocatalyst, design of photocatalysis reactor and influenc...Based on the TiO2 photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO2 photocatalyst, design of photocatalysis reactor and influencing factors for simul- taneous removal of SO2 and NO, and removal mechanism of SO2 and NO were studied. After the optimal values of concentration of O2 in flue gas, the relative humidity of flue gas and the irradiation time in the photocatalysis reactor were used, the efficiencies of removal for SO2 and NO can be achieved above 98% and about 67%, respectively. According to the results of removal products analysis, the re- moval mechanism of SO2 and NO based on TiO2 photocatlysis can be put forward, namely, SO2 was oxidized to SO3 partly, the bulk of NO was oxidized to NO2, and both were removed by resorbing finally.展开更多
In membrane contactors,maintaining a high SO_(2)absorption flux and an excellent wetting resistance are crucial for hazardous gas removal.In this study,we adopted an electrospinning strategy to fabricate highly robust...In membrane contactors,maintaining a high SO_(2)absorption flux and an excellent wetting resistance are crucial for hazardous gas removal.In this study,we adopted an electrospinning strategy to fabricate highly robust superhydrophobic dual-layer Elec-PVDF/SiO_(2)composite membrane contactors used for flue gas desulfurization.The composite membrane contactor consisted of a durable and ultrathin three-dimensional(3D)superhydrophobic surface and a porous supporting layer,where the formulation was optimized by regulating the PVDF concentration,solvent ratio and SiO_(2)particles content in electrospinning solution.The scanning electronic microscopy(SEM),EDS-mapping,water contact angle(WCA)and surface roughness of as-prepared Elec-PVDF/SiO_(2)composite membrane contactors were conducted to explore the physical and chemical structure.The SiO_(2)nanoparticles were uniformly loaded in ElecPVDF/SiO_(2)composite membrane contactor,and constructed micro-nano dual-coarse lotus-leaf-like morphology,which noticeably elevated surface roughness(Ra).The SiO_(2)nanoparticles also functioned as hydrophobic modifiers,which boosted the WAC up to 155.The SO_(2)absorption fluxes and SO_(2)removal efficiencies were investigated.In particular,the membrane contactor doped with 20 wt%SiO_(2)nanoparticles significantly elevated the stability of desulfurization performance.Besides,the membrane mass transfer coefficient(Km)and corresponding membrane mass transfer resistance(H/Km)were explored.展开更多
基金supported by National Natural Science Foundation of China (Major Program: 61590923)International (Regional) Cooperation and Exchange Project(No. 61720106008)+2 种基金National Natural Science Foundation of China (No. 61873093)National Science Fund for Distinguished Young Scholars (61725301)the Fundamental Research Funds for the Central Universities
文摘Absorptive separation for resource utilization by selective SO2 removal from flue gas is a potential method applicable in practice. A flue gas desulfurization process for SO2 utilization by selective absorption in a lab-scale absorption tower at atmospheric pressure using N-formylmorpholine (NFM) as the absorbent is developed to capture and concentrate the SO2 from flue gas, in which the CO2 content is several orders higher than that of SO2. The investigation of the effects of different operating conditions on the SO2 removal efficiency shows that the SO2 removal efficiency can be obviously enhanced by increasing NFM concentration, or decreasing the absorption temperature, the superficial gas velocity, the gas-liquid ratio, or the SO2 concentration in absorption solution. Under the optimum operating conditions (covering a temperature of 40 °C, a superficial gas velocity of <0.0165 m/s, a gas-liquid ratio of 200—250, a SO2 concentration in lean NFM solution of 0—10 mg/L, and a NFM concentration of 3 mol/L), the SO2 removal rate reaches over 99.5% while the absorption of CO2 is negligible. Similarly, the SO2 removal rate is as high as 99.5% obtained in consecutive absorption-desorption cycles. Desorption experiment results indicate that the absorption of sulfur dioxide is completely reversible and the release of SO2 from NFM is very easy and rapid at 104 °C. The absorption simulation result for desulfurization of flue gas vented from the industrial catalytic cracking regenerator shows that 98.0% of SO2 can be absorbed in the absorber and most of them are released in the desorber. The experimental and simulated results show that the desulfurization ability and regenerability of NFM solution is encouraging for the development of FGD process to capture the SO2 from flue gas.
基金Supported by the National High Technology Research and Development Program of China(2009AA05Z302)
文摘A sodium–zinc sorbent based flue gas desulfurization technology(Na–Zn-FGD) was proposed based on the experiments and analyses of the thermal decomposition characteristics of Ca SO3 and Zn SO3·2.5H2 O, the waste products of calcium-based semi-dry and zinc-based flue gas desulfurization(Ca–SD-FGD and Zn–SD-FGD) technologies, respectively. It was found that Zn SO3·2.5H2 O first lost crystal H2 O at 100 °C and then decomposed into SO2 and solid Zn O at 260 °C in the air, while Ca SO3 is oxidized at 450 °C before it decomposed in the air. The experimental results confirm that Zn–SD-FGD technology is good for SO2 removal and recycling, but with problem in clogging and high operational cost. The proposed Na–Zn-FGD is clogging proof, and more cost-effective. In the new process, Na2CO3 is used to generate Na2SO3 for SO2absorption, and the intermediate product Na HSO3 reacts with Zn O powders, producing Zn SO3·2.5H2 O precipitate and Na2SO3 solution. The Na2SO3 solution is clogging proof, which is re-used for SO2 absorption. By thermal decomposition of Zn SO3·2.5H2 O, Zn O is re-generated and SO2 with high purity is co-produced as well. The cycle consumes some amount of raw material Na2CO3 and a small amount of Zn O only. The newly proposed FGD technology could be a substitute of the traditional semi-dry FGD technologies.
文摘With the rapid development of industry and energy,the emission of a large number of SO2 has brought serious harm to the global environment.This paper introduces several main SO2 control technologies and describes the progress of the advanced desulfurization technologies at home and abroad.At last,higher requirements on desulfurization technology are raised.
文摘Research and development of efficient, economical and resource-based flue gas desulfurization technology has always been a hot spot in the field of air pollution control. Molecular sieve materials have been paid attention to by SO<sub>2</sub> adsorbent researchers due to their huge specific surface area. In this paper, 13X zeolite was modified with Cu(NO<sub>3</sub>) <sub>2</sub>·3H<sub>2</sub>O to obtain 13x-Xwt %CuO (calculated by the amount of CuO loaded). The adsorption time and capacity of SO<sub>2</sub> penetration sorbent and the isothermal curve of N<sub>2</sub> adsorption-desorption were studied. The results are as follows: 13X-3wt%CuO has the best adsorption effect, the penetration adsorption time is 110 min, the penetration adsorption capacity is 43.41 mg·g<sup>-1</sup>, the saturation adsorption capacity is 49.27 mg·g<sup>-1</sup>;The amount of CuO loading has a great influence on the adsorption effect of modified 13X molecular sieve on SO<sub>2</sub>. SEM and BET characterization showed that CuO modification did not change the external morphology of 13X molecular sieve, changed the pore size, but did not block the original channel of the molecular sieve, before and after modification belong to the type I adsorption isothermal curve. The pore size distribution and type of molecular sieve, as well as the content and type of alkali metal cations jointly control the adsorption process of SO<sub>2</sub> by 13X-xwt %CuO. XPS characterization showed that Cu(NO<sub>3</sub>) <sub>2</sub> decomposed into CuO and Cu<sub>2</sub>O during roasting at 450°C, CuO/Cu<sub>2</sub>O ≈ 1.5. The R<sup>2</sup> values of the quasi-second-order kinetic models obtained from the 13X-Xwt %CuO particle diffusion kinetic models were all above 0.99, indicating that the quasi-second-order kinetic equations were more relevant. Particle diffusion dynamics model in fitting results show that the adsorption process can be divided into two stages, the first phase of surface adsorption and diffusion rate in the granules common control process, more accurate dynamics model of the secondary in the second phase particle diffusion rate control stage, mainly for the micropore adsorption or chemical adsorption, quasi level 2 dynamic model conformity of variation;C is a constant not equal to 0, indicating that the adsorption of SO<sub>2</sub> is not completely through the form of intra-particle diffusion, and a small amount of chemisorption exists. And it is the compound effect of multiple adsorption mechanisms.
基金supported by the National Key R&D Program of China (No. 2016YFC0400406)
文摘An organic macromolecule, poly(1-vinylimidazole), with an appropriate polymerization degree was proposed and mixed with water to form a novel aqueous absorbent for SO_2 capture. This aqueous solution absorbent has the advantages of simple preparation, good physicochemical properties, environment-friendliness, high ability in deep removal of SO_2, and excellent reusability. Moreover, pH-responsive behavior, pH buffering absorption mechanism, and their synergistic effect on absorption performance were revealed. The solubilities of SO_2 in the absorbent were measured in detail, and the results demonstrated excellent absorption capacity and recyclability. Then, mathematic models that describe SO_2 absorption equilibrium were established, and the corresponding parameters were estimated. More importantly, on the basis of model and experimental data, the absorption and desorption could maintain high efficiency within a wide operating region. In summary, this work provided a low-cost, efficient, and unique absorbent for SO_2 capture and verified its technical feasibility in industrial application.
基金Supported by National Natural Science Foundation of China(61873006,61673053)National Key Research and Development Project(2018YFC1602704,2018YFB1702704)。
文摘In order to improve the slurry pH control accuracy of the absorption tower in the wet flue gas desulfurization process,a model free adaptive predictive control algorithm for the desulfurization slurry pH which is based on a cyber physical systems framework is proposed.First,aiming to address system characteristics of non-linearity and pure hysteresis in slurry pH change process,a model free adaptive predictive control algorithm based on compact form dynamic linearization is proposed by combining model free adaptive control algorithm with model predictive control algorithm.Then,by integrating information resources with the physical resources in the absorption tower slurry pH control process,an absorption tower slurry pH optimization control system based on cyber physical systems is constructed.It is turned out that the model free adaptive predictive control algorithm under the framework of the cyber physical systems can effectively realize the high-precision tracking control of the slurry pH of the absorption tower,and it has strong robustness.
文摘Based on the TiO2 photocatalysis mechanism, a new method of simultaneous desulfurization and denitrification from flue gas was proposed. Preparation of TiO2 photocatalyst, design of photocatalysis reactor and influencing factors for simul- taneous removal of SO2 and NO, and removal mechanism of SO2 and NO were studied. After the optimal values of concentration of O2 in flue gas, the relative humidity of flue gas and the irradiation time in the photocatalysis reactor were used, the efficiencies of removal for SO2 and NO can be achieved above 98% and about 67%, respectively. According to the results of removal products analysis, the re- moval mechanism of SO2 and NO based on TiO2 photocatlysis can be put forward, namely, SO2 was oxidized to SO3 partly, the bulk of NO was oxidized to NO2, and both were removed by resorbing finally.
基金the financial support from the National Key Research and Development Plan(2017YFC0404001)National Natural Science Foundation of China(No.21676201,21706189,21978217)+1 种基金Tianjin Municipal Education Commission Scientific Research Project(2017KJ074)Science and Technology Plans of Tianjin(18JCQNJC06800,18PTSYJC00190,17PTSYJC00050).
文摘In membrane contactors,maintaining a high SO_(2)absorption flux and an excellent wetting resistance are crucial for hazardous gas removal.In this study,we adopted an electrospinning strategy to fabricate highly robust superhydrophobic dual-layer Elec-PVDF/SiO_(2)composite membrane contactors used for flue gas desulfurization.The composite membrane contactor consisted of a durable and ultrathin three-dimensional(3D)superhydrophobic surface and a porous supporting layer,where the formulation was optimized by regulating the PVDF concentration,solvent ratio and SiO_(2)particles content in electrospinning solution.The scanning electronic microscopy(SEM),EDS-mapping,water contact angle(WCA)and surface roughness of as-prepared Elec-PVDF/SiO_(2)composite membrane contactors were conducted to explore the physical and chemical structure.The SiO_(2)nanoparticles were uniformly loaded in ElecPVDF/SiO_(2)composite membrane contactor,and constructed micro-nano dual-coarse lotus-leaf-like morphology,which noticeably elevated surface roughness(Ra).The SiO_(2)nanoparticles also functioned as hydrophobic modifiers,which boosted the WAC up to 155.The SO_(2)absorption fluxes and SO_(2)removal efficiencies were investigated.In particular,the membrane contactor doped with 20 wt%SiO_(2)nanoparticles significantly elevated the stability of desulfurization performance.Besides,the membrane mass transfer coefficient(Km)and corresponding membrane mass transfer resistance(H/Km)were explored.
