Preparation And Desulfurization Performance Of Metal Based Ionic Liquids And Biomass Functional Desulfurizer

Biogas as a renewable energy has gradually replaced non renewable energy such as coal,oil and natural gas.The main components of biogas include methane(CH4)and some impurity gases such as carbon dioxide(CO2)and hydrogen sulfide(H2S).H2 S is a colorless,poisonous and irritant odor.In the pipeline transportation,its existence is very easy to cause corrosion of pipeline,and it is easy to cause catalyst poisoning and environmental pollution in the process of biogas utilization.Therefore,H2 S will be removed before biogas utilization.In this paper,a series of metal based functionalized ionic liquids have been synthesized and applied to remove H2 S from biogas.?)The Fe based functionalized ionic liquid 1.6Et3NHCl-Fe Cl3 was synthesized and the immobilized Fe based functional ionic liquid was prepared by physical impregnation to the surface of activated carbon and noted as 1.6Et3NHCl-Fe Cl3-AC.The structure of these sorbents were characterized by FT-IR,SEM,nitrogen adsorption-desorption isotherms and TGA.The adsorption performance of these sorbents were studied over the source of activated carbon,the immobilization amount of ionic liquid,the temperature of desulfurization by solid phase desulfurization system.The results show that when the activated carbon source is coconut shell carbon,the ionic liquid load is 20 wt%,and the desulfurization temperature is 20?,the desulfurization material 1.6Et3NHCl-Fe Cl3-AC has the maximum meticulous desulphurization sulfur capacity of 2.16 mg·g-1 and the desulfurization capacity of the corresponding ionic liquid 1.6Et3NHCl-Fe Cl3 is 10.8 mg·g-1.Then the adsorbed 1.6Et3NHCl-Fe Cl3-AC1 was regenerated by air stripping oxidation regeneration.The first adsorption capacity of the regenerated material was better than the raw material.?)The ionic liquid 1.6Et3NHCl-Fe Cl3 was immobilized to four kinds of porous materials such as active carbon,silica gel,alumina ball and active adsorption resin,and noted as 1.6Et3NHCl-Fe Cl3-AC,1.6Et3NHCl-Fe Cl3-SG,1.6Et3NHCl-Fe Cl3-AOO and 1.6Et3NHCl-Fe Cl3-ABS,respectively.The properties of the desulfurization material were confirmed by FT-IR spectrum,nitrogen adsorption-desorption isotherms and the desulphurization product has been analyzed by UV-vis and XRD.The results showed that the desulphurization material 1.6Et3NHCl-Fe Cl3-SG with the ionic liquid loading of 20 wt% and the desulfurization temperature is 30 ? has the maximum desulfurization sulfur capacity about 7.2 mg·g-1.The desulfurization capacity of the corresponding ionic liquid 1.6Et3NHCl-Fe Cl3 is 36 mg·g-1.The results of XRD and UV analysis showed that the desulfurization product was S0.Then the adsorbed 1.6Et3NHCl-Fe Cl3-SG was regenerated by air stripping oxidation regeneration and the regenerated desulfurization material still show the high desulfurization capacity.?)Four functional ionic liquids [Apmim]Cl-Cu Cl2,[Bmim]Cl-Cu Cl2,[Bmim]Cl-Cu Cl2-Ch and Et3NHCl-Cu Cl2 were synthesized,and then these ionic liquids were successfully immobilized on silica based silica black by reverse load method,noted as [Apmim]Cl-Cu Cl2-WB,[Bmim]Cl-Cu Cl2-WB,[Bmim]Cl-Cu Cl2-Ch-WB and Et3NHCl-Cu Cl2-WB,respectively.The characterization of supported adsorbent was studied by FT-IR,SEM,N2 adsorption-desorption isotherms.The results showed that the desulfurization performance of amine desulphurization material Et3NHCl-Cu Cl2-WB was significantly better than that of imidazole based desulphurizing materials [Bmim]Cl-Cu Cl2-WB and [Bmim]Cl-Cu Cl2-Ch-WB.The desulfurization capacity of Et3NHCl-Cu Cl2-WB increased with the increase of loading,but it is not a multiple increase in ideal state.With the increase of temperature,the desulfurization capacity first increased and then decreased.With the increase of gas velocity,the breakthrough time of desulfurization decreased,but the meticulous sulfur content increased first and then decreased.The desulfurization material Et3NHCl-Cu Cl2-WB with the ionic liquid loading is 10 wt%,the desulfurization temperature is 30?,and the gas mass flow is 150 m L min-1,it has the maximum fine sulfur capacity of 12.90 mg·g-1 at this time,and the corresponding ionic liquid sulfur capacity is 64.5 mg·g-1,which is far higher than the sulfur capacity of the Fe based ionic liquid.The sulfur capacity of the Et3NHCl-Cu Cl2-WB desulfurizer can still be maintained at 55 mg·g-1 through the regeneration of the high temperature oxygen-cooling-original regeneration method for four times.?)Six kinds of phosphomo molybdenum heteropoly acid based of ionic liquids [Bmim]3PM-[Bmim]Ac,[Bmim]3PM-[Bmim]BF4,[Emim]3PM-[Emim]Ac,[Emim]3PM-[Emim]BF4,[Hmim]3PM-[Hmim]Ac and [Hmim]3PM-[Hmim]BF4 were synthesized,and the desulfurization performance was studied by the liquid phase desulphurization system about the ionic liquid concentration and the desulfurization temperature.The experimental results show that the ionic liquid desulfurizer [Hmim]3PM-[Hmim]Ac with the concentration of [Hmim]3PM is 0.002 mol·L-1 and the desulfurization temperature is 25 ? has the highest desulfurization sulfur capacity can be up to 9.95 g·L-1.Then the adsorbed [Hmim]3PM-[Hmim]Ac was regenerated by the microwave assisted-air regeneration method and the sulfur capacity of the desulfurizer could be as high as 7.11 g·L-1 after five regeneration times.