JP2012025933A - Desulfurization method of fossil fuel and device using the desulfurization method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a desulfurization method of fossil fuels.SOLUTION: The desulfurization method combines the fossil fuels with an aqueous mixture mutually to form a mixture, and the mixture is then subjected to reactive mixing to form oxides of sulfur compounds in the fuel, wherein the aqueous mixture is obtained by mixing ozone or hydrogen peroxide and a tetraoctylphosphonium salt as a surfactant. The polar sulfone is removed via another mixing step. A desulfurization device provides continuous mixing-assisted desulfurization function and removes sulfur from fossil fuels such as diesel fuel.

Description

  The present invention relates to a desulfurization system for petroleum, fossil fuels, and petroleum-based fuels.

  In the current transportation industry, diesel fuel is a widely used fossil fuel. Since diesel engines are superior to gasoline engines in terms of energy saving, demand for diesel fuel is expected to rise in the future as environmental protection awareness and green movements increase day by day. Diesel fuel is generally a mixture of alkanes, cycloalkanes, and aromatic hydrocarbons, and is a relatively complex mixture. The number of carbon atoms ranges from 9 to 28, and the boiling point ranges from 150 to 390. ° C. Their relative distribution is mainly determined by the following parameters: specific fuel feedstock, refining process, and mixed plans based on consumers' daily commercial demands. For example, sulfides such as alkylbenzothiophenes and alkyldibenzothiophenes are often detected in diesel oil.

  Sulfur content in diesel oil presents environmental difficulties, for example, during combustion, it generates sulfur dioxide (SO2) and sulfate particulate matter, which belongs to serious harmful substances and is therefore a health hazard to the public. On the other hand, it causes extremely serious injury. In addition, sulfur causes other problems, such as damage to catalytic converters, partial corrosion of internal combustion engines, and air pollution that is becoming increasingly common. The sulfur contained in gasoline and other petroleum products also harms the outside, so the US Environmental Protection Agency has already issued relevant regulations, and the upper limit of the sulfur content of petroleum The upper limit of the sulfur content of diesel oil is reduced from 300ppm to 30ppm from 300ppm to 15ppm, ensuring the safety and health of the general public.

  The hydrodesulfurization method is a kind of desulfurization method, which can remove sulfur from diesel oil by a chemical method known on a large scale. A known hydrodesulfurization process is a hydro-treatment process, which decomposes sulfide compounds in diesel oil with hydrogen gas and catalyst to form hydrogen sulfide.

  However, in the desulfurization process, even a small amount of unreacted hydrogen sulfide causes great harm. Hydrogen sulfide is a significant threat to workers because it is extremely toxic and may have resulted in the death of a large number of personnel at the work site. Also, under the relatively new and strict regulations of the US Environmental Protection Agency, when performing a hydrodesulfurization process, there is a high probability that hydrogen gas will leak from the outer wall of the reactor.

  Oxidative desulfurization is a desulfurization scheme applied to conventional diesel oil, which is based on the following operating principle: The polarity of sulfur compounds is higher than that of hydrocarbons. Also, sulfates, such as sulfones, are more polar than sulfides. More importantly, sulfones formed from sulfides are obtained more quickly and easily than hydrocarbons. Therefore, sulfides with relatively poor polarity can be converted into more polar sulfones or sulfoxides, and sulfur compounds can be extracted from fossil fuels relatively easily and melted in aqueous solutions.

  US Pat. No. 6,402,939 describes the following technical features: Organic sulfides are removed from fossil fuels by combining oxidative desulfurization and ultrasonic techniques. Among them, the oxidative desulfurization method is achieved by combining fossil fuel and hydroperoxide as an oxidant in an aqueous phase fluid, and ultrasonic waves are added on the mixture to increase the reactivity of various substances in the mixture. Ultrasound-assisted oxidative desulfurization (UAOD) is performed under normal temperature and pressure, which can selectively remove sulfur compounds from hydrocarbons. However, if quaternary ammonium bromide is used as a surfactant, by-products such as bromide are generated. The sonoreactor used by the desulfurization process also has a number of drawbacks, such as requiring very expensive instruments, which are relatively complex in technology such as RF amplifiers and function generators. It requires parts, requires a relatively high power consumption for the generation of ultrasonic waves, requires a relatively high operating temperature (usually 70-80 ° C), and long-term ultrasonics are long-chain carbonized. It can also cause damage to hydrogen (e.g. cracking). Also, only when the corresponding function generators and RF amplifiers are increased, it can be applied to relatively large-scale production, which also brings mass production limitations of conventional ultrasonic reactors or ultrasonic desulfurization equipment. .

  In batch production, using a probe type reactor and applying ultrasonic waves to the oxidative desulfurization method can improve the removal rate of sulfur, but all the reactants are one. And held in a controlled environment for a certain time until the desired reaction result is reached. Again, such a reaction process is often relatively slow, takes a relatively long time, and requires that the product be separated prior to the end of the treatment process.

  In order to overcome the above problems, an object of the present invention is to provide a mixed auxiliary oxidative desulfurization method applied to fossil fuels. The fossil fuel is combined with an aqueous oxidant solution, which includes a hydroperoxide solution or an ozone solution. The aqueous phase oxidant solution contains quaternary ammonium as a surfactant, and the quaternary ammonium has a positive charge and a nitrogen atom having four substituents and a negatively charged counter ion. (Counter ion). In this example, the quaternary ammonium has a carbon chain containing at least one 8 or more carbon atoms. Quaternary ammonium serves as a surfactant, improves the amount of sulfide converted to sulfone, and does not generate byproducts such as bromide.

  Another object of the present invention is to provide a mixed auxiliary oxidative desulfurization applied to fossil fuels. The fossil fuel is combined with an aqueous phase hydroperoxide solution or an aqueous phase ozone solution. The hydroperoxide solution or ozone solution contains quaternary ammonium, and the quaternary ammonium is used as a surfactant to improve the amount of sulfide that is converted into sulfone in the organic fuel. The mixed auxiliary oxidative desulfurization method uses a plurality of mixing tanks and a plurality of whirlwind separators, and does not require a complicated, unreliable, and expensive ultrasonic generator. In addition, since no ultrasonic generator is used, it is not necessary to use a refrigerant during the fossil fuel desulfurization process and to cool the multiphase reaction medium. Further, the amount of energy consumption required for this mixed auxiliary oxidative desulfurization method is also reduced. Furthermore, since there is no need to use a function generator and RF amplifier, the mixed assisted oxidative desulfurization method is more suitable for large-scale production compared to conventional ultrasonic generators or ultrasonic desulfurization methods. In addition, in the long term, the mixed auxiliary oxidative desulfurization method does not cause damage (for example, generation of cracks) to the long chain hydrocarbon.

  Another object of the present invention is to provide a continuous flow system, which is used for fossil fuel oxidative desulfurization. The oxidative desulfurization system is a continuous flow unit having a plurality of modular mixing tanks, and the continuous flow unit includes at least two mixing tanks, a mixer, at least two whirling separators, and an evaporation tower. A mixer is connected to each mixing vessel and used to stir and mix to efficiently produce a foamed emulsion and a whirl separator is continuously connected in series with the mixing vessel. The evaporation tower is connected to one of the whirl separators and one of the mixing tanks to generate sulfone. Moreover, in order to process more fuel and promote oxidation, a plurality of sets of mixing tanks and vortex separators can be increased, and the plurality of sets of mixing tanks and vortex separators include a plurality of evaporation towers, Connect in parallel or directly.

  The method for removing sulfides from the liquid fossil fuel of the present invention comprises (a) combining an oxidant solution, a metal catalyst, and an interfacial lubricant to form a multiphase reaction medium, and (b) a desulfurization reaction. In the vessel, the multiphase reaction medium is mixed and reacted for a certain period of time, the sulfide in the liquid fossil fuel is oxidized to sulfone, and a plurality of bubbles are formed, the reaction area is increased, and the reaction efficiency is increased. Including promoting.

  The method for removing sulfides of the present invention further comprises separating the oil phase fluid from the aqueous phase fluid using a first whirl separator.

  The method for removing sulfides of the present invention further includes mixing and separating the oil phase fluid from the polar solvent fluid by a polar solution extractor.

  The method for removing sulfides of the present invention further comprises generating a plurality of bubbles in a polar solvent extractor, the majority of these bubbles having a diameter of less than 1 mm.

  The method for removing sulfides of the present invention further comprises recycling a water phase solvent solution comprising a surfactant, an oxidant solution, and a metal catalyst.

  The method for removing sulfides of the present invention further includes using a second whirl separator to separate the oil phase fluid from the polar solvent fluid.

  The method of removing sulfides of the present invention further includes separating and collecting the sulfone and using it to generate an organic phase fluid that is essentially free of sulfone.

  In the method for removing sulfide according to the present invention, the surfactant is quaternary ammonium, and the quaternary ammonium has four substituents, and these substituents have 1 to 20 carbon atoms. It is one kind of material selected from the group consisting of an alkyl group having an atom, an aryl group, and an aralkyl group, of which at least one substituent is an alkyl group having 8 or more carbon atoms.

  In the method for removing sulfides of the present invention, the surfactant is a tetraoctylphosphonium salt.

  In the method for removing sulfide according to the present invention, the oxidizing agent solution contains hydrogen peroxide, hydroperoxide, or ozone.

  In the method for removing sulfide according to the present invention, the mixing ratio of the liquid fossil fuel and the oxidant solution is between 1: 1 and 1: 3.

  In the method for removing sulfides of the present invention, the metal catalyst is iron (II) ion, iron (III) ion, copper (I) ion, copper (II) ion, chromium (III) ion, chromium (VI) ion. , Molybdate, tungstate, and vanadate, one material selected from the group consisting of the metal catalyst, the liquid fossil fuel, and the oxidant solution form a multiphase reaction medium To do.

  In the method for removing sulfide according to the present invention, the metal catalyst is phosphotungstic acid.

  In the method for removing sulfides according to the present invention, the liquid fossil fuel is selected from crude oil, shale oil, diesel oil, gasoline, dredged oil, liquefied petroleum lees, and residual petrochemical fuel oil.

  In the method for removing sulfide according to the present invention, the liquid fossil fuel is diesel oil or a diesel oil mixture.

  The method for removing sulfides of the present invention comprises: (a) combining an oxidant solution, a metal catalyst, and an interfacial lubricant to form a multiphase reaction medium, of which the oxidant solution contains ozone And (b) mixing and reacting the multiphase reaction medium for a fixed and sufficient time to oxidize the sulfide in the liquid fossil fuel to sulfone.

  The method for removing sulfides from the liquid fossil fuel of the present invention comprises: (a) combining an oxidant solution, a metal catalyst, and an interfacial lubricant to form a multiphase reaction medium, of which the surface activity The agent includes a tetraoctylphosphonium salt, and (b) includes mixing and reacting the multiphase reaction medium for a fixed and sufficient time to oxidize sulfide in the liquid fossil fuel to sulfone.

  In the continuous desulfurization apparatus of the present invention, each mixing tank is connected to a mixer, and the mixer is used for stirring and mixing to generate a plurality of bubbles, and the majority of these bubbles have a diameter smaller than 1 mm. Connected to a mixing tank, a plurality of whirling separators connected to the mixing tank in a series connection manner, and one whirling separator among them. And an evaporation tower.

  In the continuous desulfurization apparatus of the present invention, the mixer is connected to the mixing tank, and the mixing tank is connected to a recirculation circuit.

  The continuous desulfurization apparatus according to the present invention further includes a diesel supply tank containing diesel oil fuel having a high sulfur content, an oxidant supply tank containing an oxidant aqueous phase solution, and an interfacial lubricant container containing a surfactant. And a metal catalyst container containing a metal catalyst, wherein the plurality of mixing tanks include a first mixing tank, the plurality of whirling separators includes a first whirling separator, and the first whirling air The separator is a diesel oil / water phase separation tank, and the diesel oil supply tank, the oxidant supply tank, the surfactant container, and the metal catalyst container are interconnected with the inlet of the first mixing tank. The first whirling separator is interconnected with the outlet of the first mixing tank.

  In the continuous desulfurization apparatus of the present invention, the aqueous phase fluid separated by the first whirling separator is recirculated to the first mixing tank column via a recirculation circuit.

  In the continuous desulfurization apparatus of the present invention, a catalyst activation vessel is provided in the recirculation circuit.

  In the continuous desulfurization apparatus according to the present invention, the plurality of mixing tanks further include a second mixing tank, the plurality of whirling separators further include a second whirling separator, and the second mixing tank includes a polar solution extractor. And connecting between the first vortex separator and the second vortex separator.

  The continuous desulfurization apparatus of the present invention further includes a diesel oil holding tank, in which the second whirling separator separates diesel oil having a low sulfur content and stores it in the diesel oil holding tank.

  The continuous desulfurization apparatus of the present invention further includes a recirculation circuit, and the recirculation circuit is connected to the second mixing tank.

  In the continuous desulfurization apparatus of the present invention, a solution recovery tank is provided in the recirculation circuit.

  In the continuous desulfurization apparatus of the present invention, the mixer is an ultrasonic oscillator, a mechanical stirring mixer, or a high-pressure water column mixer.

  The continuous desulfurization apparatus of the present invention contains a first mixing tank, a diesel oil fuel having a high sulfur content, interconnected with an inlet of the first mixing tank, and an oxidant aqueous phase solution. An oxidant supply tank interconnected with the inlet of the first mixing tank; a surfactant; an interfacial lubricant container interconnected with the inlet of the first mixing tank; and a metal catalyst. A metal catalyst container interconnected to the inlet of the first mixing tank, a diesel oil / water phase separation tank, and a first whirl separator connected to the first mixing tank in a series connection manner; A polar solution extractor, interconnected with the first whirling separator and interconnected with the first whirling separator to generate an organic phase essentially free of sulfone. A second whirling separator to be used, an evaporation tower interconnected with the second whirling separator, and the second whirling component A diesel oil holding tank connected to the separator, wherein the aqueous phase fluid separated by the first whirl separator is recirculated through the recirculation circuit into the first mixing tank, The organic phase, which is essentially free of sulfone, separated by the vortex separator is transmitted to the evaporation tower, and the second vortex separator separates the diesel oil having a low sulfur content, in the diesel oil holding tank. Save to.

  The present invention provides a mixed assisted oxidative desulfurization process applied to fossil fuels, wherein the fossil fuels are combined with an aqueous phase oxidant solution, the aqueous phase oxidant solution comprising a hydroperoxide solution or an ozone solution. The aqueous phase oxidant solution contains a quaternary ammonium as a surfactant, and the quaternary ammonium is a positively charged and negatively charged pair with a nitrogen atom having four valence groups. It is a compound composed of ions. In this example, the quaternary ammonium has a carbon chain containing at least one 8 or more carbon atoms. Quaternary ammonium serves as a surfactant, improves the amount of sulfide converted to sulfone, and does not generate byproducts such as bromide.

  The present invention provides mixed assisted oxidative desulfurization applied to fossil fuels, which are combined with aqueous phase hydroperoxide solutions or aqueous phase ozone solutions. The hydroperoxide solution or ozone solution contains quaternary ammonium, and the quaternary ammonium is used as a surfactant to improve the amount of sulfide that is converted into sulfone in the organic fuel. The mixed auxiliary oxidative desulfurization method uses a plurality of mixing tanks and a plurality of whirlwind separators, and does not require a complicated, unreliable, and expensive ultrasonic generator. In addition, since no ultrasonic generator is used, a multiphase reaction medium is cooled by using a refrigerant during the desulfurization process of the fossil fuel. Further, the amount of energy consumption required for this mixed auxiliary oxidative desulfurization method is also reduced. Furthermore, since there is no need to use a function generator and RF amplifier, the mixed assisted oxidative desulfurization method is more suitable for large-scale production compared to conventional ultrasonic generators or ultrasonic desulfurization methods. In addition, in the long term, the mixed auxiliary oxidative desulfurization method does not cause damage (for example, generation of cracks) to the long chain hydrocarbon.

  The present invention provides a continuous flow system, which is used for fossil fuel oxidative desulfurization. The oxidative desulfurization system is a continuous flow unit having a plurality of modular mixing tanks, and the continuous flow unit includes at least two mixing tanks, a mixer, at least two whirling separators, and an evaporation tower. A mixer is connected to each mixing vessel and used to stir and mix to efficiently produce a foamed emulsion and a whirl separator is continuously connected in series with the mixing vessel. The evaporation tower is connected to one of the whirl separators and one of the mixing tanks to generate sulfone. Moreover, in order to process more fuel, a plurality of sets of mixing tanks and vortex separators can be increased, and the plurality of sets of mixing tanks and vortex separators can be connected in parallel or directly to a plurality of evaporation towers. Connecting.

It is a figure which shows the continuous desulfurization apparatus of a present Example. It is a figure which shows the desulfurization process of the portable continuous desulfurization apparatus of FIG.

  In order to facilitate understanding of the above objects, features and advantages of the present invention, examples will be given below and described in detail with reference to the drawings.

  Many deep desulfurization methods need to be relatively expensive. In the past 40 years, scientists have tried to develop many deep desulfurization methods, of which oxidative desulfurization is a low consumption, high efficiency deep desulfurization technology. is there. In oxidative desulfurization, it is necessary to select an appropriate catalyst and a strong oxidant and combine an appropriate surfactant, and thus the desulfurization efficiency of the oil product can be greatly improved. The reaction process converts organic sulfur in the oil product to sulfur oxide with polarity, and the sulfur is removed by a polar solvent / adsorbent.

  Here, hydroperoxide refers to a compound, and R in the molecular structure means a hydrogen atom, an organic group, or an inorganic group. Among them, hydroperoxides in which R is an organic group can be dissolved in water, for example, methyl hydroperoxide, ethyl hydroperoxide, isopropyl hydroperoxide, n-butyl hydroperoxide, sec-butyl hydroperoxide, tert-butyl hydroperoxide 2-methoxy-2-propyl hydroperoxide, tert-amyl hydroperoxide, and cyclohexyl hydroperoxide. Examples of the hydroperoxide in which R is an inorganic group include peroxynitrite, perphosphoric acid, and persulfuric acid. Suitable hydroperoxides are hydrogen peroxide (of which R is a hydrogen atom) and tert-alkyl peroxides, such as tert-butyl hydroperoxide.

  The fossil fuel and oxidizer aqueous solution are mixed to form an aqueous fluid, wherein the oxidant aqueous phase solution contains hydrogen peroxide, hydroperoxide, or ozone. The relative ratio of liquid fossil fuel and oxidant aqueous phase solution is between 1: 1 and 1: 3, preferably 1: 1.25. In the oxidant aqueous phase solution, the concentration of hydroperoxide is between 1% and 30%. While the relative ratio affects process efficiency and fluid handling difficulty, it is not critical in the present invention. However, in most cases, ozone can be added to the oxidant aqueous phase solution to produce a suitable effect. The method of adding ozone can be achieved, for example, with an ozone generator (model number: Pacific Ozone L22). Inject ozone bubbles into the aqueous phase liquid or ozone directly into the solution. Among them, the flow rate of ozone is between 0.01 g / hr and 1 g / hr. Moreover, the density | concentration in the oxidizing agent aqueous phase solution of ozone is 0.01g / L-1g / L, and is in a saturated state suitably.

  The content of hydroperoxide relative to the fossil fuel and aqueous phase solution is still variable, and the conversion can only be accompanied by the ratio of hydroperoxide, but has minor changes. Good results are obtained when the hydroperoxide is hydrogen peroxide and its deposition relatively accounts for 1% to 30% of the total aqueous and organic phase solution, preferably 3% to 30%. Obtainable. For hydroperoxides other than hydrogen peroxide, the preferred relative volume is the corresponding molar amount.

  In this example, the metal catalyst is included in the reaction system and regulates the activity of the hydroxyl radical, which is generated from hydroperoxide. This metal catalyst is, for example, a transition metal catalyst, a Fenton catalyst (i.e., an iron salt), or a metal ion catalyst, and the metal ion of the metal ion catalyst is: For example, iron (II) ion, iron (III) ion, copper (I) ion, copper (II) ion, chromium (III) ion, chromium (VI) ion, molybdenum ion, tungsten ion, and vanadium ion. For dredging systems, such as crude oil systems, Fenton catalysts are preferred. For other systems, such as diesel oil systems and other systems where dibenzothiophene is an important composition, tungstate is a suitable metal catalyst. The tungstate includes tungstic acid, substituted tungstic acids, or metal tungstates, for example, phosphotungstic acid. The added amount of the above metal catalyst needs to reach a catalytically effective amount. The so-called effective catalyst amount is intended to direct the reaction process toward a predetermined target (ie, oxidize sulfide to sulfone). The amount that can be reacted. In most cases, when the hydroperoxide solution is 25 g, the catalytically effective amount is from 0.01 kg to 0.5 kg (3% to 30% volume concentration), preferably 0.2 kg. In this example, the surfactant is a tetraoctylphosphonium salt, and the tetraoctylphosphonium salt is, for example, tetraoctylphosphonium bromide, tetraoctylphosphonium chloride, tetraoctylphosphonium iodide, tetraoctylphosphonium acetate. Or tetraoctylphosphonium chromate. The chemical structural formula of the tetraoctylphosphonium salt is as follows.

R ₁ , R ₂ , R ₃ , and R ₄ are alkyl radicals and have 8 carbon atoms in the alkyl branch and alkyl straight chain, and X − is a negative ion. It is. In most proposals, when the hydroperoxide solution is 25 g, the catalytically effective amount of tetraoctylphosphonium salt used as a surfactant intervenes in 0.01 kg to 0.5 kg (3% to 30% volume concentration), which is preferable. Is 0.2kg. The aqueous oxidizer solution, surfactant, metal catalyst, and diesel oil having a relatively high sulfur content are mixed via a plurality of conduits and conveyed to the first mixing tank. With conventional flow valves and flow control systems, the flow rate of the feed stream in each conduit can be controlled independently. In the first mixing tank, these reactants can be thoroughly mixed by the mixer. Also, in the oil / aqueous emulsion in the first mixing tank, the contact area where many bubbles are generated oxidizes sulfide to sulfone, or accelerates the reaction rate of sulfone. Can do.

  After the completion of the mixing reaction, the resulting mixture contains an aqueous phase and an organic phase, of which the organic phase contains a sulfone mostly composed of an oxidation reaction. Prior to removal of the sulfone, the resulting mixture can undergo phase separation. By demulsification, the phase separation operation can be completed. Moreover, the process of demulsification can be completed by a conventional method. For those having ordinary skill in the fields of emulsification and continuous stirring, the above system is self-evident, especially in the water-in-oil emulsion field.

  Compared to existing sulfides in fossil fuels, sulfone has a relatively high polarity, so after undergoing a process such as mixing and separation into polar substances by a polar solution extractor, the sulfone is water phase, organic It can be easily removed from the phase or a mixture of both. In this embodiment, the polar solution extractor is arranged in the mixing tank of the mixer. The extraction effect can be increased by adding many microbubbles into the sufficiently stirred and mixed emulsified mixture, because the contact area between the polar solution and the fossil fuel is increased. These microbubbles can be liquid bubbles or gas bubbles, and these liquid bubbles are, for example, oil phase bubbles or water phase bubbles. In other embodiments, the polar solution extractor can be a liquid-solid adsorption unit. Aluminum oxide can be filled into the solid adsorber tube column and can assist the absorption process by gravity and vacuum techniques. In the polar solution extractor, a solution such as acetonitrile can be used as the polar solution. Acetonitrile can be easily separated from the sulfone by the method of distillation (boiling point between 550K and 950K). Of these, the weight percent of solvent and oils can be maintained at 1: 1 (eg, 1 kg diesel oil combined with 1 kg acetonitrile).

  As used herein, “liquid fossil fuel” refers to any carbon-containing liquid refined from petroleum, coal, and other natural materials. These fuels can be fuels for transportation such as gasoline, diesel oil, airplane fuel, rocket fuel, or can be residual petrochemical fuel oil such as heavy oil or residual fuel.

  The execution method of the mixed auxiliary oxidative desulfurization method uses, for example, a continuous flow system, which can be operated in a stable state, and in the operation process, the reactants are reacted in a reaction vessel. the product is continuously removed from the reaction vessel.

  The present embodiment discloses a continuous desulfurization apparatus 10, which can process a large amount of diesel fuel in a short time, has high desulfurization efficiency, low cost input, low maintenance cost, etc. Has the advantage of Moreover, the operating temperature of the continuous desulfurization apparatus 10 is lower than that of the ultrasonic generator. Generally, the operating temperature is raised to 50-60 ° C. by the chemical reaction of the aqueous phase fluid. This continuous desulfurization apparatus 10 can remove a sulfur content of approximately 95%. When improving yield and effect, two continuous desulfurization devices 10 can be run in parallel to achieve a higher desulfurization rate.

  FIG. 1 shows a continuous desulfurization apparatus 10 of this embodiment. Among them, the oxidant supply tank 30 is used for supplying an oxidant aqueous phase solution, and the diesel oil supply tank 20 is used for supplying diesel oil fuel having a high sulfur content. Among them, the oxidant supply tank 30 and the diesel oil supply tank 20 are connected to the first mixing tank 100 by a plurality of conduits. Further, the surfactant container 40 and the metal catalyst container 50 are also connected to the first mixing tank 100. Among them, the flow rates of the oxidant supply tank 30, the diesel oil supply tank 20, the surfactant container 40, and the metal carrier container 50 can be controlled independently by a conventional flow valve and control system.

  The mixture participating in the reaction is mixed in the first mixing tank 100 by adding the surfactant and the metal catalyst, and further with the aid of the mixer 110. Here, the first mixing tank 100 can also be regarded as a desulfurization reactor. The mixing reaction process performed in the oil phase / water phase emulsion of the first mixing tank 100 includes a process of oxidizing sulfide to sulfoxide or sulfone. After mixing, the mixture participating in the reaction is transported to the first whirling separator 140. The first whirling separator 140 can be regarded as a diesel oil / water phase separation tank. In this diesel oil / water phase separation tank, an aqueous phase fluid (including an oxidizer and a catalyst) and an oil phase fluid (including a diesel oil and a sulfone) are phase-separated. In this way, a low sulfur content diesel oil can be produced in the subsequent treatment process. Thereafter, after a predetermined time, the aqueous phase fluid passes through the catalyst activation vessel 55 through the recirculation circuit and circulates into the first mixing tank 100.

  In the present embodiment, the mixer 110 is a mechanical stirring type mixer, which mixes the solution in the first mixing tank 100 using a mechanical stirring method. However, those skilled in the art can also use a mixer capable of achieving a mixing effect such as an ultrasonic oscillator or a high-pressure water column mixer, and the so-called high-pressure water column mixer uses a high-pressure water column jet to achieve the mixing effect. It is.

  A second mixing tank 200 is installed between the first whirling separator 140 and the second whirling separator 240. The second mixing tank 200 is a polar solution extractor. After passing through the mixing and extraction process in the second mixing tank 200 with the assistance of the mixer 110, an oil containing a by-product such as sulfone and diesel oil having a low sulfur content. The phase fluid is separated. Thereafter, the oil phase fluid is transmitted to the second whirling separator 240, which separates the diesel oil having a low sulfur content and stores it in the pillars of the diesel oil holding tank 11. In addition, a polar solution containing a by-product such as sulfone is transmitted into the evaporation tower 300, and the polar solution is recovered and reused and stored in a solution recovery tank 65. Among them, by-products such as sulfone can be obtained from the evaporation tower 300.

  Various fuels having different sulfur contents can be subjected to an optimized mixed auxiliary oxidative desulfurization process to remove 95% or more of sulfur, or the concentration of sulfur can be reduced to 15ppm or less. Tetraoctylphosphonium salts can also prevent the generation of byproducts such as bromides. Also, the suitable interphase conversion capability can also allow the transition metal catalyst to have a relatively high recovery rate and a suitable reuse rate, so that even with diluted hydroperoxide and ozone solutions, the same desulfurization is still possible. Efficiency can be obtained.

  Referring to FIG. 2, FIG. 2 shows the desulfurization process of the portable continuous desulfurization apparatus of FIG. 1, which removes sulfur from the liquid fossil fuel, which includes the following steps: .

  In step S100, the liquid fossil fuel flowing out from the diesel oil supply tank 20 and the oxidant solution flowing out from the oxidant supply tank 30 are phase-mixed, and the oxidant solution is an ozone solution or a hydrogen peroxide solution containing water. . In addition, the surfactant stored in the surfactant container 40 and the metal catalyst stored in the metal catalyst container 50 are mixed together to form a multiphase reaction medium. Surfactants such as tetraoctylphosphonium salts have four substituents, and the substituents are selected from the group consisting of alkyl groups having 1 to 20 carbon atoms, aryl groups, and aralkyl groups. One material selected, of which at least one substituent is an alkyl group having 8 or more carbon atoms. The metal medium stored in the metal medium container 50 is a transition metal medium such as phosphotungstic acid. In addition, for example, in a sulfur-containing diesel oil used as a liquid fossil fuel for every 25 kg, the amount of surfactant used is about 0.1 kg, the amount of metal catalyst used is about 0.2 kg, and the sulfur-containing diesel oil and Combine the same volume of hydrogen peroxide or ozone solution, among which the hydrogen peroxide or ozone volume concentration is between 3% and 30%.

  In step 105, the multiphase reaction medium is mixed for a predetermined and sufficient time to oxidize sulfides in diesel oil to sulfone to form an emulsion bubble. After sufficiently stirring and mixing the multiphase reaction medium in the first mixing tank 100, the diameter of the generated bubbles is less than 1 mm, or the diameter of most of the bubbles is less than 1 mm. In a preferred situation, the majority of the foam diameter is kept at about 10 μm and the remaining majority of the foam diameter is less than 0.1 mm.

  In step S110, the oil phase fluid and the water phase fluid can be separated by the first whirling separator 140. Thereafter, in step S130, the second whirling separator 140 can phase separate the solution containing the polar solvent and the nonpolar solution.

  In step 115, the oil phase fluid in the polar solvent can be mixed and separated by the second mixing tank 200 or what is called a polar solution extractor. The polar solvent in the second mixing tank 200 is, for example, acetonitrile, and in a situation where the boiling point is 550K to 950K, acetonitrile can be easily separated from the sulfone by a distillation method. Solvent and oil weight percentages are kept 1: 1, for example, 1 kg diesel oil is combined with 1 kg acetonitrile. The diameters of the foamed emulsions formed are all less than 1 mm, or most of the bubbles are less than 1 mm, and in a preferred situation, the diameter of most of the bubbles is kept at about 10 μm, and The diameter of the remaining numerous bubbles is less than 0.1 mm. In step S105 and step S115, the generated bubbles can be bubbles or liquid bubbles that do not mix.

  In step S <b> 120, the interfacial lubricant and the metal catalyst can be collected by the first whirling separator 140 and recirculated in the catalyst activation vessel 55. At the same time, in step 125, the solvent used in the second mixing vessel 200, such as acetonitrile, can be collected and recovered by the distillation process in the distillation column 300.

  In step S140, the distillation column 300 separates by-products such as sulfone located in the second mixing tank 200 and the second whirling separator 240 from the polar fluid and the nonpolar fluid. In step S <b> 150, the sulfone is transferred from the distillation column 300 into the sulfone holding container 70. Thereafter, in step S135, an organic fluid that is nonpolar and substantially free of sulfone is collected in the clean diesel oil holding tank 11.

  In the present invention, preferred embodiments have been disclosed as described above, but these are not intended to limit the present invention in any way, and anyone who is familiar with the technology can make various modifications within the scope and spirit of the present invention. Changes and modifications can be made. Therefore, the scope of protection of the present invention is based on the contents specified in the claims.

DESCRIPTION OF SYMBOLS 10 Continuous desulfurization apparatus 11 Diesel oil holding tank 20 Diesel oil supply tank 30 Oxidant supply tank 40 Surfactant container 50 Metal catalyst container 55 Catalyst activation container 65 Solution recovery tank 70 Sulfone holding container 100 1st mixing tank 200 2nd mixing Tank 110 Mixer 140 First whirling separator 240 Second whirling separator 300 Evaporating tower S100 to S150 Flowchart steps

Claims (28)

(A) an oxidant solution, a metal catalyst, and an interfacial lubricant are bonded together to form a multiphase reaction medium;
(B) In the desulfurization reactor, the multiphase reaction medium is mixed and reacted for a fixed and sufficient time to oxidize sulfides in the liquid fossil fuel to sulfone, and further form a plurality of bubbles to increase the reaction area. And removing sulfide from the liquid fossil fuel comprising promoting reaction efficiency.   The method for removing sulfide according to claim 1, further comprising separating the oil phase fluid from the aqueous phase fluid using a first whirl separator.   The method for removing sulfide according to claim 2, further comprising mixing the oil phase fluid and separating from the polar solvent fluid by a polar solution extractor.   The method of claim 3, further comprising generating a plurality of bubbles in a polar solvent extractor, wherein a majority of these bubbles have a diameter of less than 1 mm.   The method for removing sulfide according to claim 2, further comprising recycling the aqueous phase solvent solution containing the surfactant, the oxidant solution, and the metal catalyst.   The method for removing sulfide according to claim 2, further comprising using a second whirl separator to separate the oil phase fluid from the polar solvent fluid.   7. The method of removing sulfides of claim 6 further comprising separating and collecting the sulfone and generating an organic phase fluid that is essentially free of sulfone.   Further, the surfactant is a quaternary ammonium, and the quaternary ammonium has four substituents, and these substituents have an alkyl group having 1 to 20 carbon atoms, an aryl group, and an aralkyl. The method for removing a sulfide according to claim 1, wherein the material is one material selected from the group consisting of groups, and at least one of the substituents is an alkyl group having 8 or more carbon atoms. .   The method for removing sulfide according to claim 8, wherein the surfactant is a tetraoctylphosphonium salt.   The method for removing sulfide according to claim 1, wherein the oxidant solution contains hydrogen peroxide, hydroperoxide, or ozone.   The method for removing sulfide according to claim 1, wherein the mixing ratio of the liquid fossil fuel and the oxidant solution is between 1: 1 and 1: 3.   The metal catalyst is iron (II) ion, iron (III) ion, copper (I) ion, copper (II) ion, chromium (III) ion, chromium (VI) ion, molybdate, tungstate, and vanadium. The sulfide according to claim 1, wherein the metal catalyst, the liquid fossil fuel, and the oxidant solution are one material selected from the group consisting of acid salts and form a multiphase reaction medium. how to.   The method for removing sulfide according to claim 12, wherein the metal catalyst is phosphotungstic acid.   The method for removing sulfide according to claim 1, wherein the liquid fossil fuel is selected from crude oil, shale oil, diesel oil, gasoline, kerosene, liquefied petroleum soot, and residual petrochemical fuel oil.   The method for removing sulfide according to claim 1, wherein the liquid fossil fuel is diesel oil or a diesel oil mixture. (A) an oxidant solution, a metal catalyst, and an interfacial lubricant are mutually bonded to form a multiphase reaction medium, wherein the oxidant solution contains ozone,
(B) A method of removing sulfides from a liquid fossil fuel, comprising mixing and reacting a multiphase reaction medium for a fixed and sufficient time to oxidize sulfides in the liquid fossil fuel to sulfone. (A) oxidant solution, metal catalyst, and interfacial lubricant are bonded together to form a multiphase reaction medium, wherein the surfactant comprises a tetraoctylphosphonium salt,
(B) A method of removing sulfides from a liquid fossil fuel, comprising mixing and reacting the multiphase reaction medium for a predetermined and sufficient time to oxidize sulfides in the liquid fossil fuel to sulfone. A plurality of mixing vessels each connected to a mixer, wherein the mixer is used for stirring and mixing to generate a plurality of bubbles, the majority of the bubbles having a diameter of less than 1 mm;
A plurality of whirling separators connected to each other in a series connection method,
An evaporator tower connected to one of the vortex separators, wherein the vortex separator produces an organic phase essentially free of sulfones;
Including continuous desulfurization equipment.   The continuous desulfurization apparatus according to claim 18, wherein the mixer is connected to the mixing tank and the mixing tank is connected to a recirculation circuit. In addition, a diesel supply tank containing diesel fuel with a high sulfur content;
An oxidant supply tank containing the oxidant aqueous phase solution;
An interfacial lubricant container containing a surfactant;
A metal catalyst container containing a metal catalyst, wherein the plurality of mixing tanks include a first mixing tank, the plurality of whirling separators includes a first whirling separator, and the first whirling separator Is a diesel oil / water phase separation tank, the diesel oil supply tank, the oxidant supply tank, the surfactant container, and the metal catalyst container are interconnected with the inlet of the first mixing tank, The continuous desulfurization apparatus according to claim 18, wherein the first whirling separator is connected to an outlet of the first mixing tank.   The continuous desulfurization apparatus according to claim 20, wherein the aqueous phase fluid separated by the first whirl separator is recirculated to the first mixing tank column via a recirculation circuit.   The continuous desulfurization apparatus according to claim 21, wherein a catalyst activation vessel is provided in the recirculation circuit.   The plurality of mixing tanks further include a second mixing tank, the plurality of whirling separators further include a second whirling separator, the second mixing tank is a polar solution extractor and the first whirling wind The continuous desulfurization apparatus according to claim 20, wherein a separator and the second whirlwind separator are connected.   The continuous desulfurization apparatus according to claim 23, further comprising a diesel oil holding tank, wherein the second whirling separator separates diesel oil having a low sulfur content and stores the diesel oil in the diesel oil holding tank.   The continuous desulfurization apparatus according to claim 23, further comprising a recirculation circuit, wherein the recirculation circuit is connected to the second mixing tank.   The continuous desulfurization apparatus according to claim 25, wherein a solution recovery tank is provided in the recirculation circuit.   The continuous desulfurization apparatus according to claim 23, wherein the mixer is an ultrasonic oscillator, a mechanical stirring mixer, or a high-pressure water column mixer. A first mixing tank;
A diesel supply tank containing diesel fuel with a high sulfur content and interconnected with the inlet of the first mixing tank;
Containing an oxidant aqueous phase solution and interconnecting with an inlet of the first mixing tank;
An interfacial lubricant container containing a surfactant and interconnected with the inlet of the first mixing vessel;
A metal catalyst container containing a metal catalyst and interconnected with an inlet of the first mixing tank;
A first whirling separator that is a diesel oil / water phase separation tank and interconnects with the first mixing tank in a series connection manner;
A polar solution extractor, a second mixing vessel interconnected with the first whirlwind separator,
A second vortex separator interconnected with the first vortex separator and used to generate an organic phase essentially free of sulfone;
An evaporator tower interconnected with the second whirlwind separator;
A diesel oil holding tank connected to the second whirlwind separator;
Of which the aqueous phase fluid separated by the first whirl separator is recirculated through the recirculation circuit into the first mixing tank and separated by the second whirl separator. A continuous desulfurization apparatus in which the organic phase in which no water is present is transmitted to the evaporation tower and the second whirling separator separates diesel oil having a low sulfur content and stores it in the diesel oil holding tank.