Claims (9)
一種化石燃料之超音波輔助氧化脫硫方法，包含：將一水相觸媒溶液與一油相化石燃料混合，以形成一混合溶液，其中該油相化石燃料至少包含有機硫化合物，該有機硫化物包括噻吩(thiophene；T)、苯并噻吩(benzothiophene；BT)、二苯并噻吩(dibenzothiophene；DBT)或上述之衍生物，該水相觸媒溶液至少包含六價鐵金屬催化劑與四辛基銨鹽界面活性催化劑，該六價鐵金屬催化劑為六價鐵酸鹽，該六價鐵酸鹽包括高鐵酸鋰、高鐵酸鈉、高鐵酸鈣或上述之任意組合，且該水相觸媒溶液與該油相化石燃料之重量比為1：1至3：1；對該混合溶液進行一超音波震盪處理，以形成一乳化溶液，其中該六價鐵金屬催化劑係將該油相化石燃料之該有機硫化合物氧化為硫氧化合物；對該乳化溶液進行一相分離步驟，以從該乳化溶液分離出該油相化石燃料，其中該相分離步驟更至少包含：從該乳化溶液分離出該水相觸媒溶液，其中該水相觸媒溶液至少包含三價鐵離子；以及對該水相觸媒溶液進行一再活化處理，使該三價鐵離子氧化成該六價鐵金屬催化劑，其中該再活化處理包括一濕式氧化法；以及去除該油相化石燃料之該硫氧化合物，以獲得一脫硫油相化石燃料，其中該有機硫化合物之移除率為70.0百分比至100.0百分比。
A method for ultrasonic assisted oxidative desulfurization of fossil fuel, comprising: mixing an aqueous phase catalyst solution with an oil phase fossil fuel to form a mixed solution, wherein the oil phase fossil fuel comprises at least an organic sulfur compound, the organic sulfurization The composition includes thiophene (T), benzothiophene (BT), dibenzothiophene (DBT) or a derivative thereof, and the aqueous phase catalyst solution contains at least a hexavalent iron metal catalyst and a tetraoctyl group. An ammonium salt interface active catalyst, the hexavalent iron metal catalyst is hexavalent ferrite, the hexavalent ferrite comprises lithium ferrate, sodium ferrate, calcium ferrate or any combination thereof, and the aqueous catalyst solution And the weight ratio of the oil phase fossil fuel is 1:1 to 3:1; the ultrasonic solution is subjected to an ultrasonic vibration treatment to form an emulsified solution, wherein the hexavalent iron metal catalyst is the oil phase fossil fuel The organic sulfur compound is oxidized to a sulfur oxide compound; the emulsified solution is subjected to a phase separation step to separate the oil phase fossil fuel from the emulsified solution, wherein the phase separation step is at least The method comprises: separating the aqueous phase catalyst solution from the emulsified solution, wherein the aqueous phase catalyst solution comprises at least ferric ion; and re-activating the aqueous phase catalyst solution to oxidize the ferric ion The hexavalent iron metal catalyst, wherein the reactivation treatment comprises a wet oxidation method; and removing the sulfur oxide compound of the oil phase fossil fuel to obtain a desulfurized oil phase fossil fuel, wherein the organic sulfur compound is removed The rate is 70.0% to 100.0%.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中該四辛基銨鹽包括四辛基氟化銨(tetraoctylammonium fluoride；TOAF)、四(十八烷基)溴化銨(tetraoctadecylammonium bromide；TODAB)、四辛基溴化銨(tetraoctylammonium bromide；TOAB)、四丁基溴化銨(tetrabutylammonium bromide；TBAB)、甲基三丁基氯化銨(methyltributylammonium chloride；MBAC)、甲基三丁基氫氧化銨(methyltributylammonium hydroxide；MBAH)、四甲基氟化銨(tetramethylammonium fluoride；TMAF)或上述之任意組合。
The ultrasonic assisted oxidative desulfurization method for fossil fuel according to claim 1, wherein the tetraoctyl ammonium salt comprises tetraoctylammonium fluoride (TOAF) and tetrakis(octadecyl) bromide. Ammonium (tetraoctadecylammonium bromide; TODAB), tetraoctylammonium bromide (TOAB), tetrabutylammonium bromide (TBAB), methyltributylammonium chloride (MBAC), Methyltributylammonium hydroxide (MBAH), tetramethylammonium fluoride (TMAF) or any combination of the above.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中該六價鐵金屬催化劑以及該四辛基銨鹽界面活性催化劑於該水相觸媒溶液之含量分別為0.04至2重量百分比。
The ultrasonic assisted oxidative desulfurization method for fossil fuel according to claim 1, wherein the hexavalent iron metal catalyst and the tetraoctyl ammonium salt interfacial catalyst are respectively 0.04 in the aqueous catalyst solution. Up to 2 weight percent.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中該六價鐵金屬催化劑以及該四辛基銨鹽界面活性催化劑於該水相觸媒溶液之含量分別為0.08至1重量百分比。
The ultrasonic assisted oxidative desulfurization method for fossil fuel according to claim 1, wherein the hexavalent iron metal catalyst and the tetraoctyl ammonium salt interfacial catalyst are respectively 0.08 in the aqueous catalyst solution. Up to 1 weight percent.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中該水相觸媒溶液與該油相化石燃料之重量比為1：1至1.25：1。
The ultrasonic assisted oxidative desulfurization method for fossil fuel according to claim 1, wherein the weight ratio of the aqueous phase catalyst solution to the oil phase fossil fuel is 1:1 to 1.25:1.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中該超音波震盪處理係於0℃至90℃以及1大氣壓下進行5分鐘至30分鐘。
The ultrasonic assisted oxidative desulfurization method of fossil fuel according to claim 1, wherein the ultrasonic vibration treatment is performed at 0 ° C to 90 ° C and at 1 atm for 5 minutes to 30 minutes.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中去除該硫氧化合物之步驟係利用一極性吸附材料吸附該硫氧化合物。
The ultrasonic assisted oxidative desulfurization method of fossil fuel according to claim 1, wherein the step of removing the oxysulfide uses a polar adsorbent to adsorb the oxysulfide.
根據申請專利範圍第7項所述之化石燃料之超音波輔助氧化脫硫方法，其中該極性吸附材料為酸性氧化鋁吸附材料。
The ultrasonic assisted oxidative desulfurization method of fossil fuel according to claim 7, wherein the polar adsorbent is an acidic alumina adsorbent.
根據申請專利範圍第1項所述之化石燃料之超音波輔助氧化脫硫方法，其中該硫氧化合物包括包括亞碸基化合物、碸基化合物或其衍生物。
The ultrasonic assisted oxidative desulfurization method of fossil fuel according to claim 1, wherein the oxysulfide compound comprises a mercapto compound, a mercapto compound or a derivative thereof.